Patent Publication Number: US-4319036-A

Title: Carboalkoxy alkyl norbornanes and process for preparing same

Description:
BACKGROUND OF THE INVENTION 
     The present invention relates to carboalkoxy alkyl norbornanes having the generic formula: ##STR3## wherein the dashed line represents either a carbon-carbon single bond or a carbon-carbon double bond; R 1 , R 2 , R 3  and R 4  represents hydrogen or methyl; with the proviso that one of R 1  and R 2  is methyl and the other of R 1  or R 2  is hydrogen; and with the further proviso that R 3  and R 4  are not both methyl, produced by the novel process of our invention, and to novel compositions using one or more of such norbornane derivatives to alter, modify or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials. 
     There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply, and to provide more uniform properties in the finished product. 
     Fruity, burnt fruit-like, raspberry, sweet, seedy, berry-like, red berry-like, blueberry-like, spicy, black pepper-like, herbaceous, clove-like, vermouth-like, strawberry-like and balsamic aromas with fruity, burnt fruit-like, raspberry, seedy, sweet, berry-like, red berry-like, blueberry-like, spicy, black-pepper-like, herbaceous, clove-like, vermouth-like, strawberry-like, balsamic and bitter tastes are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors. 
     Spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity, berry-like, juicyfruit, woody, piney, blueberry, banana, green, herbaceous, strawberry-like and dill aroma and taste characteristics both prior to and on smoking in the mainstream and in the side stream. 
     Intense and pleasant fruity, banana-like, creamy, camphoraceous, herbaceous, sweet, spicy, woody, eucalyptol-like, rum/butterscotch-like, balsamic, green, minty, borneol-like and 37 medicinal&#34; aromas with strong camphor, minty and calamnus-like undertones are desirable in several types of perfume compositions, perfumed articles and colognes. 
     Arctander, &#34;Perfume and Flavor Chemicals&#34;, 1969, Volume I discloses the use in perfume compositions and in foodstuff flavors of camphene carbinyl acetate thus: 
     &#34;1029: 2,2-Dimethyl-Delta-2-betanorbornane-2-ethylacetate &#34;Camphene carbinyl acetate&#34;. ##STR4## Mild and sweet-woody odor with a floral-piney undertone. The commercial products are probably not well defined single chemicals, and great variations in odor have been observed. 
     This ester has been developed in line with the research on Sandalwood type odors. The parent alcohol &#34;Camphene carbinol&#34; was once considered useful as a Sandalwood type material, but is has found more use as a sweetening and enriching ingredient in sophisticated Pine fragrances. The title ester finds limited use in perfume compositions of woody character, Fougeres, Pine fragrances, etc. and it blends very well with the Cyclohexanol derivatives, Ionones, iso-Bornylacetate, Nitromusks, etc.&#34; 
     Mellor and Webb, J. Chem. Soc. Perkin Trans II, 1974 (I) 26-31 discloses production of the compounds having the structures: ##STR5## together with several other methyl substituted isomers thereof in admixture, according to the reaction: ##STR6## The Mellor and Webb article however, does not disclose the reaction to take place at low temperatures in the presence of an alkyl aluminum halide or dialkyl aluminum halide whereby but two isomers are produced in a controlled fashion in high yields thus yielding an organoleptically acceptable mixture of carboalkoxy norbornane derivatives. 
     Thus, nothing in the prior art indicates production for organoleptic uses of compounds having the generic structure: ##STR7## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond and R 1 , R 2 , R 3 , R 4  and R 5  are as defined above. 
     U.S. Pat. No. 4,143,074 discloses, generically, compounds which are esters and contain the norbornyl moiety having the structures: ##STR8## wherein either or both of R 1  or R 2  is hydrogen or lower alkyl, R 3  is hydrogen or lower alkyl and n is zero or 1 and in addition, the compound having the structure: ##STR9## wherein R 6  is alkyl having from one up to eight carbon atoms. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 sets forth the GLC profile for the reaction product of Example I containing compounds having the structures: ##STR10## 
     FIG. 2A is the NMR spectrum for fraction 8 of the distillation product of the reaction product of Example I having the structure: ##STR11## 
     FIG. 2B represents the NMR spectrum for fraction 2 of the distillation product of the reaction product of Example I having the structure: ##STR12## 
     FIG. 3A represents the infrared spectrum for fraction 8 of the distillation product of the reaction product of Example I having the structure: ##STR13## 
     FIG. 3B represents the infrared spectrum for fraction 2 of the distillation product of the reaction product of Example I having the structure: ##STR14## 
     FIG. 4 represents the mass spectrum for the reaction product of Example I containing compounds having the structures: ##STR15## 
     FIG. 5 represents the GLC profile for the reaction product of Example II containing compounds having the structures: ##STR16## 
     FIG. 6A represents the NMR spectrum of peak 1 of the GLC profile of FIG. 5 consisting essentially of the compound having the structure: ##STR17## 
     FIG. 6B represents the NMR spectrum for fraction 6 of the distillation product of the reaction product of Example II consisting essentially of the compound having the structure: ##STR18## 
     FIG. 7A represents the infrared spectrum for peak 1 of the GLC profile of FIG. 5 of the reaction product of Example II consisting essentially of the compound having the structure: ##STR19## 
     FIG. 7B represents the infrared spectrum for fraction 6 of the distillation product of the reaction product of Example II having the structure: ##STR20## 
     FIG. 8 represents the mass spectrum of the reaction product of Example II containing compounds having the structures: ##STR21## 
     FIG. 9 represents the GLC profile of the reaction product of Example III containing compounds having the structures: ##STR22## 
     FIG. 10A represents the NMR spectrum for fraction 10 of the distillation product of the reaction product of Example III containing the compound having the structure: ##STR23## 
     FIG. 10B represents the NMR spectrum for fraction 6 of the distillation product of the reaction product of Example III containing the compound having the structure: ##STR24## 
     FIG. 11A represents the infrared spectrum for fraction 10 of the distillation product of the reaction product of Example III containing the compound having the structure: ##STR25## 
     FIG. 11B represents the infrared spectrum for fraction 6 of the distillation product of the reaction product of Example III containing the compound having the structure: ##STR26## 
     FIG. 12 represents the mass spectrum for the reaction product of Example III containing compounds having the structures: ##STR27## 
     FIG. 13 represents the GLC profile of the crude reaction product (washed before distilling) of Example IV containing the compounds having the structures: ##STR28## 
     FIG. 14 represents the GLC profile for bulked fractions 7-12 inclusive of the distillation product of the reaction product of Example IV (conditions: Carbowax column programmed at 80°-122° C. at 8° C. per minute). 
     FIG. 15A represents the NMR spectrum for the reaction product of Example IV containing the compound having the structure: ##STR29## 
     FIG. 15B represents the NMR spectrum for the reaction product of Example IV containing the compound having the structure: ##STR30## 
     FIG. 16A represents the infrared spectrum for the reaction product of Example IV containing the compound having the structure: ##STR31## 
     FIG. 16B represents the infrared spectrum for the reaction product of Example IV containing the compound having the structure: ##STR32## 
     FIG. 17 represents the mass spectrum for the reaction product of Example IV containing the compounds having the structures: ##STR33## 
     FIG. 18 represents the GLC profile for the reaction product of Example V containing the compounds having the structures: ##STR34## 
     FIG. 19A represents the NMR spectrum for fraction 9 of the distillation product of the reaction product of Example V containing the compound having the structure: ##STR35## 
     FIG. 19B represents the NMR spectrum for fraction 1 of the distillation product of the reaction product of Example V containing the compound having the structure: ##STR36## 
     FIG. 20A represents the infrared spectrum for fraction 9 of the distillation product of the reaction product of Example V containing the compounds having the structure: ##STR37## 
     FIG. 20B represents the infrared spectrum for fraction 1 of the distillation product of the reaction product of Example V containing the compound having the structure: ##STR38## 
     FIG. 21 represents the mass spectrum for the reaction product of Example V containing the compounds having the structures: ##STR39## 
     FIG. 22 represents the GLC profile for the reaction product of Example VI containing the compounds having the structures: ##STR40## 
     FIG. 23A represents the NMR spectrum for fraction 14 of the distillation product of the reaction product of Example VI containing the compound having the structure: ##STR41## 
     FIG. 23B represents the NMR spectrum for fraction 4 of the distillation product of the reaction product of Example VI containing the compound having the structure: ##STR42## 
     FIG. 24A represents the infrared spectrum for fraction 14 of the distillation product of the reaction product of Example VI containing the compound having the structure: ##STR43## 
     FIG. 24B represents the infrared spectrum for fraction 4 of the distillation product of the reaction product of Example VI containing the compound having the structure: ##STR44## 
     FIG. 25 represents the mass spectrum for the reaction product of Example VI containing the compounds having the structures: ##STR45## 
     FIG. 26 represents the GLC profile for the reaction product of Example VII containing the compounds having the structures: ##STR46## 
     FIG. 27 represents the NMR spectrum for the reaction product of Example VII containing a mixture of the compounds having the structures: ##STR47## 
     FIG. 28 represents the infrared spectrum for the reaction product of Example VII containing a mixture of the compounds having the structures: ##STR48## 
     FIG. 29 represents the mass spectrum for the reaction product of Example VII containing a mixture of the compounds having the structures: ##STR49## 
     FIG. 30 sets forth the GLC profile for the reaction product of Example VII-A (bulked fractions 3-5 after distillation) consisting of the compounds having the structures: ##STR50## 
     FIG. 31-A sets forth the NMR spectrum for fraction 1 of the distillation product of the reaction product of Example VII-A consisting of the compound having the structure: ##STR51## 
     FIG. 31-B sets forth the NMR spectrum for peak 2 of the GLC profile of the reaction product of Example VII-A consisting of the compound having the structure: ##STR52## 
     FIG. 32-A sets forth the infrared spectrum for fraction 1 of the distillation product of the reaction product of Example VII-A consisting of the compound having the structure: ##STR53## 
     FIG. 32-B sets forth the infrared spectrum for peak 2 of the GLC profile of the reaction product of Example VII-A consisting of the compound having the structure: ##STR54## 
     FIG. 33-A sets forth the mass spectrum for fraction 1 of the distillation product of the reaction product of Example VII-A consisting of the compound having the structure: ##STR55## 
     FIG. 33-B sets forth the mass spectrum for peak 2 of the GLC profile of the reaction product of Example VII-A consisting of the compound having the structure: ##STR56## 
    
    
     THE INVENTION 
     It has now been discovered that novel solid and liquid foodstuff, chewing gum, medicinal product and toothpaste compositions and flavoring compositions therefor having the fruity, burnt fruit, raspberry, seedy, sweet, berry-like, red berry-like, blueberry-like, spicy, black pepper-like, herbaceous, clove-like, vermouth-like, strawberry-like and balsamic aroma characteristics and flavor characteristics as well as bitter taste characteristics; as well as novel smoking tobacco and smoking tobacco flavoring compositions having spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity, berry-like, juicyfruit, woody, piney, blueberry, banana, green, herbaceous, strawberry-like and dill aroma and taste prior to and on smoking in both the mainstream and the sidestream; as well as novel perfume compositions, colognes and perfumed articles (e.g. solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softeners and dryer-added fabric softener articles) having intense and long lasting fruity, banana, creamy, camphoraceous, herbaceous, sweet, spicy, woody, eucalyptol-like, rum/butterscotch-like, balsamic, green, minty, borneol-like, and medicinal aromas with strong camphor, minty and calamnus-like undertones may be provided by utilization of one or more of the substituted norbornane derivatives having the generic structure: ##STR57## wherein the dashed line represents either a carbon-carbon single bond or a carbon-carbon double bond and R 1 , R 2 , R 3  or R 4  represent either hydrogen or methyl with the proviso that one of R 1  and R 2  is methyl and the other of R 1  and R 2  is hydrogen; and with the further proviso that R 3  and R 4  are not both methyl, in foodstuffs, chewing gums, toothpastes, medicinal products, perfume compositions, perfumed articles, colognes and smoking tobaccos as well as smoking tobacco substitutes. 
     Unless otherwise specified, representations herein are intended to indicate &#34;cis&#34; isomers, &#34;trans&#34; isomers, mixtures of &#34;cis&#34; and &#34;trans&#34; isomers and &#34;endo&#34; isomers and &#34;exo&#34; isomers with respect to the norbornane ring moiety and dextro and laevorotatory isomers as well as racemic mixtures of optical isomers of the norbornane derivatives of our invention. 
     Thus, the generic structure: ##STR58## is intended to mean both &#34;endo&#34; and &#34;exo&#34; isomers having the structures: ##STR59## 
     The novel substituted norbornane derivatives of our invention useful as indicated supra may be produced by reacting a 1-methylcyclopentadiene or 2-methylcyclopentadiene having one of the structures: ##STR60## or a mixture of these methylcyclopentadienes defined according to the generic structure: ##STR61## with an alkyl acrylate derivative defined according to the generic structure: ##STR62## which structure represents a &#34;cis&#34; isomer or a &#34;trans&#34; isomer or a mixture of &#34;cis&#34; and &#34;trans&#34; isomers. Thus, the &#34;trans&#34; isomer may be represented by the structure: ##STR63## and the &#34;cis&#34; isomer may be represented by the structure: ##STR64## 
     The catalyst for this reaction may be an alkyl aluminum dihalide or a dialkyl aluminum halide for example RAlCl 2  or R 2  AlCl wherein R represents methyl, ethyl or n-propyl or i-propyl. The preferred catalyst is ethyl aluminum dichloride. Other Lewis acids such as aluminum trichloride, stannic chloride, zinc chloride, ferric chloride and titanium tetrachloride have been attempted to be used but such attempts have proved to be unsuccessful with minimal or no yields of product being produced. The temperature range of the reaction may vary from about 0° C. up to about 50° C. with ambient temperatures, from 20° up to 30° C. being preferred. The reaction pressure will not affect the yield but conveniently and economically, a reaction pressure of atmospheric is preferred. Thus, the catalyst for the reaction may be defined according to the formula: R m  &#39; AlCl n  wherein R&#39; is C 1  -C 3  alkyl and the sum, m+n, equals 3; with m being one or two and n being one to two. The resulting reaction mass is a mixture of compounds containing unsaturation in the norbornane moiety, defined according to the generic structures: ##STR65## 
     These compounds may be used &#34;as is&#34; for their organoleptic properties or the mixture of compounds may be further hydrogenated using hydrogen gas at superatmospheric pressures. When it is desired to use the compounds &#34;as is&#34; for their organoleptic properties it is preferable to refine the reaction mass as by fractional distillation thereby creating a product useable as set forth above. 
     When the hydrogenation is carried out on the mixture of products containing compounds having the structures: ##STR66## compounds containing the structures: ##STR67## will be produced. It is preferable to carry out the hydrogenation at pressures of from about 20 psig up to about 2,000 psig with a pressure range of from about 40 up to about 80 psig being preferred. It is also preferable for the reaction to be carried out in the presence of a catalyst such as Raney Nickel, palladium on carbon, palladium on calcium carbonate, palladium on barium sulfate and platinum. When using the palladium-salt catalyst it is preferred to use from about 3% up to about 12% palladium on salt, for example 5% palladium on calcium carbonate. 
     Thus, the reaction sequence which is embodied within our invention may be illustrated as follows: ##STR68## wherein one of R 3  or R 4  is hydrogen and the other of R 3  or R 4  is methyl; wherein R 5  represents C 1  -C 4  lower alkyl; wherein R&#39; represents C 1  -C 3  alkyl; and wherein M+N equals three with M being equal to one or two and N being equal to one or two. 
     The following tables set forth the product covered by our invention and the alkyl acrylate precursor reactant starting materials to be reacted with the methylcyclopentadienes to produce said products and in addition sets forth the organoleptic properties of the products of our invention: 
     
                       TABLE I                                                     
______________________________________                                    
Alkylacrylate                                                             
           Reaction Product                                               
                          Reaction Product                                
Reactant   Names          Structures                                      
______________________________________                                    
Methylcrotonate                                                           
           Methyl ester of 1,3- and 3,5-dimethyl norbornene-2- carboxylic 
           acid                                                           
                           ##STR69##                                      
                          and                                             
                           ##STR70##                                      
Methylcrotonate                                                           
           Methyl ester of 1,3- and 3,5-dimethyl norbornene-2- carboxylic 
           acid                                                           
                           ##STR71##                                      
                          and                                             
                           ##STR72##                                      
Ethylcrotonate                                                            
           Ethyl ester of 1,3- and 3,5-dimethyl norbornene-2- carboxylic  
           acid                                                           
                           ##STR73##                                      
                          and                                             
                           ##STR74##                                      
Ethylacrylate                                                             
           Ethyl ester of 1- and 5-methyl- 5-norbornene-2- carboxylic     
           acid                                                           
                           ##STR75##                                      
                          and                                             
                           ##STR76##                                      
Ethylacrylate                                                             
           Ethyl ester of 1- and 5-methyl- norbornane-2- carboxylic       
                           ##STR77##                                      
                          and                                             
                           ##STR78##                                      
n-Butylacrylate                                                           
           n-Butyl ester of 1- and 5-methyl- 5-norbornene-2- carboxylic   
           acid                                                           
                           ##STR79##                                      
                          and                                             
                           ##STR80##                                      
Ethyl- methacrylate                                                       
           Ethyl esters of 1,2- and 2,5- dimethyl-5-nor- bornene-2-carboxy
           - lic acid                                                     
                           ##STR81##                                      
                          and                                             
                           ##STR82##                                      
Ethylcrotonate                                                            
           Ethyl ester of 1,3- and 3,5-dimethyl norbornane-2- carboxylic  
           acid                                                           
                           ##STR83##                                      
                          and                                             
                           ##STR84##                                      
______________________________________                                    
 
    
     
                                           TABLE II                                
__________________________________________________________________________
                             Smoking                                      
Reaction Product                                                          
          Fragrance                                                       
                   Food Flavor                                            
                             Tobacco Flavor                               
Name      Properties                                                      
                   Properties                                             
                             Properties                                   
__________________________________________________________________________
Methyl ester of                                                           
          A fruity, ba-                                                   
                   A burnt fruit                                          
                             Sweet, fruity,                               
1,3- and 3,5-                                                             
          nana, creamy                                                    
                   aroma and berry-like, woody                            
dimethyl norbor-                                                          
          aroma with                                                      
                   taste at 0.1                                           
                             aroma prior to                               
nene-2-carboxylic                                                         
          camphoraceous                                                   
                   ppm       smoking and a                                
acid      and minty          sweet, fruity                                
          undertones         aroma on smoking                             
                             both in the main-                            
                             and sidestreams                              
Methyl ester of                                                           
          A fruity, cam-                                                  
                   A fruity and                                           
                             Prior to smoking                             
1,3- and 3,5-                                                             
          phoraceous and                                                  
                   blackberry-                                            
                             a sweet, woody                               
dimethyl norbor-                                                          
          herbaceous                                                      
                   like aroma and                                         
                             spicy, cooling                               
nane-2-carboxylic                                                         
          aroma    taste at 0.1                                           
                             and clove-like                               
acid               ppm       aroma profile;                               
                             and on smoking                               
                             a sweet, spicy,                              
                             cooling and                                  
                             woody aroma and                              
                             taste in both                                
                             the main stream                              
                             and the side                                 
                             stream                                       
Ethyl ester of                                                            
          A sweet, spicy                                                  
                   A sweet, fruit,                                        
                             A sweet, fruity,                             
1,3- and 3,5-                                                             
          herbal, woody,                                                  
                   berry-like,                                            
                             berry, spicy,                                
dimethyl norbor-                                                          
          eucalyptol-like                                                 
                   spicy, black                                           
                             cinnamon bark-                               
nene-2-carboxylic                                                         
          aroma profile                                                   
                   pepper-like,                                           
                             like and clove-                              
acid      with a dis-                                                     
                   herbaceous,                                            
                             like aroma and                               
          tinct calamnus                                                  
                   clove-like                                             
                             taste profile                                
          undertone                                                       
                   aroma and prior to and on                              
                   taste profile                                          
                             smoking in the                               
                   at 10 ppm main stream and                              
                   causing it to                                          
                             the side stream                              
                   be useful in                                           
                   blueberry,                                             
                   tobacco, clove                                         
                   and raspberry                                          
                   flavor food-                                           
                   stuffs                                                 
Ethyl ester of                                                            
          A sweet, fruity                                                 
                   A sweet, fruity                                        
                             A fruity, banana-                            
1- and 5-methyl-                                                          
          (banana-like)                                                   
                   red berry-like,                                        
                             like, green and                              
5-norbornene-2-                                                           
          creamy and                                                      
                   raspberry and                                          
                             strawberry-like                              
carboxylic acid                                                           
          minty aroma                                                     
                   seedy aroma and                                        
                             aroma and taste                              
          profile with                                                    
                   taste profile                                          
                             both prior to                                
          the minty                                                       
                   with an addi-                                          
                             and on smoking                               
          notes outstand-                                                 
                   tional strawberry                                      
                             in the main                                  
          ing on dryout                                                   
                   taste nuance at                                        
                             stream and in                                
                   0.02 ppm causing                                       
                             the side stream                              
                   it to be useful                                        
                   in red berry,                                          
                   cherry, rasp-                                          
                   berry and straw-                                       
                   berry flavors                                          
Ethyl ester of                                                            
          A fruity, bana-                                                 
                   A sweet, fruity,                                       
                             A sweet, fruity,                             
1- and 5-methyl-                                                          
          na like, and                                                    
                   raspberry, ver-                                        
                             &#34; juicyfruit&#34;,                               
5-norbornene-2-                                                           
          creamy aroma                                                    
                   mouth-like and                                         
                             woody, piney,                                
carboxylic acid                                                           
          profile  blueberry aroma                                        
                             and blueberry                                
                   with fruit,                                            
                             aroma and                                    
                   raspberry and                                          
                             taste profile                                
                   blueberry taste                                        
                             prior to and                                 
                   characteristics                                        
                             on smoking in                                
                   at 0.01 ppm and                                        
                             the mainstream                               
                   at 1 ppm causing                                       
                             and in the side                              
                   it to be useful                                        
                             stream                                       
                   for vermouth,                                          
                   blueberry and                                          
                   raspberry flavors                                      
                   and mouthwash and                                      
                   toothpaste                                             
                   flavors                                                
n-Butyl ester of                                                          
          A balsamic and                                                  
                   A fruity, straw-                                       
                             An earthy,                                   
1- and 5-methyl-                                                          
          rum/butterscotch                                                
                   berry, blueberry                                       
                             mushroom aroma                               
5-norbornene-2-                                                           
          aroma profile                                                   
                   and balsamic                                           
                             prior to and                                 
carboxylic acid    aroma profile                                          
                             on smoking                                   
                   with blueberry,                                        
                   balsamic and                                           
                   bitter taste                                           
                   characteristics                                        
                   at 2 ppm                                               
Ethyl esters of                                                           
          A green, minty,                                                 
                   A fruit, rasp-                                         
                             A sweet, green,                              
1,2- and 2,5-                                                             
          borneol-like,                                                   
                   berry and seedy                                        
                             herbaceous,                                  
dimethyl-5-nor-                                                           
          spicy, somewhat                                                 
                   aroma and taste                                        
                             dill and fruity                              
bornene-2-carboxy-                                                        
          medicinal aroma                                                 
                   profile with                                           
                             aroma and taste                              
lic acid  profile remin-                                                  
                   additional                                             
                             profile both                                 
          iscent of                                                       
                   bitter taste                                           
                             prior to and                                 
          pepacuana boric                                                 
                   nuances at 0.2                                         
                             on smoking in                                
          extract  ppm       mainstream and                               
                             in the side                                  
                             stream                                       
Ethyl esters of                                                           
          A fruity,                                                       
                   A fruity, blue-                                        
1,3- and 3,5-                                                             
          piney, herb-                                                    
                   berry and                                              
dimethyl-5-nor-                                                           
          aceous and                                                      
                   herbaceous aroma                                       
bornane-2-carboxy-                                                        
          cassis aroma                                                    
                   character with a                                       
lic acid  profile with                                                    
                   sweet, fruity                                          
          calamnus under-                                                 
                   and blueberry                                          
          tones    flavor charact-                                        
                   eristic at                                             
                   0.02 parts per                                         
                   million                                                
__________________________________________________________________________
 
    
     When the norbornane derivatives of our invention are used as food flavor adjuvants, the nature of the co-ingredients included with each of the said norbornane derivatives in formulating the product composition will also serve to alter, modify, augment or enhance the organoleptic characteristics of the ultimate foodstuff treated therewith. 
     As used herein in regard to flavors, the terms &#34;alter&#34;, &#34;modify&#34; and &#34;augment&#34; in their various forms mean &#34;supplying or imparting flavor character or note to otherwise bland, relatively tasteless substances or augmenting the existing flavor characteristic where a natural flavor is deficient in some regard or supplementing the existing flavor impression to modify its quality, character or taste&#34;. 
     The term &#34;enhance&#34; is used herein to mean the intensification of a flavor or aroma characteristic or note without the modification of the quality thereof. Thus, &#34;enhancement&#34; of a flavor or aroma means that the enhancement agent does not add any additional flavor note. 
     As used herein, the term &#34;foodstuff&#34; includes both solid and liquid ingestible materials which usually to, but need not, have nutritional value. Thus, foodstuffs include soups, convenience foods, beverages, dairy products, candies, vegetables, cereals, soft drinks, snacks and the like. 
     As used herein, the term &#34;medicinal product&#34; includes both solids and liquids which are ingestible non-toxic materials which have medicinal value such as cough syrups, cough drops, aspirin and chewable medicinal tablets. 
     The term &#34;chewing gum&#34; is intended to mean a composition which comprises a substantially water-insoluble, chewable plastic gum base such as chicle, or substitutes therefor, including jelutong, guttakay, rubber or certain comestible natural or synthetic resins or waxes. Incorporated with the gum base in admixture therewith may be plasticizers of softening agents, e.g., glycerine; and a flavor composition which incorporates one or more of the norbornane derivatives of our invention, and in addition, sweetening agents which may be sugars, including sucrose or dextrose and/or artificial sweeteners such as cyclamates or saccharin. Other optional ingredients may also be present. 
     Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in the relevant literature. It is a requirement that any such material be &#34;ingestibly&#34; acceptable and thus non-toxic and otherwise non-deleterious particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material used is not caused to have unacceptable aroma and taste nuances. Such materials may in general be characterized as flavoring adjuvants or vehicles comprising broadly stabilizers, thickeners, surface active agents, conditioners, other flavorants and flavor intensifiers. 
     Stabilizer compounds include preservatives, e.g., sodium chloride; antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and 3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene (2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like and sequestrants, e.g., citric acid. 
     Thickener compounds include carriers, binders, protective colloids, suspending agents, emulsifiers and the like, e.g., agar agar, carrageenan; cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth; gelatin, proteinaceous materials; lipids; carbohydrates; starches, pectins and emulsifiers, e.g., mono- and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose corn syrup and the like. 
     Surface active agents includes emulsifying agents, e.g., fatty acids such as capric acid, caprylic acid, palmitic acid, myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate, hydrogenated tallow alcohol and the like. 
     Conditioners include compounds such as bleaching and maturing agents, e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide, succinic anhydride and the like, buffers and neutralizing agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar the the like; colorants, e.g., carminic acid, cochineal, tumeric and curcuma and the like; firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e.g., aluminum calcium sulfate and tribasic calcium phosphate; enzymes; yeast foods, e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g., iron salts such as ferric phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like. 
     Other flavorants and flavor intensifiers include aldehydes, esters, natural oils, alcohols, sulfides, ketones, lactones, carboxylic acids and hydrocarbons such as heliotropin, terpinenol-4, benzaldehyde, anisaldehyde, phenyl acetaldehyde, benzyl formate, benzyl acetate, cis-3-hexenyl benzoate, methyl hexanoate, hexanal, eucalyptol, eugenol, acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil, limonene, gum camphor, isobornyl acetate, borneol, cinnamic aldehyde, cuminic aldehyde, furfural, methyl cinnamate, cassia oil, vanillin, maltol, parahydroxybenzyl acetate, dimethyl sulfide, alphaionone, acetic acid, isobutyl acetate, acetone, butyric acid, formic acid, valeric acid, amyl acetate, amyl butyrate, anethol, benzyl salicylate, diacetyl, dimethyl anthranilate, ethyl methylphenylglycidate, ethyl succinate, ethyl valerate, geraniol, cis-3-hexen-1-ol, 2-hexenyl acetate, 2-hexenyl butyrate, hexyl butyrate, 4-(p-hydroxyphenyl)-2-butanone, betaionone, isobutyl cinnamate, jasmine, lemon essential oil, methyl butyrate, methyl caproate, methyl disulfide, methyl p-naphthyl ketone, orris butter, rose absolute, terpenyl acetate, gamma-undecalactone, vanilla and alcohol. 
     The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e., foodstuff, whether simulated or natural, and should, in any event, (i) be organoleptically compatible with the norbornane derivatives of our invention by not covering or spoiling the organoleptic properties (aroma and/or taste) thereof; (ii) be non-reactive with the norbornane derivatives of our invention and (iii) be capable of providing an environment in which the norbornane derivatives can be dispersed or admixed to provide a homogeneous medium. In addition, selection of one or more flavoring adjuvants, as well as the quantities thereof will depend upon the precise organoleptic character desired in the finished product. Thus, in the case of flavoring compositions, ingredient selection will vary in accordance with the foodstuff, chewing gum, medicinal product or toothpaste to which the flavor and/or aroma are to be imparted, modified, altered or enhanced. In contradistinction, in the preparation of solid products, e.g., simulated foodstuffs, ingredients capable of providing normally solid compositions should be selected such as various cellulose derivatives. 
     As will be appreciated by those skilled in the art, the amount of norbornane derivatives employed in a particular instance can vary over a relatively wide range, depending upon the desired organoleptic effects to be achieved. Thus, correspondingly, greater amounts would be necessary in those instances wherein the ultimate food composition to be flavored is relatively bland to the taste, whereas relatively minor quantities may suffice for purposes of enhancing the composition merely deficient in natural flavor or aroma. The primary requirement is that the amount selected to be effective, i.e., sufficient to alter, modify, or enhance the organoleptic characteristics of the parent composition, whether foodstuff per se, chewing gum, per se, medicinal product per se, toothpaste per se, or flavoring composition. 
     The use of insufficient quantities of norbornane derivatives will, of course, substantially vitiate any possibility of obtaining the desired results while excess quantities prove needlessly costly and, in extreme cases, may disrupt the flavor-aroma balance, thus proving self-defeating. Accordingly, the terminology &#34;effective amount&#34; and &#34;sufficient amount&#34; is to be accorded a significance in the context of the presence invention consistent with the obtention of desired flavoring effects. 
     Thus, and with respect to ultimate food compositions, chewing gum compositions, medicinal product compositions and toothpaste compositions, it is found that quantities of norbornane derivatives ranging from a small but effective amount, e.g., 0.01 parts per million up to about 100 parts per million based on total composition are suitable. Concentrations in excess of the maximum quantity stated are not normally recommended, since they fail to prove commensurate enhancement of organoleptic properties. In those instances, wherein the norbornane derivatives are added to the foodstuff as an integral component of a flavoring composition, it is, of course, essential that the total quantity of flavoring composition employed be sufficient to yield an effective norbornane derivative concentration in the foodstuff product. 
     Food flavoring compositions prepared in accordance with the present invention preferably contain the norbornane derivatives in concentrations ranging from about 0.01% up to about 15% by weight based on the total weight of the said flavoring composition. 
     The composition described herein can be prepared according to conventional techniques well known as typified by cake batters and fruit drinks and can be formulated by merely admixing the involved ingredients within the proportions stated in a suitable blender to obtain the desired consistency, homogeneity of dispersion, etc. Alternatively, flavoring compositions in the form of particulate solids can be conveniently prepared by mixing the norbornane derivatives with, for example, gum arabic, gum tragacanth, carrageenan and the like, and thereafter spray-drying the resultant mixture whereby to obtain the particular solid product. Preprepared flavor mixes in powder form e.g., a fruit-flavored powder mix are obtained by mixing the dried solid components, e.g., starch, sugar and the like and norbornane derivatives in a dry blender until the requisite degree of uniformity is achieved. 
     It is presently preferred to combine with the norbornane derivatives of our invention, the following adjuvants: 
     Heliotropin; 
     Terpinenol-4; 
     Benzaldehyde; 
     Anisaldehyde; 
     Phenylacetaldehyde; 
     Benzyl formate; 
     Benzyl acetate; 
     Cis-3-hexenyl benzoate; 
     Methyl hexanoate; 
     Hexanal; 
     Eucalyptol; 
     Eugenol; 
     Acetaldehyde; 
     Ethyl acetate; 
     Ethyl butyrate; 
     Turpentine gum oil; 
     Limonene; 
     Gum camphor; 
     Isoburnyl acetate; 
     Borneol; 
     Cinnamic aldehyde; 
     Cuminic aldehyde; 
     Furfural; 
     Methyl cinnamate; 
     Cassia oil; 
     Vanillin; 
     Malto; 
     Parahydroxybenzylacetone; 
     Dimethyl sulfide; 
     Alpha-ionone; 
     Acetic acid; 
     Isobutyl acetate; 
     Acetone; 
     Butyric acid; 
     Formic acid; 
     Valeric acid; 
     Amyl acetate; 
     Amyl butyrate; 
     Anethol; 
     Benzyl salicylate; 
     Diacetyl; 
     Dimethyl anthranilate; 
     Ethyl methylphenylglycidate; 
     Ethyl succinate; 
     Ethyl valerate; 
     Geraniol; 
     Cis-3-hexen-1-ol; 
     2-Hexenyl acetate; 
     2-Hexenyl butyrate; 
     Hexyl butyrate; 
     4-(p-Hydroxyphenyl)-2-butanone; 
     Beta-ionone; 
     Isobutyl cinnamate; 
     Jasmine; 
     Lemon essential oil; 
     Methyl butyrate; 
     Methyl capronate; 
     Methyl disulfide; 
     Methyl p-naphthyl ketone; 
     Orris butter; 
     Rose absolute; 
     Terpenyl acetate; 
     Gamma-undecalactone; 
     Vanilla; and 
     Alcohol. 
     An additional aspect of our invention provides an organoleptically improved smoking tobacco product and additives therefor, as well as methods of making the same which overcome problems heretofore encountered in which desired spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity, berry-like, juicyfruit, woody, piney, blueberry, banana, green, herbaceous, strawbery-like, and dill flavor characteristics of natural tobacco (prior to smoking and, on smoking, in the mainstream and in the sidestream) as well as cooling effects, are created or enhanced or modified or augmented and may be readily controlled and maintained at the desired uniform level regardless of variations in the tobacco components of the blend. 
     This invention further provides improved tobacco additives and methods whereby various desirable natural aromatic tobacco flavoring characteristics with spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity, berry-like, juicyfruit, woody, piney, blueberry, banana, green, herbaceous, strawberry-like and dill notes may be imparted to smoking tobacco products and may be readily varied and controlled to produce the desired uniform flavoring characteristics. 
     In carrying out this aspect of our invention, we add to smoking tobacco materials or a suitable substitute therefor (e.g., dried lettuce leaves) an aroma and flavor additive containing as an active ingredient one or more norbornane derivatives of our invention. 
     In addition to the norbornane derivatives of our invention other flavoring and aroma additives may be added to the smoking tobacco material or substitute therefor either separately or in mixture with the norbornane derivatives as follows: 
     I. Synthetic Materials 
     Beta-ethyl-cinnamaldehyde; 
     Eugenol; 
     Dipentene; 
     Damascenone; 
     Maltol; 
     Ethyl maltol; 
     Delta undecalactone; 
     Delta decalactone; 
     Benzaldehyde; 
     Amyl acetate; 
     Ethyl butyrate; 
     Ethyl valerate; 
     Ethyl acetate; 
     2-Hexenol-1; 
     2-Methyl-5-isopropyl-1,3-nonadiene-8-one; 
     2,6-Dimethyl-2,6-undecadiene-10-one; 
     2-Methyl-5-isopropylacetophenone; 
     2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)decahydronaphthalene; 
     Dodecahydro-3a,6,6,9a-tetramethylnaphtho-(2,1-b-)furan 
     4-Hydroxyhexanoic acid, gamma lactone; and Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No. 3,589,372, issued on June 29, 1971. 
     II. Natural Oils 
     Celery seed oil; 
     Coffee extract; 
     Bergamot oil; 
     Cocoa extract; 
     Nutmeg oil; and 
     Origanum oil. 
     An aroma and flavoring concentrate containing one or more norbornane derivatives of our invention and, if desired, one or more of the above indicated additional flavoring additives may be added to the smoking tobacco material, to the filter or to the leaf or paper wrapper. The smoking tobacco material may be shredded, cured, cased and blended tobacco material or reconstituted tobacco material or tobacco substitutes (e.g., lettuce leaves) or mixtures thereof. The proportions of flavoring additives may be varied in accordance with taste but insofar as enhancement or the imparting of spicy and/or cooling and/or clove-like and/or cinnamon bark-like and/or sweet and/or fruity and/or berry-like and/or juicyfruit and/or woody and/or piney and/or blueberry and/or banana and/or green and/or herbaceous and/or strawberry-like and/or dill notes, we have found that satisfactory results are obtained if the proportion by weight of the sum total of norbornane derivative(s) to smoking tobacco material is between 50 ppm and 1,500 ppm (0.015%-0.15%). We have further found that satisfactory results are obtained if the proportions by weight of the sum total of norbornane derivative used to flavoring material is between 1,500 and 15,000 ppm (0.15%-1.5%). 
     Any convenient method for incorporating the norbornane derivative(s) into the tobacco product may be employed. Thus, the norbornane derivative(s) taken alone or along with other flavoring additives may be dissolved in a suitable solvent such as ethanol, diethyl ether and/or volative organic solvents and the resulting solution may either be spread on the cured, cased and blended tobacco material or the tobacco material may be dipped into such solution. Under certain circumstances, a solution of the norbornane derivative(s) taken alone or taken further together with other flavoring additives as set forth above, may be applied by means of a suitable applicator such as a brush or roller on the paper or leaf wrapper for the smoking product, or it may be applied to the filter by either spraying, or dipping, or coating. 
     Furthermore, it will be apparent that only a portion of the tobacco or substitute therefor need be treated and the thus treated tobacco may be blended with other tobaccos before the ultimate tobacco product is formed. In such cases, the tobacco treated by have the norbornane derivative(s) in excess of the amounts or concentrations above indicated so that when blended with other tobaccos, the final product will have the precentage within the indicated range. 
     In accordance with one specific example of our invention an aged, cured and shredded domestic burley tobacco is sprayed with a 20% ethanol solution of the mixture of 1,3- and 3,5-dimethyl-2-norbornane carboxylic acid methyl esters having the structures: ##STR85## in an amount of mixture to provide tobacco composition containing 800 ppm by weight of the mixture of the two esters on a dry basis. Thereafter the alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques. The cigarette when treated as indicated has a desired and pleasing aroma which is detectable in the mainstream and the sidestream when the cigarette is smoked. This aroma is described as being sweeter, more aromatic, more tobacco-like having sweet, spicy, cooling, woody and clove-like notes. 
     While our invention is particularly useful in the manufacture of smoking tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other tobacco products, formed from sheeted tobacco dust or fines may also be used. Likewise, the norbornane derivative(s) of our invention can be incorporated with materials such as filter tip materials (e.g. cellulose acetate filters wherein spicy, cooling, clove-like, cinnamon bark-like, sweet, fruity, berry-like, juicyfruit, woody, piney, blueberry, banana, green, herbaceous, strawberry-like and/or dill effects are desired), seam paste, packaging materials and the like which are used along with tobacco to form a product adapted for smoking. Furthermore, the norbornane derivative(s) can be added to certain tobacco substitutes of natural or synthetic origin (e.g., dried lettuce leaves) and, accordingly, by the term &#34;tobacco&#34; as used throughout this specification is meant any composition intended for human consumption by smoking or otherwise, whether composed of tobacco plant parts or substitute materials or both. 
     The norbornane derivative(s) and one or more auxiliary perfume ingredients, including, for example, hydrocarbons, alcohols, ketones, aldehydes, nitriles, esters, lactones or cyclic esters, synthetic essential oils and natural essential oils, may be admixed so that the combined odors of the individual components produce a pleasant and desired fragrance, particularly and preferably in fruity, banana, creamy, camphoraceous, herbaceous, sweet, spicy, woody, eucalyptol-like, rum/butterscotch, balsamic, green, and/or minty fragrances. Such perfume compositions usually contain (a) the main note or the &#34;bouquet&#34; or foundation stone of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation and substances which retard evaporation; and (d) topnotes which are usually low boiling fresh smelling materials. 
     In perfume compositions, it is the individual components which contribute to their particular olfactory characteristics, however the over-all sensory effect of the perfume composition will be at least the sum total of the effects of each of the ingredients. Thus, one or more of the norbornane derivative(s) of our invention can be used to alter, modify or enhance the aroma characteristics of a perfume composition, for example, by utilizing or moderating the olfactory reaction contributed by another ingredient in the composition. 
     The amount of norbornane derivative(s) of our invention which will be effective in perfume compositions as well as perfumed articles and colognes depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 0.01% of norbornane derivative(s) or even less (e.g., 0.005%) can be used to impart a fruity, banana, creamy, camphoraceous, herbaceous, sweet, spicy, woody, eucalyptol-like, rum/butterscotch, balsamic, green, minty, borneol-like and/or medicinal odor with camphor, minty and calamnus-like nuances to soaps, detergents (including anionic, nonionic, cationic and zwitterionic solid or liquid detergents), cosmetics, fabric softeners, dryer-added fabric softener articles, fabric whiteners and optical brighteners or other products. The amount employed can range up to 70% of the fragrance components and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought. 
     The norbornane derivative(s) of our invention are useful (taken alone or together with other ingredients in perfume compositions) in detergents and soaps, space odorants and deodorants, perfumes, colognes, toilet water, bath preparations, such as lacquers, brilliantines, pomades and shampoos; cosmetic preparations, such as creams, deodorants, hand lotions and sun screens; powders such as talcs, dusting powders, face powders and the like. As little as 0.01% of the norbornane derivative(s) will be suffice to impart an intense fruity, banana, creamy, camphoraceous, herbaceous, sweet, spicy, woody, eucalyptol-like, rum/butterscotch, balsamic, green, minty, borneol-like and/or medicinal note to various types of perfume formulations including the woody perfume formulations. Generally no more than 3% of the norbornane derivative(s) based on the ultimate end product (perfumed article) is required. 
     In addition, the perfume composition or fragrance composition of our invention can contain a vehicle, or carrier for the norbornane derivative(s). The vehicle can be a liquid such as a non-toxic alcohol, a non-toxic glycol, or the like. The carrier can also be an absorbent solid, such as a gum (e.g., gum arabic), or components for encapsulating the composition (such as gelatin). 
     It will thus be apparent that the norbornane derivative(s) of our invention can be utilized to alter, modify or enhance sensory properties, particularly organoleptic properties such as (flavor(s) and/or fragrance(s) of a wide variety of consumable materials. 
     The following examples serve to illustrate processes for specifically producing the norbornane derivative(s) useful in our invention. 
     The following examples also serve to illustrate specific embodiments of our invention. 
     It will be understood that these examples are illustrative and the invention is to be considered to be restricted thereto only as indicated in the appended claims. 
     All parts and percentages given herein are by weight unless otherwise specified. 
     EXAMPLE I 
     PREPARATION OF 1,3-DIMETHYL-5-NORBORNENE-2-CARBOXYLIC ACID METHYL ESTER AND 3,5-DIMETHYL-5-NORBORNENE-2-CARBOXYLIC ACID METHYL ESTER ##STR86## 
     Into a 3 liter flask equipped with stirrer, thermometer, condenser, addition funnel and cooling bath are charged 1000 ml toluene, 500 grams methyl crotonate, 45 grams ethyl aluminum dichloride. The resulting mixture is cooled to 20°-25° C. Over a period of 50 minutes while maintaining the reaction mass at 24°-25° C., 320 grams of methyl cyclopentadiene (mixture of 1-methyl-1,3-cyclopentadiene and 2-methyl-1,3-cyclopentadiene (50% in toluene solution)) is added. After the completion of the addition of the methyl cyclopentadiene mixture, the reaction mass is stirred for a period of 3 hours at 21°-25° C. At the end of the three hour period the reaction mass is heated to 40° C. and the temperature is maintained at 40° C. for a period of 2.7 hours. At the end of the 2.7 hour period the reaction mass is cooled to 20° C. and is poured into one liter of 10% hydrochloric acid solution. The reaction mass now exists in two phases. The aqueous phase is separated from the organic phase. The aqueous phase is extracted with 500 ml toluene. The toluene extract and organic phase are combined. The resulting organic phase is then washed as follows: 
     One 1 liter portion water; 
     One 1 liter portion saturated sodium carbonate; 
     One 1 liter portion water. 
     The toluene is then removed under reduced pressure. The resulting organic material is then distilled in a 12 inch Goodloe column yielding the following fractions: 
     
         ______________________________________                                    
        Vapor   Liquid                Weight of                           
Fraction                                                                  
        Temp.   Temp.   mm/Hg. Reflux Fraction                            
No.     (°C.)                                                      
                (°C.)                                              
                        Pressure                                          
                               Ratio  (g.)                                
______________________________________                                    
1       41/43   70/71   2.1/2.0                                           
                               9:1    21.0                                
2       48      72      2.0    9:1    22.6                                
3       45      73      2.0    9:1    21.8                                
4       48      73      2.0    9:1    22.2                                
5       48      72      2.0    9:1    16.7                                
6       48      73      2.0    9:1    22.0                                
7       49      74      2.0    9:1    19.9                                
8       49      86      2.0    9:1    20.5                                
9       50/35   95/205  2.5/1.0                                           
                               9:1    12.0                                
______________________________________                                    
 
    
     Fractions 4-7 are bulked for purposes of flavor evaluation. The bulked fractions 4-7 as analyzed by NMR, IR and mass spectral analysis contain a mixture of compounds having the structures: ##STR87## Fractions 4-7 bulked has a burnt fruit aroma and flavor characteristic at 0.1 ppm. 
     Fractions 4-7 bulked has a fruity, banana, creamy aroma with camphoraceous, minty undertones. 
     FIG. 1 represents the GLC profile for the reaction product of Example I containing the compounds having the structures: ##STR88## 
     FIG. 2A represents the NMR spectrum for fraction 8 of the foregoing distillation containing only the compound having the structure: ##STR89## 
     FIG. 2B represents the NMR spectrum for fraction 2 of the foregoing distillation containing the compound having the structure: ##STR90## 
     FIG. 3A represents the infrared spectrum for fraction 8 of the foregoing distillation containing only the compound having the structure: ##STR91## 
     FIG. 3B represents the infrared spectrum for fraction 2 of the foregoing distillation containing only the compound having the structure: ##STR92## 
     FIG. 4 represents the mass spectrum for the reaction product of Example I containing the compounds having the structures: ##STR93## 
     EXAMPLE II 
     PREPARATION OF 1,3-DIMETHYL-5-NORBORNANE-2-CARBOXYLIC ACID METHYL ESTER AND 3,5-DIMETHYL-5-NORBORNANE-2-CARBOXYLIC ACID METHYL ESTER ##STR94## 
     Into a 500 ml pressure bottle held in a Parr shaker is charged 100 ml isopropyl alcohol and 160 grams (0.89 moles) of the methyl cyclopentadiene/methyl crotonate adduct having the structures: ##STR95## prepared according to Example I and 4 grams of Raney Nickel. The Parr shaker is purged with hydrogen and charged to 50 psig. Shaking is begun and the Parr shaker is recharged with hydrogen when necessary in order to maintain the pressure at 50 psig. A total pressure drop of 74 pounds of hydrogen is observed. A GLC profile (conditions: Carbowax column programmed at 80°-220° C. at 8° C. per minute) indicates some change. NMR analysis indicates that all of the olefin is consumed. 
     At the end of the reaction the pressure bottle is opened and the Raney Nickel catalyst is filtered and the solvent is stripped off under reduced pressure. The resulting residue is distilled yielding 122 grams of product. The distillation takes place on a 12&#34;×2&#39; Goodloe column yielding the following fractions: 
     
         ______________________________________                                    
        Vapor   Liquid                 Weight of                          
Fraction                                                                  
        Temp.   Temp.    mm/Hg. Reflux Fraction                           
No.     (°C.)                                                      
                (°C.)                                              
                         Pressure                                         
                                Ratio  (g.)                               
______________________________________                                    
1       37/41   72/75    .65/.8 9:1    21                                 
2       42      76        .65   9:1    25                                 
3       43      78        .65   9:1    23                                 
4       44      80       .8     9:1    19                                 
5       45      95       .8     9:1    22                                 
6       60      215      .8     9:1    12                                 
______________________________________                                    
 
    
     NMR, mass spectral and IR analysis yields the information that the resulting product is a mixture of the compounds having the structures: ##STR96## 
     FIG. 5 sets forth the GLC profile for the reaction product produced according to this example. FIG. 6A sets forth the NMR spectrum for peak 1 of the GLC profile which consists essentially of the compound having the structure: ##STR97## FIG. 6B sets forth the NMR spectrum for fraction 6 of the foregoing distillation which consists essentially of the compound having the structure: ##STR98## FIG. 7A sets forth the infrared spectrum for peak 1 of the foregoing GLC profile which consists essentially of the compound having the structure: ##STR99## FIG. 7B sets forth the infrared spectrum for fraction 6 of the foregoing distillation which consists essentially of the compound having the structure: ##STR100## FIG. 8 sets forth a mass spectrum for the reaction product of this example which contains the compounds having the structures: ##STR101## 
     The resulting mixture, from a food flavor standpoint, has a fruity, blueberry aroma and flavor characteristic at 0.1 ppm. The resulting mixture from a fragrance standpoint, has a fruit, camphoraceous and herbaceous aroma profile. 
     The mixture of this example also has a sweet, woody, spicy, cooling and clove-like aroma profile prior to smoking and a sweet, spicy, cooling and woody aroma and taste profile on smoking tobacco articles in both the mainstream and the sidestream. 
     EXAMPLE III 
     PREPARATION OF THE ETHYL ESTER OF 1,3 AND 3,5-DIMETHYL 5-NORBORNENE CARBOXYLIC ACID ##STR102## 
     Into a 5 liter reaction vessel equipped with stirrer, thermometer, condenser, addition funnel, nitrogen purge and cooling bath are added 1000 ml toluene; 600 grams ethyl crotonate; and 50 grams of a 25% solution of ethyl aluminum dichloride in anhydrous toluene. The resulting mixture is cooled to 20°-25° C. and over a period of 3 hours while maintaining the temperature of the reaction at 20°-23° C., 378 grams of methyl cyclopentadiene mixture containing compounds having the structures: ##STR103## are added. 
     The reaction mass is then poured into one liter of a 10% aqueous hydrochloric acid solution. The reaction mass now exists in two phases; an aqueous phase and an organic phase. The aqueous phase is removed from the organic phase and the aqueous phase is extract with one 500 ml volume of toluene. The toluene and organic phases are combined and washed as follows: 
     A. One 1 liter portion of water; 
     B. One 1 liter portion of saturated sodium bicarbonate solution; and 
     C. One 1 liter portion of water. 
     The solvent is stripped off via vacuum. The resulting material is then distilled using a 12 inch Goodloe column yielding the following fractions: 
     
         ______________________________________                                    
       Vapor    Liquid                 Weight of                          
Fraction                                                                  
       Temp.    Temp.    mm/Hg.  Reflux                                   
                                       Fraction                           
No.    (°C.)                                                       
                (°C.)                                              
                         Pressure                                         
                                 Ratio (g.)                               
______________________________________                                    
1      32       53       2.0     9:1   43.8                               
2      30       62       1.0     9:1   43.0                               
3      38       73       1.8     9:1   38.3                               
4      40       73       .86     9:1   37.5                               
5      44       74       .86     9:1   44.5                               
6      44       76       .86     9:1   37.0                               
7      44       82       .86     9:1   52.7                               
8      44       90       .86     9:1   43.6                               
9      44       102      .85     9:1   48.7                               
10     55       130      .85     9:1   16.2                               
11     65       220      2.5     9:1   48.8                               
______________________________________                                    
 
    
     NMR, IR and mass spectral analysis yields the information that the reaction product contains compounds having the structures: ##STR104## 
     FIG. 9 sets forth the GLC profile prior to distillation of the resulting reaction product. 
     FIG. 10A sets forth the NMR spectrum for fraction 10 of the foregoing distillation containing only the product having the structure: ##STR105## 
     FIG. 10B is the NMR spectrum for the compound contained in fraction 6 of the foregoing distillation, having the structure: ##STR106## 
     FIG. 11A is the infrared spectrum for the compound of fraction 10 of the foregoing distillation having the structure: ##STR107## 
     FIG. 11B is the infrared spectrum for the compound contained in fraction 6 of the foregoing distillation, having the structure: ##STR108## 
     FIG. 12 is the mass spectrum for the mixture of compounds produced by the foregoing reaction having the structures: ##STR109## 
     Bulked fractions 5-11 containing the compounds having the structures: ##STR110## from a fragrance standpoint has a sweet, spicy, herbal, woody, eucalyptol-like aroma with distinct calamnus undertones. 
     Bulked fractions 5-11 from a food flavor standpoint has a sweet, fruity, berry-like, spicy, black pepper-like, herbaceous and clove-like aroma and taste profile at 10 ppm causing said bulked fractions to be useful in blueberry flavored tobacco (cloves) flavor and raspberry flavor. 
     Bulked fractions 5-11 from a tobacco flavor standpoint has a sweet, fruity, berry, spicy, cinnamon bark-like and clove-like aroma and taste profile both prior to and on smoking in the mainstream and in the sidestream of smoking tobacco articles such as cigarettes and cigars. 
     EXAMPLE IV 
     PREPARATION OF ETHYL ESTERS OF 1- AND 5-METHYL-5-NORBORNENE-2-CARBOXYLIC ACIDS ##STR111## 
     Into a three liter flask equipped with thermometer, stirrer, condenser, addition funnel, cooling bath and nitrogen purge are placed one gram of hydroquinone, 1000 ml toluene and 50 grams of 25% ethyl aluminum dichloride dissolved in anhydrous toluene. The reaction mass is cooled to about 10° C. and, over a period of 30 minutes, 600 grams of ethyl acrylate is added to the resulting mixture. During the addition the temperature of the mixture is maintained at between 10° C. and 14° C. 
     Over a period of three hours while maintaining the reaction temperature at 20°-23° C., 389 grams of a mixture of 1-methyl-1,3-cyclopentadiene and 2-methyl-1,3-cyclopentadiene is added to the reaction mixture. At the end of the three hour period GLC analysis indicates the reaction to be complete. 
     The resulting reaction mass is poured into one liter of 10% aqueous hydrochloric acid. The reaction mass now exists in two phases; an organic phase and an aqueous phase. The aqueous phase is separated from the organic phase and the organic phase is washed as follows: 
     A. One 1 liter portion of water; 
     B. One 1 liter portion of saturated sodium bicarbonate solution; 
     C. One 1 liter portion of water; 
     D. One 1 liter portion of water. 
     The pH of the resulting washing is about six. 
     The resulting organic layers are combined and the toluene is stripped off under vacuum. Calcium carbonate and primol® is added to the reaction mass and the reaction mass is distilled yielding the following fractions on a 12 inch Goodloe column: 
     
         ______________________________________                                    
       Vapor    Liquid                 Weight of                          
Fraction                                                                  
       Temp.    Temp.    mm/Hg. Reflux Fraction                           
No.    (°C.)                                                       
                (°C.)                                              
                         Pressure                                         
                                Ratio  (g.)                               
______________________________________                                    
1      48/48    63/65    3.0/3.0                                          
                                9:1    23.8                               
2      50       64       3.0    9:1    19.3                               
3      50       64       2.8    9:1    20.5                               
4      53       64       2.6    9:1    19.1                               
5      54       64       2.6    9:1    20.2                               
6      55       65       2.8    9:1    19.9                               
7      56       66       2.7    9:1    25.2                               
8      54       66       2.5    9:1    21.7                               
9      54       66       2.5    9:1    48.6                               
10     54       66       2.5    9:1    55.8                               
11     54       67       2.5    9:1    48.7                               
12     57       77       2.5    9:1    59.7                               
13     57       77       2.5    9:1    47.2                               
14     57       87       2.5    9:1    58.0                               
15     55/58     87/108  2.5/2.5                                          
                                4:1    33.0                               
16     45       110      3.0    4:1     6.6                               
______________________________________                                    
 
    
     Fractions 7-12 are bulked and NMR, IR and mass spectral analysis yield the information that these fractions consist essentially of a mixture of compounds having the structures: ##STR112## 
     FIG. 13 is the GLC profile of the crude reaction product washed, but before distilling. (Conditions: Carbowax column programmed at 80°-122° C. at 8° C. per minute). 
     FIG. 14 is the GLC profile of fractions 7-12 from the foregoing distillation, bulked. 
     FIG. 15A is the NMR spectrum for the compound having the structure: ##STR113## 
     FIG. 15B is the NMR spectrum for the compound having the structure: ##STR114## 
     FIG. 16A is the infrared spectrum for the compound having the structure: ##STR115## 
     FIG. 16B is the infrared spectrum for the compound having the structure: ##STR116## 
     FIG. 17 is the mass spectrum for the mixture of compounds having the structures: ##STR117## 
     The mixture of compounds having the structures: ##STR118## from a fragrance standpoint has a sweet, fruity (banana-like) and creamy aroma profile with minty nuances intense on dryout. 
     From a food flavor standpoint, the resulting mixture has a sweet, fruity, red berry, raspberry and seedy aroma and taste and in addition a strawberry taste at 0.02 ppm. Thus, this material is useful in red berry, cherry, raspberry and strawberry flavored foodstuffs. 
     The resulting mixture has a fruity, banana, green and strawberry-like aroma and taste both prior to and on smoking smoking tobacco articles in both the mainstream and the sidestream. 
     EXAMPLE V 
     PREPARATION OF THE ETHYL ESTERS OF 1- AND 5-METHYL NORBORNANE-2-CARBOXYLIC ACIDS ##STR119## 
     Into a 500 ml pressure bottle attached to a Parr shaker is charged 200 grams (1.11 moles) of the reaction mixture (bulked fractions 7-12) produced according to Example IV consisting essentially of compounds having the structures: ##STR120## 5 grams of Raney Nickel and 125 ml of isopropyl alcohol. The Parr shaker apparatus is purged six times with hydrogen and the 500 ml pressure bottle with contents is pressurized to 50 psig. The bottle is closed and shaking is begun and continued until the hydrogen uptake ceases. This period of time takes 4.25 hours. The 500 ml pressure bottle is recharged when necessary. At the end of the reaction the 500 ml pressure bottle is opened and the reaction mass is filtered and the solvent stripped in vacuum. The resulting residue is distilled on a 1&#39; Goodloe-silver column and yields the following fractions: 
     
         ______________________________________                                    
       Vapor    Liquid                 Weight of                          
Fraction                                                                  
       Temp.    Temp.    mm/Hg. Reflux Fraction                           
No.    (°C.)                                                       
                (°C.)                                              
                         Pressure                                         
                                Ratio  (g.)                               
______________________________________                                    
1      54/42    77/77    2.8/.8 9:1    18.5                               
2      42       77       0.75   9:1    22.2                               
3      42       78       0.70   9:1    22.0                               
4      46       85       0.70   9:1    23.0                               
5      50       87       1.4    9:1    18.0                               
6      50       90       0.8    9:1    21.0                               
7      51       111      0.7    9:1    19.0                               
8      45       170      0.75   9:1    23.0                               
9      39       214      0.76   9:1     3.0                               
______________________________________                                    
 
    
     NMR, IR and mass spectral analysis on fractions 1 and 9 yield the information that the resulting mixture contains and consists essentially of the compounds having the structures: ##STR121## 
     FIG. 18 is the GLC profile for the resulting reaction mixture. 
     FIG. 19A is the NMR spectrum for fraction 9 of the foregoing distillation containing and consisting of the compound having the structure: ##STR122## 
     FIG. 19B is the NMR spectrum for fraction 1 of the foregoing distillation consisting of the compound having the structure: ##STR123## 
     FIG. 20A is the infrared spectrum for fraction 9 of the foregoing distillation consisting of the compound having the structure: ##STR124## 
     FIG. 20B is the infrared spectrum for fraction 1 of the foregoing distillation consisting of the compound having the structure: ##STR125## 
     FIG. 21 is the mass spectrum for the reaction product produced according to this example containing the mixture of compounds having the structures: ##STR126## 
     From a fragrance standpoint bulked fractions 6-8 have a fruity, banana, and creamy aroma profile. 
     From a food flavor standpoint, bulked fractions 6-8 have a sweet, fruity, raspberry, vermount-like and blueberry aroma profile with a fruity, raspberry and blueberry taste profile at 0.01 ppm and at 1 ppm causing this mixture to be useful for vermouth, blueberry, raspberry mouthwash and toothpaste flavors. 
     From a tobacco flavor standpoint, bulked fractions 6-8 has prior to and on smoking in the mainstream and in the sidestream a sweet, fruity, &#34;juicyfruit&#34;, woody, piney and blueberry aroma and taste profile. 
     EXAMPLE VI 
     PREPARATION OF 1- AND 5-METHYL-5-NORBORNENE-2-CARBOXYLIC ACID n-BUTYL ESTERS ##STR127## 
     Into a 3 liter reaction flask equipped with stirrer, thermometer, reflux condenser, dropping funnel and cooling bath is placed 700 ml toluene and 60 grams of ethyl aluminum dichloride. While maintaining the temperature of the mixture at 20°-25° C., via the dropping funnel is added 300 grams of n-butyl acrylate over a period of 20 minutes. 
     While keeping temperature at 20°-25° C. over a 40 minute period, 380 grams of a 50% solution of 1-methyl-1,3-cyclopentadiene and 2-methyl-1,3-cyclopentadiene is added to the reaction mass. 
     After about 2 hours an additional 30 grams of ethyl aluminum dichloride is added and the reaction mass is stirred for another 1.5 hours while maintaining the temperature thereof at 20°-25° C. 
     Reaction mass is then added to 1 liter of 10% hydrochloric acid. The reaction mass now exists in two phases; an organic phase and an aqueous phase. The organic phase is removed and washed as follows: 
     A. One 1 liter portion of water; 
     B. One 1 liter portion of saturated sodium carbonate; 
     C. One 1 liter portion of water. 
     The solvent is then removed by vacuum distillation and the resulting product is distilled on a 12&#34; Goodloe column yielding the following fractions: 
     
         ______________________________________                                    
       Vapor   Liquid                Weight of                            
Fraction                                                                  
       Temp.   Temp.    mm/Hg. Reflux                                     
                                     Fraction                             
No.    (°C.)                                                       
               (°C.)                                               
                        Pressure                                          
                               Ratio (g.)                                 
______________________________________                                    
1      70/70   107/113  1.0/1.0                                           
                               9:1/4:1                                    
                                     16.0                                 
2      70      113      1.0    4:1   18.0                                 
3      69      112      1.0    4:1   14.2                                 
4      69      113      1.0    9:1   22.6                                 
5      71      116      1.0    9:1   23.4                                 
6      71      116      1.0    9:1   21.4                                 
7      74      116      1.0    9:1   8.7                                  
8      72      121      1.2    9:1   17.4                                 
9      73      122      1.5    9:1   18.5                                 
10     74      123      1.2    9:1   18.6                                 
11     74      123      1.2    9:1   22.6                                 
12     82      130      1.3    9:1   18.1                                 
13     82      133      1.3    9:1   21.2                                 
14     82      138      1.3    9:1   22.5                                 
15     82      140      1.4    9:1   20.3                                 
16     82      148      1.4    9:1   25.6                                 
17     82      182      1.2    9:1   23.7                                 
18     84      190      1.2    9:1   6.0                                  
______________________________________                                    
 
    
     NMR, IR and mass spectral analysis yielding the information that the resulting product is a mixture of compounds having the structures: ##STR128## 
     FIG. 22 sets forth the GLC profile for the reaction product. 
     FIG. 23A sets forth the NMR spectrum for fraction 14 for the foregoing fractional distillation and this fraction consists of compound having the structure: ##STR129## 
     FIG. 23B sets forth the NMR spectrum for fraction 4 of the foregoing distillation consisting of the compound having the structure: ##STR130## 
     FIG. 24A sets forth the infrared spectrum for fraction 14 of the foregoing distillation consisting of the compound having the structure: ##STR131## 
     FIG. 24B sets forth the infrared spectrum for fraction 4 of the foregoing distillation consisting of the compound having the structure: ##STR132## 
     FIG. 25 sets forth the mass spectrum for the reaction product containing the compounds having the structures: ##STR133## 
     From a fragrance standpoint bulked fractions 2-18 have a balsamic and rum/butterscotch aroma profile. 
     From a food flavor standpoint, bulked fractions 5-14 have a fruity, strawberry, blueberry, balsamic aroma profile with a blueberry, balsamic and bitter flavor profile at 2 ppm. 
     From a tobacco flavor standpoint, bulked fractions 5-14 have an earthy and mushroom aroma and taste both prior to and on smoking in the mainstream and in the sidestream. 
     EXAMPLE VII 
     PREPARATION OF ETHYL ESTERS OF 1,2- AND 2,5-DIMETHYL-5-NORBORNENE-2-CARBOXYLIC ACIDS ##STR134## 
     Into a 5 liter flask equipped with condenser, thermometer, addition funnel, nitrogen purge and cooling bath are placed 1000 ml toluene, 50 grams of ethyl aluminum dichloride and 680 grams of ethyl methacrylate. The resulting mixture is cooled to 20°-25° C. and over a period of 3 hours while maintaining the temperature at 23°-24° C. 400 grams of a mixture of 1-methyl-1,3-cyclopentadiene and 2-methyl-1,3-cyclopentadiene is added to the reaction mass. 
     The reaction mass is then poured into 1 liter of 10% aqueous hydrochloric acid. The reaction mass now exists in two phases; an aqueous phase and an organic phase. The aqueous phase is extracted with one 500 ml portion of toluene and the toluene extract is combined with the organic layer. The resulting organic phase is washed as follows: 
     A. One 1 liter portion of water; 
     B. One 1 liter portion of saturated sodium bicarbonate; 
     C. One 1 liter portion of water. 
     The resulting product is then stripped of solvent under vacuum. Primol® and Ionox® are then added to the reaction mass. The reaction mass is then distilled on an 18&#34; Goodloe column yielding the following fractions: 
     
         ______________________________________                                    
       Vapor   Liquid                Weight of                            
Fraction                                                                  
       Temp.   Temp.   mm/Hg.  Reflux                                     
                                     Fraction                             
No.    (°C.)                                                       
               (°C.)                                               
                       Pressure                                           
                               Ratio (g.)                                 
______________________________________                                    
1      55/56    84/85  5.5/5.5 9:1   8.3                                  
2      60      83      4.0     9:1   41.9                                 
3      66      84      4.0     9:1   40.0                                 
4      67      85      4.0     9:1   44.4                                 
5      67      88      4.0     9:1   40.8                                 
6      67      93      4.0     9:1   40.7                                 
7      68      101     4.0     9:1   39.1                                 
8      69      110     4.0     9:1   51.3                                 
9      70      125     4.0     9:1   39.4                                 
10     70      157     4.0     9:1   16.0                                 
11     72/75   170/220 4.0/4.0 9:1   10.0                                 
______________________________________                                    
 
    
     NMR, IR and mass spectral analysis yield the information that the resulting product contains two compounds having the structures: ##STR135## 
     These materials are not separable via ordinary commercial physical separation procedures or commercial unit operations. 
     FIG. 26 sets forth the GLC profile for the resulting mixture containing the compounds having the structures: ##STR136## 
     FIG. 27 sets forth the NMR spectrum for the mixture of compounds having the structures: ##STR137## 
     FIG. 28 sets forth the infrared spectrum for the compounds having the structures: ##STR138## in admixture. 
     FIG. 29 sets forth the mass spectrum for the reaction product as produced above containing and consisting of the structures: ##STR139## 
     Bulked fractions 4-10 from a fragrance standpoint has a green, minty, spicy aroma with medicinal nuances and a pepacuana bark extract type undertone. 
     From a food flavor standpoint the resulting mixture containing the compounds having the structures: ##STR140## has a fruity, raspberry and seedy aroma and flavor characteristic with additional bitter flavor nuance at 0.2 ppm. 
     From a tobacco flavor standpoint, the resulting mixture has a sweet, green, herbaceous, dill and fruity aroma and taste both prior to and on smoking in smoking tobacco in the main stream and in the side stream. 
     EXAMPLE VII-A 
     PREPARATION OF 1,3-AND 3,5-DIMETHYL NORBORNANE CARBOXYLIC ACID ESTERS ##STR141## 
     Into a 500 ml pressure bottle equipped with Parr shaker is placed 200 grams of the reaction product of Example III containing the compound having the structures: ##STR142## 100 ml isopropyl alcohol and 5 grams of Raney nickel. The 500 ml pressure bottle is then closed and placed under hydrogen pressure. The Parr shaker is shaken under while maintaining the hydrogen pressure at 50 psig for a period of 5.5 hours at a temperature of 20°-30° C. The Parr shaker and pressure bottle apparatus is then opened and the reaction mass is filtered and the solvent is removed from the reaction mass. The resulting reaction product is then distilled yielding the following fractions: 
     
         ______________________________________                                    
        Vapor   Liquid                Weight of                           
Fraction                                                                  
        Temp.   Temp.   mm. Hg.                                           
                               Reflux Fraction                            
No.     (°C.)                                                      
                (°C.)                                              
                        Pressure                                          
                               Ratio  (g.)                                
______________________________________                                    
1       53/55   70/73   1.2/1.2                                           
                               9:1/9:1                                    
                                      5.7                                 
2       55      73      1.2    3:1    18.5                                
3       54      73      1.2    3:1    15.9                                
4       57      74      1.2    3:1    13.0                                
5       58      74      1.2    3:1    17.3                                
6       62      75      1.2    3:1    14.6                                
7       64      75      1.5    3:1    25.3                                
8       60      80      1.4    3:1    17.6                                
9       58      78      1.2    3:1    24.9                                
10      59      80      1.2    3:1    18.5                                
11      59      82      1.2    3:1                                        
______________________________________                                    
 
    
     Fractions 3-8 are bulked and NMR, IR and mass spectral analyses yield the information that bulked fractions 3-8 consist of the compounds having the structures: ##STR143## 
     Fraction 1 of the foregoing distillation contains the pure compound having the structure: ##STR144## 
     Peak 2 of the foregoing GLC analysis consists of the compound having the structure: ##STR145## 
     FIG. 31-A is the NMR spectrum for the compound having the structure: ##STR146## of fraction 1 of the foregoing distillation. 
     FIG. 31-B is the NMR spectrum for the compound having the structure: ##STR147## of peak 2 of the foregoing GLC profile. 
     FIG. 32-A is the infrared spectrum for fraction 1 of the foregoing distillation consisting of the compound having the structure: ##STR148## 
     FIG. 32-B is the infrared spectrum for peak 2 of the foregoing GLC profile consisting of the compound having the structure: ##STR149## 
     FIG. 33-A is the mass spectrum for fraction 1 of the foregoing distillation consisting of the compound having the structure: ##STR150## 
     FIG. 33-B is the mass spectrum for peak 2 of the foregoing GLC profile consisting of the compound having the structure: ##STR151## 
     EXAMPLE VIII 
     The following spicy, floral and herbal type formulae are prepared: 
     
         ______________________________________                                    
                 Parts by Weight                                          
  Ingredient       VIII(A)    VIII(B)                                     
______________________________________                                    
Geranium Bourbon   20.0       20.0                                        
Rosemary Oil Spanish                                                      
                   10.0       10.0                                        
Lavender Oil Barreme                                                      
                   10.0       10.0                                        
Thyme Oil White    10.0       10.0                                        
Amyl Cinnamic Aldehyde 10.0                                               
                   10.0                                                   
Sauge Sclaree French                                                      
                   5.0        5.0                                         
Sandalwood Oil     5.0        5.0                                         
Galbanum Oil       5.0        5.0                                         
Patchouli Oil Light                                                       
                   5.0        5.0                                         
Cedarwood Oil Light                                                       
                   15.0       15.0                                        
Product produced according                                                
                   5.0        --                                          
to Example III, bulked                                                    
fractions 5-11 containing                                                 
compounds having the                                                      
structures:                                                               
 ##STR152##                                                               
 ##STR153##                                                               
Product produced according                                                
                   --         5.0                                         
to Example V containing                                                   
bulked fractions 1-9                                                      
and consisting of the                                                     
compounds having the                                                      
structures:                                                               
 ##STR154##                                                               
 ##STR155##                                                               
______________________________________                                    
 
    
     When the compositions of matter prepared according to Example III or Example V are incorporated into the formulae at 5.0% both compositions of matter add a pleasant fruity, tagette character to these spicy, herbal, floral type perfume formulations. 
     EXAMPLE IX 
     A jasmine formulae is produced containing the following ingredients: 
     
         ______________________________________                                    
   Ingredients    Parts by Weight                                         
______________________________________                                    
Isoeugenol        2.0                                                     
Benzyl Propionate 10.0                                                    
Benzyl Acetate    13.0                                                    
Benzyl Alcohol    14.0                                                    
Benzyl Benzoate   9.0                                                     
Linalool          8.0                                                     
Phytol            30.0                                                    
Methyl Oleate     4.0                                                     
Methyl Palmitate  4.0                                                     
Indole - 10% in Diethyl                                                   
                  1.0                                                     
 Phthalate                                                                
Composition produced                                                      
                  5.0                                                     
according to Example IV                                                   
containing bulked                                                         
fractions 7-12 and                                                        
containing the compounds                                                  
having the structures:                                                    
 ##STR156##                                                               
 ##STR157##                                                               
______________________________________                                    
 
    
     The material produced according to Example IV incorporated into the formula above at 5.0% gives rise to the pleasant fruityness aroma undertone of this jasmine formulation. 
     EXAMPLE X 
     The following sweet, floral formula is produced: 
     
         ______________________________________                                    
  Ingredients     Parts by Weight                                         
______________________________________                                    
Hexyl Cinnamic Aldehyde                                                   
                  12.0                                                    
Benzyl Propionate 8.0                                                     
Isoeugenol        2.0                                                     
Indole - 10% in Diethyl                                                   
                  1.0                                                     
 Phthalate                                                                
Linalool          8.0                                                     
Benzyl Acetate    8.0                                                     
Vetivert Oil - Bourbon                                                    
                  2.0                                                     
Gamma Methyl Ionone                                                       
                  1.0                                                     
Phenyl Ethyl Alcohol                                                      
                  6.0                                                     
Patchouli Oil Light                                                       
                  1.0                                                     
Lavandin Abrialis 4.0                                                     
Hydroxy Citronellal                                                       
                  4.0                                                     
Bergamot Oil M.P.F.                                                       
                  6.0                                                     
Benzyl Salicylate 13.0                                                    
Musk Ambrette     8.0                                                     
Coumarin          6.0                                                     
Composition of matter pro-                                                
                  10.0                                                    
duced according to Ex. II                                                 
consisting of bulked                                                      
fractions 4-6 and consist-                                                
ing the compounds having                                                  
the structures:                                                           
 ##STR158##                                                               
 ##STR159##                                                               
______________________________________                                    
 
    
     At the 10% level in the foregoing sweet, floral formulation the compounds having the structures: ##STR160## produced according to Example II contribute an intense and pleasant fruity, floralcy to this sweet, floral fragrance. 
     EXAMPLE XI 
     A stable lotion is prepared with the following formulations: 
     
         ______________________________________                                    
Ingredients           Parts by Weight                                     
______________________________________                                    
poly(N,N-dimethyl-3,5-dimethyl-                                           
                      1.0                                                 
ene piperidinium chloride)                                                
(Merquat 100, Merck &amp; Co., U.S.A.,                                        
average molecular weight 50,000-                                          
100,000,viscosity in 40% aqueous                                          
solution, 10,000 cps.                                                     
cocoamidopropyl dimethyl glycine                                          
(betaine)             5.7                                                 
myristyl dimethylamine oxide                                              
                      12.0                                                
stearic monoethanolamide opacifier                                        
                      2.0                                                 
perfume as indicated in Table III                                         
                      0.5                                                 
(below) giving rise to the                                                
aroma profiles as indicated in                                            
Table III (below)                                                         
water, colour, salts, U.V.                                                
absorber              q.s. to 100                                         
______________________________________                                    
 
    
     Two or three bottle capfuls of the above lotion held under the tap releasing the water into the bathtub yields a copiously foamed bubble bath with no visible precipitation flocculation, or &#34;bathtub ring&#34; even using hard water. Bathing in this bath is found to have a cleansing and pleasing emollient effect on the skin as described above. 
     When, after immersion in this bath, the body is soaped, rinsed and dried, an even better, more long-lasting emollient, moisturizing effect on the skin is observed. The foam or bubbles are substantially unaffected by the soaping step, and no precipitate, flocculate or &#34;bathtub ring&#34;, or any bothersome film or coating on the bathtub surface is found. 
     The aroma produced is as is set forth in Table III below: 
     
                       TABLE III                                                   
______________________________________                                    
  Product           Aroma Profile                                         
______________________________________                                    
Product produced according to                                             
                   A fruity, banana and                                   
Example I, bulked fractions                                               
                   creamy aroma with                                      
4-7 consisting of compounds                                               
                   camphoraceous and                                      
having the structures:                                                    
                   minty undertones.                                      
 ##STR161##                                                               
 ##STR162##                                                               
Product produced according to                                             
                   A fruity, camphoraceous                                
Example II, bulked fractions                                              
                   and herbaceous aroma.                                  
4-6 consisting of the compounds                                           
having the structures:                                                    
 ##STR163##                                                               
 ##STR164##                                                               
Product produced according to                                             
                   A sweet, spicy, herbal                                 
Example III, bulked fractions                                             
                   woody and eucalyptol-                                  
7 and 8 consisting of the                                                 
                   like aroma with a dis-                                 
compounds having the structures:                                          
                   tinct calamnus undertone.                              
 ##STR165##                                                               
 ##STR166##                                                               
Product produced according to                                             
                   A sweet, fruity (banana)                               
Example IV, bulked fractions                                              
                   creamy and minty aroma                                 
7-12 consisting of compounds                                              
                   with the minty nuances                                 
having the structures:                                                    
                   increasing in intensity                                
                   on dryout.                                             
 ##STR167##                                                               
 ##STR168##                                                               
Product produced according to                                             
                   A fruity, banana and                                   
Example V, bulked fractions                                               
                   creamy aroma profile.                                  
6-8 consisting of the compounds                                           
having the structures:                                                    
 ##STR169##                                                               
 ##STR170##                                                               
Product produced according to                                             
                   A rum/butterscotch                                     
Example VI, bulked fractions                                              
                   and balsamic aroma.                                    
5-14 containing and consisting                                            
of the compounds having the                                               
structures:                                                               
 ##STR171##                                                               
 ##STR172##                                                               
Product produced according to                                             
                   A green, minty, borneol-                               
Example VII, bulked fractions                                             
                   like, spicy, somewhat                                  
6-9 consisting of the compounds                                           
                   medicinal aroma reminis-                               
having the structures:                                                    
                   cent of pepacuana bark                                 
                   extract with strong                                    
                   pepacuana bark-like under-                             
                   tones.                                                 
 ##STR173##                                                               
 ##STR174##                                                               
Fragrance formulation of                                                  
                   A spicy, floral, herbal                                
Example VIII(A)    aroma with pleasant                                    
                   fruity tagette character-                              
                   istics.                                                
Fragrance formulation of                                                  
Example VIII(B)    A spicy, floral, herbal                                
                   aroma with pleasant                                    
                   fruity tagette character-                              
                   istics.                                                
Fragrance formulation of                                                  
                   A jasmine aroma with a                                 
Example IX         pleasant fruityness.                                   
Fragrance formulation of                                                  
                   A sweet, floral aroma                                  
Example X          with excellent fruity                                  
                   floralcy undertones.                                   
______________________________________                                    
 
    
     EXAMPLE XII 
     The following formulation is prepared with results in properties and use similar to those described in Example XI. 
     
         ______________________________________                                    
Ingredients          Parts by Weight                                      
______________________________________                                    
&#34;Merquat 100&#34;        1.0                                                  
cocoamidopropyl dimethyl glycine                                          
                     8.0                                                  
myristyl dimethyl amine                                                   
                     16.0                                                 
oxide                                                                     
Perfume ingredient as set forth                                           
                     0.8                                                  
In Table IV (below) giving                                                
rise to the aroma profiles as                                             
set forth in Table IV (below)                                             
Water                q.s. to 100                                          
______________________________________                                    
 
    
     The composition is a clear liquid. Its viscosity may be increased by addition of a lauric or myristic diethanolamide or a soluble polyethylene glycol ester such as polyethylene glycol 6000. In addition, this composition may be rendered opaque by addition of stearic monoethanolamide stearate, polyethylene glycol 600 monostearate or a glyco amido stearate such as &#34;Cerasynt 1P&#34;. 
     
                       TABLE IV                                                    
______________________________________                                    
  Product           Aroma Profile                                         
______________________________________                                    
Product produced according to                                             
                   A fruity, banana and                                   
Example I, bulked fractions                                               
                   creamy aroma with                                      
4-7 consisting of compounds                                               
                   camphoraceous and                                      
having the stuctures:                                                     
                   minty undertones.                                      
 ##STR175##                                                               
Product produced according to                                             
                   A fruity, camphoraceous                                
Example II, bulked fractions                                              
                   and herbaceous aroma.                                  
4-6 consisting of the compounds                                           
having the structures:                                                    
 ##STR176##                                                               
Product produced according to                                             
                   A sweet, spicy, herbal                                 
Example III, bulked fractions                                             
                   woody and eucalyptol-                                  
7 and 8 consisting of the                                                 
                   like aroma with a dis-                                 
compounds having the stuctures:                                           
                   tinct calamnus undertone.                              
 ##STR177##                                                               
Product produced according to                                             
                   A sweet, fruity (banana)                               
Example IV, bulked fractions                                              
                   creamy and minty aroma                                 
7-12 consisting of compounds                                              
                   with the minty nuances                                 
having the structures:                                                    
                   increasing in intensity                                
                   on dryout.                                             
 ##STR178##                                                               
Product produced according to                                             
                   A fruity, banana and                                   
Example V, bulked fractions                                               
                   creamy aroma profile.                                  
6-8 consisting of the compounds                                           
having the structures:                                                    
 ##STR179##                                                               
Product produced according to                                             
                   A rum/butterscotch                                     
Example VI, bulked fractions                                              
                   and balsamic aroma.                                    
5-14 containing and consisting                                            
of the compounds having the                                               
structures:                                                               
 ##STR180##                                                               
Product produced according to                                             
                   A green, minty, borneol-                               
Example VII, bulked fractions                                             
                   like, spicy, somewhat                                  
6-9 consisting of the compounds                                           
                   medicinal aroma reminis-                               
having the structures:                                                    
                   cent of pepacuana bark                                 
                   extract with strong                                    
                   pepacuana bark-like under-                             
                   tones.                                                 
 ##STR181##                                                               
Fragrance formulation of                                                  
                   A spicy, floral, herbal                                
Example VIII(A)    aroma with pleasant                                    
                   fruity tagette character-                              
                   istics.                                                
Fragrance formulation of                                                  
                   A spicy, floral, herbal                                
Example VIII(B)    aroma with pleasant                                    
                   fruity tagette character-                              
                   istics                                                 
Fragrance formulation of                                                  
                   A jasmine aroma with a                                 
Example IX         pleasant fruityness.                                   
Fragrance formulation of                                                  
                   A sweet, floral aroma                                  
Example X          with excellent fruity                                  
                   floralcy undertones.                                   
______________________________________                                    
 
    
     EXAMPLE XIII 
     The following shampoo is prepared containing the following ingredients: 
     
         ______________________________________                                    
Ingredients           Parts by Weight                                     
______________________________________                                    
Tridecyloxy polyethoxy ethanol                                            
of ten ethoxy groups  17.3                                                
Polyoxyethylene (20) sorbitan                                             
monolaurate           7.5                                                 
Myristyl dimethylamine oxide                                              
(30% active)          25.0                                                
C.sub.10 -C.sub.20 fatty acyl monoethanolamide                            
(cocomonoethanolamide)                                                    
                      2.5                                                 
Polyacrylamide of molecular weight                                        
of about 1,500,00     0.2                                                 
Hydrogen peroxide (30% aqueous                                            
solution)             0.5                                                 
Perfume ingredient as indicated at                                        
Table V (below) giving rise to                                            
the aroma profiles as indicated                                           
in Table V (below)    1.0                                                 
Deionized water (3 micromhos/cm                                           
conductivity)         46.0                                                
______________________________________                                    
 
    
     A shampoo of the above composition is made in the following matter. First, the tridecyloxy polyethoxy ethanol is added to a clean mixing tank, with the agitator on, and the amine oxide, polyoxyethylene sorbitan monolaurate and cocomonoethanolamide are added sequentially, with continued agitation. The mix is then heated to 68° C., until the cocomonoethanolamine is melted and/or dissolved. The hydrogen peroxide solution is then admixed with the mentioned nonionics and mixing is continued for about half an hour, in which the peroxide destroys any free amines or other harmful impurities that may be present. The mix is then cooled to 38° C. 
     In a separate mixer the polyacrylamide is gradually added to the formula weight of deionized water, with the mixer on. Addition is effected carefully and slowly (the polyacrylamide is sprinkled in) to avoid the production of &#34;fish eyes&#34; in the mix. After dissolving of the polyacrylamide the solution thereof is added to the first mixing tank with agitation and is blended with the nonionics, such mixings being at room temperature. Subsequently the perfume as indicated in Table V (below giving rise to the aroma profile as set forth in Table V (below) is admixed with the balance of the composition and mixing is continued for another half hour. 
     
                       TABLE V                                                     
______________________________________                                    
  Product           Aroma Profile                                         
______________________________________                                    
Product produced according to                                             
                   A fruity, banana and                                   
Example I, bulked fractions                                               
                   creamy aroma with                                      
4-7 consisting of compounds                                               
                   camphoraceous and                                      
having the structures:                                                    
                   minty undertones.                                      
 ##STR182##                                                               
Product produced according to                                             
                   A fruity, camphoraceous                                
Example II, bulked fractions                                              
                   and herbaceous aroma.                                  
4-6 consisting of the compounds                                           
having the structures:                                                    
 ##STR183##                                                               
Product produced according to                                             
                   A sweet, spicy, herbal                                 
Example III, bulked fractions                                             
                   woody and eucalyptol-                                  
7 and 8 consisting of the                                                 
                   like aroma with a dis-                                 
compounds having the structures:                                          
                   tinct calamnus undertone.                              
 ##STR184##                                                               
Product produced according to                                             
                   A sweet, fruity (banana)                               
Example IV, bulked fractions                                              
                   creamy and minty aroma                                 
7-12 consisting of compounds                                              
                   with the minty nuances                                 
having the structures:                                                    
                   increasing in intensity                                
                   on dryout.                                             
 ##STR185##                                                               
Product produced according to                                             
                   A fruity, banana and                                   
Example V, bulked fractions                                               
                   creamy aroma profile.                                  
6-8 consisting of the compounds                                           
having the structures:                                                    
 ##STR186##                                                               
Product produced according to                                             
                   A rum/butterscotch                                     
Example VI, bulked fractions                                              
                   and balsamic aroma.                                    
5-14 containing and consisting                                            
of the compounds having the                                               
structures:                                                               
 ##STR187##                                                               
Product produced according to                                             
                   A green, minty, borneol-                               
Example VII, bulked fractions                                             
                   like, spicy, somewhat                                  
6-9 consisting of the compounds                                           
                   medicinal aroma reminis-                               
having the structures:                                                    
                   cent of pepacuana bark                                 
                   extract with strong                                    
                   pepacuana bark-like under-                             
                   tones.                                                 
 ##STR188##                                                               
Fragrance formulation of                                                  
                   A spicy, floral, herbal                                
Example VIII(A)    aroma with pleasant                                    
                   fruity tagette character-                              
                   istics.                                                
Fragrance formulation of                                                  
                   A spicy, floral, herbal                                
Example VIII(B)    aroma with pleasant                                    
                   fruity tagette character-                              
                   istics.                                                
Fragrance formulation of                                                  
                   A jasmine aroma with a                                 
Example IX         pleasant fruityness.                                   
Fragrance formulation of                                                  
                   A sweet, floral aroma                                  
Example X          with excellent fruity                                  
                   floralcy undertones.                                   
______________________________________                                    
 
    
     The product made is an excellent shampoo of satisfactory viscosity and aroma, foaming power, foam stability, low conductivity and good shampooing effects. The viscosity is about 1,000 centipoises at 20° C. and the conductivity, using the Hach Conductivity Meter, is 750 micromhos/cm. The foaming power is 250 ml and the foam stability is 22 seconds, by the test method previously described. In comparison, a commercial shampoo based on triethanolamine lauryl sulphate detergent has a conductivity of about 22,000 micromhos/cm, a viscosity of about 1,500 centipoises, a foaming power of about 380 ml and a foam stability of 60 seconds. 
     In panel evaluations of the experimental shampoo compared to a different commercial product, in actual shampooing, the experimental formula was adjudged significantly better in being less drying, producing a softer feel for the wet hair, leaving the wet hair easier to comb, being less prone to accumulate static charges (less flyaway) and having a foam of better appearance and feel. Additionally, the experimental product was judged better in almost all hair effect properties, with the control only being about equal to it in curl retention. In properties other than those mentioned the experimental product was better in rinsability, the control was better in foam build-up rate and the foams were about equal in volume and stability. 
     In the shampooing described herein and in subsequent Examples the human hair is washed on the head by wetting the hair with warm tap water at about 42° C., applying 15 grams of shampoo to the hair, lathering it into the hair for a minute, rinsing with warm tap water for 30 seconds, re-lathering with 7 grams of shampoo for a minute and rinsing off for 30 seconds, after which the hair is towel dried and dried further with an automatic hair dryer. 
     EXAMPLE XIV 
     FABRIC FRESHENER COMPOSITION 
     A fabric freshener composition is prepared as follows: 
     
         ______________________________________                                    
Ingredients        Parts by Weight                                        
______________________________________                                    
Sodium bicarbonate 3                                                      
&#34;Kyro&#34; EOB (Trade Mark)*                                                  
                   1                                                      
Perfume ingredient as set                                                 
forth in Table VI below                                                   
giving rise to an aroma                                                   
as set forth in Table VI                                                  
below              1                                                      
Water              0.05                                                   
______________________________________                                    
 
    
     The composition of this Example is prepared by simply mixing the ingredients. 
     The above described composition is applied to a lightly soiled and wrinkled fabric as droplets (ca. 5.0 mm avg. size) using a trigger acton sprayer having a nozzle which is adjustable to provide composition droplets in the desired range. The composition is applied at a rate of about 1 gram of composition to about 10 grams of fabric. 
     The fabric is then placed in an automatic dryer and dried, with tumbling action, at a temperature of 60° C.-80° C. for a period of 15 minutes. The fabric is rendered free of wrinkles and static, and has a fresh appearance and pleasant odor profile as set forth in Table VI below. Surprisingly, the sodium bicarbonate is not visible on the refreshed fabric. 
     In the foregoing procedure, substantially the same results were obtained when sodium carbonate is substituted for the sodium bicarbonate. 
     
                       TABLE VI                                                    
______________________________________                                    
Product             Aroma Profile                                         
______________________________________                                    
Product produced according to                                             
                  A fruity, baanana and                                   
Example I, bulked fractions                                               
                  creamy aroma with                                       
4-7 consisting of compounds                                               
                  camphoraceous and                                       
having the structures:                                                    
                  minty undertones.                                       
 ##STR189##                                                               
and                                                                       
 ##STR190##                                                               
Product produced according to                                             
                  A fruity, camphoraceous                                 
Example II, bulked fractions                                              
                  and herbaceous aroma.                                   
4-6 consisting of the compounds                                           
having the structures:                                                    
 ##STR191##                                                               
and                                                                       
 ##STR192##                                                               
Product produced according to                                             
                  A sweet, spicy, herbal                                  
Example III, bulked fractions                                             
                  woody and eucalyptol-                                   
7 and 8 consisting of the                                                 
                  like aroma with a dis-                                  
compounds having the structures:                                          
                  tinct calamnus undertone.                               
 ##STR193##                                                               
and                                                                       
 ##STR194##                                                               
Product produced according to                                             
                  A sweet, fruity (banana)                                
Example IV, bulked fractions                                              
                  creamy and minty aroma                                  
7-12 consisting of compounds                                              
                  with the minty nuances                                  
having the structures:                                                    
                  increasing in intensity                                 
                  on dryout.                                              
 ##STR195##                                                               
and                                                                       
 ##STR196##                                                               
Product produced according to                                             
                  A fruity, banana and                                    
Example V, bulked fractions                                               
                  creamy aroma profile.                                   
6-8 consisting of the compounds                                           
having the structures:                                                    
 ##STR197##                                                               
and                                                                       
 ##STR198##                                                               
Product produced according to                                             
                  A rum/butterscotch                                      
Example VI, bulked fractions                                              
                  and balsamic aroma.                                     
5-14 containing and consisting                                            
of the compounds having the                                               
structures:                                                               
 ##STR199##                                                               
and                                                                       
 ##STR200##                                                               
Product produced according to                                             
                  A green, minty, borneol-                                
Example VII, bulked fractions                                             
                  like, spicy, somewhat                                   
6-9 consisting of the compounds                                           
                  medicinal aroma reminis-                                
having the structures:                                                    
                  cent of pepacuana bark                                  
                  extract with strong                                     
                  pepacuana baark-like under-                             
                  tones.                                                  
 ##STR201##                                                               
and                                                                       
 ##STR202##                                                               
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII (A)  aroma pleasant                                          
                  fruity tagette character-                               
                  istics.                                                 
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII (B)  aroma with pleasant                                     
                  fruity tagette character-                               
                  istics.                                                 
Fragrance formulation of                                                  
                  A jasmine aroma with a                                  
Example IX        pleasant fruityness.                                    
Fragrance formulation of                                                  
                  A sweet, floral aroma                                   
Example X         with excellent fruity                                   
                  floralcy undertones.                                    
______________________________________                                    
 * A commercial nonionic surfactant comprising an average of eleven carbon
 atoms, ethoxylated to an average of 9 ethyleneoxy groups per molecule.   
 
    
     EXAMPLE XV 
     PERFUMED LIQUID DETERGENT 
     Concentrated liquid detergents (lysine salts of n-dodecyl benzene sulfonic acid as more specifically described in U.S. Pat. No. 3,948,818, issued on Apr. 6, 1976) with aromas as indicated in Table VII below are prepared containing 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.40%, 0.50% and 0.80% of the perfume ingredient as set forth in Table VII below. The detergents are prepared by adding a homogeneously mixing the appropriate quantity of perfume ingredient as set forth in Table VII below. The detergents all possess aromas as set forth in Table VII below with the intensity of each increasing with greater concentrations of the perfume ingredient is indicated in Table VII below. 
     
                       TABLE VII                                                   
______________________________________                                    
Product             Aroma Profile                                         
______________________________________                                    
Product produced according to                                             
                  A fruity, baanana and                                   
Example I, bulked fractions                                               
                  creamy aroma with                                       
4-7 consisting of compounds                                               
                  camphoraceous and                                       
having the structures:                                                    
                  minty undertones.                                       
 ##STR203##                                                               
and                                                                       
 ##STR204##                                                               
Product produced according to                                             
                  A fruity, camphoraceous                                 
Example II, bulked fractions                                              
                  and herbaceous aroma.                                   
4-6 consisting of the compounds                                           
having the structures:                                                    
 ##STR205##                                                               
and                                                                       
 ##STR206##                                                               
Product produced according to                                             
                  A sweet, spicy, herbal                                  
Example III, bulked fractions                                             
                  woody and eucalyptol-                                   
7 and 8 consisting of the                                                 
                  like aroma with a dis-                                  
compounds having the structures:                                          
                  tinct calamnus undertone.                               
 ##STR207##                                                               
and                                                                       
 ##STR208##                                                               
Product produced according to                                             
                  A sweet, fruity (banana)                                
Example IV, bulked fractions                                              
                  creamy and minty aroma                                  
7-12 consisting of compounds                                              
                  with the minty nuances                                  
having the structures:                                                    
                  increasing in intensity                                 
                  on dryout.                                              
 ##STR209##                                                               
and                                                                       
 ##STR210##                                                               
Product produced according to                                             
                  A fruity, banana and                                    
Example V, bulked fractions                                               
                  creamy aroma profile.                                   
6-8 consisting of the compounds                                           
having the structures:                                                    
 ##STR211##                                                               
and                                                                       
 ##STR212##                                                               
Product produced according to                                             
                  A rum/butterscotch                                      
Example VI, bulked fractions                                              
                  and balsamic aroma.                                     
5-14 containing and consisting                                            
of the compounds having the                                               
structures:                                                               
 ##STR213##                                                               
and                                                                       
 ##STR214##                                                               
Product produced according to                                             
                  A green, minty, borneol-                                
Example VII, bulked fractions                                             
                  like, spicy, somewhat                                   
6-9 consisting of the compounds                                           
                  medicinal aroma reminis-                                
having the structures:                                                    
                  cent of pepacuana bark                                  
                  extract with strong                                     
                  pepacuana bark-like under-                              
                  tones.                                                  
 ##STR215##                                                               
and                                                                       
 ##STR216##                                                               
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII (A)  aroma with pleasant                                     
                  fruity tagette character-                               
                  istics.                                                 
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII (B)  aroma with pleasant                                     
                  fruity tagette character-                               
                  istics.                                                 
Fragrance formulation of                                                  
                  A jasmine aroma with a                                  
Example IX        pleasant fruityness.                                    
Fragrance formulation of                                                  
                  A sweet, floral aroma                                   
Example X         with excellent fruity                                   
                  floralcy undertones.                                    
______________________________________                                    
 
    
     EXAMPLE XVI 
     PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME 
     The perfume ingredient as set forth in Table VIII below is incorporated into colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 5.0% and 6.0% in 75%, 80%, 85%, 90% and 95% aqueous ethanol solutions. Distinct and definite aromas as set forth in Table VIII below are imparted to the colognes. The perfume ingredients as indicated in Table VIII below are also added to handkerchief perfumes at concentrations of 15%, 20%, 25%, 30% and 35% (in 75%, 80%, 85%, 90% and 95% aqueous ethanol) and aroma profiles as set forth in Table VIII are imparted to the handkerchief perfume. 
     
                       TABLE VIII                                                  
______________________________________                                    
Product             Aroma Profile                                         
______________________________________                                    
Product produced according to                                             
                  A fruity, banana and                                    
Example I, bulked fractions                                               
                  creamy aroma with                                       
4-7 consisting of compounds                                               
                  camphoraceous and                                       
having the structures:                                                    
                  minty undertones.                                       
 ##STR217##                                                               
and                                                                       
 ##STR218##                                                               
Product produced according to                                             
                  A fruity, camphoraceous                                 
Example II, bulked fractions                                              
                  and herbaceous aroma.                                   
4-6 consisting of the compounds                                           
having the structures:                                                    
 ##STR219##                                                               
and                                                                       
 ##STR220##                                                               
Product produced according to                                             
                  A sweet, spicy, herbal                                  
Example III, bulked fractions                                             
                  woody and eucalyptol-                                   
7 and 8 consisting of the                                                 
                  like aroma with a dis-                                  
compounds having the structures:                                          
                  tinct calamnus undertone.                               
 ##STR221##                                                               
and                                                                       
 ##STR222##                                                               
Product produced according to                                             
                  A sweet, fruity (banana)                                
Example IV, bulked fractions                                              
                  creamy and minty aroma                                  
7-12 consisting of compounds                                              
                  with the minty nuances                                  
having the structures:                                                    
                  increasing in intensity                                 
                  on dryout.                                              
 ##STR223##                                                               
and                                                                       
 ##STR224##                                                               
Product produced according to                                             
                  A fruity, banana and                                    
Example V, bulked fractions                                               
                  creamy aroma profile.                                   
6-8 consisting of the compounds                                           
having the structures:                                                    
 ##STR225##                                                               
and                                                                       
 ##STR226##                                                               
Product produced according to                                             
                  A rum/butterscotch                                      
Example VI, bulked fractions                                              
                  and balsamic aroma.                                     
5-14 containing and consisting                                            
of the compounds having the                                               
structures:                                                               
 ##STR227##                                                               
and                                                                       
 ##STR228##                                                               
Product produced according to                                             
                  A green, minty, borneol-                                
Example VII, bulked fractions                                             
                  like, spicy, somewhat                                   
6-9 consisting of the compounds                                           
                  medicinal aroma reminis-                                
having the structures:                                                    
                  cent of pepacuana bark                                  
                  extract with strong                                     
                  pepacuana bark-like under-                              
                  tones.                                                  
 ##STR229##                                                               
and                                                                       
 ##STR230##                                                               
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII (A)  aroma with pleasant                                     
                  fruity tagette character-                               
                  istics.                                                 
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII (B)  aroma with pleasant                                     
                  fruity tagette character-                               
                  istics.                                                 
Fragrance formulation of                                                  
                  A jasmine aroma with a                                  
Example IX        pleasant fruityness.                                    
Fragrance formulation of                                                  
                  A sweet, floral aroma                                   
Example X         with excellent fruity                                   
                  floralcy undertones.                                    
______________________________________                                    
 
    
     EXAMPLE XVII 
     BLUEBERRY FLAVOR FORMULATION 
     The following formulation is prepared: 
     
         ______________________________________                                    
Ingredients         Parts By Weight                                       
______________________________________                                    
Heliotropin         3.0                                                   
Terpinenol-4 (10% in 95%                                                  
aqueous food grade ethanol)                                               
                    0.2                                                   
Benzaldehyde        1.5                                                   
Anisaldehyde        0.2                                                   
Phenyl acetaldehyde 0.4                                                   
Benzyl formate      0.5                                                   
Benzyl acetate      2.0                                                   
Cis-3-hexenyl benzoate (10%                                               
in 95% aqueous food grade                                                 
ethanol)            0.5                                                   
Methyl hexanoate    2.0                                                   
Hexanal             1.0                                                   
Eucalyptol (1% in 95% aqueous                                             
food grade ethanol) 0.5                                                   
Eugenol             0.2                                                   
Acetaldehyde        3.0                                                   
Ethyl acetate       21.0                                                  
Ethyl butyrate      26.0                                                  
Propylene glycol    38.0                                                  
                    100.0                                                 
______________________________________                                    
 
    
     The above formulation is split into 5 portions. To the first four portions are added at the rate of 1%, the norbornane derivatives of Table IX. To the fifth portion nothing is added. All five formulations with and without said norbornyl derivatives are combined with water at the rate of 100 ppm. The flavor of the first four portions each including a norbornyl derivative prepared according to the preceeding examples as indicated in Table IX below have fruity, blueberry characteristics with several other nuances as indicated in Table IX below and are all closely similar to the flavor of wild blueberries. It is therefore preferred to use the formulations containing the norbornyl derivatives as listed in Table IX below, to the basic blueberry formulation which does not contain any of said norbornyl derivatives. 
     
                       TABLE IX                                                    
______________________________________                                    
Norbornyl Derivative                                                      
                  Flavor Characteristics                                  
______________________________________                                    
Composition produced according                                            
                  A fruity, blueberry aroma                               
to Example II consisting of                                               
                  and taste.                                              
bulked fractions 4-6 contain-                                             
ing the compounds having                                                  
the structures:                                                           
 ##STR231##                                                               
 ##STR232##                                                               
The composition of Example III                                            
                  A sweet, fruity, berry-                                 
bulked fractions 7 and 8 con-                                             
                  like, spicy, black pepper-                              
taining the compounds having                                              
                  like, herbaceous and clove-                             
the structures:   like aroma and taste                                    
                  characteristic.                                         
 ##STR233##                                                               
 ##STR234##                                                               
Composition of Example V                                                  
                  A sweet, fruity, raspberry,                             
bulked fractions 6-8 con-                                                 
                  vermouth-like and blueberry                             
taining the compounds hav-                                                
                  aroma profile with a fruity,                            
ing the structures:                                                       
                  raspberry and blueberry                                 
                  flavor profile.                                         
 ##STR235##                                                               
 ##STR236##                                                               
Composition produced                                                      
                  A fruity, strawberry, blue-                             
according to Example VI                                                   
                  berry, balsamic aroma profile                           
bulked fractions 5-14                                                     
                  with blueberry, balsamic and                            
containing the compounds                                                  
                  bitter profile at 2ppm.                                 
having the structures:                                                    
 ##STR237##                                                               
 ##STR238##                                                               
______________________________________                                    
 
    
     EXAMPLE XVIII 
     USE OF NORBORNANE DERIVATIVES FOR RASPBERRY FLAVORS 
     The following basic raspberry formulation is prepared: 
     
         ______________________________________                                    
Ingredients         Parts By Weight                                       
______________________________________                                    
Vanillin            2                                                     
Maltol              4                                                     
Parahydroxy benzyl acetone                                                
                    5                                                     
Dimethyl sulfide    1                                                     
Alpha-ionone (10% in propylene                                            
glycol)             2                                                     
Ethyl butyrate      6                                                     
Ethyl acetate       16                                                    
Isobutyl acetate    14                                                    
Acetic acid         10                                                    
Acetaldehyde        10                                                    
Propylene glycol    930                                                   
                    1000                                                  
______________________________________                                    
 
    
     The above formulation is split into five parts. Two the first four parts, at the rate of 0.3% are added the norbornyl derivative produced according to the preceeding examples, as set forth in Table X below. No additive is added to the fifth part. The five formulations are compared in water at the rate of 50 ppm. The four flavors containing the norbornyl derivatives have more ripe raspberry tastes and woody, raspberry kernel characters. They also have additional nuances as set forth in Table X below. Therefore the raspberry formulations containing the four norbornyl derivatives as additives have more natural-like and more characteristic raspberry flavors and are therefore preferred. 
     
                       TABLE X                                                     
______________________________________                                    
Norbornyl Derivative                                                      
                  Flavor Profile                                          
______________________________________                                    
Product produced accord-                                                  
                  A sweet, fruity, berry-like,                            
ing to Example III,                                                       
                  spicy, black pepper-like,                               
bulked fractions 7 and 8                                                  
                  herbaceous and clove-like                               
consisting of compounds                                                   
                  aroma and taste.                                        
having the structures:                                                    
 ##STR239##                                                               
 ##STR240##                                                               
Product produced according                                                
                  A sweet, fruity, red berry,                             
to Example IV, bulked                                                     
                  raspberry-like and seedy                                
fractions 7-12 consisting                                                 
                  aroma profile with a sweet,                             
of the compounds having                                                   
                  fruity, red berry-like,                                 
the structures:   raspberry-like, seedy and                               
                  strawberry taste profile                                
 ##STR241##                                                               
 ##STR242##                                                               
Product produced according                                                
                  A sweet, fruity, raspberry,                             
to Example V, bulked                                                      
                  vermouth-like and blueberry                             
fractions 6-8, consisting                                                 
                  aroma profile with a fruity,                            
of the compounds having                                                   
                  raspberry and blueberry                                 
the structures:   flavor profile.                                         
 ##STR243##                                                               
 ##STR244##                                                               
Product produced according                                                
                  A fruity, raspberry and seedy                           
to Example VII, bulked                                                    
                  aroma profile with a fruity,                            
fractions 6-9, consisting                                                 
                  raspberry, seedy and bitter                             
of the compounds having                                                   
                  flavor profile                                          
the structures:                                                           
 ##STR245##                                                               
 ##STR246##                                                               
 
    
     EXAMPLE XIX 
     FRUITED TAPIOCA CREAM 
     The contents of Ann Page Tapioca pudding mix (ingredients: sugar, corn starch, tapioca, sodium chloride, tapioca flavor and artificial color; Net weight 138 grams) is emptied into a sauce pan. Three cups of milk are added together with one beaten egg yolk previously blended therewith. The resulting mix is cooked over medium heat stirring constantly while slowly adding at the rate of 0.2%, either one of the flavor materials of Example XVII (blueberry flavor) or one of the flavor materials of Example XVIII (raspberry flavor) each of the materials containing one of the norbornyl derivatives of Table IX or of Table X as the case may be. The resulting mixture after heating, is then cooled to room temperature in the saucepan. One egg white is slowly added to the resulting mixture together with three tablespoons of sugar. The resulting mixture is then blended and chilled yielding pleasantly tasting blueberry or raspberry tapioca cream deserts depending upon whether the materials of Example XVII or Example XVIII are added. 
     EXAMPLE XX 
     FLAVORED INSTANT PUDDING 
     A pudding mix (Royal Instant, Net weight 3.5 ozs. produced by Standard Brands Inc., New York, N.Y. 10022) is intimately admixed with 2 cups of cold fresh whole milk. To this mixture, at the rate of 0.3%, is added one of the blueberry flavors of Example XVII containing the norbornyl derivative as listed in Table IX or one of the raspberry flavors of Example XVIII containing one of the norbornyl derivatives as listed in Table X. The resulting mixture is blended in a Waring blender for a period of three minutes. The resulting mixture is then cooled at 15° C. for a period of five minutes. The resulting puddings have excellent natural blueberry or natural raspberry flavors as the case may be, depending on whether the blueberry flavors of Example XVII or whether the raspberry flavors of Example XVIII are used. 
     EXAMPLE XXI 
     A. POWDER FLAVOR COMPOSITION 
     20 Grams of one of the flavor compositions of Example XVII (containing at least one of the norbornyl derivatives of Table IX) is emulsified in a solution containing 300 grams gum acacia and 700 grams water. The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500° F., an outlet temperature of 200° F., and a wheel speed of 50,000 rpm. 
     B. SUSTAINED RELEASE FLAVOR 
     The following mixture is prepared: 
     
         ______________________________________                                    
Ingredients          Parts By Weight                                      
______________________________________                                    
Liquid Blueberry Flavor,                                                  
composition of Ex. XVII                                                   
                     20                                                   
Propylene glycol     9                                                    
Cab-O-Sil®  M-5 (Brand of                                             
Silica produced by the                                                    
Cabot Corp. of 125 High St.                                               
Boston, Mass. 02110;                                                      
Physical Properties:                                                      
Surface area: 200 m.sup.2 /gm                                             
Nominal partical size: 0.012                                              
microns                                                                   
Density: 2.3 lbs./cu. ft.                                                 
                     5.00                                                 
______________________________________                                    
 
    
     The Cab-O-Sil is dispersed in the liquid blueberry flavor compositions (containing the norbornyl derivatives) of Example XVII with vigorous stirring, thereby resulting in a viscous liquid. 71 Parts by weight of the powder flavor composition of Part A, supra, is then blended into the said viscous liquid, with stirring, at 25° C. for a period of 30 minutes resulting in a dry, free flowing sustained release flavor powder. 
     EXAMPLE XXII 
     10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by weight of water at a temperature of 150° F. The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120° F. 20 Parts by weight of the one of the liquid flavor compositions of Example XVII (containing at least one of the norbornyl derivatives of Table IX) is added to the solution which is then homogenized to form an emulsion having particle size typically in the range of 2-5 microns. This material is kept at 120° F. under which conditions the gelatin will not jell. 
     Coascervation is induced by adding, slowly and uniformyl 40 parts by weight of a 20% aqueous solution of sodium sulphate. During coacervation the gelatin molecules are deposited uniformly about each oil droplet as a nucleus. 
     Gelatin is effected by pouring the heated coascervate mixture into 1,000 parts by weight of 7% aqueous solution of sodium sulphate at 65° F. The resulting jelled coascervate may be filtered and washed with water at temperatures below the melting point of gelatin, to remove the salt. 
     Hardening of the filtered cake, in this example, is effected by washing with 200 parts by weight of 37% solution of formaldehyde in water. The cake is then washed to remove residual formaldehyde. 
     EXAMPLE XXIII 
     100 Parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example XXI. 300 Parts of sucrose and 100 parts of corn syrup are added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co. 
     The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The stripsare cut into lengths of 3 inches each. On chewing, the chewing gum as a pleasant, long lasting blueberry flavor. 
     EXAMPLE XXIV 
     CHEWING GUM 
     100 Parts by weight of chicle are mixed with 18 parts by weight of the flavor prepared in accordance with Example XXII. 300 Parts of sucrose and 100 parts of corn syrup are then added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co. 
     The resulting chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long lasting blueberry flavor. 
     EXAMPLE XXV 
     TOOTHPASTE FORMULATION 
     The following separate groups of ingredients are prepared: 
     
         ______________________________________                                    
Parts By Weight                                                           
               Ingredients                                                
______________________________________                                    
Group &#34;A&#34;                                                                 
30.200         Glycerine                                                  
15.325         Distilled Water                                            
 .100          Sodium Benzoate                                            
 .125          Saccharin Sodium                                           
 .400          Stannous Fluoride                                          
Group &#34;B&#34;                                                                 
12.500         Calcium Carbonate                                          
37.200         Dicalsium Phosphate (Dihydrate)                            
Group &#34;C&#34;                                                                 
2.000          Sodium N-Lauroyl Sarcosinate                               
               (foaming agent)                                            
Group &#34;D&#34;                                                                 
1.200          Flavor Material of Ex. XVI                                 
100.00 Total                                                              
PROCEDURE:                                                                
 1.  The ingredients in Group &#34;A&#34; are stirred and                         
     heated in a steam jacketed kettle to 160° F.                  
2.   Stirring is continued for an additional three to                     
     five minutes to form a homogeneous gel.                              
3.   The powders of Group &#34;B&#34; are added to the gel,                       
     while mixing, until a homogeneous paste is formed.                   
4.   With stirring, the flavor of &#34;D&#34; is added and                        
     lastly the sodium n-lauroyl sarcosinate.                             
5.   The resultant slurry is then blended for one hour.                   
     The completed paste is then transferred to a three                   
     roller mill and then homogenized, and finally tubed.                 
______________________________________                                    
 
    
     The resulting toothpaste when used in a normal toothbrushing procedure yields a pleasant blueberry flavor, of constant strong intensity throughout said procedure (1-1.5 minutes). 
     EXAMPLE XXVI 
     CHEWABLE VITAMIN TABLETS 
     The flavor material (containing norbornyl derivatives) of Table X of Example XVIII is added to a chewable vitamin tablet formulation at the rate of 10 gm/Kg which chewable vitamin tablet formulation is prepared as follows: 
     In a Hobart Mixer the following materials are blended to homogeneity: 
     
         ______________________________________                                    
                    Gms/1000 Tablets                                      
______________________________________                                    
Vitamin C (ascorbic acid) as                                              
ascorbic acid-sodium ascorbate                                            
mixture 1:1           70.00                                               
Vitamin B.sub.1 (thiamine mononitrate                                     
331/3 % (Hoffman La Roche)                                                
                      4.0                                                 
Vitamin B.sub.2 (roboflavin) as Rocoat®                               
roboflavin 331/3 %    5.0                                                 
Vitamin B.sub.6 (pyridoxine hydrochloride)                                
as Rocoat®  pyridoxine hydrochloride                                  
331/3 %               4.0                                                 
Niacinamide as Rocoat®  niacinamide                                   
331/3 %               33.0                                                
Calcium pantothenate  11.5                                                
Vitamin B.sub.12 (cyanocobalamin) as                                      
Merck 0.1% in gelatin 3.5                                                 
Vitamin E (d1-alpha tocopheryl                                            
acetate) as dry Vitamin E acetate                                         
331/3 % Roche         6.6                                                 
d-Biotin              0.044                                               
Flavor of Example XVIII containing                                        
norbornyl derivatives of Table X                                          
                      (as indicated above)                                
Certified lake color  5.0                                                 
Sweetener - sodium saccharin                                              
                      1.0                                                 
Magnesium stearate lubricant                                              
                      10.0                                                
Mannitol q.s. to make 500.0                                               
______________________________________                                    
 
    
     Preliminary tablets are prepared by slugging with flat-faced punches and grinding the slugs to 14 mesh. 13.5 G dry Vitamin A Acetate and 0.6 g Vitamin D are then added as beadlets. The entire blend is then compressed using concave punches at 0.5 g each. 
     Chewing of the resultant tablets yields a pleasant long lasting, consistently strong raspberry flavor for a period of 12 minutes. 
     EXAMPLE XXVII 
     CHEWING TOBACCO 
     Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15% Pennsylvania leaf) the following casing is sprayed at a rate of 30%: 
     
         ______________________________________                                    
Ingredients        Parts By Weight                                        
______________________________________                                    
Corn Syrup         60                                                     
Licorice           10                                                     
Glycerine          20                                                     
Fig Juice          4.6                                                    
Prune Juice        5                                                      
Flavor Material of Ex. XVII                                               
Containing Norbornyl Deriva-                                              
tives as listed in Table IX                                               
                   0.4                                                    
______________________________________                                    
 
    
     The resultant product is redried to a moisture content of 20%. On chewing, this tobacco has an excellent substantially consistent, long-lasting blueberry nuance in conjunction with the tobacco note. 
     EXAMPLE XXVIII 
     TOBACCO FORMULATION 
     A tobacco mixture is produced by admixing the following ingredients: 
     
         ______________________________________                                    
Ingredient      Parts by Weight                                           
______________________________________                                    
Bright          40.1                                                      
Burley          24.9                                                      
Maryland        1.1                                                       
Turkish         11.6                                                      
Stem (flue-cured)                                                         
                14.2                                                      
Glycerine       2.8                                                       
Water           5.3                                                       
______________________________________                                    
 
    
     Cigarettes are prepared from this tobacco. The following flavor formulation is prepared: 
     
         ______________________________________                                    
Ingredient     Parts by Weight                                            
______________________________________                                    
Ethyl butyrate .05                                                        
Ethyl valerate .05                                                        
Maltol         2.00                                                       
Cocoa extract  26.00                                                      
Cofee extract  10.00                                                      
Ethyl alcohol  20.00                                                      
Water          41.90                                                      
______________________________________                                    
 
    
     The above-stated tobacco flavor formulation is applied at the rate of 0.1% to all of the cigarettes produced using the above tobacco formulation. Half of the cigarettes are then treated with 500 to 1,500 ppm of one of the following norbornyl derivatives of Table XI as follows: 
     TABLE XI 
     A. Product produced according to Example II, bulked fractions 4-6 consisting of the compounds having the structures: ##STR247## B. Composition of matter produced according to Example III bulked fractions 7 and 8 consisting of the compounds having the structures: ##STR248## 
     The control cigarettes not containing the norbornyl derivatives as set forth in Table XI and the experimental cigarettes which contain the norbornyl derivatives as set forth in Table XI are evaluated by paired comparison and the results are as follows: 
     The experimental cigarettes, are found, on smoking, to have a sweeter, spicy, woody-oriental, clove-like taste with much more body and much more natural tobacco-like aroma prior to smoking and on smoking in the mainstream and the sidestream. The experimental cigarettes containing the product produced according to Example II in addition have cooling nuances. The experimental cigarettes produced containing the product produced according to Example III also have cinnamon bark nuances prior to and on smoking in the mainstream and in the sidestream. 
     All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter. 
     Accordingly, it is concluded that the norbornyl derivatives set forth in Table XI produced according to the processes of Examples II and III enhance the tobacco-like taste and aroma particularly the oriental-like taste of the blended cigarette imparting to it sweet, spicy and woody-oriental tobacco-like nuances and in addition clove-like nuances. 
     EXAMPLE XXIX 
     The following is a description of a preferred embodiment of the invention as carried out using a process wherein minute capsules having a diameter in the range of 50 up to 500 microns were added to a wet web of reconstituted tobacco (weight ratio of dry web to dry capsules=1:0.04. The capsules and binder materials (weight ratio of dry capsule to dry binder=1:0.1 when placed among the tobacco fibers, wet them and entangle with them and clothe them, thus in effect securing and binding the capsules against migration through the sheet, thereby forming a subsident stratum. The majority of binder and associated capsules are caught in the sheet. Substantially no capsules migrate through the sheet. When the wet tobacco wet is dried, the binder shrinks by loss of solvent, leaving the dried polymeric binder material, and the capsules remain in place relatively with respect to sheet thickness. The sheets containing the capsules are then shredded and used in producing smoking articles such as cigarettes. Such cigarettes are formed using a wrapper, containing a fill of tobacco extending from one end of the wrapper to the other, and intimately admixed with the tobacco, a plurality of microcapsules each comprising an aromatic volatile synthetic clove oil flavorant. The capsules are homogeneously spaced in contiguous relationship with the tobacco such that as the burning front of the tobacco advances the length of the tobacco article, a concomitant elevation of temperature initiates consecutive rupture of the capsules (1) releasing the volatile synthetic clove oil-containing material which emanates with smoke from the smoking article into the smoker&#39;s mouth and (2) yielding a crackling sound audible to the human ear. 
     Tragacanth gum solution and starch solution were prepared in the following manner: 
     PART A 
     Concentrated Tragacanth Gum Solution (Binder) 
     4.5 Pounds of dry tragacanth gum powder were stirred into 50 gallons of water, using a suitable mixer. Five minutes after all the powder had been added, the mixer was turned off. The tragacanth gum solution was allowed to stir for 2 hours, and then the mixer was turned on for 5 minutes. Sitting for 2 additional hours, enabled the tragacanth gum to hydrate. After five minutes, the mixer was turned off, and the 55 gallon drum was covered. Just prior to combining the tragacanth gum solution and the capsular slurry, 50 gallons of tragacanth gum solution was diluted with water to 3 percent tragacanth gum on a solids basis. 
     PART B 
     Starch Solution 
     The hydrolyzed starch solution was prepared by heating a slurry of the starch at 190 degrees Fahrenheit for a minumum of 15 minutes to provide a 1 percent by weight, starch-in-water solution. 
     Capsule slurries were prepared in the following manner: 
     PART C 
     Preparation of Synthetic Clove Oil 
     A mixture is prepared containing the following ingredients: 
     
         ______________________________________                                    
Ingredient              Percentage                                        
______________________________________                                    
α-Caryophyllene   2.0                                               
β-Caryophyllene    2.0                                               
γ-Caryophyllene   10.0                                              
Furfural                0.1                                               
Eugenol                 65.0                                              
Eugenyl Acetate         5.0                                               
Acetyl Eugenols         5.9                                               
Norbornol Derivatives as follows:                                         
A. Product produced according to                                          
                        5.0                                               
Example II, bulked fractions                                              
4-6 consisting of the compounds                                           
having the structures:                                                    
 ##STR249##                                                               
 ##STR250##                                                               
B. Composition of matter produced                                         
                        5.0                                               
according to Example III bulked                                           
fractions 7 and 8 consisting of                                           
compounds having the structures:                                          
 ##STR251##                                                               
 ##STR252##                                                               
______________________________________                                    
 
    
     PART D 
     Preparation of Capsular Slurry-Encapsulation of Synthetic Clove Oil 
     Ten grams of gum arabic were dissolved at room temperature in 220 grams of deionized water. The mixture was agitated until the gum arabic was fully dissolved. In a separate 240 milliliter Erlenmeyer flask, 10.0 grams of modified gelatin was mixed with 220.0 grams of deionized water. The gelatin was allowed to tumefy at room temperature and also then warmed in a water bath to about 40° C. With stirring so that the gelatin was dissolved. 
     The gelatin solution and the gum arabic solution were poured into a beaker equipped with a stirrer. A flocculence indicating the precipitation of the gelatin was noted. The temperature of the mixture was decreased to 35° C. The speed of the stirrer was adjusted so that it was turning only enough to keep the phases mixed. The pH of the mixture was 4.50. 
     Into the beaker containing the mixture of gum arabic and gelatin was poured 118.0 grams of synthetic clove oil as prepared in Part C. The speed of the stirrer was then adjusted to mix the colloids and the oil. The oil separated into droplets. Two drops of octyl alcohol were added to prevent foaming. The progress of the coacervation was monitored by means of microscopic examination. 
     The temperature of the mixture was lowered to room temperature, e.g., 24° C. At the higher temperature of 31° C., colloid deposition was observed on the oil droplets. At 24° C., little colloid could be observed in aqueous portions of the mixture. Deposition had ceased. Stirring was continued for 30 minutes, whereupon the reaction mixture was cooled on an ice bath to 4° C. The reaction mixture was maintained at this temperature for 200 minutes. (When hardening was desired, 1.0 milliliters of a 25 percent glutaraldehyde in water per gram of gelatin is added.) 
     The internal phase of the capsules thus formed was approximately 80-90 percent of the total weight of the capsules. 
     The capsules thus produced had diameters in the range of from 50 up to 500 microns. They were coated with the binder onto a tobacco sheet material which was shredded and used as a fill in the manufacture of a smoking article. 
     PART E 
     Variation of the Encapsulation of Synthetic Clove Oil 
     A variation of the encapsulation procedure set forth immediately supra is shown below. 
     The solution of gum arabic was warmed to 38° C., placed in a Waring blender and stirred. The clove oil prepared in Part C was added gradually while the speed of the blender was being increased until the size of the clove oil droplets was approximately 50-500 microns. The mixture thus formed was poured into a 1,000 milliliter beaker containing gelatin, also at 38° C., and was stirred thoroughly. The temperature was then allowed to drop to room temperature and then further decreased to a temperature of 4° C. to 10° C. by means of an ice bath. 
     It is evident that the tobacco film or filaments can be made from various types and combinations of tobacco. For instance, the tobacco sheet material can be made from relatively expensive tobacco such as Latakia in which it is highly desirous to use all waste because of the high price thereof. So, also, it may be formed of Burley or one or more scrap or waste cigarette type tobaccos and incorporated in accordance with a particular cigarette manufacture&#39;s formula as if it were natural cigarette tobacco leaves. Any desired formula can thus be maintained in accordance with the demands of a manufacturer&#39;s particular brand using one or more types of natural shredded tobacco leaves and admixed desired quantities of shredded capsule containing tobacco film material or filaments, either as a blending or flavoring medium or both or for purposes of bulking. 
     In the case of the manufacture of cigarettes, according to the present invention, tobacco films are shredded into strands or the film is formed directly into filaments substantially the width of the strands of natural shredded tobacco and of any desired length. In the case of cigars, the capsule containing films are use in large pieces much as long filler tobacco and forming long filler cigars. In all cases the shredded film or filaments or film used in cigarettes and cigars can be handled either manually or by machine in the same manner as natural shredded tobacco leaves or whole leaves or portions thereof. The amount of shredded capsule-containing reconstituted tobacco or pieces of this material employed in a particular blend in cigarettes or cigars, respectively, will vary according to types of tobacco used in the sheet material and the requirements oa a particular manufacture. 
     EXAMPLE XXX 
     PREPARATION OF A DETERGENT COMPOSITION 
     A total of 100 grams of detergent powder (a low phosphate content detergent composition which contains 12% by weight phosphate builder, 8% hardness mineral ion insensitive detergent, 0.9% by weight maleic anhydride-vinyl compound co-polymer and 2% alkylene oxide condensation product prepared according to Example IV at column XI, of U.S. Pat. No. 4,000,080 issued on Dec. 28, 1976) is intimately admixed with 0.15 grams of one of the perfume materials of Table XII below until a substantially homogeneous composition is obtained. This composition has an aroma as set forth in Table XII below which is pleasant and long lasting: 
     
                       TABLE XII                                                   
______________________________________                                    
Product           Aroma Profile                                           
______________________________________                                    
Product produced according to                                             
                  A fruity, banana and                                    
Example I, bulked fractions                                               
                  creamy aroma with                                       
4-7 consisting of compounds                                               
                  camphoraceous and                                       
having the structures:                                                    
                  minty undertones.                                       
 ##STR253##                                                               
 ##STR254##                                                               
Product produced according to                                             
                  A fruity, camphoraceous                                 
Example II, bulked fractions                                              
                  and herbaceous aroma.                                   
4-6 consisting of the compounds                                           
having the structures:                                                    
 ##STR255##                                                               
 ##STR256##                                                               
Product produced according to                                             
                  A sweet, spicy, herbal                                  
Example III, bulked fractions                                             
                  woody and eucalyptol-                                   
7 and 8 consisting of the                                                 
                  like aroma with a dis-                                  
compounds having the structures:                                          
                  tinct calamnus undertone.                               
 ##STR257##                                                               
 ##STR258##                                                               
Product produced according to                                             
                  A sweet, fruity (banana)                                
Example IV, bulked fractions                                              
                  creamy and minty aroma                                  
7-12 consisting of compounds                                              
                  with the minty nuances                                  
having the structures:                                                    
                  increasing in intensity                                 
                  on dryout.                                              
 ##STR259##                                                               
 ##STR260##                                                               
Product produced according to                                             
                  A fruity, banana and                                    
Example V, bulked fractions                                               
                  creamy aroma profile.                                   
6-8 consisting of the compounds                                           
having the structures:                                                    
 ##STR261##                                                               
 ##STR262##                                                               
Product produced according to                                             
                  A rum/butterscotch                                      
Example VI, bulked fractions                                              
                  and balsamic aroma.                                     
5-14 containing and consisting                                            
of the compounds having the                                               
structures:                                                               
 ##STR263##                                                               
 ##STR264##                                                               
Product produced according to                                             
                  A green, minty, borneol-                                
Example VII, bulked fractions                                             
                  like, spicy, somewhat                                   
6-9 consisting of the compounds                                           
                  medicinal aroma reminis-                                
having the structures:                                                    
                  cent of pepacuana bark                                  
                  extract with strong                                     
                  pepacuana bark-like under-                              
                  tones.                                                  
 ##STR265##                                                               
 ##STR266##                                                               
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII(A)   aroma with pleasant                                     
                  fruity tagette character-                               
                  istics.                                                 
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII(B)   aroma with pleasant                                     
                  fruity tagette character-                               
                  istics.                                                 
Fragrance formulation of                                                  
                  A jasmine aroma with a                                  
Example IX        pleasant fruityness.                                    
Fragrance formulation of                                                  
                  A sweet, floral aroma                                   
Example X         with excellent fruity                                   
                  floralcy undertones.                                    
______________________________________                                    
 
    
     EXAMPLE XXXI 
     PERFUMED LIQUID DETERGENTS 
     Concentrated liquid detergents with aromas as set forth in Table XIII below are prepared containing 0.10%, 0.15%, and 0.20% of the perfume ingredients set forth in Table XIII below. They are prepared by adding and homogeneously mixing the appropriate quantity of perfume ingredient set forth in Table XIII below in a liquid detergent which is a homogeneous single-phase heavy duty liquid detergent composition containing: 
     a. 12.5% by weight based on the free acid form of an anionic detersive surfactant; 
     b. 0.5% magnesium sulfate; 
     c. 12% by weight of an ethoxylated nonionic detersive surfactant; 
     d. 3% by weight of a water-soluble bis(styrylsulfonate)biphenyl brightener; and 
     e. the balance of the composition being water, 
     prepared according to U.S. Pat. No. 3,998,750 issued on Dec. 21, 1976. The detergents all possess aromas as described in Table XIII below: 
     
                       TABLE XIII                                                  
______________________________________                                    
Product           Aroma Profile                                           
______________________________________                                    
Product produced according to                                             
                  A fruity, banana and                                    
Example I, bulked fractions                                               
                  creamy aroma with                                       
4-7 consisting of compounds                                               
                  camphoraceous and                                       
having the structures:                                                    
                  minty undertones.                                       
 ##STR267##                                                               
 ##STR268##                                                               
Product produced according to                                             
                  A fruity, camphoraceous                                 
Example II, bulked fractions                                              
                  and herbaceous aroma.                                   
4-6 consisting of the compounds                                           
having the structures:                                                    
 ##STR269##                                                               
 ##STR270##                                                               
Product produced according to                                             
                  A sweet, spicy, herbal                                  
Example III, bulked fractions                                             
                  woody and eucalyptol-                                   
7 and 8 consisting of the                                                 
                  like aroma with a dis-                                  
compounds having the structures:                                          
                  tinct calamnus undertone.                               
 ##STR271##                                                               
 ##STR272##                                                               
Product produced according to                                             
                  A sweet, fruity (banana)                                
Example IV, bulked fractions                                              
                  creamy and minty aroma                                  
7-12 consisting of compounds                                              
                  with the minty nuances                                  
having the structures:                                                    
                  increasing in intensity                                 
                  on dryout.                                              
 ##STR273##                                                               
 ##STR274##                                                               
Product produced according to                                             
                  A fruity, banana and                                    
Example V, bulked fractions                                               
                  creamy aroma profile.                                   
6-8 consisting of the compounds                                           
having the structures:                                                    
 ##STR275##                                                               
 ##STR276##                                                               
Product produced according to                                             
                  A rum/butterscotch                                      
Example VI, bulked fractions                                              
                  and balsamic aroma.                                     
5-14 containing and consisting                                            
of the compounds having the                                               
structures:                                                               
 ##STR277##                                                               
 ##STR278##                                                               
Product produced according to                                             
                  A green, minty, borneol-                                
Example VII, bulked fractions                                             
                  like, spicy, somewhat                                   
6-9 consisting of the compounds                                           
                  medicinal aroma reminis-                                
having the structures:                                                    
                  cent of pepacuana bark                                  
                  extract with strong                                     
                  pepacuana bark-like under-                              
                  tones.                                                  
 ##STR279##                                                               
 ##STR280##                                                               
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII(A)   aroma with pleasant                                     
                  fruity tagette character-                               
                  istics.                                                 
Fragrance formulation of                                                  
                  A spicy, floral, herbal                                 
Example VIII(B)   aroma with pleasant                                     
                  fruity tagette character                                
                  istics.                                                 
Fragrance formulation of                                                  
                  A jasmine aroma with a                                  
Example IX        pleasant fruityness.                                    
Fragrance formulation of                                                  
                  A sweet, floral aroma                                   
Example X         with excellent fruity                                   
                  floralcy undertones.                                    
______________________________________