CA1097689A - Cycloaliphatic saturated or unsaturated ketones as flavour and odour agents - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention provides cycloaliphatic unsaturated ketones, selected from a) damasc(en)one homologues having the general formula 10 wherein R stands for a hydrogen atom or a methyl radical and wherein the dotted lines represent one double bond in the posi-tions 1, 2 endocyclic or 2 exocyclic, or two conjugated double bonds in the positions 1 and 3, 2 endocyclic and 4, or 2 exo-cyclic and 3;
b) dihydrodamasc(en)ones having the general formulae 11 and 12 the dotted lines in the latter formula representing one double bond in the positions 1, 2 endocyclic or 2 exocyclic, or two conjugated double bonds in the positions 1 and 3, 2 endocyclic and 4 or 2 exocyclic and 3, and c) dehydroamascenones having the general formula 13

Description

This invention relates to novel chemical compounds and their use as flavour and odour agents. More specifically, this invell-tion rela~es to novel cycloaliphatic saturated or unsaturated ketones, wllicll are valuable food and tobacco flavour agents alld perfume odour agents.
Increasing attention is being devoted -to the preparation and utilization of artificial perfuming and odour-modifying agellts in perfumes and perfumed products, and of artificial flavouring and taste modifying agents in foodstuffs, beverages, pharmaceuticals, and tobacco. Tnis attention has been stimulated not onl~, because of the inadequate quantity of natural perfume and flavouring materials available, but, perhaps even more importantly, because of the neea for materials which can combine several natural nuances, will blend better wi-tn other perfuming or flavouring compositions, and will give perfumed or flavoured ~roducts which can be specifically tailored to a c~i~en use and because they can ~e duplicated at will. This latter factor confers a major advantage to artificial perfuming and food flavouring agents, since natural products, such as essential oils, extracts, concentrates, and the like are subject to wide variation-because of changes in the quality, type or treatment of the raw material.
It ïhas recently been shown that certain compounds structurally related to the ionones (formulae 1, 2 and 3) 1 ~ 3 ~ ~-ionone ~-ionone ~ionone 3~ play a lole in the flavour of raspberries, Burlev to~acco, coffee, tea, and apple, and in the odour of Bulgarian rose oil. The iaentification of these compounds "damascones" and "damascenones"

~k . .
. . : ., . - : .
.. . . : - - . ..

~76i~9 (formulae 4, 5 and 6) ~damascone ~-damascone ~-damascenone (after "Rosa damascena", the essential oil of which contains B~damascenone), is described in ~lelv. Chim. Acta 53 (1970) 541, id 54 (1971) 681, id 54 (1971) 1891, id 55 (1972) 1866, and id 56 (1973) 1503.
~-~amascone was found in tea.
B-Damascone is a constituent of Burley tobacco and of tea.
~-Damascenone is a component of Bulgarian rose oil, Burley to~acco, Greek tobacco, deer tongue, coffee, tea, apple and raspberry.
These three compounds are the subject of British Patent Specification 1,240,309. In flavour compositions they develop fruity, herblike, winy, woody, floral or waxy flavour notes. Tlley can be used in e.g. berry flavour compositions, wines, ~everages and tobacco products. According to this Patent Specification they also can be used in perfume compositions of the floral type.
In British Patent Specification 1,305,621 some analogues of ~- and B-damascones and of ~-damascenone are described as ; flavour and fragrant materials. Their flavouring properties are disclosed in exactly the same words as for the ~- and B-damascones and B-damascenone (compare BP 1,240,309, page 1, lines 57-70 and BP 1,305,621 page 12, lines 27-32. Compare also: BP 1,240,309 with BP 1,305,621 examples 27 and 28 example 1 id example 2 id 29 id 3 and 4 id 30 id 6 id 36).
In Dutch Patent Application 72,11248 some other analogues are descrihed. In this application the inventors state that the organolep-tic properties of the new compounds show major difference in comparison with the known ~- and ~-damascones, ~-damascenone and the cornpounds listed in British Patent 1,305,621. This is righ-tfully explained ~y the unpredic-tability of organoleptic properties in relation to chemical structures. From the examples in this patent application it becomes clear that the differences in organoleptic properties do not show or give only minor de-viations in the use of the compounds in perfume and flavour compositions, compare British patent 1,305,621 example 36 versus Dutch Patent Application 72,11248 example XVII, and also compare British patent 1,305,621 example 30 versus Dutch Patent Application 72,11248 example XV.
The preparation and use of the damascones, damascenones - and some other analogues is described in sritish patent specifica-tions 1,240,309, 1,305,621, 1,33~,339,1,336,08&alld inDutch pat~
applicatiorlsl2,11248, 72~11893,72.12426, 73.~145i,73,04364alld 73.043~5 The same and some other ways for the preparation of the damascones and damascenones are described in Helv. Chim. Acta -`
53 (1970) 531, id 53 (1970) 541, id 54 (1971~ 1767, id 54 (1971) 1805, id S4 (1971) 1899, id 56 (1973) 310, id 56 (1973) 1503, id 56 (i973) 1514, J. Am. Chem. Soc. 94 (1972) 9128, Tetrahedron ~et-ters (1973) 381, J. Chem. Soc., Chem. Comm. (1973~ 161 and in id (1973) 742.
In the J. Chem. Soc., Chem. Comm. (1973) 161 the odour o~
the two compounds having formulae 7 and 8 is descri~ed as characteristic mangolike:

a7ç~

The odor an~ taste of the cor,lpound with formula ~ has been ~escribe~ in Dutch ~atent application 73.1442~ as fresh fruity, without any woody note and -totally different from the analocJous, ring unsaturated compounds ~' Object of the invention is ~o provide novel compounds which impart a fruity flavour note to foodstuffs and tobacco products and a pleasant roselike, fruity, herbal, spicy, minty, woody floral oclour to perfumes as well as to foodstuffs.
The invention relates to cycloaliphatic saturated or unsaturated ~etones, whieh may be a) damasc(en)one homologues having the general formula 10 ?~ ,.
R
~herein R stands for a hydrogen atom or a methyl radieal and wherein -the dotted linès .represent one double bond in the positions 1~ 2 endocyclic or 2 exocylic, or two con~ugated double bonds in the positions 1 and 3, 2 endoc~clie and 4, or 2 exocyclie and 3; b) di~ and tetrahydrodamase(en)one homologues having the : general formulae 11 and 12 ~ ~f the dotted lines in the latter formula representing one double bond in the positions 1, 2 endoxyelie or 2 e~oeyelie, or two ~ - 5 ~

7~9 conjucJated dou]~le bonds in tne pQsitions 1 and 3~ 2 endocyclic and 4 or 2 exocyclic and 3; and c) dehydrodamascenone homolQgues having the seneral ~ormula 13 \/

~herein the dotted lines represent two conjuyated dou~le bonds in the positions 1 and 3 2 endocyclic and 4 or 2 exocyclic and 3.
For simplicating in referring to the various compounds of tnïs invention~ in analogy to the known ionones damascones and damascenones, the following nomenclature is used throughout this specification; compounds containing the skeleton:
a-compounds ~-compounds ~-compounds 14 = ~-compounds 15 = ~-compounds and 16 = ycompounds ~i co~ounds containing a double bond in positions 2 endocyclic.
~: compounds containing a double bond in the position y: compounds comtaining a double bond in position 2 exocyclic.
Specific compounds comprised by formula 10 in which R is hydrogen are.
lecrotonoyl-2 ethyl-6 ~dimethyl-l-cyclohexene; (17) l-crotonoyl-2-ethyl-6~6-dimethyl-2 cyclohexene; (18) l-crotonoyl-2-ethylindene-6.6-dimethylcyclohexane; (19 and 20) l-crotonoyl-2~ethyl-6.6-dimethyl-1.3 cyclohexadiene; (21) , l~crotonoyl~2-ethyl~6.6-dimethyl~2~4 cyclohexadiene; (22) l~crotonoyl-2-ethylidene~6.6~dimethyl~3-cyclohexene; (23 and 24 and in which is R = CH3 are l~crotonoyl~2~propyl~6.6~dimethyl~1 cyclohexene; (25) ; l~crotonQyle2~propyl 6.6 dimethyl~2~cyclohexene; (26) .. . .

~ 6 ~

,., l~crotonoyl-2~propylidene~6.6~di~ethxlcyclo}lexane; (27 and 28) l-crotonoyl~2 propyl~6.6~imethyl~1 3~cyclohexadiene~ (29) l~crotonoyl~2~propyl~6.6~dimethyl~2,4-cyclohexadiene; (30) l~crotonoyl~.2.propy]idene~.6,6~dimethyl~3~cyclohexene (31 and 32) 10 ~ ~ Z- ~ E- y f~ ~` ~' a Z- ~( E-O
. 25 26 27 28 ~ Z~

29 3 31 32 ~.
~ a Z- ~ E-~, 6~
S~ecific com-pounds co~rised by formulae 11 and 12 are:
1-butanoyl-2-eth~ 6 6~.dimet'nyl-cycloilexane (11) 1-bu-tanoy]-2-etllyl-6.6-dimetllyl-1 cyclohexene (33) l-butano,l-2-etilyl-6.6-dimetllyl-2-c~clohexene (34) l-butanoyl-2-et~lylidine--6.6-dimethylcyclollexane (35 and 36) l-butanoyl--2-et~lyl-6.6-dimetllyl-1.3-cyclollexadiene (37) l-butAnoyl-2-ethyl-6.6-dimethyl-2.4-cyclohexadielle (38) 1 butanoyl-2-ethvlidine-6.6~dimethyl-3-cyclohexene (39 and 40) 33 ~ 34 a 35 Z -Y 36 E -Y

O O O

37 ~ 38 a . 39 Z - Y 40 E -Y
. Specific compounds comprised by formula 13 are:
l--but-2'~ynoyl-2-ethyl-6.6-dimethyl-1.3-cyclohexadiene (41) l-but-2'-,novl 2-eth~ 6.6-dimetllyl-2.4-cyclohexadiene (42) l-but-2'-ynoi~l-2-eth~lidene-6.6-dimethyl-3-cyclo11exene (43 and 44) o O O O

41~ 42~ 43Z-y 44E-y ;~ - 8 -~97~

The novel ketones of this invention possess unique organoleptic qualitites, ma]cing them useful as flavouring agents where fruity effects are desired, and in perfumery, especially in flower perfume compositions -to which they will impart a fresi natural -topnote.
In ~eneral -the ketones oE this invention may be prepared by a variety of processes, analogous to the preparations of the damascones and damascenones, which are given in the literature cited a~ove. Some possibilities are given below and in the examples, but to tllose skilled in the art it will be clear that other metllods to synthesize the ketones of this invention can be deduced from the cited references.
In reaction sc~emeA two possible pathways for preparing tlle damascone and damascenone homologues of this invention are given starting from methyl butenol (A-]) via a citral homologue (A-3). Examples for these reactions can be found in Dutcll patent applications numbers: 64.09113 (A-l-~ A-3~ A-5), 72.11248 (A-3 A-4~ A-6), 73.04364 (A-5-~ A-6),and 68.15985 (A-6~ A-7) Also examples of tlle reactions of scheme A can be found :in the cited journal references, ~ut nowhere the compounds of this invention are mentioned.
REACTION SC~IEME A

ON R-CII~-C-c~l2-c-oc2H5 ~ ~ ~ CHO

) -') 3) citral--derivative l)cyc.lisa~io~

2)oxidation X , COOH

A ~ CE10 ~ c~clo-geranic acid l)C~i3COCH3/0ll 0 der. r ~ R ~ ry~li3~

3) citral-derivative ~ R
5)ionone-derivative.

". ~, _ g ., \ / 11 o 6)damascone-derivative , and~) 7)damascenone derivative ~ and y) In reaction scheme B tile ketones of this invention are prepared startillg from mesityl oxide. The other reactions of scheme B are illustrated in examples 7 to 11.
REACTION SCHEME B
O o ~ R-CH2-C-CH2-C OC2 5~ ~ OOC H l)reduction ~ OOC2 5 1) 2) 3) Ethy.1 safranate derivative ~ , and y) B l~Li-Ch -C~=CH, H
2)KOt.Bu - ~ ~ 2 / 4)damascenone C2-1~5 ~ l)Li-CH - ~
\ C~3~H2 ¦ 6)damascone 3~Ethyl safranate\ HQ ~x~ COOC2H 2 ~ derivative 30 derivative ~ R 5 (~9~ and~) , andy ) ~
5)cyclo-geranic ester derivative (pre-dominantly C~) . ' I~ will be clear that for the synthesis of compound B-5 from compound B-2 a shorter way is avallable. This is illustrated in reaction scheme C.
~E~CTION 'CHEME C

COOC2H5 ~ CO 2 5 ~ Wolff-Kisilner reduction~

.~ ' ~ referred reaction pathways for preparing tile di~-drodamascone and dihydrodamascenone deriyatiyes start ~7ith the corresponding side~chain unsaturated ketones. Reduction with lithium aluminium- or sodium boroh~dride converts them to the compounds with general formula 12. ll may be prepared from 12 by catal~-tic reduction with l~2/platinumoxide (reaction scheme D and E).

REACTION`SCilEME D

~ N~ ~ 2 O =

d~mascone (~3,~4,~5,36) (11) derivative (a ~ ) (predomin~
antly a) REACTION SCHEME E
O C~
; ~ 1). ~iAlH4 or ~aBH
2) KO t Bu ~

damascenone ~ (37,38,39~40 derivative : (predomin~
,~ 2Q antly y) The dehydrodamascenone derivatives may be prepared ~y a variety of processes, analogous to the preparations of the da-mascenones, which are given in the literature cited above. One .possibility is given in Reaction scheme F and in example 15.
; -REACTION SCHEME F
., .~,COOC2H5 1 ) KOH/butanol ~ Cl 1 ) ~iC~CCH3 ~ ~ _ 2 ) SOC12 ~ 2 ) KO t . Bu 1~
'. ethyl- . safranoyl- ~ ~ 41~42,43,~4 ; safranate chloride (a, ~ and y) derivative derivative .: 30 (al~ and~) ~,~ and ....
:~;

,...

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As already mentioned the cQmpounds of the invention have been found to possess very useful organoleptic properties.
Although there are mlnor differences in the flavour and fragrance character of the~ and~ i~omers of the damascone and damascenone derivatives it is not always necessary to separate them, because the mixture of isomers obtained by the processes given in the examples can be used as such for the purposes of this invention. The following odour descriptions, drafted by skilled perfumers and flavourists, are illustrative for the small mutual deviations in the odour characteristics of the isomers.
- Mixture of l-crotonoyl-2-ethyl-6.6-dimethyl-l; 3-cyclohexadiene (21) l-crotonoyl-2-ethyl--6.6-dimethyl-2.4-cyclohexadiene (22) and l-crotonoyl-2-ethylidene-6.6-dimethyl-3-cyclohexene (23 and 24) (= reaction product o~ Example 9):
Tihe main odour impression of this mixture can be described as fruity, but also observable are distinct woody, tobacco-like, and hay-like notes. The fruity character is best described as apple-like; the hay-like character can be defined as "flouve absolute"
and "clary sage".
l-~rotonoyl-2-ethyl-6.6-dimetilyl-2.4-cyclollexaalelle(22):
Tlle woody character is more pronounced than in the mixture, the fruity, hay-like and tobacco notes are weaker, but a great similarity with the mixture does exist.

76~39 - l-Crotonoyl-2-ethyl-6.6-dimethyl-1.3-cyclohexadiene (21);
The tobacco-like character and the impression of the odour of hay is somewhat stronger, the fruity, herbal notes are a little less pronounced than in tlle mixture.
- l-Crotonoyl-2-ethylidene-6.6-dimethyl--3-cyclollexene (23 and 24):
These risomers are more fruity, apple-like than the mixture, or the ~- or ~-isomers. The woody, tobacco and hay-like notes are less pronounced. But once again it is clear that the difference in odour with the mixture or the other isomers is small.

- ~ixture of l-crotonoyl-2-ethyl-6.6-dimethyl-1-cyclollexene (17), l-crotonoyl-2-ethyl-6.6-dimethyl-2-cyclohexane (18) and , ~ - 12a -l-crotonoyl-2-ethylidene-6.6-dimethylcyclohexene (19, 20) (= reaction product of example 8):
The main odour impression of this mixture is characterised as vegetab]e-spicy, with reminiscences of lavender, rosemary, spil~e and la~rel. ~ distinct roselike-minty and fruity (apple-like) note can be observed.
- l-Crotonoyl-2-ethyl-6.6-dimethyl-2-cyclohexene (18):
The rose-like/minty character, best described as "geranium", is somewhat more pronounced than in the mixture, the spicy character is a little weaker.
- l-Crotonoyl-2-ethyl-6.6-dimethyl-1-cyclohexene (17):
This isomer has a more pronounced herbal/spicy character (lavender, rosemary, spike, laurel) and a less fruity odour than the ~-isomer.
- l-Crotonoyl-2-ethylidene-6.6-dimethylcyclohexane (19 and 20, mixture of cis-trans isomers):
These isomers possess a more fruity character (appie-prune-, apricot-li~.e) than the mixture, the rose/minty and herbal notes are less, but a great similarity in odour impression with the mixture does exist.
- Mixture of l-crotonoyl-2-propyl-6.6-dimethyl-1.3-cyclohexadiene (29), l-crotonoyl-2-propyl-6.6-dimethyl~2.~-cyclohexadiene (30) and l-crotonoyl-2-propylidene-6.6-dimethyl-3-cyclohexene (31 and 32) (= reaction product of example 11).
This mixture sho~s a great similarity in odour with the ethyl analogues (21-24), the intensity is a little lower. In perfume application a higher dose has to be used. The odour character can be described as fruity, with distinct woody-, tobacco- and hay-like undertones.
- Mixture of l-crotonoyl-2-propyl-6.6-dimethyl-1-cyclohexene (25), ;~

7 ~ ~ ~
l-crotonoyl~2-propyl-6.6-dimethyl-2-cyclollexene (26) and l-crotonoyl-2-~ro~ylidene-6.6-dimethylcyclohexane (27 and 28) (= reaction produet of example 10):
The odour similarity with the ethyl analogues (21-24) is stri]cin~, but the odour intensity is smaller. The main odour characteristics are: herbal and spicy (lavender, rosemary, spike, and laurel), but also di$tinct fruity and rose/minty notes are observable.
For the dihydrodamascone and dihydrodamascenone derivatives the differences in flavour and fragranee charaeter between the ~, ~, andy isomers is even smaller than between the ~,~ , and yisomers of the corresponding side chaln unsaturated analogues. Consequently there is no need to separate the mixture of isomers obtained by the processes glven ln the examples, although lt ean be done by preparatlve G.L.C.
The followlng odour descrlptlons drafted by skllled perfumers and flavourists apply to the dl- and tetra-hydrode-rivatives:
l-butanoyl-2-ethyl-6.6-dimethylcyclohexane (11):
The main odour impression can be deserlbed as frulty-minty wlth distinct spicy, woody and roselike notes.

l-butanoyl-2-ethyl-6.6-dimethyl-1-eyelohexene (33), 1 butano~l-2-ethvl-6.6-dimetilyl-2-cyclohexene (34) and l~-butanoyl-2-ethyl-6.6-dimethyleyelohexane (35 and 36).
The main odour impression ean be descrlbed as frulty-spley witll dlstinet herbal and roseli]~e l-butanoyl-2-ethyl-6.6-dlmethyl-1.3-cyclohexadiene (37), 1-butanoyl-2-ethyl-6.6-dimethyl-2.4-eyelohexadiene (38) - l-butanoyl-2-ethylidene-6.6-dimethyl-3-eyelohexene (39 and 40).
The main odour lmpresslon is eharaeterized as frulty-floral with woody and mlnty notes.
As already mentioned, small differenees in ehemieal strueture often ereate big and unpredletable differenees ln odour , ~ - 14 `

7~

and flavour pro~erties. This is strikingly demonstrated by l-crotonoyl-2-ethyl-6.6~dimethylcyclohexane (compound 45), which was also synthesised.

o ~\~

This compound has an offensive odour, reminding of wormseedoil.
In this respect it differs considerably, not only from the com-pounds of this invention, but also from 1-crotonoyl-2.6.6-tri-methylcyclo-hexane (9). In view of all this it is remarkable that both the damasc(en)one and dihydrodamasc(en)one derivatives have a more or less pronounced fruity odour and flavour character in common.
For all practical purposes the ~, ~ and ~ isomers of the dehydrodamascenone have the same flavour and fragrance character. Consequently there is no need to separate the mixture of isomers obtained by the process yiven in example 15, although it can be done by preparative G.L.C. The odour impression of the dehydrodamascenone derivatives as judged by s~illed perfumers and flavorists, can be described as sweet frui~y and herbal with a slight minty noteO
The odour characteristics may give some general hints on the usefulness of the compounds of this invention. However, the compounds will nearly always be used in combination with other flavour and fragrance materials. One can by no means predict whether a compound with a well-defined odour will behave satis-factorily in perfume or flavour compositions. Furthermore, the mere possession of an odour is not sufficient for a compound to be useful as a perfume or flavour--ingredient. Some of the other re~uirements are:
- com~atability with other perfume and flavour materials and with ~ 15 -, .

7~

-the substrate to be perfumed or flavoured;
- flavourable toxicological and dermatological properties;
- the power to ~ive complicated perfume or ~lavour compositions a general character or a specific note as conceived by a skilled ~erEumer or flavourist.
The compounds of this invention fulfil these requirements.
As will be understood by -those skilled in the use of flavouring materials and perfume agents, it is not possible nor feasible to give specific instructions for the use of the un-saturated cycloaliphatic ketones of this invention in such arts,as there are too many factors which govern the amounts of materials to be usecl. Among such factors are the personal preference of the fLavour expert or perfumer, the cost of materials, the nature of the particular composition, the flavour or odour effect to be achieved, etc. Nonetheless, it will be readily apparent to experts how to employ the ketones of this invention in particular situations.
Perfumery compositions containing the ketones of this invention may find use in a wide variety of perfumed materials.
For exampl~, such compositions may be used in soap, detergent, or deodorant compositions, in cosmetic preparations such as cologne waters, toilet waters, face creams, body lotions, talcum powders, sun cream preparations and shave lotions. Flavour compositions containing ketones of this invention may find use in the flavouring of foodstuffs, beverages, pharmaceuticals or tobacco. The ketones may be used as such to improve the flavour of beverages such as fruit juices.
In the following examples, the invention is illustrated in a more detailed manner. All quantities in the Examples 1-6 are expressed on a weight basis unless otherwise stated. The Examples are not to be considered as necessarily constitutin~ a limitation on the present invention.

.

~¢97~

EXI~IPLE 1 _ , , , , ~, Perfume compositions of the rose-~type Two perfume compositions of the rose type were prepared by mixiny the following ingredients:
Component Composition A s Cinnamic alcohol 30 20 Tricllloromethyl pllenyl car~inyl acetate 5 10 Phenyl ethylalcohol 425 450 Geraniol 80 Citronellol 100 100 Nerol 50 60 Phenylacetaldellyde dimethylacetal 20 30 Eugenol 10% sol (1~ 10 15 Gyrane (N)2) 30 25 Phenylethyl propionate 60 60 Phenylethyl methyl ethyl carbinol 30 25 Rose oxide 10% sol. (1) 20 15 Methylionone y 5 10 Geranium oil Bourbon 25 5 Geranyl acetate 30 10 Rosana NB 131 (3) 50 35 Ylang Ylang oil I 5 -~
Linalool 20 10 Dimeth-yl benzyl carbinyl acetate ~ 15 Rhodinol - 100 1) In diethyl phthalate.
- 2) Fragrance material, available from Naarden International.
3) Rose base, available from Naarden International.

A, By adding to 99.5 g of basis composition A 0.5 g of a 1% solution in diethyl phthalate of tlle damascenone homologue of example 9 a distinct increase in radiancy is o~served. The ~ .,3~j 7~

composition becomes ~ore full bodied with a very natural and well balanced character.
B. sy adding to 99.5 g of basic composition s 0~5g of a 1% solution in diethylphthalate of the damascone homologue of ~xample 8 the composition gets a very natural character. There is a substantial increase in brillancy and the compositions gave a more full and rich impression.
sy addity to 99.5 g of the basic composition 0.5 g of a 1% solution in diethylphthalate of the mixture of example 15 the composition gets a very natural and well balanced character with a substantial increase in brilliancy.

Perfume compositions of the lavender-type Three perfume compositions of the lavender-type were prepared by mixing the following ingredients:
Component Composition A B C
Coumarine 20 10 15 Musk ketone 5 5 5 Linalool 120 150 130 Terpineol 20 10 40 Linalyl acetate 80 90 70 Rosemary oil French 70 80 60 Lavender oil French480 400 420 Clary sage oil 30 40 10 Neolavandate N 1) 30 40 Gexanium oil 5 - -Bergamot oil 60 70 100 Lemon oil 30 , 40 50 Spike oil 20 - 10 Coriander oil 5 - 5 ,j Basil oil 5 - 5 v ~ 18 . A

~ 7 ~

Component Composition A B C
Cedar leaf oil 10 - -Patchouly oil 5 20 10 Bois de Rose oil - 15 20 Dalmation Sa~e oil - 5 5 Estragon oil ~ 5 Musk R 1 )10% solution ) - 10 20 Eugenol 10% solution 2) _ 5 10 Vetiver oil ~ 5 1) Fra~rance material, available from Naarden International N.V.
~) In diethyl plltllalate.
A. Adding 0.5 g of a 1% solution in diethyl plltllalate of l-crotonoyl-2--ethyl-6.~-dimethyl-2-cyclohexene (Formula 18) to 99.5 g of basic composition A results in a more brilliant, full ~odied and true to nature cornposition.
Bl. Adding 0.5 g of a 1% solution in diethyl phthalate of l-crotonoyl-2-ethylidene-6.G-dimethylcyclohexane (mixture of cis and trans isomers, formulae 19 and 20) to 99.5 g of basic composition B gives a composition with a greatly improved odour.
The stronger radiancy gives the composition a very natural richness.
B2. ~dding 0.5 g of a 1% solution in diethylphthalate o the mixture of example 15 to 99.5 g of the basic composition giv~s a com~osition with a greatl~ improved odour. The stronger radiancy gives the composition a very natural richness.
Cl. By adding 1,0 of a 1% solution in diethylphthalate Gf l~crotonoyl-2-propyl-6.6-dimethyl-2-cyclohexene (Formula 23) to 99.0 g of basic composition C this composition gets a very natural note. There is a distinct increase in brilliance and the composition becomes fuller, richer and warmer.
C2. By adding 1.0 g of a 1% solution in diethylph-thalate ~7' ~ 1 9 7~B9 of one of the following compounds: (or a mixture of -them) to the basic composition C, l-butanoyl-2-ethyl-6.6-dimethyl~ cyclohexene (formula 33);
l-butanoyl-2-ethyl-6.6-dimethyl-2-cyclohexene (formula 34);
l-butanoyl-2-etllylidene-6.6-dimetilylcyclohexane (formula 35 and 36), -to 99.0 g of -the basic composi-tion this composition gets a very natural note. There is a distinct increase in brilliance and the composition becomes fuller, richer and warmer.

Perfume compositions of the c'nypre-type Three perfume compositions of the chypre type were pre-pared by mixing the following ingredients:
Component Composition A B C
Musk ketone 20 10 15 ~leliotropine 5 - 5 Benzyl alcollol 60 30 50 Oakmoss absolute 10% sol. 1) 20 40 30 Cistus absolute 10% sol. 1) 25 10 15 -Opopanax resinoid 10 5 5 Benzoin resinoid 20 25 15 Styrax resinoid 5 5 Vanilla resinoid 5 5 5 ~henyl ethyl alcohol 70 90 120 ~eraniol 50 30 40 ~-Hexyl cinnamicaldehyde 40 30 20 Benzyl acetate 20 30 10 Methyl ionone ~ 30 20 10 , 30 Clove bud oil 10 15 5 Patchouly oil 20 25 30 Sandalwood oil 20 25 40 7~g Component Composition A B C
Vetiver oil 10 15 20 ~Iydroxy citronellal 60 40 50 Neroli oil 10 20 5 Bergamot oil 90 100 125 Lemon oil 40 50 40 Mandarin oil 5 - -Geranium oil 10 5 Vanilline 1% soll) 15 20 5 Anthralal N ) 10% sol )5 10 15 Cassie absolute 10 15 20 Indole 10% sol. ) 10 15 20 Tetradecanal 1%sol. ) 10 15 5 Civet absolute 10% sol. 1) 30 40_ 30 Ambra tincture 3% sol. ) - 40 20 30 Musk Rl ) 10% sol. 13 20 30 30 Ylang-Ylang oil "Extra" - 5 5 Cardamom oil - 5 Hexadecanal 1% sol. ) - 5 Flouve absolute 10% sol. ) - - 10 Ginger oil 10% 501. 1) - - 5 Costus oil 1% sol. ) - - 10 1) In diethyl phthalate 2) Fragrance material, available from Naarden International N.V.
3) In 9G% ethanol.
A. Adding 0. 5 g of a 1% solution in diethyl phtllalate of 1-crotonoyl-2-ethyl-6.6 dimethyl-1.3-cyclollexandiene (Formula ', 21) to 79.5 g of basic composition results in a composition with an improved diffusion and strength. The composition gets more body, .,, ~/1 - 21 -7~

and is fuller and richer in odour.
Bl. sy adding 0~5 g of a 1~ solution in diethyl phthalate of a cis/trans mixture of l-crotonoyl 2-ethylidene--6.6-dimetllyl-3-cyclohexane (For~ulae 23 and 24) to 80.5 g of basic composition B gives a composition with a richer charac-ter. The odour is im~roved with a very natural note and there is a dis-tinct increase in brilliancy.
B2. By addiny 1.5 g of a 1% solution in dietnyl-phthalate of one of the following components (or a mixture of them):
l-butanoyl-2-ethyl-6.6 dimethyl-1.3-cyclohexadiene (37);
l-butanoyl-2-ethyl-6.6-dimethyl-2.4-cyclohexadiene (38);
l-butanoyl-2-ethylidene-6.6-dimethyl-3-cyclohexene (39 and 40) --to ~0.5 g of basic composition B gives a composition with a richer character. The odour is improved with a very natural note and there is a distinct increase in brilliancy.
Cl. By adding 1.0 g of a solution in dietilyl phtilalate of a cis/trans mixture of l-crotonoyl-2-propylidene--6.6--dimetl 3~cyclohexene (31 and 32) to 84.0 y of basic composition C the odour of the composition gains in originality. The radiance is increased, the cllaracter becomes fuller and richer, and the increase in odour-strength is suhstantial.
C2. By adding 2.0 g of a 1% solution in diethyl phthalate of l-butanoyl-2-ethyl-6.6-dimetllyl cyclohexane (11) to 84.0 g of hasic composition C the odour of the composition gains in ori-ginality. The radiance is increased, the character becomes fuller and r~cher, and the increase in odour strength is sub-stant'~l.
EXAMPI.E 4 Preparation oE an imitat~on raspberry flavour compos _ion An imitation raspberry flavour composition was prepared ~y mixiny the following ingredients:

~ 76 ~

ComponelltParts bv weight Geraniol 20 Vanilline 20 Phenyl etllylalcohol 50 Maltol 20 p~ droxy benzyl acetone 50 Methyl ionone 100 Ionone 100 Benzyl acetate 100 Isobutyl acetate 100 Ethyl acetate 100 Amyl acetate 100 Two raspberry flavoured ~everages were prepared.
A. 50 g of the basic composition were dissolved in 950g of ethanol 96%. From this solution a carbonated beverage was made using 1 ml of the etllanolic solution for each litre of finished ~ beverage.
; B~ 50 g of the basic composition and 2 g of a 0.1%
solutioin in ethanol of the mixture of damascenone llomologues 2~ o~tained in example 9 ~ere dissolved in 948 g of ethanol 96~.
In a ~air test six trained flavourists concluded that beverage B
had a more pronounced natural raspberry-like flavour than beverage ~ A.
,~ ~ EX~MPLE 5 Flavouring of a raspberry~syrup In 1000 ml of sugar syrup 30~ were dissolved 8 g of a natural raspberry concentrate. Six modifications of this basic syrup were made:
, A. by adding 10 ppm of a mixture of cis/trans isomers r 3~ of 1-crotonoyl-2-ethylidene-~.6-dimethyl-3-cyclohexene (formulae 23 and 24) to the basic syrup, and B. by adding 0.05 ppm 1-crotonoyl-2-ethyl-6.6-dimeth~

: , .
., .

:~97'~B~53 2-cyclohexene (~ormula 1~) to the basic syrup.
C. by adding 20 ppm of the mixture of isomers obtained in example 13 (37, 38, 39, 40) to the basic syrup, and D. by addins 0.1 ppm of the mixture of isomers obtained in example 12 (33, 34, 35 and 36) to the basic syrup, and E. ~y adding 10 ppm 1-butanoyl-2-ethyl-6.6~dimethyl~
cyclohexane (11) to the basic syrup.
F. by adding 5 ppm of the mixture of example 15 (41, --42, 43 and 44).
~ach modification was compared in a finished drin~ with a drink made from the basic syrup. The results were:
A. In a trianyle test 6 out of 7 trained flavourists had a preference for the beverage made from the syrup with the addition.
B. In a pair test with 12 trained flavourists an un~
animous preference existed for the beverage made from the syrup witll the addition of the damascone homologue.
C. In a triangle test 7 out of 8 trained flavourists had a preference for the ~everage made from the syrup with the addition.
D. In a pair test with 8 trained ~lavourists an un~
animous preference existed for the beverage made from the syrup witn the addition.
E. In a triangle test 6 out of 8 trained flavourists had a preference for the beverage made from the syrup with the addition.
F~ In a pair test with 12 trained flavourists an un-; animous preference existed for the beverage with the addition of the mixture of ~xample 15 (41, 42, 43 and 44)~

Preparation of an imitation apple flavour composition ~n imitation apple flavour composition is prepared ~y ., .

~ 24 -~76~

mixing the following ingredients~
ComponentParts ~y weight Amyl acetate 35 Etllyl ~utyrate 15 Hexyl acetate 3 Amyl propionate Orange oil Florida 0.4 Ethyl alcohol 945.6 A modification of this composition is made by adding to this solution 0.05 g of the damascenone homologue mixture of example 11 (~ormulae 29, 30, 31 and 32) or 0.05 g of the di-hydrodamascenone homologue mixture of example 14 (formulae 37, 38, 39 and 40).
An aged, cured, and sllredded tobacco is sprayed with the ~asic composition in an amount to provide a tobacco containing 0.1~ by weight of the additives (without the ethyl alcohol). The alcollol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techni~ues. The same procedure is followed with the modifications of tihe basic compositions.
The cigarettes were compared by a panel of trained flavourists. A strong preference existed for the tobacco treated ~itll botll the modified composition, as having a more intense and ~leasant fruity taste.

Preparation of ethyl 2-eth 1 6 6-dimeth 1-2-cyclohexenecarboxylate Y Y
In a 250 ml pressure-bottle of a Parr hydrogenation apparatus is placed 100 ml of ethyl acetate, 20.8 g of ethyl 2-etnylidene-6~6-dime-tnyl-3-cyclohexene-carboxylate and 0.1 g of Lindlar catalyst.
The hydrogenation is conducted at room temperature under a nydrogen pressure of 0.6 atm. In about two hours a nearly ~ 7 .,:
,.
quantitative H2-uptake is achieved. The catalyst is rernoved ~y filtration, the solvent distilled off and ethyl 2-ethyl-~.6--dime-thyl-2-cyclohexenecar~ox~late is obtained in about 70% purit~
the remaininy 30% ~eing the ~ ar~d ~-isomers of this ester.
~XAMPLE 8 Pre~aration of a mixture of l-crotonoyl-2-ethyl-6.6-dimethyl-1-.... ...
cyclohexene (17), l-crotonoyl-2-ethyl-6.6-dimethyl-2-cyclohexene (18? and 1-crotonoyl-2-ethylidene-6 6-dimethylcyclollexane (19, 20) -- , .? In a reaction vessel is placed under a nitrogen atmosphere 400 ml of tetrahydrofuran, 12.5 g of lithium and a trace biphenyl.
To the stirred suspension is added 20 ml of a solution of 80 g of allyl ~henylether in 100 ml of diethylether.
~ When the reaction starts (green-red colour) the reac-tion ¦ mixture is cooled to -15C and the remaining part of the allyl phenylether solu-tion is gradually added in l l/2 hour.
After one hour of additionally stirring the unreacted litnium is removed by filtration, the filtra-te containing the allyllithium solution to be used in the following reaction.
In a reaction vessel is placed under a nitrogen atmosphere 41 g of ethyl-2-ethyl-6.6~dimethyl-2-cyclohexenecarboxylate and 2~0 ml of diethylether. In two ilOUrS the allyllithium solution is gradually added at ~75C. After 10 minutes of additionally stlrring the reaction mlxture is poured out on 100 g of ice and 300 ~ of water. With vigorous shaking the initial precipitate dissolves and then the water layer is separated and extracted twice w~th pentane. The com~ined organic layers are washed with water, dried and then the organic solvent is removed by dis-tillation. The xesidue of the distillation is stirred at 25-30C
30 with a solution of l g of sodium tert. ~utylate in tert. ~utanol.
To neutralise the reaction mixture a few ml of acetic acid are ; added. Tlle organic solvent is distilled off and the residue is ~ - 26 -' ~ ' " - , ~

7~9 dissolved in toluene, washed twice with water and after removal of the toluene by distillatlon, fractionated in vacuo at a 40 cm vigreux column. Tlle second fraction of the distillate (24 g) boiled at 93-95C/2 Torr and had an n20 1.4960.
Tlle fraction consisted of about 50% of the ~-isomer (17), to~ether with about 10% of the 3-isomer (18), 25% of the cis y -isomer (19) and about 15% of the trans ~ -isomer (20)~
The isomers can be separated by preparative GLC or by column chromatograpil~.

Preparation of a mixture of l-crotonoyl-2-ethyl-6.6-dimeth~1-1.3-cyclohexadiene (21), 1-crotonoyl-2-ethyl-6.6-dimethyl-2.4-cyclo-hexadiene (22) and 1-crotonoyl-2-ethylidene-6.6-dimetllyl-3-cyclo-hexene (23 and 24) In the same way as described in example 8 an allyl-lithium solution under a nitrogen atmosphere was prepared from 25 g of lithium and 160 g of allyl phenylether.
Tlle allyllithium was brought into reaction with 83.2 g of ~thyl 2-ethylidene-6.6-dimetllyl-3-cyclohexenecarboxylate (content 80%, ~alance 15~ ~-isomer and 5~ ~ -isomer and isomerised in the way as described in Example 8.
Yield: 65.0 g of the title mixture, boiling point 103-107C at 3.5 Torr, nD 1.5185. The composition of the mixture was:
a~out 5% ~ -isomer (22) about 17% ~ -isomer (21) about 45~ cis ~isomer (23) and about 33~ trans ~--isomer (24) (Note: Hydrogenation of this mixture according to the method descri~ed in Helvetica Chimica Acta 54 (1971) 1772 gave a product 3~ containing over 40~ of the l-butanoyl analogues, demonstrating that the crotonoyl-group is too easily hydrogenated.

.

i - 27 -.
' 76~

P eparation of a mixture of l-crotonoyl-2-p-r- yl-6.6-dimetllyl-1-~y~ xene (25), 1-crotonoyl-2-~rop~1-6.6-dimetnyl-?-cyclohexene _6) and 1-crotonoyl-2-propylidene-G.6-dimethylcyclohexane (27, 28) In the same ~;ay as described in tlle examples 7 and 8 the title mixture was ~repared, starting from ethyl 2-propylidene-6.6-dimethyl-3-cyclohexene-car}~oxylate.
The relative composition of the reaction product shows a great sim1larity with the composition of the product of exam~le 8: about 55~ ~ -isomer (26), about 8% ~-isomer (25) about 24%
of the cis-y -isomer(23), and about 12% oE the trans- r -isomer (24). -The boiling point of the reaction mixture was 97-102C/
2.5 Torr. the nD was 1.4935. Separation of the isomers can be achieved by column chromatography, or pre~arative GLC.

Preparation of a mixtu_e of l-crotonoyl~2-propyl-6.6-dimethyl-1.3-cyclohexadiene (29), 1-crotonoyl-2-propyl-6.6-dimethyl-2.4-cyclohexadiène (30) and 1-crotonoyl~2-~ropylidene-6.6-3-c~clollexene (31 and 32) ~ ccording to the method described in example 9 a mixture of the title compounds was prepared starting from ethyl 2-propy-lidene-6.6-dimethyl-3-cyclohexenecar~oxylate. The reaction product consisted primarily (over 85) of the r -isomers 31 and 32), the balance being about 8% of the ~ -isomer (29) and about 6% of the -isomer (30). Boiling point: 98-103C/2 Torr; nD 1.5163.

Pre~aration of a mixture of l-butanoyl-2-ethyl-6.6-dimethyl-l-cyclohexene (33?, 1 butanoyl--2-ethyl-6.6-d1methyl-2-cyclohexene (34) and 1-~utanoyl-2-ethylidene-6.6-dimethy-lcyclohexane (35 and 36) . ~ ~
In a reaction vessel is placed 15 g of 1-crotonoyl-2-ethyl-6.6-dimethyl-2-cyclollexene, 50 ml of water and 50 ml of ':
~ - 28 -~, .
, 7~

ethanol. A solution of 1.52 g of NasH4 in 10 ml of ~ater to ~,Jhich a drop of a 50% NaOH solution was added, is gradually added in 10 min. The reaction mixture is stirred for 3 hours. Afterwards 10 ml acetic acid is gradually added. When the foaming has ceased, 30 ml of toluene is added and the organic layer is separated. The water ]ayer is extracted twice with toluene. The combined toluene layers are washed with saturated soda solution and twice with water. Tlle toluene solution is dried and the toluene is removed by distillation. The residue of the distillation stirred at 25-30C with a solution of 0.5 g potassium tert.
~utylate in tert. butanol. l~o neutralise the reaction mixture a few ml of acetic,acid are added. The organic solvent is distilled off and the residue is dissolved in toluene, washed twice with water and, after removal o~ the toluene by distillation, fractionated in vacuo. The second fraction of the distillate (12.2 g) boiled at 95-96C/2 Torr and had n20 1.4750. The fraction consisted of a mixture of the title composition with the y -isomers predominantly.
The isomers can be separated by preparative G.l,.C.

Preparation of 1-butanoyl 2-ethyl-6.6-dimethyl cyclohexane (10) The isomer mixt~re of example 12 was dissolved in 200 ml of etllanol and hydrogenated at atmospheric pressure with the aid of platinumoxide as a catalyst. The title compound was obtained in 80~ yield b.p.: 67C/2 Torr nD = 1.4670.

EX~MPLE 14 Preparation of d mixture of l-butanoyl-2-ethyl-6.6-dimethyl-1.3-cyclohexadiene (37), 1-butanoyl-2-ethyl-6.6-dimethyl-2.4-cyclo-hexadiene (38) and l-butanoy1-2-ethylidene-6.6~dimethyl-3-cyclo-, . : .
,i; hexene (39 and 40) ;,' .
1-Crotonoyl-2-ethylldene-6.6-dimethyl-3-CyCloheXene was i,' ~ reduced with NaBH4 and isomerised with potassium tert. butoxide in ;' exactly the same way as described in example 12.
,:, ,s ~ - 29 -.

',;, . : ~ . .. ' ': .
:, 6~

A mixture of tlle title compounds was obtained in 80~
yield, in whicn the y -isomer predominated. The mixture ~oiled at 76-78C/3 Torr; nD = 1.4985. The isomers can be separated by prep~rative G.L.C.
F ~IPLE 15 Preparation of a mix-ture of l-but-2'-ynoyl-2-ethyl-6.6-dimethyl-.__ _ _ 1.3-cyclollexadiene (41), 1-hut-2'-ynoyl-2-ethyl-6.6-dimethyl-2.4-cyclohexadiene (~2) and 1-but-2'-ynoyl-2-ethyl-6.6-dimethyl-3-cyclohexene (43 and-44) . _ . ~ ~
A. Preparation of -tlle safranoyl chloride derivative.
In a reaction vessel was placed 500 ml n-butanol, 100 g powdered KOH and 100 g of a mixture of ethyl 2-ethylidene-6.6-dimethyl-3-cyclohexenecarboxylate ( y -isomer) and its ~ and -isomers.
The reaction mixture was stirred under reflux for 4 hours and afterwards poured on a mixture of ice and 200 ml of concentrated hydrochloric acid. The organic layer was separated and tile water layer extracted witll butanol. The organic layers were com~ined, and the organic solvent was evaporated. A crude mixture of organic acids resulted. This mixture was gradually added to a solution of 100 ml SOC12 in 200 ml CHCl3. After the addition was complete, the mixture was refluxed for 30 min. The oxganic solvent was evaporated and the residue distilled under reduced pressure. 55 g of a mixture of ~, ~, and y safranoyl-chloxide derivatives collected.
B. Preparation of the ti-tle compounds.
In a reaction vessel was placed 200 ml tetrahydrofuran and ~.2 g propynyllithium. A solution of 40 g of the mixture of ~ ,~ , and y safranoylchloride derivatives, obtained in A, in 200 ml of tetrahydrofuran was gradually added in 30 min., during which the temperature rose to 40C. The reaction mixture was stirred for l hour and afterwards poured into a mixture of ice and diethylether.

~ - 30 -~ ~37 ~

:
The organic layer was separated and the water layer extracted twice with diethyléther.
The combined organic layers were dried on MgSO4. The ~, solvent was evaporated and the residue stirred with a solution of 1 1 c~ potassium tert. butoxide in tert. butanol. To neutralise the reaction mixture a few ml of acetic acid were added. The oryanic solvent was removed by distillation and the residue dissolved in toluene and washed twice with water. The toluene was again removed by distil]ation and the residue fractionated under reduced pressure.
A mixture of the title com~ounds was obtained Witil the ~isomer predominating. Yield: 22 g; boiling point 125C/5 Torr;
20 = 1.~225 The mixture could be separated by preparative GoL~C~

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;' 20 .,~
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SUPPLEMENTARY DISCLOSURE

:'.
The characterist~ic spectral data of the presen~
invention are given herewith ln conjunction with the accompanying drawings in which Figs. 1 to 12 are I.R. spectra and Figs. 13 and 14 are chromatograms of the compoullds. (17)-(20) form a distilled reaction mixture I and compounds (21)-(24) form a crude reaction mixture II respectively.
NMR spectra recorded in CC14 solution, ~ given in ppm relative to tetramethylsilane.
l-Butanoyl-2-ethyl-6,Ç-dimethyl-cyclohexane (11) NMR: 0.7-1.0 (12H), 1.1-2.1 (llH), 2.1-2.5 (3H). IR spectrum (Fig l) l-Crotonoyl-2-ethyl-6,6-dimethyl-cyclohex-1-ene (173 1 NMR: 0.7-1.1 (9H), 1.9 (3H, d, J=6.5Hz), 5.8-7.0 (2H). I.R.
'` ~ spectrum (Fig. 2).
~ 0~0~0~/
~-J 1-er~ton~-21-ethyl-6,6-dimethyl-cyclohex-2-ene (18) NMR: 0.7-1.1 (9H), 1.9 (3H, d, J=6.5Hz); 2.83 (lH, broad s), 5.5S (lH, broad s). n20 = 1.4971 Crofono~
l-Cronto ~ -2-ethylidene-6,6-dimethyl-cyclohexane Z
a~d E (19 and 20). IR spectrum (Fig. 33.
'!` l-Crotonoyl-2-ethyl-6,6-dimethyl cyclohexa-1,3-diene 20 121) IR spectrum (Fig~ 4~.
l-Crotonoyl-2-ethyl-6,6-dimethyl-cyclohexa-2,4-diene (22) IR spectrum (Fig. 5).
l-Crotonyl-2-ethylidene-6,6-dimethyl-cyclohex-3-ene Z (23) NMR: 0.91 (3H, s), 0.96 (3H, s), 1.68 (3H, d, J=7Hz), 1.86 (3H, d, J=6.5Hz), 3.20 (lH, broad s), 5.57 (lH, broad q, J=7Hz), 5.8-7.3 (3H~. IR spectrum (Fig. 6).
l-Crotonoyl~2-ethylidene-6,6-dimethyl-cyclohex-3-ene ~; E (24) NMR: 0.87 (3H, s), 0.91 (3H, s), 1.75 (3H, d, J=7Hz), 1.85 (3H, d, J-6.5Hz), 2.90 (lH, broad s), 5.30 (lH, broad q, 30 J=7Hz), 5.5-7.0 (3H). IR spectrum (Fig. 7).

_ ~ _ .. . ..

, ~ca76~
1-Crotonoyl-2-propyl-6,6-dimethyl-cyclohexa-2,4-diene (30) NMR: 0.8~1.1 (9H), 1.7 (3H, d, J=7Hz), 2.68 (lH, broad s), 5.9-7.1 (2H, m).
l-Crotonoyl-2-propylidene-6,6-dimethyl-cyclohex-3-ene Z (31) NMR: 0.8-1.1 (9I-I), 1.7 (3H, d, J=7Hz), 3.17 (lH, broad s), 5.9-7.1 (2EI, m).
l-Crotonoyl-2-propylidene-6,6-dimethyl-cyclohex-3-ene E (32) NMR: 0.8-1.1 (9H), 107 (3H, d, J=7Hz), 2.90 (lH, broad s), 5.9-7.1 (2H, m). IR spectrum of mixture of 31 and 32. (Fig. &).
1-Butanoyl-2~ethyl-6,6-dimethyl-cyclohex-2-ene~
~34) IR spectrum (Fig. 9), nD = 1.4750.
Obtained by NaBH4 reduction of pure 18 according to Example 12.
l-Butanoyl-2-ethylidene-6,6-dimethyl-cyclohex-3-ene Z
; (39) NMR: 0.7-1.1 (9H), 1~75 (3H, d, J=7Hz), 3.17 (lH, broad s), 5.0-6.5 (3H). IR spectrum (Fig. 10).
l-Butanoyl-2-ethylldene-6,6-dimethyl-cyclohex-3 ene E
` (40) NMR: 0.7-1.1 (9H), 1.75 (3H, d, J=7Hz),2.8 (lH, broad s), 5.0-6.5 (3H). IR spectrum (Fig. 11).
~ l-(But-2'-ynoyl)-2-ethylidene-6,6-dimethyl-cyclohex-3-ene r' 20 Z ~43) NMR: 0.7-1.2 (6H), 1.77 (3H, d, J=7IIz), 1.93 (3H, s), 3.30 (lH, broad s), 5.1-6.5 t3H).
l-(But-2'-ynoyl)-2-ethylidene-6,6-dimethyl-cyclohex~3-ene E ~t44) NMR: 0.7-102 (6H), 1.77 (3H, d, J=7Hz), 1.93 (3H, s), 2.92 (lH, broad s), 5.1-6.5 (3H). IR spectrum of mixture of 43 and 44 (Fig. 12).

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!, _~ _ ,','' ~",1

Claims (6)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Cycloaliphatic saturated or unsaturated ketones, selected from a) damasc(en)one homologues having the general formula 10 wherein R stands for a hydrogen atom or a methyl radical and wherein the dotted lines represent one double bond in the pos-itions 1, 2 endocyclic or 2 exocyclic, or two conjugated double bonds in the positions 1 and 3, 2 endocyclic and 9, or 2 exo-cyclic and 3;
b) dihydrodamasc(en)ones having the general formulae 11 and 12 the dotted lines in the latter formula representing one double bond in the positions 1, 2 endocyclic or 2 exocyclic, or two conjugated double bonds in the positions 1 and 3, 2 endocyclic and 4 or 2 exocyclic and 3; and c) dehydrodamascenones having the general formula 13 wherein the dotted lines represent two conjugated double bonds in the position 1 and 3, 2 endocyclic and 4 or 2 exocyclic and 3.

2. A ketone as claimed in claim 1 selected from 1-crotonoyl-2-ethyl-6.6-dimethyl-cyclohexene; 1-crotonoyl-2-ethyl-6.6-dimethyl-2-cyclohexene; 1-crotonoyl-2-ethylidene-6.6-dimethyl-cyclohexane; 1-crotonoyl-2-ethyl-6.6-dimethyl-1.3-cyclohexadiene;
1-crotonoyl-2-ethyl-6.6-dimethyl-2.4-cyclohexadiene; and 1-crotonoyl-2-ethylidene-6.6--dimethyl-3-cyclohexene.

3. A ketone as claimed in claim 1 selected from 1-crotonoyl-2-propyl-6.6-dimethyl-1-cyclohexene; 1-crotonoyl-2-propyl-6.6-dimetllyl-2-cyclohexene; 1-crotonoyl-2-propylidene-6.6-dimethylcyclohexane; 1-crotonoyl-2-propyl-6.6-dimethyl-1.3-cyclohexadiene; 1-crotonoyl-2-propyl-6.6-dimethyl-2.4-cyclo-hexadiene; and 1-crotonoyl-2-propylidene-6.6-dimethyl-3-cyclohexene.

4. A ketone as claimed in claim 1 selected from 1-butanoyl-2-ethyl-6.6-dimethyl-cyclohexane; 1-butanoyl-2-ethyl-6.6-dimethyl-1-cyclohexene; 1-butanoyl-2-ethyl-6.6-dimethyl-2-cyclo-hexene; 1-butanoyl-2-ethylidene-6.6-dimethylcyclohexane; 1-butanoyl-2-ethyl-6.6-dimethyl-1.3-cyclollexadiene; 1-butanoyl-2-ethyl-6.6-dimethyl-2.4-cyclohexadiene and 1-butanoyl-2-ethyl-idene-6.6-dimethyl-3-cyclohexene.

5. A ketone as claimed in claim 1 selected from l-but-2'-ynoyl-2-ethyl-6.6-dimethyl-1.3-cyclohexadiene; 1-but-2'-ynoyl-2-ethyl-6.6-dimethyl-2.4-cyclohexadiene; 1-but-2'-ynoyl-2-ethylidene-

6.6-dimethyl-3-cyclohexene.