Odorant substances

New odoriferous compounds, particularly the compounds having the following formula: ##STR1## wherein R is an aliphatic residue having the formula ##STR2## wherein R.sup.1 is a C.sub.1-4 alkyl, C.sub.1-4 alkylidene or C.sub.2-4 alkenyl, the sum of the carbon atoms being in those residues from 2 to 5, m and n being equal to zero or 1, p being 1, 2 or 3 and the dotted lines representing one or two optional double bonds. The invention also relates to a method for the preparation of new di-ketones I: as well as the use of I as odoriferous compounds in odoriferous compositions, which are characterized by a certain proportion of compounds having the formula I.

The invention is concerned with novel odorant substances. These are 
compounds of the formula 
##STR3## 
wherein R signifies an aliphatic group of the formula 
##STR4## 
in which R.sup.1 is C.sub.1-4 -alkyl, C.sub.1-4 -alkylidene or C.sub.2-4 
-alkenyl and the sum of the carbon atoms in these groups is 2-5, m and n 
are 0 or 1, p is 1, 2 or 3 and the dotted lines represent one or two 
optional double bonds. 
The alkyl, alkenyl or alkylidene groups denoted by R.sup.1 can be 
straight-chain or branched-chain. Examples of alkyl groups are methyl, 
ethyl, propyl, isopropyl, n-butyl, sec.-butyl and tert.-butyl. Vinyl, 
propenyl, isopropenyl and butenyl are examples of alkenyl groups. Examples 
of alkylidene groups are methylidene, ethylidene, propylidene, 
isopropylidene and butylidene. 
R.sup.1 is preferably methyl. p is preferably 3. When p is 2 or 3 the 
groups R.sup.1 can be the same or different. m is preferably the same as 
n; m and n both being 1 are especially preferred. 
R preferably represents one of the following groups: 
##STR5## 
The first of these groups is particularly preferred. 
Formula I is also intended to embrace the stereoisomers which occur as a 
result of the asymmetric centres, the double-bond isomers and the 
corresponding enol forms of the diketones of formula I. The enol forms of 
the 1,3-diketones are: 
##STR6## 
The present invention is also concerned with a process for the manufacture 
of the compounds of formula I. 
This process comprises reacting an enamine of cyclopentanone with an acid 
halide of the formula 
##STR7## 
wherein R has the significance given earlier and X represents halogen. 
As the acid halides there come into consideration especially the chloride, 
bromide and iodide, with the chloride being preferred. 
The manufacture of the diketones of formula I can therefore be carried out 
according to the known methodology of enamine acylation; see, for example, 
G. Stork, A. Brizzolara, H. Landesmann, J. Szmuskovicz and R. Terrel in J. 
Amer. Chem. Soc. 85, 207 (1963). 
As the enamine-former there can be used, for example, the following 
secondary amines: 
Aliphatic secondary amines such as dialkylamines (e.g. diethylamine) or 
cyclic secondary amines such as, for example, morpholine, piperidine or 
pyrrolidine. Morpholine is preferred. 
The reaction of the enamine with the halide of formula II is conveniently 
carried out in a solvent and with the exclusion of air and moisture. 
Suitable solvents are anhydrous solvents such as, for example, methylene 
chloride, chloroform, dioxan, benzene, toluene, dimethyl formamide etc; 
methylene chloride and chloroform are preferred. 
The molar ratio of enamine to halide is conveniently approximately 1:1, but 
the enamine can also be used in excess (e.g. in a two-fold amount or even 
more). However, the addition of any amine (e.g. triethylamine) can replace 
the excess of the enamine necessary to neutralize the acid formed. 
The reaction is conveniently carried out at a temperature between 0.degree. 
C. and the reflux temperature of the reaction mixture, preferably at about 
40.degree. C. For example, the mixture is left for several hours at this 
temperature. Thereupon, the mixture is cooled, conveniently to room 
temperature, and then an acid (e.g. hydrochloric acid) is added thereto. 
The amine-cleavage can then be achieved by renewed heating (e.g. at reflux 
temperature). 
The isolation of the reaction product can be carried out according to 
methods known per se. For example, the reaction product is taken up in an 
organic solvent and the organic solution is washed firstly with dilute 
hydrochloric acid such as a 10% HCl solution. After washing neutral and 
drying, the crude product can be purified by usual methods such as, for 
example, adsorption chromatography and/or distillation. 
The compounds of formula I have particular organoleptic properties, on the 
basis of which they are excellently suited as odorant substances. 
The invention is accordingly also concerned with the use of the compounds 
of formula I as odorant substances. 
The compounds of formula I possess, in particular, woody-animal like 
olfactory notes; they are distinguished, in particular, by high olfactory 
intensity associated with extraordinary diffusion and exceptional 
tenacity. 
When used in low concentrations, the compounds of formula I intensify the 
olfactory notes of odorant substance compositions, especially of woody or 
animal-like compositions or bases, and confer to these warmth and 
radiance. 
Examples of such compositions are compositions with cedarwood, sandalwood 
and patchouli notes as well as costus and castoreum notes. 
The compounds of formula I are also excellently suited for the modification 
of leather notes and chypre notes, not only of the feminine but also of 
the masculine direction. 
The compounds of formula I combine with numerous known odorant substance 
ingredients of natural or synthetic origin, whereby the range of the 
natural ingredients can embrace not only readily-volatile but also 
semi-volatile and slightly-volatile components, and the range of the 
synthetic ingredients can embrace representative from practically all 
classes of substances, as will be evident from the following compilation: 
Natural products such as ambergris, bergamotte oil, castoreum and its 
substitute, acetylated cedarwood oil (e.g. Vertofix.TM. IFF or 
Cedartone.TM. Givaudan), tree moss, tarragon oil, pine-needle oil, 
galbanum oil, geranium oil, jasmine absolute and its substitute, lavandin 
oil, lavender oil, mandarin oil, orange oil, osmanthus absolute and its 
substitute, patchouli oil, petitgrain oil Paraguay, sandalwood oil, 
vetiver oil, wormwood oil and ylang-ylang oil; 
alcohols such as borneol, cedrol, citronellol, eugenol, geraniol, 
cis-3-hexenol, linalool, 
3-methyl-5-(2',2',3'-trimethyl-cyclopent-3'-en-1'-yl)-pentan-2-ol 
(Sandalore.RTM. Givaudan), phenylpropyl alcohol, vetivenol and cinnamic 
alcohol; 
aldehydes such as p-tert.butyl-.alpha.-methyl-dihydro-cinnamaldehyde (e.g. 
Lilial.RTM. Givaudan), citral, decanal, 
3,5-dimethyl-cyclohex-3-ene-carboxaldehyde, heliotropin, 
.alpha.-hexylcinnamaldehyde, hydroxycitronellal, methylnonylacetaldehyde, 
4-[4-methyl-3-pentenyl]-cyclohex-3-ene-1-aldehyde (e.g. Myraldine.RTM. 
Givaudan), syringa aldehyde and vanillin; 
ketones such as acetylcedrene, .alpha.-ionone, camphor, menthone, 
p-methylacetophenone and methyl ionone; 
esters such as ethyl 3-ethyl-1,1-dimethyl-cyclohex-3-ene-2-carboxylate 
(Givescone.TM. Givaudan), benzyl acetete, benzyl salicylate, bornyl 
acetate, p-tert.butylcyclohexyl acetate, cedryl acetate, cis-3-hexenyl 
acetate, linalyl acetate, 
4-[4-methyl-3-pentenyl]-cyclohex-3-en-1-yl-carbinyl acetate (e.g. Myraldyl 
Acetate.TM. Givaudan), methyl dihydrojasmonate and styrallyl acetate; 
lactones such as .gamma.-undecalactone and coumarin; 
various further components often used in perfumery such as 
acetaldehyde-propylphenyl-ethyl acetal, methyl 1-methyl-cyclododecyl ether 
(e.g. Madrox.TM. Givaudan), musk compounds [musk ambrette, musk ketone, 
12-oxa-hexadecanolide (e.g. Musk 174.RTM. Naarden), 
1,1-dimethyl-4-acetyl-6-tert.-butylindane, indole)] and skatole. 
The compounds of formula I can be used in wide limits which, for example, 
can extend in compositions from 0.01% (detergents) to 10% (alcoholic 
solutions). It will, however, be appreciated that these values are not 
limiting values, since the experienced perfumer can also achieve effects 
with lower concentrations or even only traces of the compounds or can 
synthesize novel complexes with higher concentrations. The preferred 
concentrations vary between 0.5% and 1.5%. The compositions produced with 
the compounds of formula I can be used for all kinds of perfumed consumer 
goods (Eau de Cologne, eau de toilette, essences, lotions, creams, 
shampoos, soaps, salves, powder, deodorants, detergents, tobacco etc). 
The compounds of formula I can therefore be used in the production of 
odorant substance compositions and, as will be evident from the foregoing 
compilation, a wide range of known odorant substances can be used. In the 
production of such compositions, the known odorant substances specified 
earlier can be used according to methods known to the perfumer such as, 
for example, according to W. A. Poucher, Perfumes, Cosmetics and Soaps 2, 
7th Edition, Chapman and Hall, London, 1974.

EXAMPLE 1 
Dihydroisophorone 
2.2 kg of isophorone and 5 g of 5% palladium-on-carbon catalyst are added 
to a 3 liter autoclave which is fitted with heating means, cooling means 
and a stirrer. A hydrogen pressure of 8-10 atmospheres is now generated 
and the mixture is slowly warmed to 30.degree.-35.degree. C. Since the 
hydrogenation is exothermic, provision is made by cooling that a 
temperature of 50.degree. C. is not exceeded. After completion of the 
hydrogen uptake (temperature drop), the catalyst is filtered off. There 
are thus obtained 2.2 kg of crude dihydroisophorone, which is uniform 
according to gas chromatography and which is used directly. 
n.sub.D.sup.20 =1.4455. Yield: quantitative. 
Ethyl 1-hydroxy-3,3,5-trimethyl-cyclohexylacetate 
300 ml of absolute ether, 150 ml of dry benzene and 170 g of magnesium 
shavings are added to a 6 liter flask which is fitted with a stirrer, 
thermometer, dropping funnel and reflux condenser. Now, there is 
introduced dropwise a mixture of 1.100 kg of dihydroisophorone and 960 g 
of ethyl chloroacetate dissolved in 1.200 l of ether and 600 ml of 
benzene. (If the reaction does not begin during the addition of the first 
200 ml and warming at slight reflux does not begin spontaneously, then a 
few small crystals of iodine are added). The beginning of the reaction is 
recognizable by turbidity and heat-evolution. The addition of the reagents 
is continued in such a manner that the mixture boils only moderately, the 
addition being completed within 11/4 hours. Thereafter, the mixture is 
held at reflux temperature for a further 31/2 hours and, after cooling, 
added to 2.5 kg of ice and 1.2 l of concentrated hydrochloric acid. The 
organic phase is separated and washed with water (containing 1% 
concentrated hydrochloric acid), with water and several times more with 
10% sodium carbonate solution. After evaporating the solvent in vacuo, 
there remain behind 1.69 kg of crude product which are distilled. The main 
fraction (1.250 kg) is washed with 10% sodium carbonate solution and again 
distilled (100.degree. C./3 mm Hg). There are thus obtained 1.046 kg of 
ethyl 1-hydroxy-3,3,5-trimethyl-cyclohexylacetate. 
n.sub.D.sup.20 =1.4580. Yield: 62%. 
Ethyl 3,3,5-trimethyl-(1 or 6)-(cyclohexenyl or cyclohexylidene)acetate 
1.040 kg of ethyl 1-hydroxy-3,3,5-trimethyl-cyclohexylacetate, 35 g of 
potassium hydrogen sulphate and 300 ml of toluene are heated while 
stirring vigorously in a 2 liter flask which is fitted with a stirrer, 
thermometer and reflux condenser with a water-separator. 78 ml of water 
are separated within 4 hours at an internal temperature of 
140.degree.-150.degree. C. The mixture is thereupon cooled, washed with 
10% sodium carbonate solution and the toluene is evaporated in vacuo. 
There are obtained 990 g of crude product which are distilled and yield 
880 g of an isomer mixture (GC: 3 peaks). 
n.sub.D.sup.20 =1.4560-1.4640. Yield: 92%. 
3,5-Dimethyl-cyclohexanone 
128 g of 3,5-dimethyl-cyclohexanol and 500 ml of benzene are added to a 
round flask which is fitted with a stirrer, thermometer, dropping funnel 
and reflux condenser. While stirring and cooling there is now slowly added 
dropwise thereto a mixture of 119 g of sodium dichromate, 500 ml of water, 
162 ml of concentrated sulphuric acid and 50 ml of glacial acetic acid. 
Thereby the temperature should not exceed +10.degree. C. The mixture is 
stirred at this temperature for a further 3 hours and then the organic 
phase is separated. The aqueous phase is diluted with 130 ml of water and 
extracted with benzene. The combined organic phases are washed neutral and 
concentrated. The residue is distilled over a Widmer column and gives 
102.7 g of 3,5-dimethyl-cyclohexanone. 
B.p.: 55.degree. C./6 mm Hg, n.sub.D.sup.20 =1.4432. Yield: 82%. 
3,4-Dimethyl-cyclohexanone 
Corresponding oxidation of 3,4-dimethyl-cyclohexanol yields 
3,4-dimethyl-cyclohexanone. 
B.p.: 66.degree. C./11 mm Hg. 
Ethyl 3,5-dimethyl-cyclohexylideneacetate 
85 g of dry toluene are added to a round flask which is fitted with a 
stirrer, thermometer, dropping funnel and reflux condenser. Under a 
nitrogen atmosphere there are now introduced 17.2 g of sodium in small 
portions and the mixture is heated to boiling. After dissolution of the 
sodium (after about 3 hours), the mixture is cooled to 20.degree. C. and 
there is slowly added dropwise thereto (during about 11/2 hours) a mixture 
of 219 g of ethyl diethylphosphonoacetate, 95 g of 
3,5-dimethyl-cyclohexanone and 220 g of dry toluene. The temperature is 
held between 25.degree. and 30.degree. C. The mixture is stirred at this 
temperature for a further 2 days and thereupon poured on to 400 g of ice, 
extracted with toluene, washed neutral and concentrated. The residue is 
distilled over a Widmer column and thus yields 110 g of ethyl 
3,5-dimethyl-cyclohexylideneacetate. 
B.p.: 58.degree. C./0.04 mm Hg; n.sub.D.sup.20 =1.4720. Yield: 75%. 
Ethyl 3,4-dimethyl-cyclohexylideneacetate 
When 3,4-dimethyl-cyclohexanone is subjected to the foregoing Wittig-Horner 
conditions there is obtained ethyl 3,4-dimethyl-cyclohexylideneacetate. 
B.p.: 56.degree. C./0.08 mm Hg; n.sub.D.sup.20 =1.4769. 
Ethyl 2-sec.butyl-cyclohexylideneacetate 
By the analogous reaction of 2-sec.butyl-cyclohexanone there is obtained 
ethyl 2-sec.butyl-cyclohexylideneacetate. 
B.p.: 92.degree. C./0.3 mm Hg; n.sub.D.sup.20 =1.4839. 
Ethyl 3,3,5-trimethyl-cyclohexylacetate 
875 g of ethyl 3,3,5-trimethyl-(1 or 6)-(cyclohexenyl or 
cyclohexylidene)acetate, 5 g of 5% palladium-on-carbon and 25 g of sodium 
carbonate are added to a 3 liter autoclave which is fitted with heating 
means, cooling means and a stirrer. A hydrogen pressure of 20 atmospheres 
is generated and the mixture is heated to 75.degree. C. The hydrogenation 
proceeds rapidly and exothermically and the mixture must therefore be 
cooled in order that a temperature of 100.degree. C. is not exceeded. 
After cooling, the mixture is filtered. There are obtained in quantitative 
yield 875 g of a diastereomer mixture (GC: two peaks) of ethyl 
3,3,5-trimethyl-cyclohexylacetate, this mixture being used directly in the 
saponification described hereinafter. 
Ethyl 3,5-dimethyl-cyclohexylacetate 
To a 1 liter autoclave which is fitted with heating means, cooling means 
and a stirrer are added 54 g of ethyl 3,5-dimethyl-cyclohexylideneacetate, 
200 ml of absolute methanol and 3 g of Raney-nickel, which has been washed 
three times with absolute methanol. The mixture is hydrogenated at 
100.degree. C. under a hydrogen pressure of 40 atmospheres. The hydrogen 
uptake stops after 8 hours. The catalyst is filtered off, the filtrate is 
concentrated and the residue is distilled. There are obtained 52.3 g of 
ethyl 3,5-dimethyl-cyclohexylacetate. 
B.p.: 56.degree. C./0.7 mm Hg; n.sub.D.sup.20 =1.4440. Yield: 98%. 
Ethyl 3,4-dimethyl-cyclohexylacetate 
The analogous hydrogenation of ethyl 3,4-dimethyl-cyclohexylideneacetate 
yields ethyl 3,4-dimethyl-cyclohexylacetate. 
B.p.: 103.degree. C./7 mm Hg; n.sub.D.sup.20 =1.4482. 
Ethyl 2-sec.butyl-cyclohexylacetate 
The analogous hydrogenation of ethyl 2-sec.butyl-cyclohexylideneacetate 
gives ethyl 2-sec.butyl-cyclohexylacetate. 
B.p.: 88.degree. C./0.4 mm Hg; n.sub.D.sup.20 =1.4590. 
3,3,5-Trimethyl-cyclohexylacetic acid 
875 g of ethyl 3,3,5-trimethyl-cyclohexylacetate are treated in 2.2 l of 
water with 670 g of 30% sodium hydroxide and the mixture is held at reflux 
temperature for 21/2 hours while stirring. After cooling, the mixture is 
neutralized, acidified with 420 g of 63% sulphuric acid and extracted with 
cyclohexane. The cyclohexane extract is washed neutral, evaporated and the 
770 g of crude product are distilled. There are obtained 630 g of 
3,3,5-trimethyl-cyclohexylacetic acid. (Yield: 82%). 
n.sub.D.sup.20 =1.4622. 
3,3,5-Trimethyl-(1 or 6)-(cyclohexenyl or cyclohexylidene)acetic acid 
By analogous saponification of ethyl 3,3,5-trimethyl-(1 or 6)-(cyclohexenyl 
or cyclohexylidene)acetate there is obtained in a yield of 90% 
3,3,5-trimethyl-(1 or 6)-(cyclohexenyl or cyclohexylidene)acetic acid. 
M.p.: 80.degree.-82.degree. C. 
3,5-Dimethyl-cyclohexylacetic acid 
44.7 g of ethyl 3,5-dimethyl-cyclohexylacetate are treated with 300 ml of 
methanol and 15 g of potassium hydroxide, dissolved in 140 ml of water, 
and saponified by heating to reflux temperature for 3 hours. The 
working-up yields 35.6 g of a solid crude product which is used directly. 
A sample is distilled for the purpose of analysis. 
B.p.: 120.degree. C./7 mm Hg. Crude yield: 93%. 
3,4-Dimethyl-cyclohexylacetic acid 
The corresponding saponification of ethyl 3,4-dimethyl-cyclohexylacetate 
yields 3,4-dimethyl-cyclohexylacetic acid as a liquid crude product. 
B.p.: 152.degree. C./7 mm Hg. 
2-Sec. butyl-cyclohexylacetic acid 
The analogous saponification of ethyl 2-sec. butyl-cyclohexylacetate yields 
2-sec. butyl-cyclohexylacetic acid as a liquid crude product. 
B.p.: 160.degree. C./0.3 mm Hg. 
1-Methyl-2-methylene-3-(prop-1-en-2-yl)-cyclopentane-1-carboxylic acid. 
75 ml of dry tetrahydrofuran and 23 g of magnesium shavings are added to a 
round flask which is fitted with a stirrer, thermometer, dropping funnel 
and reflux condenser. Without stirring there is added thereto slowly 
(within 4 hours) a solution of 112.4 g of 
1-methyl-2-chloromethyl-3-(prop-1-en-2-yl)-cyclopent-1-ene in 100 ml of 
tetrahydrofuran. The mixture is brought to 60.degree.-65.degree. for 1 
hour and then cooled to -10.degree.. A carbon dioxide stream is conducted 
through the solution, which is cooled to -10.degree. C. The amount of 
carbon dioxide introduced is weighed; it amounts to 29.5 g. The mixture is 
left to stand at room temperature overnight. The mixture is then cooled to 
10.degree. C. and decomposed with 300 ml of a 10% hydrochloric acid 
solution. The acid solution is extracted with ether, the organic acid 
formed is taken up as the sodium salt (treatment with 10% sodium 
hydroxide) from the ether into the aqueous phase, which is washed with 
ether. After acidifying with 10% orthophosphoric acid, the mixture is 
extracted with ether and the etherial solution is dried over sodium 
sulphate. The solvent is evaporated and there are obtained 78.2 g (yield: 
66%) of crude 3-isopropenyl-2-methylene-1-methyl-cyclopentanecarboxylic 
acid, which are recrystallized with hexane. 
M.p.: 66.5.degree.-68.degree. C. 
3,3,5-Trimethyl-cyclohexylacetyl chloride 
114 g of 3,3,5-trimethyl-cyclohexylacetic acid in 350 ml of dry ether in a 
round flask which is fitted with a thermometer, stirrer, reflux condenser 
and dropping funnel are treated rapidly with 32.8 g of phosphorus 
trichloride and the mixture is subsequently held at reflux temperature for 
a further 4 hours. The phosphorous acid is decanted off and the ether is 
evaporated in vacuo. There are obtained 128 g (yield: quantitive) of crude 
3,3,5-trimethyl-cyclohexylacetyl chloride. 
3,3,5-Trimethyl-(1 or 6)-(cyclohexenyl or cyclohexylidene)acetyl chloride 
This acid chloride is obtained by the analogous treatment of 
3,3,5-trimethyl-(1or 6)-(cyclohexenyl or cyclohexylidene)acetic acid. 
Yield after distillation: 52%. 
n.sub.D.sup.20 =1.4750. 
1-Methyl-2-methylene-3-(prop-1-en-2-yl)-cyclopentane-1-carboxylic acid 
chloride 
This acid chloride is obtained by the analogous treament of 
1-methyl-2-methylene-3-(prop-1-en-2-yl)-cyclopentane-1-carboxylic acid. 
Yield after distillation: 51%. 
n.sub.D.sup.20 =1.4930. 
3,5-Dimethyl-cyclohexylacetyl chloride 
This starting material is obtained by the analogous treatment of 
3,5-dimethyl-cyclohexylacetic acid. 
B.p.: 73.degree. C./1.5 mm Hg; n.sub.D.sup.20 =1.4603. 
3,4-Dimethyl-cyclohexylacetyl chloride 
This starting material is obtained by the analogous treatment of 
3,4-dimethyl-cyclohexylacetic acid. 
B.p.: 68.degree. C./0.35 mm Hg; n.sub.D.sup.20 =1.4692. 
2-Sec.butyl-cyclohexylacetyl chloride 
This starting material is obtained by the analogous treatment of 
2-sec.butyl-cyclohexylacetate. 
B.p.: 71.degree. C./0.12 mm Hg; n.sub.D.sup.20 =1.4800. 
EXAMPLE 2 
2-(3,3,5-Trimethyl-cyclohexylacetyl)-cyclopentanone 
111 g of freshly distilled morpholinocyclopentene, 71.7 g of triethylamine 
and 900 ml of chloroform are added to a round flask which is fitted with a 
thermometer, stirrer, reflux condenser and dropping funnel and the mixture 
is cooled to 0.degree. C. Under a nitrogen atmosphere there are slowly 
added dropwise thereto 128 g of crude 3,3,5-trimethyl-cyclohexylacetyl 
chloride in 200 ml of chloroform. The flask content is stirred until it 
has reached a temperature of 20.degree. C. and it is then warmed at 
40.degree. C. for a further 7 hours. After 12 hours, 76.2 of concentrated 
hydrochloric acid in 190 ml of water are added thereto and the flask 
content is held at reflux temperature for 21/2 hours. Thereafter, the 
organic phase is separated, the aqueous phase is extracted twice with 
chloroform and the combined chloroform extracts are washed as follows: 
three times with 10% hydrochloric acid, once with water, once with 
bicarbonate solution and finally with sodium chloride solution until 
neutral. Now it is concentrated in a rotary evaporator and the crude 
product (212 g) is distilled in vacuo. There are obtained 90 g (yield: 
58%) of 2-(3,3,5-trimethylcyclohexylacetyl)-cyclopentanone. 
B.p.: 111.5.degree. C./0.25 mm Hg. 
Odour: intensively woody, animal-like; extremely diffusive, excellent 
tenacity. 
2-[3,3,5-Trimethyl-(1 or 6)-(cyclohexenyl or 
cyclohexylidene)acetyl]-cyclopentanone 
If the foregoing conditions are used on distilled 3,3,5-trimethyl-(1 or 
6)-(cyclohexenyl or cyclohexylidene)acetyl chloride, then there is 
obtained 2-[3,3,5-trimethyl-(1 or 6)-(cyclohexenyl or 
cyclohexylidene)acetyl]-cyclopentanone in a yield of 62%. 
B.p.: 103.degree. C./0.08 mm Hg. 
Odour: woody, animal-like; very diffusive. 
2-[1-Methyl-2-methylene-3-(prop-1-en-2-yl)-cyclopentylcarbonyl]-cyclopentan 
one 
The same treatment of distilled 
1-methyl-2-methylene-3-(prop-1-en-2-yl)-cyclopentane-1-carboxylic acid 
chloride give in 36.5% yield 
2-[1-methyl-2-methylene-3-(prop-1-en-2-yl)-cyclopentylcarbonyl]-cyclopenta 
none. 
B.p.: 119.degree. C./0.58 mm Hg. 
Odour: strongly woody, cedarous. 
2-(3,5-Dimethyl-cyclohexylacetyl)-cyclopentanone 
If 3,5-dimethyl-cyclohexylacetyl chloride is subjected to the treatment 
described earlier, then there is obtained 
2-(3,5-dimethylcyclohexylacetyl)-cyclopentanone. 
B.p.: 129.degree. C./0.1 mm Hg; n.sub.D.sup.20 =1.4950. 
Odour: intensively woody and animal-like; diffusive, good tenacity. 
2-(3,4-Dimethyl-cyclohexylacetyl)-cyclopentanone 
By subjecting 3,4-dimethyl-cyclohexylacetyl chloride to the procedure 
described earlier there is obtained 
2-(3,4-dimethyl-cyclohexylacetyl)-cyclopentanone. 
B.p.: 133.degree. C./0.8 mm Hg; n.sub.D.sup.20 =1.5080. 
Odour: intensively woody animal-like with a minty note, diffusive, good 
tenacity. 
2-(2-Sec.butyl-cyclohexylacetyl)-cyclopentanone 
By treating 2-sec.butyl-cyclohexylacetyl chloride in the manner described 
above there is obtained 2-(2-sec.butyl-cyclohexylacetyl)-cyclopentanone. 
B.p.: 137.degree. C./0.28 mm Hg; n.sub.D.sup.20 =1.5117. 
2-(1,2-Dimethyl-3-isopropyl-cyclopentylcarbonyl)-cyclopentanone 
9.6 g of 
2-[1-methyl-2-methylene-3-(prop-1-en-2-yl)-cyclopentylcarbonyl]-cyclopenta 
none are treated in 100 ml of absolute alcohol with 1 g of 5% 
palladium-on-carbon and the mixture is hydrogenated at normal pressure. 
After completion of the hydrogen uptake (8 hours), the mixture is 
filtered, the filtrate is concentrated and the residue is chromatographed 
on a hundred-fold amount of silica gel with toluene/ethyl acetate (1:2). 
There are obtained 1.7 g of 
2-(1,2-dimethyl-3-isopropyl-cyclopentylcarbonyl)-cyclopentanone, which are 
contaminated with a small amount (&lt;5%) of 
2-(1,2-dimethyl-3-isopropyl-cyclopent-2-en-1-yl-carbonyl)-cyclopentanone 
or 2-(1,2-dimethyl-3-isopropylidenecyclopentyl carbonyl)-cyclopentanone. 
n.sub.D.sup.20 =1.5042. 
Odour: intensively woody, diffusive, good tenacity. 
In the following Examples "compound Ia", "compound Ib" and "compound Ic" 
have the following significances: 
"Compound Ia": 2-(3,3,5-trimethyl-cyclohexylacetyl)-cyclopentanone. 
"Compound Ib": 2-(3,5-dimethyl-cyclohexylacetyl)-cyclopentanone. 
"Compound Ic": 2-(3,4-dimethyl-cyclohexylacetyl)-cyclopentanone. 
EXAMPLE 3 
(a) Perfume base in the direction of fougere 
______________________________________ 
Parts by weight 
______________________________________ 
Lavandin oil 140 
Geranium oil (African) 
140 
Coumarin 140 
Benzoin resinoid (Siam) 
140 
Tree moss absolute (aloresine) 
60 
Patchouli oil 60 
Bergamotte oil 60 
Vetiver oil (Bourbon) 
40 
Musk ketone 60 
Musk xylene 60 
900 
Compound Ia 100 
1000 
______________________________________ 
By adding 10% of the compound Ia the coumarin note, which predominates in 
the fougere base, is suppressed. At the same time, the composition becomes 
lighter and fresher. The lavender notes are emphasized in a desirable 
manner. 
(b) Spicy base 
______________________________________ 
Parts by weight 
______________________________________ 
Benzyl acetate 100 
Hydroxycitronellal 100 
Phenylethyl alcohol 100 
Amyl acetate 100 
Patchouli oil 80 
Ylang oil 50 
Eugenol 50 
Linalyl acetate 60 
Musk ketone 50 
Cedryl acetate 30 
Epoxycedrene 30 
Vertofix coeur .TM. (acetylcedrene) 
30 
Coumarin 30 
Spearmint oil 15 
Thyme oil 15 
Methyl salicylate 5 
Lemon oil 5 
Dipropyleneglycol (DPG) 
100 
950 
Compound Ia 50 
1000 
______________________________________ 
The addition of 5% of compound Ia produces not only an intensification of 
the olfactory intensity, but also an improvement in the olfactory quality 
of the spicy base. The olfactory complex clearly receives more volume. 
(c) Perfume base in the direction of wood 
______________________________________ 
Parts by weight 
______________________________________ 
Madrox .TM. Givaudan (1-methyl- 
150 
1-methoxy-cyclododecane) 
Vetivenyl acetate 150 
Sandela .RTM. Givaudan [3-isocamphyl- 
150 
(5)-cyclohexanol] 
Linalool 100 
Patchouli oil 50 
Ironal .RTM. Givaudan (6-methyl-.alpha.-ionone) 
50 
Linalyl acetate 50 
Citronellol 50 
Benzyl acetate 30 
Tree moss colourless absolute 
30 
.alpha.-Amylcinnamaldehyde 
20 
Methylnonylacetaldehyde (10% 
20 
in DPG) 
Eugenol 20 
C-11-aldehyde (10% in DPG) 
10 
Ciste oil French (labdanum) 
10 
Sandalore .RTM. Givaudan (3-methyl- 
10 
5-(2,2,3)-trimethylcyclopent-3- 
en-1-yl)pentan-2-ol 
900 
Compound Ia 100 
1000 
______________________________________ 
By adding 10% of compound Ia the olfactory intensity of the woody base is 
increased in a significant manner. The patchouli notes are modified in an 
advantageous manner in the direction of cedar, leather and animal-like 
notes. 
(d) Perfume base in the direction of chypre 
______________________________________ 
Parts by weight 
______________________________________ 
.alpha.-Ionone 200 
Musk ambrette 100 
Phenylethyl alcohol 30 
Bergamotte oil 70 
Vertofix coeur 50 
Jasmine (synthetic) 40 
Patchouli oil 40 
Rhodinol 30 
Clove base 30 
.alpha.-Hexylcinnamaldehyde 
30 
Civet oil (10% in DPG) 
20 
Sandalore .RTM. Givaudan 
10 
Artemisia essence (mugwort oil) 
10 
C-11-aldehyde (10% in DPG) 
10 
Tree moss absolute 50 
Styrallyl acetate 20 
DPG 200 
990 
Compound Ia 10 
1000 
______________________________________ 
The addition of only 1% of compound Ia to this chypre base already produces 
an olfactory intensification. At the same time, the woody notes are 
emphasized and the cedar character is accentuated. 
(e) Animal-like base 
______________________________________ 
Parts by weight 
______________________________________ 
Sandela .RTM. Givaudan 
100 
Madrox .TM. Givaudan 
100 
Vertofix coeur .TM. 100 
Patchouli oil 50 
Benzyl salicylate 40 
Linalyl acetate 40 
Myrrh oil 30 
Benzoin resinoid (Siam) 
30 
Ethylene brassylate 30 
Castoreum (synthetic) 
30 
C-11-aldehyde (10% in DPG) 
20 
C-12-aldehyde L (10% in DPG) 
20 
.beta.-Ionone 20 
p-Cresyl-phenylacetate 
5 
Indole 5 
DPG 330 
950 
Compound Ia 50 
1000 
______________________________________ 
The addition of 5% of compound Ia clearly confers to this composition more 
character and accentuates the castoreum and leather notes. 
(f) Spicy perfume base 
______________________________________ 
Parts by weight 
______________________________________ 
Bergamotte oil 200 
Patchouli oil 200 
Sandalwood oil 200 
Myrascone .TM. Givaudan 
100 
Methyl dihydrojasmonate 
70 
.alpha.-Ionone 50 
p.Tert.butyl-cyclohexanol 
50 
acetate 
Basil oil 30 
900 
Compound Ia 100 
1000 
______________________________________ 
By adding 10% of compound Ia this olfactory complex becomes more aromatic 
and more spicy. It receives more "volume" and, at the same time, becomes 
more harmonic and rounded-off. 
(g) Perfumery base in the direction of chypre 
______________________________________ 
Parts by weight 
______________________________________ 
Hydroxycitronellal 100 
Bergamotte oil 80 
Methyl dihydrojasmonate 
80 
.alpha.-Hexylcinnamaldehyde 
80 
Phenylethyl alcohol 80 
Tree moss absolute (colourless) 
40 
Patchouli oil 40 
Linalool 40 
.alpha.-Ionone 40 
Musk ketone 40 
Vetiver oil 20 
Sandalwood oil 20 
Benzyl acetate 20 
Styrallyl acetate 5 
Undecalactone 5 
C-11-aldehyde (10% in DPG) 
5 
Civet oil (10% in DPG) 
5 
Dipropyleneglycol 200 
900 
Compound Ib 100 
1000 
______________________________________ 
By adding 10% of the compound Ib the base receives a woody-cedarous note 
which usually can only be achieved by adding cedarwood oil. At the same 
time, the base becomes much more powerful, tangy, fresher and also drier. 
From the former feminine basic composition there is produced a base which 
is very well suited for mens colognes. 
(h) Perfumery base in the direction of tea 
______________________________________ 
Parts by weight 
______________________________________ 
Bergamotte oil 150 
Linalool 100 
Hydroxycitronellal 100 
Methyl dihydrojasmonate 
60 
Patchouli oil 40 
Basil oil 30 
Methyleugenol 20 
.beta.-Ionone 20 
Formiate oxyoctaline (3,4, 
10 
5,6,7,8,9,10-octahydro-1,2, 
8,10-tetramethyl-5-formoxy- 
naphthalene) 
Galaxolide .RTM. (1,3,4,6,7,8- 
10 
hexahydro-4,6,6,7,8,8-hexa- 
methyl-cyclopenta-.gamma.-2-benzo- 
pyran)IFF 
Bornyl acetate 10 
2,2,8-Trimethyl-7-nonen-3-ol 
10 
Tree moss absolute (colourless) 
10 
Lemon oil 10 
Vertofix .TM. 10 
Indole (10% in dipropyleneglycol) 
10 
Dipropyleneglycol 350 
950 
Compound Ic 50 
1000 
______________________________________ 
By adding 5% of the compound Ic the original base becomes much softer and 
powdery. Moreover, it now becomes flowery and pleasantly tangy, herby, and 
spicy.