Branched chain saturated ketones, organoleptic uses thereof and process for preparing same

Described is the novel compound genus defined according to the structure: ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.3 lower alkyl useful in augmenting or enhancing the aroma or taste of consumable materials including perfumes, colognes, perfumed articles (including solid or liquid anionic, cationic, nonionic or zwitterionic detergents and perfumed polymers) smoking tobacco or smoking tobacco articles.

BACKGROUND OF THE INVENTION 
Materials which can provide amber, woody and fruity aroma profiles with 
vetiver-like topnotes particularly those materials which are relatively 
inexpensive are highly sought after in the art of perfumery. Many of the 
natural materials which provide such fragrance profiles and contribute 
desired nuances to perfumery compositions and perfumed article substances 
are high in cost, vary in quality from one batch to another and/or are 
generally subject to the usual variations of natural products. 
There is, accordingly, a continuing effort to find synthetic materials 
which will replace the essential fragrance notes provided by natural 
essential oils or compositions thereof. Unfortunately, many of these 
synthetic materials either have the desired nuances only to a relatively 
small degree or else contribute undesirable or unwanted odor to the 
composition. The search for materials which can provide a more refined 
amber, woody, fruity and vetiver-like aroma has been difficult and 
relatively costly in the areas of both natural products and synthetic 
products. 
Materials which can provide woody, oriental and minty aroma and taste 
profiles both prior to and on smoking in the mainstream and the sidestream 
of smoking tobacco articles are desirable for augmenting or enhancing the 
aroma and taste of smoking tobacco and smoking tobacco articles, e.g. 
cigarettes and cigars. 
Even more desirable is a product that can serve to substitute for 
difficult-to-obtain natural perfumery oils and expensive synthetic 
ingredients of perfume compositions and, at the same time, substitute for 
expensive flavoring ingredients in smoking tobacco and in smoking tobacco 
articles. 
None of the chemicals of the prior art which are ketones have aroma 
profiles or chemical structures which are even remotely similar to the 
compounds of my invention.

DISCLOSURES INCORPORATED BY REFERENCE HEREIN 
The following application for U.S. Letters Patent and issued Patents are 
incorporated by reference herein: 
(a) U.S. Application For Letters Patent, Ser. No. 160,788 filed on June 19, 
1980 now U.S. Pat. No. 4,287,084 issued on Sept. 1, 1981 (entitled: "Use 
of Mixture of Aliphatic C.sub.10 Branched Olefins in Augmenting or 
Enhancing the Aroma of Perfumes and/or Perfumed Articles") setting forth 
the use of the compounds having the structures: 
##STR8## 
or generically the compounds defined according to the structure: 
##STR9## 
wherein R.sub.1 ", R.sub.2 ", R.sub.3 ", R.sub.4 " and R.sub.5 " 
represents hydrogen or methyl with three of R.sub.1 ", R.sub.2 ", R.sub.3 
", R.sub.4" and R.sub.5 " representing methyl and the other two of R.sub.1 
", R.sub.2 ", R.sub.3 ", R.sub.4 " and R.sub.5 " representing hydrogen; 
(b) Application for U.S. Letters Patent, Ser. No. 188,576 filed on Sept. 
18, 1980 now U.S. Pat. No. 4,303,555 issued on Dec. 1, 1981, a 
continuation-in-part of Ser. No. 160,788 filed on June 19, 1980; and 
(c) Application for U.S. Letters Patent, Ser. No. 184,132 filed on Sept. 4, 
1980 now U.S. Pat. No. 4,321,255 issued on Mar. 23, 1982, entitled 
"Branched Ketones, Organoleptic Uses Thereof and Process for Preparing 
Same" disclosing the reaction: 
##STR10## 
wherein R.sub.1 ', R.sub.2 ' and R.sub.3 ' represent C.sub.1 -C.sub.3 
lower alkyl and R.sub.4 ' is either of R.sub.1 ', R.sub.2 ' or R.sub.3 ' 
and wherein X' is also chloro, or bromo, and the use of the resulting 
compounds for their organoleptic properties. 
The instant application is directed to the use of the compounds defined 
according to the generic structure: 
##STR11## 
as starting materials wherein R.sub.4 ' is C.sub.1 -C.sub.3 lower alkyl 
and wherein one of the dashed lines represents a carbon-carbon double bond 
and each of the other of the dashed lines represent carbon-carbon single 
bonds produced according to the process of Application for United States 
Letters Patent, Ser. No. 184,132 filed on Sept. 4, 1980 now U.S. Pat. No. 
4,321,255 issued on Mar. 23, 1982, entitled "Branched Ketones, 
Organoleptic Uses Thereof and Process for Preparing Same." 
THE INVENTION 
It has now been determined that certain branched chain saturated ketones 
are capable of imparting a variety of flavors and fragrances to various 
consumable materials. Briefly, our invention contemplates branched chain 
saturated ketones defined according to the generic structure: 
##STR12## 
wherein R.sub.1 is C.sub.1 -C.sub.3. 
The branched chain saturated ketones of my invention are either usable in 
admixture with one another, or the isomers are usable in admixture with 
one another such as mixtures of the stereoisomers defined according to the 
structures: 
##STR13## 
Insofar as the hydrogenation reaction is concerned with the ketone having 
the structure: 
##STR14## 
as the starting material or one of the ketones defined according to the 
structure: 
##STR15## 
as being a starting material, the ketone is reacted with hydrogen in the 
presence of a Raney nickel catalyst or a palladium on carbon catalyst or a 
"Lindlar" catalyst (palladium on calcium carbonate) or palladium on barium 
sulfate. The percentage of palladium in the palladium on carbon catalyst 
or in the palladium on calcium carbonate catalyst or in the pallaidum on 
barium sulfate catalyst varies from about 2% up to about 7% with a 
percentage of palladium in the palladium on carbon catalyst or in the 
palladium on calcium carbonate catalyst or in the palladium on barium 
sulfate catalyst being preferred to be 5%. The temperature of reaction for 
the hydrogenation may vary from about 130.degree. up to about 250.degree. 
C. with a preferred reaction temperature of 150.degree. to 180.degree. C. 
The pressure of hydrogen over the reaction mass may vary from about 50 
psig to about 200 psig with the most preferred pressure being 50 to 80 
psig. It is preferred in order to form the product having the structure: 
##STR16## 
that the reaction be carried out in the absence of a solvent. 
When a palladium containing catalyst is used, the percentage of catalyst in 
the reaction mass may vary from 0.125% up to about 2.0% with a percentage 
of catalyst of about 0.25% being preferred. When a Raney nickel catalyst 
is used the percentage of catalyst in the reaction mass may vary from 
about 3% up to about 10% with a percentage of catalyst of about 5% being 
preferred. 
In general the reaction is illustrated thusly: 
##STR17## 
wherein R.sub.1 represents C.sub.1 -C.sub.3 alkyl. 
The individual branched chain saturated ketones of my invention can be 
obtained in purer form or in substantially pure form by conventional 
purification techniques. Thus, the products can be purified by 
distillation, extraction, crystallization, preparative chromatographic 
techniques (including high pressure liquid chromatography) and the like. 
It has been found desirable to purify the branched chain unsaturated 
secondary alcohols of our invention by fractional distillation under 
vacuum. 
It will be appreciated from the present disclosure that the branched chain 
saturated ketones and mixtures thereof according to the present invention 
can be used to alter, vary, fortify, modify, enhance or otherwise improve 
the flavor and aroma of a wide variety of materials which are ingested, 
consumed or otherwise organoleptically sensed, particularly including 
perfume compositions, perfumed articles and smoking tobacco compositions 
and smoking tobacco articles. 
The term "alter" in its various forms will be understood herein to mean the 
supplying or imparting of a flavor character or note or aroma character to 
an otherwise bland, relatively aromaless or tasteless substance, or 
augmenting an existing flavor or aroma characteristic where the natural 
flavor or aroma is deficient in some regard or supplementing the existing 
flavor or aroma impression to modify the organoleptic character. 
The term "enhance" is intended herein to mean the intensification of a 
particular aroma or taste nuance (particularly in perfumes, perfumed 
articles or smoking tobaccos) without the changing of the quality of said 
nuance and without adding an additional aroma or taste nuance to the 
consumable material, the organoleptic properties of which are enhanced. 
The term "tobacco" will be understood herein to mean a natural product such 
as, for example, burley, Turkish tobacco, Maryland tobacco, flue-cured 
tobacco and the like including tobacco-like or tobacco-based products such 
as reconstitued or homogenized leaf and the like, as well as tobacco 
substitutes intended to replace natural tobacco, such as lettuce and 
cabbage leaves and the like. The tobaccos and tobacco products in which 
the branched chain saturated ketones of my invention and useful include 
those designed or used for smoking such as in cigarette, cigar and pipe 
tobacco, as well as products such as snuff, chewing tobacco and the like. 
The branched chain saturated ketones of my invention can be used to 
contribute warm, vetiver-like, woody, fruity and amber aromas. As 
olfactory agents the branched chain unsaturated secondary alcohols of this 
invention can be formulated into or used as components of a "perfume 
composition". 
The term "perfume composition" is used herein to mean a mixture of organic 
compounds, including, for example, alcohols, other than the alcohols of 
this invention, aldehydes, ketones, nitriles, esters, and frequently 
hydrocarbons which are admixed so that the combined odors of the 
individual components produce a pleasant or desired fragrance. Such 
perfume compositions usually contain: (a) the main note of the "bouquet" 
or foundation-stone of the composition; (b) modifiers which round off and 
accompany the main note; (c) fixatives which include odorous substances 
which lead 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, the individual component will contribute its 
particular olfactory characteristics but the overall effect of the perfume 
composition will be the sum of the effect of each ingredient. Thus, the 
individual compounds of this invention, or mixtures thereof, can be used 
to alter the aroma characteristics of a perfume composition, for example, 
by highlighting or moderating the olfactory reaction contributed by 
another ingredient in the composition. 
The amount of branched chain saturated ketones of this invention which will 
be effective in perfume compositions depends on may factors, including the 
other ingredients, their amounts and the effects which are desired. It has 
been found that perfume compositions containing as little as 0.05% and as 
much as 5% of the branched chain saturated ketones of this invention can 
be used to impart, augment or enhance warm, intense, amber, woody, fruity 
and vetiver aroma profiles to soaps, cosmetics, solid or liquid anionic, 
cationic, nonionic and zwitterionic detergents and other products. The 
amount employed can range up to 50% of the fragrance and can be as low as 
1% of the original fragrance and will depend on considerations of cost, 
nature of the end product, the effect desired in the finished product and 
the particular fragrance sought. 
The branched chain saturated ketones of this invention can be used alone or 
in a perfume composition as an olfactory component in detergents, and 
soaps, space odorants and deodorants, perfumes, colognes, toilet waters, 
bath salts, hair 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 
powder, and the like. When used as an olfactory component of a perfumed 
article, as little as 0.05% of one or more of the branched chain saturated 
ketones will suffice to impart warm, vetiver, woody, amber and fruity 
aroma nuances. Generally no more than 5.0% is required. 
In addition, the perfume composition can contain a vehicle or carrier for 
the branched chain saturated ketones taken alone or taken together with 
other ingredients. The vehicle can be a liquid such as an alcohol such as 
ethanol, a glycol such as propylene glycol, or the like. The carrier can 
be an absorbent solid such as a gum or a microporous polymer or components 
for encapsulating the composition such as by means of coacervation. 
An additional aspect of our invention provides an organoleptically improved 
smoking tobacco products and additives therefor, as well as methods of 
making the same which overcome specific problems heretofore encountered in 
which specific desired oriental and woody flavor and aroma characteristics 
are created or enhanced 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 woody, oriental flavor and aroma characteristics 
may be imparted to smoking tobacco products and may be readily varied and 
controlled to produce the desired uniform flavoring characteristics prior 
to and on smoking in the mainstream and in the sidestream. 
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 at least one 
of the secondary alcohols of my invention. 
In addition to the one or more secondary alcohols of my invention, other 
flavoring and aroma additives may be added to the smoking tobacco material 
or substitute therefor either separately or in admixture with the 
secondary alcohols as follows: 
I. Synthetic Materials: 
Beta-ethyl-cinnamaldehyde; 
Eugenol; 
Dipentene; 
Beta-Damascone; 
1-[3-(methylthio)butyrol[2,3,3-trimethyl-cyclohexene; 
Beta-Damascenone; 
Maltol; 
Ethyl maltol; 
Delta undecalactone; 
Delta decalactone; 
Benzaldehyde; 
Amyl acetate; 
Ethyl butyrate; 
Ethyl acetate; 
2-Hexenol-1; 
2-methyl-isopropyl-1,3-nonadiene-8-one; 
2,6-Dimethyl-2,6-undecadiene-10-one; 
2-Methyl-5-isopropyl acetophenone; 
2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene; 
Dodecahydro-3a,6,6,9a-tetramethyl naphtho-(2-1-b)-furan; 
4-Hydroxy hexanoic acid, gamma lactone; 
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 of the branched 
chain saturated ketones of my invention 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 the 
augmentation, or the enhancement or the imparting of the woody, oriental 
and minty notes are concerned, we have found that satisfactory results are 
obtained if the proportion by weight of the sum total of saturated ketons 
of my invention is between 250 ppm and 1,500 ppm (0.025%-1.5%) of the 
active ingredients to the smoking tobacco material. I have further found 
that satisfactory results are obtained if the proportion by weight of the 
sum total of saturated ketones used to flavoring material is between 2,500 
and 10,000 ppm (0.25%-1.5%). 
Any convenient method for incorporating the secondary alcohols in the 
tobacco product may be employed. Thus, the secondary alcohols taken along 
or along with other flavoring additives may be dissolved in a suitable 
solvent such as ethanol, n-pentane, diethyl ether and/or other volatile 
organic solvents and the resulting solution may either be sprayed on the 
cured, cased and blended tobacco material or the tobacco material may be 
dipped into such solution. Under certain circumstances, a solution of one 
or more saturated ketones of this invention taken alone or further 
together with other flavoring additives as said 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 may have one or more of the saturated 
ketones of this invention in excess of the amounts or concentrations above 
indicated so that when blended with other tobaccos, the final product will 
have the percentage within the indicated range. 
In accordance with one specific example of my invention, an aged, cured and 
shredded domestic burley tobacco is spread with a 20% ethyl alcohol 
solution of a mixture of compounds having the structure: 
##STR18## 
produced according to Example V, infra, in an amount to provide a tobacco 
composition containing 800 ppm by weight of the secondary alcohol mixture 
on a dry basis. Thereafter, the ethyl 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 main and side streams when the cigarette is 
smoked. This aroma is described as being sweet, oriental-like, woody and 
Turkish tobacco-like nuances. 
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 saturated ketones of my invention can be incorporated 
with materials such as filter tip materials, seam paste, packaging 
materials and the like which are used along with tobacco to form a product 
adapted for smoking. Furthermore, the saturated ketones of this invention 
can be added to certain tobacco substitutes of natural or synthetic origin 
(e.g. dried lettuce leaves) and, accordingly, by term "tobacco" 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 following examples A-I are given to illustrate techniques for producing 
the precursors for the compounds of my invention as it is presently 
preferred to practice it. Example II and onwards are given to illustrate 
embodiments of my invention as it is presently preferred to practice it. 
It will be understood that these examples are illustrative and the 
invention is not to be considered restricted thereot except as indicated 
in the appended claims. 
EXAMPLE A 
Preparation of Di-isoamylene Derivatives 
Reaction: 
##STR19## 
(wherein in each of the molecules indicated, one of the dashed lines is a 
carbon-carbon double bond and the other of the dashed lines are 
carbon-carbon single bonds). 
Di-isoamylene is prepared according to one of the procedures set forth in 
the following references: 
i--Murphy & Lane, Ind. Eng. Chem., Prod. Res. Dev., Vol. 14, No. 3, 1975 p. 
167 (Title: Oligomerization of 2-Methyl-2-Butene in Sulfuric and 
Sulfuric-Phosphoric Acid Mixtures). 
ii--Whitmore & Mosher, Vol. 68, J. Am. Chem. Soc., February, 1946, p. 281 
(Title: The Depolymerization of 3,4,5,5-Tetramethyl-2-hexene and 
3,5,5-Trimethyl-2-heptene in Relation to the Dimerization of Isoamylenes) 
The resulting material was distilled in a fractionation column in order to 
separate the di-isoamylene from the higher molecular weight polymers, 
which are formed during the reaction as by-products. 
FIG. AA represents the GLC profile for the reaction product of Example A 
using a 70% sulfuric acid catalyst at 35%C. 
FIG. AB represents the GLC profile for the reaction product of Example A 
using an Amberlyst.RTM.15 acidic ion exchange resin catalyst at a 
temperature of 150.degree. C. 
FIG. AC represents the GLC profile for the reaction product of Example A, 
using an Amberlyst.RTM.15 catalyst at 100.degree. C. 
FIG. AD represents the GLC profile for the reaction product of Example A, 
using a sulfuric acid catalyst and an alpha-methylstyrene diluent at 
35.degree. C. according to the conditions of United Kingdom Patent 
Specification No. 796,130 (crude reaction product). 
FIG. AE represents the GLC profile for the reaction product of Example A, 
using a sulfuric acid catalyst, at 35.degree. C. and an alpha-methyl 
styrene diluent according to the conditions of United Kingdom Patent 
Specification No. 796,130 (distilled reaction product) further (boiling 
range 36.degree.-38.degree. C. at 4-5 mm.Hg. pressure). 
FIG. BA represents the NMR spectrum for Peak of the GLC profile of FIG. AE. 
FIG. BB represents the infra-red spectrum for Peak 1 of the GLC profile of 
FIG. AE. 
FIG. CA represents the NMR spectrum for Peak 2 of the GLC profile of FIG. 
AE. 
FIG. CB represents the infra-red spectrum for Peak 2 of the GLC profile of 
FIG. AE. 
FIG. D represents the NMR spectrum for Peak 2 of the GLC profile of FIG. 
AB. 
EXAMPLE I 
Preparation of Acetyl Derivative of Diisoamylene 
Reaction: 
##STR20## 
wherein in each of the structures containing dashed lines, these 
structures represent mixtures of molecules wherein in each of the 
molecules, one of the dashed lines respresents a carbon-carbon double bond 
and each of the other of the dashed lines respresent carbon-carbon single 
bonds. 
Into a 2-liter reaction flask equipped with stirrer, thermometer, reflex 
condenser and heating mantle, is placed 1000 g of acetic anhydride and 80 
g of boron trifluoride diethyl etherate. The resulting mixture is heated 
to 80.degree. C. and, over a period of 40 minutes, 690 g of diisoamylene 
prepared according to the illustration in Example A, supra is added. The 
reaction mass is maintained at 82.degree.-85.degree. C. for a period of 
5.5 hours, whereupon it is cooled to room temperature. The reaction mass 
is then added to one liter of water and the resulting mixture is stirred 
thereby yielding two phases; an organic phase and an aqueous phase. The 
organic phase is separated from the aqueous phase and neutralized with two 
liters of 12.5% sodium hydroxide followed by one liter of saturated sodium 
chloride solution. The resulting organic phase is then dried over 
anhydrous sodium sulfate and distilled in a one plate distillation column, 
yielding the following fractions: 
______________________________________ 
Vapor Liquid Weight of 
Fraction Temp. Temp. mm/Hg Fraction 
No. (.degree.C.) 
(.degree.C.) 
Pressure 
(g.) 
______________________________________ 
1 33/68 62/77 8/8 161 
2 69 79 4 100 
3 72 86 3.0 191 
4 88 134 3.0 189 
______________________________________ 
The resulting material is then distilled on a multi-plate fractionation 
column, yielding the following fractions at the following reflux ratios: 
______________________________________ 
Vapor Liquid Reflux Weight of 
Fraction 
Temp. Temp. mm/Hg Ratio Fraction 
No. (.degree.C.) 
(.degree.C.) 
Pressure 
R/D (g.) 
______________________________________ 
1 30/65 62/83 5/5 9:1 30.8 
2 68 84 5 9:1 52.8 
3 68 85 5 9:1 34 
4 69 87 5 9:1 43 
5 69 87 5 9:1 34 
6 71 88 4 4:1 41 
7 70 88 5 4:1 36.5 
8 71 91 5 4:1 42 
9 73 95 3 4:1 42.5 
10 80 106 3 4:1 39 
11 80 142 3 4:1 50.8 
12 80 220 3 4:1 24 
______________________________________ 
fractions 2-9 are bulked. 
GLC, NMR, IR and mass spectral analyses yield the information that the 
resulting bulked fractions is a mixture of cis and trans isomers having a 
generic structure: 
##STR21## 
wherein in each of the molecules, one of the dashed lines is a 
carbon-carbon double bond and the other of the dashed lines is a 
carbon-carbon single bond and, primarily, this mixture contains the 
molecular species (cis and trans isomers) as follows: 
##STR22## 
FIG. 1 sets forth the GLC profile for the reaction product of Example I, 
containing compounds defined according to the structure: 
##STR23## 
wherein in each molecule of the mixture, one of the dashed lines is a 
carbon-carbon double bond and the other of the dashed lines are 
carbon-carbon single bonds. 
FIG. 2A represents the infra-red spectrum of Peak 3 of the GLC profile of 
FIG. 1. 
FIG. 2B represents the infra-red spectrum of Peak 4 of the GLC profile of 
FIG. 1. 
FIG. 2C represents the infra-red spectrum for Peak 5 of the GLC profile of 
FIG. 1. 
FIG. 2D represents the infra-red spectrum for Peak 7 of the GLC profile of 
FIG. 1. 
FIG. 2E represents the infra-red spectrum for Peak 7 of the GLC profile of 
FIG. 1. 
FIG. 2F represents the infra-red spectrum for Peak 8 of the GLC profile of 
FIG. 1. 
FIG. 2G represents the infra-red spectrum for Peak 9 of the GLC profile of 
FIG. 1. 
FIG. 2H represents the infra-red spectrum for Peak 10 of the GLC profile of 
FIG. 1. 
FIG. 2K represents the NMR spectrum for the compound having the structure: 
##STR24## 
produced according to Example I. 
FIG. 2L represents the NMR spectrum for the compound containing the 
structure: 
##STR25## 
produced according to Example I. 
EXAMPLE II 
Preparation of Saturated Ketone 
Reaction: 
##STR26## 
Into a 1 liter autoclave equipped for pressures up to 1000 psig is placed 
498 g of a mixture of compounds defined according to the structure: 
##STR27## 
(wherein in the mixture in each of the molecules one of the dashed lines 
represents a carbon-carbon double bond and each of the other of the dashed 
lines represent single bonds, produced according to Example I, bulked 
distillation fraction 2-9) and 2.5 g of 5% Palladium on carbon. The 
reaction mass is pressurized with hydrogen to a pressure in the range of 
40-60 psig and the temperature of 165.degree. C. and maintained at that 
temperature and pressure for a period of 4 hours. The autoclave is then 
cooled and opened and the reaction mass is filtered yielding 475.1 grams 
of product. The product is then fractionally distilled on a 14 inch 
vigreux column, yielding the following fractions: 
______________________________________ 
Vapor Liquid Vacuum Weight 
Fraction Temp. Temp. mm. Hg. 
of 
No. (.degree.C.) 
(.degree.C.) 
Pressure 
Fraction 
______________________________________ 
1 66/82 105/90 14/14 8.4 
2 85 94 14 8.1 
3 87 95 14 7.3 
4 88 95 -- 8.5 
5 88 95 -- 12.0 
6 88 95 -- 10.7 
7 89 95 14 18.1 
8 89 95 14 19.4 
9 89 95 14 19.5 
10 89 95 14 31.8 
11 89 95 14 29.6 
12 89 95 14 47.7 
13 90 95 14 45.3 
14 90 95 14 47.7 
15 90 98 14 41.0 
16 91 98 14 43.6 
17 92 99 14 13.4 
18 92 101 14 19.8 
19 92 103 14 17.7 
20 94 110 14 9.0 
21 90 150 14 5.8 
22 89 230 14 3.6 
______________________________________ 
FIG. 3 is the GLC profile for bulked fractions 10-16 of the foregoing 
distillation (conditions: 10".times.1/4 inch, 10% carbo x, programmed at 
80.degree.-225.degree. C. at 8.degree. C. per minute). 
FIG. 4 is the NMR spectrum for bulked fractions 10-16 of the foregoing 
distillation (solvent: CFCl.sub.3 ; field strength 100 MHz). 
FIG. 5 is the infra-red spectrum for bulked fractions 10-16 of the 
foregoing distillation. 
EXAMPLE III 
Perfume Formulation 
The following vetiver perfume formulation is prepared: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Vetivone 25 
Saturated Ketone 
having the structure: 
##STR28## 
(Produced according to 
25 
Example II, bulked 
fractions 10-16) 
Vetiverol 5 
Musk ketone 8 
Styrax essence 4.5 
______________________________________ 
The addition of the saturated ketone having the structure: 
##STR29## 
prepared according to Example III imparts to this vetiver formulation an 
intense woody, fruity and amber nuances. 
EXAMPLE IV 
Perfumed Liquid Detergent 
Concentrated liquid detergents with aromas as described in Table I below 
(which detergents are produced from the lysine salt of n-dodecyl benzene 
sulfonic acid as more specifically described in U.S. Pat. No. 3,948,818 
issued on Apr. 6, 1976) are prepared containing one of the substances set 
forth in Table I below. They are prepared by adding and homogeneously 
mixing the appropriate quantity of substance as indicated in Table I 
below. The detergents all possess aroma profiles as set forth in Table I 
below, the intensity increasing with greater concentrations of the 
composition of matter as set forth in Table I below: 
TABLE I 
______________________________________ 
Aroma Ingredient Aroma Profile 
______________________________________ 
Saturated ketone having 
Anintense woody, amber and 
the structure: fruity aroma profile. 
##STR30## 
produced according to 
Example III, bulked 
fractions 10-16. 
Perfume composition 
A vetiver aroma with intense 
of Example III. woody, amber and fruity under- 
tones. 
______________________________________ 
EXAMPLE V 
Preparation of a Soap Composition 
One hundred grams of soap chips (IVORY.RTM.) manufactured by the Procter & 
Gamble Company of Cincinnati, Ohio, are melted and intimately admixed with 
one of the aroma materials as set forth in Table I of Example IV supra, 
the amount of composition of matter of Table I of Example IV being one 
gram of each composition of matter. The conditions of mixing are: 
180.degree. C., 3 hours, 12 atmospheres pressure. At the end of the mixing 
cycle, while the soap is still under 12 atmospheres pressure, the mixture 
of soap and perfume ingredient is cooled to room temperature. At this 
temperature, the resulting mixture is in a solid state. The resulting soap 
block is then cut up into soap cakes. Each of the soap cakes manifests an 
excellent aroma as set forth in Table I of Example IV. None of the soap 
samples show any discoloration even after two weeks in the oven at 
90.degree. F. 
EXAMPLE VI 
Preparation of a Detergent Composition 
A total of 100 grams of a detergent powder (nonionic detergent powder 
containing a proteolytic enzyme prepared according to Example I of 
Canadian Pat. No. 985,190 issued on Mar. 9, 1976) is mixed with 0.15 grams 
of one of the compositions of matter as set forth in Table I of Example IV 
until a substantially homogeneous composition is obtained. Each of the 
compositions has excellent aroma profiles as set forth in Table I of 
Example IV. 
EXAMPLE VII 
Perfumed Liquid Detergents 
Concentrated liquid detergents with rich, pleasant aromas as set forth in 
Table I of Example IV are prepared containing 0.10%, 0.15% and 0.20% of 
each of the compositions of matter set forth in Table I of Example IV. 
They are prepared by adding and homogeneously admixing the appropriate 
quantity of composition of matter of Table I of Example IV in the liquid 
detergent. The liquid detergents are all produced using anionic detergents 
containing a 50:50 mixture of sodium lauroyl sarcosinate and potassium 
N-methyl lauroyl tauride. The detergents all possess pleasant aromas as 
defined in Table I of Example IV, the intensity increasing with greater 
concentrations of composition of matter of Table I of Example IV. 
EXAMPLE VIII 
Tobacco Formulation 
A tobacco mixture is prepared by admixing the following ingredients: 
______________________________________ 
Ingredients 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: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Ethyl butyrate .05 
Ethyl valerate .05 
Maltol 2.00 
Cocoa extract 26.00 
Coffee extract 10.00 
Ethyl alcohol 20.00 
Water 41.90 
______________________________________ 
The above stated tobacco flavor formulation is applied at the rate of 1.0% 
to all of the cigarettes produced using the above tobacco formulation. 
One-half of the cigarettes are then treated with 500 or 1000 ppm of the 
saturated ketone defined according to the structure: 
##STR31## 
The other half of the cigarettes are "control cigarettes" and do not 
contain any of the saturated ketone of Example II but only contain 
untreated flavor formulation as set forth above. The control cigarettes 
and the treated experimental cigarettes are then evaluated by paired 
comparison and the results are as follows: 
The experimental cigarettes are found to have more body and to be, on 
smoking, more Turkish tobacco-like, more aromatic and to have sweet, 
woody/oriental and fruity aroma nuances in both the main stream and the 
side stream.