Cyclohexane-, cyclohexene- and cyclohexadiene-, bicyclo (2.2.1)-heptenecarboxylic acid esters, and also perfume compositions and perfumed products which contain one or more of said compounds as perfume component

Perfume compositions containing at least one compound having the formula 1 ##STR1## wherein said compounds have the substituents as defined in claim 1. Perfumed compositions and perfumed products containing them are characterized by flowery, fruity, green and spicy odors, sometimes accompanied by a slight minty nuance with animal and/or wood notes in the after-odor.

The invention relates to isopropyl-substituted cyclohexane-, cyclohexene-, 
cyclohexadiene-, bicyclo[2.2.1]heptane- and 
bicyclo[2.2.1]heptenecarboxylic acid esters, to perfume compositions which 
contain one or more of said compounds as perfume component, and also to 
products perfumed with said compounds or compositions containing said 
compounds. 
There is a continuing interest in the use of synthetic fragrances in 
perfumes and products to be perfumed such as cosmetics, soaps, detergents, 
household products, etc. This interest is stimulated by the inadequate 
quantity and the varying quality of natural fragrances. 
Surprisingly, it has now been found that esters of isopropyl-substituted 
cyclohexane-, cyclohexene-, cyclohexadiene-, bicyclo[2.2.1]heptane-, and 
bicyclo[2.2.1]heptenecarboxylic acids having a structure according to the 
general formula 1 
##STR2## 
wherein X and Y each represent a hydrogen atom or X and Y together 
represents a methylene bridge, 
R represents an alkyl, alkenyl or cycloalkyl group containing 1-6 carbon 
atoms, and 
R.sub.1 -R.sub.4 each represent a hydrogen atom or a methyl group, with the 
proviso that 
if X and Y each represent a hydrogen atom, the following cases apply: 
if R.sub.1 represents a methyl group, R.sub.4 represents a methyl group and 
R.sub.2 and R.sub.3 represent a hydrogen atom; 
if R.sub.3 represents a methyl group, R.sub.1 and R.sub.4 both represent a 
hydrogen atom; and 
if neither R.sub.1 nor R.sub.3 represents a methyl group, R.sub.2 and 
R.sub.4 both represent, or one of the two represents, or neither of the 
two represents, a methyl group; and 
if X and Y together represent a methylene bridge, at most one of the 
symbols R.sub.1 -R.sub.4 represents a methyl group; 
the double dotted line represents a single or a double bond, in which case 
if X and Y and also R.sub.1 -R.sub.3 represent a hydrogen atom and R.sub.4 
represents a methyl group, the double dotted line together with a single 
dotted line, or two single dotted lines, may together represent a pair of 
conjugated double bonds, and 
if X and Y and also R.sub.1 -R.sub.3 represent a hydrogen atom, R.sub.4 may 
also represent a methylene group, in which case the double dotted line 
together with the dotted line directed towards R.sub.4 represent a pair of 
conjugated double bonds, 
are valuable fragrances with a powerful odour which persists for a long 
time. 
The fragrances according to the invention are characterized by flowery, 
fruity, green and spicy odours, sometimes accompanied by a slight minty 
nuance, with animal and/or woody notes in the after-odour. The preference 
is for the compounds in which either X and Y together form a methylene 
bridge, or X, Y, R.sub.1 and R.sub.3 are all a hydrogen atom, R.sub.4 is a 
methyl group and R.sub.2 represents a hydrogen atom or a methyl group. 
More particularly, the preference is for compounds in which R is an alkyl 
group containing 1-3 carbon atoms. 
Various alkyl esters of substituted cyclohexene- and 
cyclohexadienecarboxylic acids are known as fragrances. By far the 
majority of said compounds are characterized by the .alpha.,.alpha., 
.alpha.'-trimethyl substitution pattern known from, inter alia, saffronic 
and geranic acid. 
Esters of the last-named acids are described, inter alia, in the U.S. Pat. 
No. 4,144,199 and the European Patent Application No. 56,109, while 
related esters are described in the European Patent Application No. 
21,100. Similar esters in which one of the three methyl groups is replaced 
by an ethyl group are described in the U.S. Pat. Nos. 4,144,199 and 
4,113,663. From the abovementioned publications it emerges that the odours 
of said compounds sometimes exhibit similarities to each other, but are 
also very different in many cases. This is in agreement with the empirical 
fact that even small differences in chemical structure may result in large 
and unpredictable differences in olfactory properties. 
None of the abovementioned publications, however, reports anything relating 
to isopropyl-substituted cyclohexane-, cyclohexene- or 
cyclohexadienecarboxylic acid esters such as the compounds according to 
the present invention. 
Esters of some bicyclo[2.2.1]heptane- and heptenecarboxylic acids are also 
known as fragrances. Thus, the U.S. Pat. No. 4,319,036 reports that 
certain methyl- and dimethyl-substituted bicyclo[2.2.1]heptane- and 
heptenecarboxylic alkyl esters can be used as fragrances and flavourings. 
Esters of other methyl- and dimethylbicyclo[2.2.1]heptane- and 
heptenecarboxylic acids are described in the European Pat. No. 40,894 as 
fragrances with a strong odour reminiscent of coniferous wood. However, 
neither of the two publications reports anything relating to 
isopropyl-substituted bicycloheptane- or heptenecarboxylic acid esters 
such as the compounds according to the present invention. 
The Dutch Patent Application No. 76.05914 describes the fact that 
monoesters derived from methyl-, dimethyl- and 
isopropylbicyclo[2.2.1]heptane- and heptenecarboxylic acids and alkylene- 
or dialkylene glycols have a physiological cooling effect when they are 
brought into contact with internal or external surface tissues of the body 
(skin, mucous membranes). Said application, however, does not report 
anything relating to the odour or to possible fragrance properties of said 
compounds. 
The compounds according to the invention can be prepared by methods known 
per se for such compounds, for example by a Diels-Alder reaction of 
butadiene, isoprene, 1,3-pentadiene, 2,4-hexadiene, 
2-methyl-1,3-pentadiene, 2,3-dimethylbutadiene, cyclopentadiene or 
methylcyclopentadiene with 4-methyl-2-pentenoic acid or esters derived 
therefrom as dienophile. The products obtained from the acid can then be 
esterified in the usual manner. If trans-4-methyl-pentenoic acid or an 
ester derived therefrom is used as dienophile in the Diels-Alder reaction, 
as is indicated by way of example for the dienes 1,3-pentadiene and 
2-methyl-1,3-pentadiene in Reaction Scheme I, for cyclopentadiene in 
Reaction Scheme II and for methylcyclopentadiene in Reaction Scheme III, 
the isomers are then formed in which the isopropyl group and the ester 
group are situated in the trans-configuration with respect to each other 
on the ring system. Said isomers are indicated in Reaction Scheme I by 
cis-trans and trans-trans, depending on the position of the methyl group. 
In Reaction Scheme II, the two isomers are indicated by endo and exo, 
depending on the position of the isopropyl group and the ester group with 
respect to the methylene bridge. In the reaction shown in Reaction Scheme 
III, the starting point is a mixture of two methylcyclopentadienes. The 
reaction product is a mixture of isomers in which the methyl group takes 
up one of the four positions indicated by arrows. For each of these 
isomeric structures, however, it is again true that, as in Reaction Scheme 
II, it exists as an endo and an exo isomer. The mixtures of isomers 
described above may be separated partially and in some cases even 
completely by common separation techniques. This is not necessary, 
however, for application as a fragrance and the mixtures obtained can be 
used as such. The same applies to the use of said mixtures as starting 
substances for the former reactions shown in Reaction Scheme I, II and 
III. 
The hydrogenation can be carried out in the usual manner by means of 
H.sub.2 under the influence of known hydrogenation catalysts. 
The bromination and dehydrobromination shown in Reaction Scheme I can be 
carried out by methods known per se; the bromination by means of 
N-bromosuccinimide or a similar brominating agent, the dehydrobromination 
under the influence of a base. In this case, a mixture of the isomers 1c, 
1d and 1e is formed which, for the most part, consists of compound 1c 
(Reaction Scheme I). Here, too, no further separation of the isomers is 
necessary for application as a fragrance. 
##STR3## 
As already mentioned, the compounds according to the invention are valuable 
fragrances. In particular, the compounds 1a (Reaction Scheme I) and 2a 
(Reaction Scheme II) in which R is an alkyl group containing 1-3 carbon 
atoms are notable for a powerful odour which persists for a long time. 
These last-named compounds are new. 
The term "perfume composition" is in this case understood to mean a mixture 
of fragrances and optionally auxiliary substances, if desired dissolved in 
a suitable solvent or mixed with a pulverulant substrate, which mixture is 
used to impart a desired odour to the skin and/or products of all kinds. 
Examples of such products are: soaps, detergents, air fresheners, room 
sprays, pomanders, candles, cosmetics such as creams, ointments, toilet 
waters, pre- and aftershave lotions, talcum powders, hair-care agents, 
body deodorants and antiperspirants. 
Fragrances and fragrance mixtures which can be used in combination with the 
compounds according to the invention for the preparation of perfume 
compositions are, for example: natural products such as essential oils, 
absolutes, resinoids, resins, concretes etc., but also synthetic 
fragrances such as hydrocarbons, alcohols, aldehydes, ketones, ethers, 
acids, esters, acetals, ketals, nitriles etc., including saturated and 
unsaturated compounds, aliphatic, carbocyclic and heterocyclic compounds. 
Examples of fragrances which may be used in combination with the compounds 
according to the invention are: geraniol, geranyl acetate, linalool, 
linalyl acetate, tetrahydrolinalool, citronellol, citronellyl acetate, 
dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, 
terpinyl acetate, nopol, nopyl acetate, 2-phenylethanol, 2-phenylethyl 
acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl 
benzoate, styrallyl acetate, amyl salicylate, dimethylbenzylcarbinol, 
trichloromethylphenylcarbinyl acetate, p-tert-butylcyclohexyl acetate, 
isononyl acetate, vetiveryl acetate, vetiverol, 
.alpha.-hexylcinnamaldehyde, 2-methyl-3-(p-tert-butylphenyl)propanol, 
2-methyl-3-(p-isopropylphenyl)propanal, 3-(p-tert-butylphenyl)propanal, 
tricyclodecenyl acetate, tricyclodecenyl propionate, 
4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde, 
4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde, 
4-acetoxy-3-pentyltetrahydropyran, methyl dihydrojasmonate 
2-n-heptylcyclopentanone, 3-methyl-2-pentyl-2-cyclopentanone, decanal, 
dodecanal, 9-decen-1-ol, phenoxyethyl isobutyrate, phenylacetaldehyde 
dimethylacetal, phenylacetaldehyde diethylacetal, geranyl nitrile, 
citronellyl nitrile, cedryl acetate, 3-isocamphylcyclohexanol, cedryl 
methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliotropin, 
coumarin, eugenol, vanillin, diphenyl oxide, hydroxycintronellal, ionones, 
methylionones, isomethylionones, irones, cis-3-hexenol and esters thereof, 
indan musk fragrances, tetralin musk fragrances, isochroman musk 
fragrances, macrocyclic ketones, macrolactone musk fragrances, ethylene 
brassylate, aromatic nitromusk fragrances. 
Auxiliary substances and solvents which can be used in perfume compositions 
which contain compounds according to the invention are for example: 
ethanol, isopropanol, diethylene glycol monomethyl ether, dipropylene 
glycol, diethyl phthalate, triethyl citrate etc. 
The quantities in which the compounds according to the invention can be 
used in perfume compositions or products to be perfumed may vary within 
wide limits and depend, inter alia, on the nature of the product in which 
the fragrance is used, on the nature and the quantity of the other 
components in the perfume composition and on the odour effect which is 
intended. For this reason it is possible to specify only very rough limits 
which, however, provide those skilled in the art with sufficient 
information to be able to use the compounds according to the invention 
independently. In most cases a quantity of only 0.1% by weight in a 
perfume composition will already be sufficient to obtain a clearly 
perceptible odiferous effect. On the other hand, to achieve special 
odiferous effects, it is possible to use quantities of 50% by weight or 
even more in a composition. In products perfumed by means of perfume 
compositions, these concentrations are proportionately lower, depending on 
the quantity of composition used in the product.

The examples below serve solely to illustrate the preparation and use of 
the compounds according to the invention. The invention is, however, not 
limited thereto. 
EXAMPLE 1 
Preparation of ethyl 6-isopropyl-2-methyl-3-cyclohexene-1-carboxylate (1a, 
R=ethyl, R.sub.2 =H) 
A mixture of 70 g (0.61 mol) of trans-4-methyl-2-pentenoic acid and 49 g 
(0.72 mol) of 1,3-pentadiene was heated for 12 hours at approx. 
200.degree. C. in an autoclave. After the reaction mixture had cooled, it 
was checked by means of GLC for the presence of 4-methyl-2-pentenoic acid. 
A further 25 g (0.36 mol) of 1,3-pentadiene were added, after which the 
mixture was again heated for 12 hours at 200.degree. C. This procedure was 
repeated until no further decrease in the content of 4-methyl-2-pentenoic 
acid was any longer observed. The reaction mixture obtained was dissolved 
in 300 ml of ether and extracted with 300 ml of 10% NaOH solution. The 
alkaline solution thus obtained was acidified with 40 g of concentrated 
sulphuric acid and then extracted three times with ether. The ether 
extract was washed with water, dried on MgSO.sub.4, evaporated down and 
distilled. 73 g of 6-isopropyl-2-methyl-3-cyclohexene-1-carboxylic acid 
were obtained, b.p.: 95.degree.-100.degree. C./70 Pa. 
50 g (0.27 mol) of the abovementioned acid dissolved in 100 ml of 
dichloromethane were added in 45 min to a solution of 41 g (0.34 mol) of 
thionyl chloride in 100 ml of dichloromethane which was kept at 40.degree. 
C. during this process. The mixture was then stirred for 4 hours under 
reflux, evaporated down and the evaporation residue distilled. 52 g of 
acid chloride were obtained, b.p.: 80.degree. C./0.7 kPa. 
The acid chloride thus obtained was added dropwise to 46 g of ethanol, the 
temperature being kept below 5.degree. C. by cooling. The mixture was 
stirred for a further 30 min at this temperature, after which a solution 
of 0.26 mol of sodium ethylate in 100 ml of ethanol was added dropwise at 
the same temperature. The reaction mixture was then stirred for a further 
hour at room temperature, poured out into water and extracted 3 times with 
ether. The ether extract was washed once with water, dried on MgSO.sub.4 
and evaporated down. The evaporation residue was distilled, 54 g of the 
desired compound being obtained as a mixture of approx. 1 part of 
cis-trans isomer and 2 parts of trans-trans isomer, b.p.: 85.degree. 
C./0.7 kPa. 
The mixture of isomers was separated into the two components by 
fractionated distillation in a "spinning band" column. 
Cis-trans-ethyl 6-isopropyl-2-methyl-3-cyclohexene-1-carboxylate: b.p.: 
80.degree. C./0.4 kPa; NMR (100 MHz, dissolved in CCl.sub.4, .delta. in 
ppm with respect to TMS): 0.74 (3H, d, J=7 Hz); 0.8-1.0 (6H, d.d, J=7 Hz); 
1.24 (3H, t, J=7 Hz); 1.5-2.1 (5H); 2.48 (1H, m); 4.08 (2H, k, J=7 Hz); 
5.55 (2H). The comound has a fruity odour reminiscent of apple and 
somewhat rose-like with a woody note in the after-odour. 
Trans-trans-ethyl 6-isopropyl-2-methyl-3-cyclohexene-1-carboxylate: b.p.: 
75.degree. C./0.4 kPa; NMR: 0.82 (3H, d, J=7 Hz); 0.92 (3H, d, J=7 Hz); 
0.92 (3H, d, J=7 Hz); 1.25 (3H, t, J=7 Hz); 1.4-2.1 (5H); 2.43 (1H, m); 
4.10 (2H, m); 5.36 (1H, d with fine structure, J=10 Hz); 5.60 (1H, d with 
fine structure, J=10 Hz). 
The compound has a flowery odour reminiscent of rose and somewhat fruity, 
with spicy and balsamic notes in the after-odour. 
EXAMPLE 2 
Preparation of ethyl 2-isopropyl-6-methylcyclohexane-1-carboxylate (1b, 
R=ethyl, R.sub.2 =H) 
0.5 g of 5% palladium on charcoal as a catalyst was added to 10.5 g of 
ethyl 6-isopropyl-2-methyl-3-cyclohexene-1-carboxylate (mixture of isomers 
obtained according to Example 1) dissolved in 100 ml of ethanol, after 
which the mixture was hydrogenated at 20.degree. C. for 1 hour under a 
hydrogen pressure of 100 kPa. The catalyst was then filtered off, the 
filtrate evaporated down and the evaporation residue distilled. 9.4 g of 
the desired compound were obtained as a mixture of the cis-trans and the 
trans-trans isomer. b.p.: 96.degree.-97.degree. C./1 kPa; NMR (of the 
mixture): 0.7-1.0 (9H); 1.24 (3H, t); 1.0-2.5 (10H); 3.9-4.2 (2H). 
The mixture of isomers has a fruity and somewhat rose-like odour with a 
woody note in the after-odour. 
EXAMPLE 3 
Preparation of ethyl 6-isopropyl-2-methylcyclohexadiene-1-carboxylate (1c, 
1d and 1e, R=ethyl) 
A mixture of 10.5 g (0.05 mol) of ethyl 
6-isopropyl-2-methyl-3-cyclohexene-1-carboxylate (mixture of isomers 
obtained according to Example 1) and 9.8 g (0.055 mol) of 
N-bromosuccinimide dissolved in 75 ml of CCl.sub.4 was stirred for 3 hours 
under reflux. After cooling the reaction mixture was filtered and the 
filter cake was washed with some cold CCl.sub.4. The filtrate was 
evaporated down and the evaporation residue dissolved in 50 ml of 
dimethylformamide. 1.2 g of LiF and 3.4 g of Li.sub.2 CO.sub.3 were added 
to this solution and the mixture was heated at 120.degree. C. with 
continuous stirring for 1 hour. After cooling, 150 ml of water were added 
and the mixture was extracted 3 times with 50 ml of petroleum ether 
40`-60. The extract was washed with water, dried and evaporated down, 
after which the residue was distilled. 8.1 g were obtained of a mixture, 
60% of which consisted of the 2,4-cyclohexadiene isomer and the rest of 
the 1,3- and 2(exocyclic), 3-isomers of said compound. b.p.: 
85.degree.-88.degree. C./0.6 kPa; NMR (data of the 2,4-isomer): 0.87 (3H, 
d, J=7 Hz); 0.90 (3H, d, J=7 Hz); 1.24 (3H, t, J=7 Hz); 1.6 (1H, m); 1.77 
(3H, broad s); 2.54 (1H, m); 2.86 (1H, d, J=7 Hz); 4.07 (2H, k, J=7 Hz); 
5.3-5.9 (3H). 
The mixture of isomers has a spicy and fruity odour with flowery and woody 
notes. 
EXAMPLE 4 
Preparation of ethyl 2,4-dimethyl-6-isopropyl-3-cyclohexene-1-carboxylate 
(1a, R=ethyl, R.sub.2 =methyl) 
A mixture of 82 g (1.0 mol) of 2-methyl-1,3-pentadiene and 92.3 g (0.65 
mol) of ethyl trans-4-methyl-2-pentenoate was heated at 
175.degree.-185.degree. C. in an autoclave for 6 hours. After cooling, the 
reaction mixture was distilled. 57 g were obtained of the desired compound 
as a mixture of approx. 60% cis-trans- and 40% trans-trans-isomer. b.p.: 
90.degree.-91.degree. C./0.7 kPa, NMR (cis-trans-isomer): 0.75 (3H, d, J=7 
Hz); 0.8-1.0 (6H, d.d., J=7 Hz); 1.25 (3H, t, J=7 Hz); 1.64 (3H, broad s); 
1.5-2.6 (6H); 4.09 (2H, k, J=7 Hz); 5.30 (1H). NMR (trans-trans-isomer): 
0.8-1.0 (9H, 3xd, J=7 Hz); 1.27 (3H, t, J=7 Hz); 1.64 (3H, broad s); 
1.5-2.6 (6H); 4.13 (2H, m); 5.12 (1H). 
The mixture has a spicy and woody odour reminiscent of juniper berries. 
EXAMPLE 5 
Preparation of ethyl 3-isopropyl-5-bicyclo[2.2.1]heptene-2-carboxylate (2a, 
R=ethyl) 
A mixture of 75 g (0.53 mol) of ethyl trans-4-methyl-2-pentenoate and 40 g 
(0.30 mol) of cyclopentadiene dimer dissolved in 130 ml of benzene was 
heated for 6 hours at 175.degree. C. in an autoclave. After cooling, the 
reaction mixture was evaporated down and the evaporation residue 
distilled. 50 g were obtained of the desired compound as a mixture of 
approx. 25% endo- and 75% exo-isomer; b.p.: 85.degree.-87.degree. C./0.6 
kPa. The mixture has a fruity odour reminiscent of grapefruit with a spicy 
note and a woody note in the after-odour. 
The mixture was separated into the two components by fractionated 
distillation in a "spinning band" column. 
Endo ethyl 3-isopropyl-5-bicycloheptene-2-carboxylate: NMR: 0.7-1.0 (6H); 
1.20 (3H, t, J=7 Hz); 2.40 (1H); 3.03 (1H); 3.99 (2H, k, J=7 Hz); 5.8-6.2 
(2H). 
Exo ethyl 3-isopropyl-5-bicycloheptene-2-carboxylate: NMR: 0.7-1.0 (6H); 
1.24 (3H, t, J=7 Hz); 1.68 (2H); 1.95 (1H); 2.84 (2H); 4.07 (2H, k, J=7 
Hz); 6.08 (2H). 
EXAMPLE 6 
Preparation of methyl 3-isopropyl-5-bicyclo[2.2.1]heptene-2-carboxylate 
(2a, R=methyl) 
In the same manner as that described in Example 5, starting from 68 g of 
methyl 4-methyl-2-pentenoate and 40 g of cyclopentadiene dimer, 57 g were 
obtained of the desired compound as a mixture consisting of 25% endo- and 
75% exo-isomer; b.p.: 81.degree.-85.degree. C./0.7 kPa. The mixture has a 
woody-spicy and flowery odour with green and minty notes. 
EXAMPLE 7 
Preparation of ethyl 3-isopropylbicyclo[2.2.1]heptane-2-carboxylate (2b, 
R=ethyl) 
0.35 g of 5% palladium on charcoal as catalyst was added to 6.5 g of ethyl 
3-isopropyl-5-bicycloheptene-2-carboxylate (mixture of isomers obtained 
according to Example 5) dissolved in 30 ml of ethanol, after which the 
mixture was hydrogenated at 20.degree. C. for 1 hour under a hydrogen 
pressure of 100 kPa. The catalyst was then filtered off, the filtrate 
evaporated down and the evaporation residue distilled. 5.7 g were obtained 
of the desired compound as a mixture of endo- and exo-isomer. b.p.: 
89.degree. C./0.7 kPa; NMR (of the mixture): 0.7-1.0 (6H); 1.2 (3H, t); 
1.0-2.5 (11H); 3.9-4.2 (2H). 
The mixture has a fresh fruity and somewhat green odour with woody and 
slightly animal notes in the after-odour. 
EXAMPLE 8 
Preparation of ethyl 6-isopropyl-3-methyl- and 
6-isopropyl-4-methyl-3-cyclohexene-1-carboxylate 
A mixture of 68 g (1 mol) of isoprene and 92.3 g (0.65 mol) of ethyl 
trans-4-methyl-2-pentenoate was heated at approx. 175.degree. C. for 6 
hours in an autoclave. A further 1 mol of isoprene was then added and 
heated for 6 hours, and this procedure was repeated a further time. The 
reaction mixture obtained was distilled after cooling. 52 g were obtained 
of a mixture of the two abovementioned compounds, approx. 55% of which 
consists of the 4-methyl isomer and 45% of the 3-methyl isomer. b.p.: 
105.degree. C./0.7 kPa; NMR (both isomers): 0.83 (3H, d, J=7 Hz); 0.93 
(3H, d, J=7 Hz); 1.24 (3H, t, J=7 Hz); 1.64 (3H, broad s); 1.5-2.6 (7H); 
4.10 (2H, m); 5.30 (1H). 
The mixture has a fruity-flowery and woody odour with green and spicy 
notes. 
EXAMPLE 9 
Preparation of 3-methylbutyl 
3-isopropyl-5-bicyclo[2.2.1]heptene-2-carboxylate (2a, R=3-methylbut-1-yl) 
In the same manner as described in Example 5, starting from 60 g (0.33 mol) 
of 3-methylbut-1-yl trans-4-methyl-2-pentenoate and 25 g (0.185 mol) of 
cyclopentadiene dimer, 32 g were obtained of the desired compound as a 
mixture consisting of 35% endo- and 65% exo-isomer. b.p.: 
82.degree.-92.degree. C./35 Pa. NMR (endo-isomer): 0.7-1.1 (12H); 2.40 
(1H); 2.72 (1H); 3.05 (1H); 3.97 (2H, t, J=7 Hz); 5.8 -6.2 (2H). NMR 
(exo-isomer): 0.7-1.1 (12H); 1.95 (1H); 2.86 (2H); 4.05 (2H, t, J=7 Hz); 
6.1 (2H). 
The mixture has a woody-spicy and flowery odour with green and minty notes. 
EXAMPLE 10 
Preparation of allyl 3-isopropyl-5-bicyclo[2.2.1]heptene-2-carboxylate (2a, 
R=allyl) 
In the same manner as that described in Example 1, the desired compound was 
obtained by first preparing 
3-isopropyl-5-bicyclo[2.2.1]heptene-2-carboxylic acid (endoexo-mixture) 
starting from trans-4-methyl-2-pentenoic acid and cyclpentadiene dimer; 
b.p.: 105.degree. C./70 Pa. The acid chloride was then prepared by means 
of thionyl chloride and 12 g (0.06 mol) thereof were converted into the 
desired ester with 4 g (0.07 mol) of allyl alcohol. 13 g were obtained of 
a mixture, 30% of which consisted of endo-isomer and 70% of exo-isomer. 
b.p.: 91.degree.-93.degree. C./0.5 kPa. NMR (endo-isomer): 0.7-1.0 (6H); 
2.46 (1H); 2.70 (1H); 3.08 (1H); 4.4-4.6 (2H); 5.0-5.4 (2H); 5.6-6.1 (1H); 
5.8-6.2 (2H). NMR (exo-isomer): 0.7-1.0 (6H); 1.98 (1H); 2.88 (2H); 
4.4-4.6 (2H); 5.0-5.4 (2H); 5.6-6.1 (1H); 6.08 (2H). 
The mixture has an odour resembling orange blossom with light minty notes. 
EXAMPLE 11 
Preparation of ethyl 
3-isopropyl-methyl-5-bicyclo[2.2.1]heptene-2-carboxylate (3a, R=ethyl) 
A mixture of 75 g (0.53 mol) of ethyl trans-4-methyl-2-pentenoate and 48 g 
(0.30 mol) of methylcyclopentadiene dimer dissolved in 130 ml of benzene 
was heated at 175.degree. C. for 6 hours in an autoclave. After cooling, 
the reaction mixture was evaporated down and the evaporation residue 
distilled. 69 g were obtained of the desired compound as a mixture of the 
isomers 3a indicated in Reaction Scheme III. b.p.: 60.degree.-65.degree. 
C./13 Pa. NMR (of the mixture): 0.8-1.0 (6H); 1.2 (3H); 1.76 (3H, broad 
s); 4.0 (2H); 5.3-5.8 (1H). 
The mixture has a fruity and flowery odour with spicy notes. 
EXAMPLE 12 
A rose perfume for use in shower and bath foam preparations was prepared 
according to the recipe below: 
______________________________________ 
2-Phenylethanol 459 parts by weight 
Rose bath 002* 150 parts by weight 
Citronellol 100 parts by weight 
Geraniol 100 parts by weight 
.alpha.-Ionone 20 parts by weight 
Trichloromethylphenylcarbinyl 
20 parts by weight 
acetate 
Dimethylbenzylcarbinyl acetate 
20 parts by weight 
Linalool 15 parts by weight 
Benzyl acetate 10 parts by weight 
Clove oil 5 parts by weight 
4-Methyl-2-(2-methylpropen-1-yl)- 
1 part by weight 
tetrahydropyran 
Ethyl 6-isopropyl-2-methyl-3- 
100 parts by weight 
cyclohexene-1-carboxylate 
(mixture of isomers obtained according 
to Example 1) 
Total: 1,000 parts by weight 
______________________________________ 
*Perfume base marketed by Naarden International N.V. 
EXAMPLE 13 
A perfume composition of the fern type for use in aftershave lotion was 
prepared according to the following recipe: 
______________________________________ 
Lavandin oil 245 parts by weight 
Benzyl salicylate 200 parts by weight 
Dihydromyrcenol 150 parts by weight 
Patchouli oil 100 parts by weight 
Isolongifolanone 100 parts by weight 
Rosemary oil, French 
50 parts by weight 
5-Acetyl-3-isopropyl-1,1,2,6- 
50 parts by weight 
tetramethylindan 
Ethyl 2,4-dihydroxy-3,6- 
25 parts by weight 
dimethylbenzoate 
Armoise oil 15 parts by weight 
Geranium oil, Bourbon 
10 parts by weight 
2,4-Dimethylcyclohexene-3- 
5 parts by weight 
carbaldehyde 
Ethyl 3-isopropylmethyl-5- 
50 parts by weight 
bicyclo [2.2.1] heptene-2-carboxy- 
late (mixture of isomers obtained 
according to Example 11) 
Total: 1,000 parts by weight 
______________________________________ 
EXAMPLE 14 
An aftershave lotion perfumed with the composition according to Example 9 
was prepared according to the recipe below: 
______________________________________ 
A 0.3 part by weight of 1-menthol 
0.5 part by weight of Uvinol D 50.sup.1 
30.2 parts by weight of propylene glycol 
535 parts by weight of ethanol 
B 2.0 parts by weight of aluminium chlorohydrate 
allantoinate 
2.0 parts by weight of lactic acid 
400 parts by weight of distilled water 
C 20 parts by weight of perfume (Example 9) 
10 parts by weight of Cremophor RH 40.sup.2 
______________________________________ 
.sup.1 Trademark of BASF for 2,2',4,4tetrahydroxybenzophenone 
.sup.2 Trademark of BASF for a reaction product of hydrogenated castor oi 
and epoxy ethane. 
The components mentioned under A, B and C were separately mixed to form the 
mixtures A, B and C. Mixture B was then added to mixture A while stirring 
thoroughly. Mixture C was then added and the total homogenized by 
stirring. In this way, a somewhat astringent aftershave lotion was 
obtained with a pleasant fern odour. 
EXAMPLE 15 
A perfume composition of the flowery-spicy type was prepared according to 
the recipe below: 
______________________________________ 
Isononyl acetate 150 parts by weight 
Diethyl malonate 100 parts by weight 
2-Phenylethanol 100 parts by weight 
Methyl dihydrojasmonate 
100 parts by weight 
.beta.-Ionone 50 parts by weight 
Tricyclodecenyl acetate 
40 parts by weight 
Benzyl acetate 40 parts by weight 
Orange oil, Florida 40 parts by weight 
5-Phenyl-3-methylpentan-1-ol 
40 parts by weight 
.alpha.-Amyl-cinnamaldehyde 
30 parts by weight 
Terpinyl acetate 30 parts by weight 
4-Acetoxy-3-pentyltetrahydropyran 
30 parts by weight 
2,6-Dimethylhepten-5-al.sup.1 
25 parts by weight 
Ethyl pelargonate 20 parts by weight 
Nonadienal.sup.2 20 parts by weight 
Ethyl saffronate 10 parts by weight 
.alpha.-Damascone 5 parts by weight 
.alpha.-Allylionone 5 parts by weight 
Methyl nonen-2-oate 5 parts by weight 
Ethyl phenyl glycidate 
3 parts by weight 
.gamma.-Undecalactone 
2 parts by weight 
.gamma.-Decalactone 1 part by weight 
Ethyl 3-isopropyl-5-bicyclo- 
54 parts by weight 
[2.2.1] heptene-2-carboxylate 
(mixture of isomers obtained 
according to Example 5) 
Total: 900 parts by weight 
______________________________________ 
.sup.1 10% solution in dipropylene glycol. 
.sup.2 0.5% solution in dipropylene glycol. 
EXAMPLE 16 
A perfume composition for a men's cologne was prepared according to the 
following recipe: 
______________________________________ 
Bergamot oil 150 parts by weight 
Cedryl acetate 100 parts by weight 
Methyl dihydrojasmonate 
100 parts by weight 
Lavender oil French 75 parts by weight 
Acetyl cedrene 50 parts by weight 
Lavandin oil 50 parts by weight 
5-Acetyl-3-isopropyl-1,1,2,6- 
30 parts by weight 
tetramethylindan 
Rosemary oil Spanish 
30 parts by weight 
Benzyl salicylate 25 parts by weight 
11-Oxahexadecanolide 
20 parts by weight 
Coumarin 15 parts by weight 
Orange oil Florida 15 parts by weight 
Patchouli oil 10 parts by weight 
Eugenol 10 parts by weight 
Petitgrain oil 10 parts by weight 
3-Isocamphylcyclohexanol 
10 parts by weight 
Mousse de chene absolute 
10 parts by weight 
Geranium oil 10 parts by weight 
Coriander oil 10 parts by weight 
Labdanum absolute 5 parts by weight 
Pimento berry oil 5 parts by weight 
Clary sage oil 5 parts by weight 
Cardamom oil 3 parts by weight 
3-(p-tert-butylphenyl)-2- 
2 parts by weight 
methylpropanol 
Ethyl 2,4-dimethyl-6-isopropyl- 
50 parts by weight 
cyclohex-3-encarboxylate (mixture 
of isomers obtained according to 
Example 4) 
Total: 800 parts by weight 
______________________________________