Abstract:
Esters of 1,2,3,6-tetrahydrobenzyl alcohol have been found to exhibit powerful odorous notes such as floral, woody and fruity notes, rendering such compounds valuable as fragrance materials either alone or in compositions. These 1,2,3,6-tetrahydrobenzyl alcohol esters are prepared by reacting 1,2,3,6-tetrahydrobenzyl alcohol with an appropriate organic acid.

Description:
BACKGROUND OF THE INVENTION 
     1,2,3,6-tetrahydrobenzyl alcohol, a known chemical, can be derived from 1,2,3,6-tetrahydrobenzaldehyde by reduction of the aldehyde group. 1,2,3,6-tetrahydrobenzoic acid, another known compound, derived from the same aldehyde has been reacted with alcohols to obtain aromatic esters useful as fragrances, see British Pat. No. 309,911. 
     It is well known in perfumery that esters of acids and esters of alcohols which have identical basic carbon skeletons have completely different sensory properties with regard to odor, e.g. benzyl acetate and ethyl benzoate, which respectively have the structures ##STR1## possess distinctive and different aromas. 
     It has now unexpectedly been found that esters of 1,2,3,6-tetrahydrobenzyl alcohol have great value as fragrance materials. 
     SUMMARY OF THE INVENTION 
     Specifically, this invention relates to novel esters of 1,2,3,6-tetrahydrobenzyl alcohol useful as fragrance materials and having the structure ##STR2## wherein R is hydrogen, an aliphatic group which is saturated or unsaturated, contains at most one double bond, and has 2 to 6 carbon atoms, a phenyl group, or a cyclopentyl group. 
     The invention further concerns fragrance compositions containing esters of 1,2,3,6-tetrahydrobenzyl alcohol having the structure ##STR3## wherein R is hydrogen, an aliphatic group which is saturated or unsaturated, contains at most one double bond, and has 1 to 6 carbon atoms, a phenyl group, or a cyclopentyl group. 
     The esters of 1,2,3,6-tetrahydrobenzyl alcohol are prepared by reacting this alcohol with an organic acid having the structure RCOOH wherein R is hydrogen or a hydrocarbon group as indicated hereinabove. These esters are useful as fragrance materials. 
     Accordingly, one object of this invention is to provide compounds which are useful as fragrance materials. 
     Another object of this invention is to provide compositions containing the same and/or 1,2,3,6-tetrahydrobenzyl acetate which are useful as fragrance materials. 
     How these and other objects of this invention are accomplished will become apparent in light of the detailed description and claims which follow. In at least one embodiment of the practices of this invention at least one of the foregoing objects will be achieved. 
     DETAILED DESCRIPTION OF THE INVENTION 
     It has been discovered that compounds of the general structure ##STR4## wherein R is hydrogen or an aliphatic group which is saturated or unsaturated, contains at most one double bond, and has 1 to 6 carbon atoms, a phenyl group, or a cyclopentyl group, exhibit odorous notes such as floral, woody and fruity notes making such compounds and compositions containing the same valuable and useful as fragrance adjuncts. Each of these compounds has a specific odor which is distinct and different from the next and each has its own specific and valuable odor-impact. Each compound has a pleasant and characteristic odor, and thus can be used directly or as part of a fragrant composition in amounts ranging from about 0.001 to 20% by weight thereof. Particularly desirable results are obtained with amounts in the range from 0.1 to 10%, but higher amounts of about 10 to 60% by weight are also useful. 
     The characteristic fragrances of a series of esters of 1,2,3,6-tetrahydrobenzyl alcohol including compounds wherein R is an alkyl, alkenyl having only one double bond, phenyl, or cyclopentyl are shown in Table I. Of these compounds all are new compounds except 1,2,3,6-tetrahydrobenzyl acetate. However, this compound has never before been known to be useful as a fragrance material and therefore, its use in fragrance compositions is one aspect of this invention. 
     
                       TABLE I______________________________________Compound             Characteristic Fragrance______________________________________1,2,3,6-Tetrahydrobenzyl formate                Floral, spicy, cinnamon-                clove character1,2,3,6-Tetrahydrobenzyl acetate                Floral, green, herbal,                fresh hay1,2,3,6-Tetrahydrobenzyl propionate                Fruity, tutti-fruity1,2,3,6-Tetrahydrobenzyl isobutyrate                Floral, rose1,2,3,6-Tetrahydrobenzyl isovalerate                Top-note: cheesy,                pleasant                fruity main-character                pineapple, tutti-fruity1,2,3,6-Tetrahydrobenzyl hexanoate                Fruity, sweet, pineapple1,2,3,6-Tetrahydrobenzyl benzoate                Nutty, floral, jasmine,                honey-almond1,2,3,6-Tetrahydrobenzyl crotonate                Flowery, mushroom,                rose, jasmine1,2,3,6-Tetrahydrobenzyl senecioate                Jasmine, floral1,2,3,6-Tetrahydrobenzyl cyclopentanecarboxylate          Floral, fruity, peach______________________________________ 
    
     The esters of 1,2,3,6-tetrahydrobenzyl alcohol are conveniently prepared by reacting this alcohol with an organic acid having the structure RCOOH wherein R is hydrogen, an aliphatic group which is saturated or unsaturated, contains at most one double bond, and has 1 to 6 carbon atoms, a phenyl group or a cyclopentyl group. 
    
    
     1,2,3,6-tetrahydrobenzyl alcohol is commercially available or is prepared from commercially available 1,2,3,6-tetrahydrobenzaldehyde. The method of preparing the alcohol from 1,2,3,6-tetrahydrobenzaldehyde is set forth more fully in Example 1. Examples 2-11 which follow describe the preparation of specific esters in accordance with this invention, but are not intended to limit in any way the scope thereof. 
     EXAMPLE 1 ##STR5## 
     Procedure: (The Reaction was conducted in a Nitrogen Atmosphere) 
     The following were combined in a 12 liter flask fitted with an agitator, condenser, thermometer, nitrogen inlet, and an addition funnel. 
     2400 mls. incorporated 
     459 g. sodium borohydride (11.8% in sodium hydroxide solution, aqueous) agitated and cooled to 15° C. 
     Then the following was added over a one hour and 15 minutes period at 10°-20° C.--440 g. 1,2,3,6-tetrahydrobenzaldehyde. 
     Upon completion of addition the cooling bath was removed, and the reaction slurry was agitated for four hours and fifty minutes at a temperature between 16°-26° C. 
     Then with continued agitation, 500 mls. of water were added to dissolve the solids. The agitation was stopped, and the layers were separated. The lower aqueous layer was discarded. 
     The organic layer was cooled to 10°-15° C. in a 5 liter flask and acidified with 60 mls. of concentrated hydrochloric acid (acid to congo red). 
     The solution was agitated for 10 minutes, the excess acid was neutralized with a 10% aqueous sodium bicarbonate solution till slightly basic. Isopropanol was removed on a steam bath by distillation through a 6&#34; packed column with an ejector vacuum. 200 mls. of hexane were added to the cooled residue. Washed with-5×75 mls. salt water. Reaction product: Neutral to Litmus. The solvent was removed by distillation on a steam bath through a 6&#34; Vigreaux column with ejector vacuum--and the fractionation continued. 
     
         __________________________________________________________________________FractionTemp. Vapor       Temp. Flask              mls.                 wt. R.I. 20°                          Vac.                              Remarks__________________________________________________________________________I    62°-94° C.       97°-971/2° C.               2  2.1 g                     1.4780                          20mm                              FrontII   *94°-95° C.       971/2°-119° C.              395                 381.7 g                     1.4836                          20mm                              MainIII  *95°-951/2° C.       119°-129° C.               8  6.8 g                     1.4836                          20mm                              Main__________________________________________________________________________ 
    
     Residue--37.2 g; Yield: theoretical: 448 g, actual: 388.5 g (86.7% of theory); Analysis: GLC--one peak--99.9% purity; b 20  94°-951/2° C.; n d   20  1.4836. 
     EXAMPLE 2 ##STR6## 
     Procedure 
     The following were combined in a 500 ml. flask fitted with a thermometer and a Dean Stark water trap connected to a water cooled reflux condenser-- 
     56 g. 1,2,3,6-tetrahydrobenzyl alcohol 
     25.3 g. formic acid (technical) 
     100 mls. benzene 
     0.1 g. p-toluenesulfonic acid 
     The above solution was heated to reflux. 
     Refluxing was continued for 52 minutes at a flask temperature between 87°-94° C. A total of 12 mls. of formic acid and water solution separated in the Dean Stark trap. 
     The aqueous layer was charged back into the reaction flask and refluxing continued for one hour till no more of the water was produced: A total of 12 mls. of aqueous material separated. 
     The reaction product was cooled and washed with: 
     2×100 mls. 10% aqueous sodium bicarbonate solution 
     4×75 mls. water until neutral to Litmus. 
     The solvent was removed on a steam bath by distillation with an ejector vacuum through a 6&#34; Vigreaux column and fractionation continued. 
     
         __________________________________________________________________________FractionTemp. Vapor       Temp. Flask              mls.                 wt.                    R.I. 20°                         Vac.                             Remarks__________________________________________________________________________I    711/2°-72° C.       721/2° C.               3  3.9g                    1.4630                         10mmII   72°-73° C.       721/2°-78° C.              58 60.1g                    1.4636                         10mm                             Main__________________________________________________________________________ 
    
     Residue--3 g; Yield: theoretical: 70 g, actual: 60.1 g (85.9% of theory); Analysis: GLC--96.3290% purity; b 10  72°-73° C.; n d   20  1.4636. 
     EXAMPLE 3 ##STR7## 
     Procedure 
     The following were combined in a 500 ml. flask fitted with a thermometer, and a Dean Stark water trap connected to a water cooled condenser-- 
     56 g. 1,2,3,6-tetrahydrobenzyl alcohol 
     40.7 g. propionic acid 
     100 ml. benzene 
     0.5 g. p-toluenesulfonic acid 
     The above solution was heated to reflux collecting the water of reaction in the trap. 
     Time at reflux--5 hours and 14 minutes 
     Temp. flask--84°-961/2° C. 
     Mls. collected: 9.8 (Theory 9 ml) H 2  O 
     Reaction product cooled to room temperature and washed with: 
     2×50 mls. 10% aqueous sodium carbonate solution. 
     4×50 mls. water until neutral to Litmus. 
     The solvent was removed on a steam bath by distillation with ejector vacuum through a 6&#34; Vigreaux column and the fractionation continued. 
     
         __________________________________________________________________________Fraction Temp. Vapor         Temp. Flask                mls.                   wt.                      RI 20°                          Vac                             Remarks__________________________________________________________________________I     82°-821/2° C.         84°-86° C.                 3  3.0g                      1.4550                          5mm                             FrontII    821/2°-83° C.         84° C.                79 79.2g                      1.4530                          5mm                             Main__________________________________________________________________________ 
    
     Residue--1 g. Yield: theoretical 84 g; actual 79.2 g (94.3%); Analysis: GLC--99.26%; b 5  921/2°-93° C.; n d   20  --1.4530. 
     EXAMPLE 4 ##STR8## 
     Procedure 
     The following were combined in a 500 ml. flask fitted with a thermometer aand a Dean Stark trap connected to a water cooled reflux condenser. 
     42.5 g. 1,2,3,6-tetrahydrobenzyl alcohol 
     41.5 g. isobutyric acid 
     0.5 g. p-toluenesulfonic acid 
     100 mls. benzene 
     The above solution was heated to reflux removing the water formed as an azeotrope of benzene and water. 
     Time of heating at reflux--7 hours and 50 minutes 
     Temperature of flask at reflux--92°-95° C. 
     Collected--7.5 mls. (Theory; 6.8 mls.) H 2  O 
     The reaction product was washed with: 
     2×50 ml. 10% aqueous sodium carbonate solution 
     5×75 ml. water until neutral to Litmus. 
     The combined aqua washings were extracted with 75 ml. benzene, the extract washed with water until neutral to Litmus and combined with the main organic part. 
     The solvent was removed on a steam bath by distillation with ejector vacuum through a 6&#34; Vigreaux column and the fractionation continued-- 
     
         __________________________________________________________________________Fraction Temp. Vapor         Temp. Flask                mls.                   wt.                      RI 20°                          Vac:                             Remarks__________________________________________________________________________I     77°-881/2° C.         88°-90° C.                4   4.4g                      1.4546                          5mm                             FrontII    *881/2°-89° C.         90°-95°                ˜56                   58.9g                      1.4549                          5mm                             Main__________________________________________________________________________ 
    
     Residue: 2.6 g. Yield: theoretical 69.1 g; actual 58.9 g (85.2% of theory); Analysis: GLC--99.4% purity; b 5  881/2°-89° C.; n d   20  1.4549 
     EXAMPLE 5 ##STR9## 
     Procedure 
     The following were combined in a 500 ml. flask fitted with a thermometer and a Dean Stark water trap connected to a water cooled reflux condenser-- 
     56 g 1,2,3,6-tetrahydrobenzyl alcohol 
     56.1 g. isovaleric acid 
     0.5 g. p-toluenesulfonic acid &amp; 
     100 mls. benzene 
     The above solution was heated at reflux, at a temperature between 90°-97° C. for five hours and thirty minutes, collecting 10 mls. of water--(Theory 9 mls) 
     IR shows no (OH) 
     The reaction product was cooled and washed with-- 
     2×50 mls. 10% aqueous sodium carbonate solution 
     4×50 mls. water solution, until neutral to Litmus. 
     The solvent was removed on a steam bath by distillation through a 6&#34; Vigreaux column with ejector vacuum--and fractionation was continued through a 6&#34; Vigreaux column. 
     
         __________________________________________________________________________ Fraction Temp. Vapor        Temp. Flask               mls.                  wt. RI  Vac.                             Remarks__________________________________________________________________________I      88°-102° C.        102°-104° C.                6  5.8 g                      1.4540                          5mmII    102°-103° C.        104°-1091/2° C.               93 86.1 g.                      1.4561                          5mm                             Main__________________________________________________________________________ 
    
     Residue: 2.6 g. Yield: theoretical 93.0 g; actual 86.1 g (87.9% of theory); Analysis: GLC--99.69% purity; b 5  102°-103° C.; n d   20  1.4561 
     EXAMPLE 6 ##STR10## 
     Procedure 
     The following were combined in a 500 ml. flask fitted with a Dean Stark water trap connected to a water cooled reflux condenser and a thermometer-- 
     56 g. 1,2,3,6-tetrahydrobenzyl alcohol 
     63.8 g. hexanoic acid 
     1 g. p-toluenesulfonic acid 
     100 ml. benzene 
     The above solution was heated to reflux collecting the water formed in the trap. 
     Time of reflux: 4 hours and 5 minutes 
     Temperature in flask at reflux: 80°-97° C. 
     Collected: 9.2 mls. water (Theory--9 ml.) IR: No-OH present 
     The reaction mixture was cooled to room temperature and washed with-- 
     2×50 mls 10% sodium carbonate aqueous solution 
     3×75 mls. water until neutral to Litmus. 
     The solvent was removed on a steam bath by distillation with ejector vacuum through a 6&#34; Vigreaux column--and the fractionation continued under a vacuum--of 2 mm. 
     
         __________________________________________________________________________Fraction Temp. Vapor        Temp. Flask               mls.                  wt. RI 20°                          Vac:                             Remark__________________________________________________________________________I     102°-1061/2° C.        110°-111° C.                2 13 g.                      1.4580                          2mm                             FrontII    1061/2°-107° C.        111°-114° C.               90 88.6 g.                      1.4590                          2mm                             Main__________________________________________________________________________ 
    
     Residue--4 g. Yield: theoretical: 105 g; actual 88 g; Analysis: GLC--99.464% purity; b 2  1061/2°-107° C.; n d   20  1.4590 
     EXAMPLE 7 ##STR11## 
     Procedure 
     The following were combined in a 500 ml. flask fitted with a thermometer and a Dean Stark water trap connected to a water cooled reflux-condenser. 
     42.5 g. tetrahydrobenzyl alcohol 
     51.0 g. benzoic acid 
     0.5 g. p-toluenesulfonic acid 
     100 mls. benzene 
     Heated to reflux for 2 hours and 30 minutes at a flask temperature between 89°-92° C. collecting: 3 mls. of water. 
     The reaction product was cooled and stood overnight at room temperature. 
     The next day an additional 0.5 g. of p-toluenesulfonic acid was added and continued heating at reflux (Flask Temperature 91°-93° C.) for 51/2 hours--collecting a total of 6.3 mls. of water. (Theory--(6.8 mls.)). 
     The reaction product was cooled and washed with, 
     100 mls. 10% sodium carbonate aqueous solution 
     4×75 mls. water (salt solution) until neutral to Litmus. 
     The solvent was removed by distillation from a steam bath and the reaction product fractionated through a 6&#34; Vigreaux column. 
     
         __________________________________________________________________________Fraction Temp. Vapor        Temp. Flask               mls.                  wt. RI 20°                          Vac.                             Remarks__________________________________________________________________________I      62°-138° C.        110°-140° C.                6  6.1g                      1.4978                          2mmII    138°-1391/2° C.        140°-156° C.               60 63.5g                      1.5331                          2mm                             Main__________________________________________________________________________ 
    
     Residue--4.5 g. Yield: theoretical: 82.1 g; actual 63.5 g (77.3% of theory) Analysis: GLC 99.86% purity; b 2  138°-139° C.; n d   20  1.5331 
     EXAMPLE 8 ##STR12## 
     Procedure 
     The following were charged to a 500 ml. 3-neck flask fitted with an agitator, thermometer, reflux condenser and a water trap: 
     28 g. of 1,2,3,6-tetrahydrobenzyl alcohol 
     25.8 g. crotonic acid 
     100 ml. of benzene 
     0.5 g. of p-toluenesulfonic acid 
     The reaction mixture was refluxed until no more water was formed. 
     Note: During the course of the reaction additional 0.5 g. of p-toluenesulfonic acid were added. 
     Time of reaction: 311/2 hours. 
     Temperature of reaction: 91°-92° 
     Amount of water collected: 5.5 ml. 
     The reaction mixture was cooled to room temperature, neutralized with 10% aqueous sodium carbonate solution. Washed three times with 25 ml. of water until neutral to Litmus. The solvent was distilled off on steam bath, ejector vacuum. The reaction product was fractionated through a 6&#34; Vigreaux column. 
     
         __________________________________________________________________________ Fractionation through a 6&#34; Vigreaux ColumnFractionTemp. Vapor       Temp. Flask              Vac.                 mls.                     Wt.                        R.I. 20°                             Remarks__________________________________________________________________________I    77.5°       82°-83°              2mm                  2 ml.                      2 g.                        1.4802                             FrontII   77.5-78.5°       83°-95°              2mm                 39 ml.                     39 g.                        1.4820                             Main__________________________________________________________________________ 
    
     Residue: 5 g. Yield: theoretical 45 g, actual 39 g (86.7% of theoretical); Analysis: GLC--99.9% purity; b 2  77.5°-78.5° C.; n d   20  1.4820. 
     EXAMPLE 9 ##STR13## 
     Procedure 
     The following were charged to a 500 ml. 3-neck flask fitted with an agitator, thermometer, reflux condenser and a watet trap: 
     28 g. 1,2,3,6-tetrahydrobenzyl alcohol 
     30 g. senecioic acid 
     1.5 g. p-toluenesulfonic acid 
     100 ml. benzene 
     The reaction mixture was refluxed with water trap. 
     Time of reaction: 27 hours and 45 minutes 
     Temperature of reaction: 87°-89° C. 
     Amount of water collected: 4.5 ml. The reaction product was neutralized with a 10% aqueous sodium carbonate solution, washed two times with 30 ml. of water until neutral to Litmus. 
     The solvent was distilled off on steam bath--ejector vacuum. 
     The reaction product was fractionated through a 6&#34; Vigreaux column. 
     
         __________________________________________________________________________ Fractionation through a 6&#34; Vigreaux columnFractionTemp. Vapor       Temp. Flask              Vac.                 Vol.                     Wt.                        R.I. 20°                             Remark__________________________________________________________________________I    80°-88°        92°-104°              2mm                  6 ml.                      6 g.                        1.4888                             FrontII   88°-88.5°       104°-121°              2mm                 36 ml.                     35 g.                        1.4872                             Main__________________________________________________________________________ 
    
     Residue: 4 g. Yield: theoretical 48.5 g, actual 35 g (72.16% of theoretical) Analysis: GLC 99% purity, b 2  88°-88.5° C., n d   20  1.4872 
     EXAMPLE 10 ##STR14## 
     Procedure 
     The following were combined in a 300 ml. flask fitted with a thermometer and a Dean Stark trap connected to a water cooled condenser: 
     11.5 g. 1,2,3,6-tetrahydrobenzyl alcohol 
     12 g. cyclopentanecarboxylic acid 
     75 mls. benzene 
     0.2 g. p-toluenesulfonic acid 
     The above solution was heated to reflux removing the water formed as an azeotrope of benzene and water. 
     Time of heating--16 hours at 45 minutes 
     Temperature in Flask at reflux--84°-88° C. 
     Collected: 1.6 mls. water 
     The reaction product was cooled and washed with: 
     100 mls. of 10% sodium carbonate solution, aqueous 
     5×75 mls. water until neutral of Litmus. 
     The solvent was removed on a steam bath by distillation with ejector vacuum through a 6&#34; Vigreaux column and the fractionation continued 
     
         __________________________________________________________________________Fraction Temp. Vapor        Temp. Flask               mls.                  wt.                     Vac.                         R.I.                             Remarks__________________________________________________________________________I     97°-971/2° C.        103°-105° C.                3  2.8g                     0.5mm                         1.4810                             FrontII    971/2°-98° C.        103°-105°               18 15.6g                     0.5mm                         1.4814                             Main__________________________________________________________________________ 
    
     Residue--2.6 g. Yield: theoretical 21.4 g, actual 15.6 g (72.9% of theory) Analysis: GLC one peak (99.9%) purity b 0 .5 971/2--98° C. n d   20  1.4814 
     EXAMPLE 11 ##STR15## 
     Procedure 
     The following were combined in a 500 ml. flask fitted with a thermometer, 7&#34; Vigreaux column, distilling condenser, and a receiver. 
     42.5 g. 1,2,3,6-tetrahydrobenzyl alcohol 
     60.5 g. acetic anhydride 
     300 mls. toluene 
     0.5 g. sodium acetate 
     The reaction mixture was heated at a flask temperature of 114°-121° C. over a three hour and 50 minute period; distilling the azeotrope of acetic acid and toluene, at a vapor temperature of 104°-109° C. 178 mls. distillate were collected. 
     The excess acetic anhydride and toluene were removed from the reaction product by distillation from a steam bath under ejector vacuum through a 7&#34; Vigreaux column. Then the last traces of low boilers were removed with a vacuum of 10 mm at a flask temperature of 80° C. The residue was cooled, and diluted with 150 mls. of hexane and washed with: 
     2×200 mls. 10% sodium carbonate aqueous solution 
     4×75 mls. water. The reaction product was neutral to Litmus. 
     The solvent was removed by distillation on a steam bath with ejector vacuum through a 6&#34; Vigreaux column and fractionation continued. 
     
         __________________________________________________________________________FractionTemp. Vapor       Temp. Flask              mls.                 wt.                    R.I. 20°                         Vac.                             Remarks__________________________________________________________________________I    85° C.       86° C.               4  4.0g                    1.4593                         10mm                             FrontII   85°-86° C.       86°-87° C.              50 50.8g                    1.4594                         10mm                             Main__________________________________________________________________________ 
    
     Residue--3 g. Yield: theoretical 58.5 g., actual 50.8 g. (86.8% of theory); Analysis: GLC--99.74% purity; b 10  85°-86° C.; n d   20  1.4594 
     The 1,2,3,6-tetrahydrobenzyl alcohol esters of this invention, as disclosed hereinabove are useful as fragrance materials or as components of perfume compositions containing other aroma chemicals. Accordingly, one or a combination of these compounds are useful as perfumes or as part of fragrance compositions or are generally usefully incorporated in other compositions, e.g. cosmetics, such as lotions and creams, soaps, room-sprays, and sachets in order to impart a desirable fragrance thereto. 
     When employed as perfumes, or in fragrant compositions or when employed in other compositions to impart a desired fragrance thereto, the compounds of this invention are incorporated therein in a amount effective to impart a desired fragrance, such as an amount in the range 0.001 to 20% by weight, usually an amount in the range 0.1 to 10% by weight. 
     Formulations of fragrances employing a compound in accordance with this invention are set forth hereinafter. Accompanying Table II shows the makeup of a Tutti Fruity fragrance employing the compounds 1,2,3,6-tetrahydrobenzyl isovalerate and 1,2,3,6-tetrahydrobenzyl proprionate; Table III shows a floral fragrance composition employing 1,2,3,6-tetrahydrobenzyl hexanoate and 1,2,3,6-tetrahydrobenzyl benzoate; Table IV, a new-mown hay fragrance composition employing 1,2,3,6-tetrahydrobenzyl acetate and 1,2,3,6-tetrahydrobenzyl isobutyrate; Table V, a chypre fragrance composition employing 1,2,3,6-tetrahydrobenzyl hexanoate; Table VI, a carnation fragrance composition containing 1,2,3,6-tetrahydrobenzyl formate; Table VII, a rose fragrance composition employing 1,2,3,6-tetrahydrobenzyl isobutyrate and 1,2,3,6-tetrahydrobenzyl crotonate; Table VIII, a floral composition (Phantasy Bouquet) employing 1,2,3,6-tetrahydrobenzyl senecioate and Table IX, a lilac fragrance composition employing 1,2,3,6-tetrahydrobenzyl cyclopentanecarboxylate. 
     
                       TABLE II______________________________________Tutti Fruity% Wt.      Component______________________________________0.52       Ethyl Formate8.7        Ethyl Caproate2.2        Ethyl Propionate2.3        Propyl Acetate0.72       Isobutyl Acetate9.0        Ethyl Butyrate5.9        1,2,3,6-Tetrahydrobenzyl Isovalerate0.81       Ethyl Isovalerate10.9       Isoamyl Acetate9.0        1,2,3,6-Tetrahydrobenzyl Propionate11.49      Limonene0.6        n-Butyl Butyrate0.25       Ethyl Caproate0.81       Isoamyl Butyrate2.3        Ethyl Lactate0.7        Ethyl Pelargonate14.45      Carvone0.9        Cinnamic Aldehyde18.0       Eugenol0.45       Heliotropin100.0%______________________________________ 
    
     
                       TABLE III______________________________________Floral% Wt.      Component______________________________________17.1       Amyl Salicylate17.1       Isobutyl Salicylate8.6        Linalool4.3        Hydroxycitronellal4.9        1,2,3,6-Tetrahydrobenzyl Hexanoate5.7        Heliotropin5.7        1,2,3,6-Tetrahydrobenzyl Benzoate3.4        Coumarin1.4        2,4-Dihydroxy-3-methyl Benzoate8.6        Phenylethyl Alcohol1.7        Vanillin11.4       Linalyl Acetate2.9        Geranyl Acetate7.2        Cassie Absolute100.0%______________________________________ 
    
     
                       TABLE IV______________________________________New-Mown Hay% Wt.   Component______________________________________12.5    Oil Bergamot18.8    Linalyl Acetate3.8     Coumarin3.8     Tonka Absolute3.8     1,2,3,6-Tetrahydrobenzyl Acetate2.5     Dimethyl Hydroquinone1.2     Oil Patchouly2.5     2,4-Dihydroxy-3-methyl Benzaldehyde1.2     1,2,3,6-Tetrahydrobenzyl Isobutyrate6.2     Linalool12.5    Linalyl Acetate1.2     Oil Clary Sage28.1    Hydroxycitronellal1.2     Hexyloxyacetonitrile   1,1,4,4-Tetramethyl-6-Ethyl-1,2,3,4-0.7     Tetrahydronaphthalene-7-Nitrile (Musk Nitrile)100.0%______________________________________ 
    
     
                       TABLE V______________________________________Chypre% Wt.   Component______________________________________13.3    Linalool1.0     Oil Lavender10.0    Heliotropin16.7    Oil Ylang Ylang6.7     1,2,3,6-Tetrahydrobenzyl Hexanoate16.6    Oil Orange6.7     Oil Geranium Bourbon3.3     Hexyloxyacetaldehyde Dimethyl Acetal   Hexyloxyacetaldehyde Dipropyleneglycol3.3     Hemiacetal1.7     Civet absolute4.0     Labdanum Resinoid10.0    Musk Xylol   1,1,4,4-Tetramethyl-6-Ethyl-1,2,3,4-6.7     Tetrahydronaphthalene-7-Nitrile (Musk Nitrile)100.0%______________________________________ 
    
     
                       TABLE VI______________________________________Carnation% Wt.      Component______________________________________10         Oil Pimento20         Eugenol5          Iso-Eugenol5          1,2,3,6-Tetrahydrobenzyl Formate5          Oil Nutmeg5          Oil Cananga3          Methyl Ionone2          Anisic Aldehyde10         Geraniol10         Oil Petitgrain Terpenless5          Hexyloxyacetaldehyde Dimethyl-Acetal7          1,1,4,4-Tetramethyl-6-Ethyl-1,2,3,4-      Tetrahydronaphthalene-7-Nitrile      (Musk Nitrile)2          Hexyloxyacetonitrile6          Isobutyl Phenylacetate5          Hydrocinnamic Aldehyde100%______________________________________ 
    
     
                       TABLE VII______________________________________Rose% Wt.      Component______________________________________48.9       Phenylethyl Alcohol12.2       Oil Geranium Palmarosa12.2       Citronellol6.1        Geraniol6.1        Phenylethyl Butyrate6.1        Phenylethyl Acetate0.6        Rose Oxide0.6        Nonyl Aldehyde1.2        Methyl Ionone1.2        1,2,3,6-Tetrahydrobenzyl Isobutyrate0.6        1,2,3,6-Tetrahydrobenzyl Crotonate1.8        Rhodinol Acetate0.5        Musk Ketone0.7        1,1,4,4-Tetramethyl-6-Ethyl-1,2,3,4-      Tetrahydronaphthalene-7-Nitrile      (Musk Nitrile)1.2        Alpha Terpineol100.0%______________________________________ 
    
     
                       TABLE VIII______________________________________Phantasy Bouquet% Wt.      Component______________________________________10         Oil Neroli, bigarade10         Oil Orange Blossom10         1,2,3,6-Tetrahydrobenzyl Senecioate8          Coumarin4          Vanillin4          Hexyloxyacetaldehyde Dipropyleneglycol      Hemi-Acetal8          Alpha Ionone10         Oil Vetiver20         Phenylethyl Alcohol4          Oil Clove4          Oil Sandalwood4          1,1,4,4-Tetramethyl-6-Ethyl-1,2,3,4-      Tetrahydronaphthalene-7-Nitrile      (Musk Nitrile)2          Musk Ketone2          Hexyloxyacetaldehyde Dimethyl Acetal100%______________________________________ 
    
     
                       TABLE IX______________________________________Lilac% Wt.   Component______________________________________60      Alpha-Terpineol2       Heliotropin10      Oil Ylang-Ylang12      Phenylethyl Alcohol5       Methyl-Ionone1       1,2,3,6-Tetrahydrobenzyl cyclopentanecarboxylate10      Resinoid Benzoin100%______________________________________ 
    
     As will be apparent to those skilled in the art in the light of the foregoing disclosure, many modifications, alterations and substitutions are possible in the practice of this invention without departing from the spirit or scope thereof.