DERIVES ODORANTS D'ALCANOYLOXYMETHYL, CYCLOHEXENE

ODORANT ALKANOYLOXYMETHYL CYCLOHEXENE DERIVATIVES

Abrégé anglais

Abstract
Compounds of the general formula
<IMG> (I)
,wherein R represents a (C1-3-alkanoyl)-
oxymethyl group in the 3- or 4-position and
the broken line denotes an optional carbon-
-carbon bond,
and isomer mixtures thereof, are described. The compounds
are useful as odorants.

Revendications

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the manufacture of mixtures of isomeric cyclohexenes
of the general formula
<IMG> (I)
, wherein R represents a (C1-3-alkanoyl)-oxymethyl group
in the 3- or 4-position and the broken line denotes an
optional carbon-carbon bond,
which process comprises reacting an isomeric mixture of compounds of the
general formula
<IMG>
(II)
, wherein the hydroxymethyl group is present in the 3- or
4- position and the broken line has the significance given
above,
with a C1-3-alkanoylating agent; said process including, if desired, a
hydrogenation of the exocyclic double-bond prior to or subsequent to said
reaction.
2. A process according to claim 1, wherein said C1-3-alkanoylating
agent is an acetylating agent.
3. A method of imparting an odour to materials, which method comprises
applying to said materials or incorporating therein an odour-imparting amount
of mixtures of isomeric cyclohexenes of the general formula
13

<IMG> (I)
, wherein R represents a (C1-3-alkanoyl)-oxymethyl group in the 3- or 4-
position and the broken line denotes an optional carbon-carbon bond, or an
odorant composition containing such cyclohexenes.
4. A method according to claim 3, wherein there is used a mixture of
5-[3- and 4-(acetoxymethyl)-1-cyclohexenyl]-2-methyl-2-pentene or an odorant
composition containing this compound.
5. An odorant composition which contains as an essential odour-
imparting ingredient a mixture of isomeric cyclohexenes of the general formula
<IMG> (I)
, wherein R represents a (C1-3-alkanoyl)-oxymethyl group in the 3- or 4-
position and the broken line denotes an optional carbon-carbon bond.
6. An odorant composition according to claim 5, wherein said cyclo-
hexene derivative is a mixture of 5-[3- and 4-(acetoxymethyl)-1-cyclohexenyl]-
2-methyl-2-pentene.
7. Mixtures of isomeric compounds of the general formula
<IMG> (I)
, wherein R represents a (C1-3-alkanoyl)-oxymethyl group in the 3- or 4-
position and the broken line denotes an optional carbon-carbon bond.
8. A mixture of 5-[3- and 4-(acetoxymethyl)-1-cyclohexenyl]-2-methyl-
2-pentene.
14

9. A mixture of 5-[3- and 4-(formyloxy-methyl)-1-cyclohexenyl]-2-
methyl-2-pentene.
10. A mixture of 5-[3- and 4-(propionyloxymethyl)-1-cyclohexenyl]-2-
methyl-2-pentene.

Description

~03930S
The present invention relates to novel odorants. ~ore particularly,
the invention is concerned with isomeric cyclohexenes, a process for the
manufacture thereof and odorant compositions containing same. The invention
is also concerned with a method of imparting an odour to materials by means
of said isomeric cyclohexenes. -
The mixtures of isomeric cyclohexenes provided by the present
invention are compounds of the general formula
~ R (I)
,wherein R represents a (Cl 3-alkanoyl)-oxymethyl group
in the 3- or 4-position and the broken line denotes an
optional carbon-carbon bond.
It will be appreciated that formula I is intended to include all
of the possible isomers of the compounds denoted thereby.
According to the process provided by the present invention, the
- isomerlc mixtures of cyclohexenes aforesaid (that is to say, the compounds
of formula I) are manufactured by reacting an isomeric mixture of compounds
of the general formula
6 ~ CH2H (II)
, .,
, wherein the hydroxymethyl group is present in the 3- or
4-position and the bro~en line has the significance given
~: earlier,
with a Cl 3-alkanoylating agent; said process including, if desired, a
:; hydrogenation of the exocyclic double-bond prior to or subsequent to said
reaction.
- 2 -
~"

-, 1039~5 ,
The reaction of a compound of formula II with a Cl 3-alkanoylating
agent, which may alternatively be described as a formylation, acetylation
or propionylation of a compound of formula II, can be carried out according
to methods known per se.
A suitable formylating agent is, for example, a mixture of acetic
anhydride and formic acid with which the compounds of formula II can be
- formylated at room temper~ture.
Suitable acetylating agents are, for example, acetic anhydride,
especially in the presence of sodium acetate or concentrated phosphoric acid,
or an acetyl halide such as acetyl chloride in the presence of an organic
base such as pyridine or dimethyl aniline.
. ~,
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.: '` :
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-- 3 --
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1039305
The propionylation can be carried out in a correspond-
- ing manner. Thus it can be carried out using propionic anhydride,
especially in the presence of sodium propionate or concentrated
phosphoric acid, or with a propionyl halide such as propionyl
chloride in the presence of an organic base such as pyridine,
dimethylaniline etc. The propionylation can, however, also be
carried out using propionic acid itself in the presence of a
strong acid such as sulphuric acid or p-toluenesulphonic acid
etc.
Furthermore, the acylation can be carried out using
a corresponding isopropenyl ester (isopropenyl formate,
isopropenyl acetate or isopropenyl propionate) in the presence
of an acid such as, for example, p-toluenesulphonic acid.
As will be evident, this acylation procedure may be described
as an interchange of ester radicals.
The hydrogenation of the exocyclic double-bond in
; a compound of formula II or a Cl 3-alkanoyl derivative thereof
can be carried out, for example, catalytically. Raney-nickel
is, for example, a suitable catalyst. The catalytic hydrogena-
tion is conveniently carried out in a solvent (e.g. an alcohol
such as methanol) and at room temperature.
According to a preferred embodiment of the process
; provided by the present invention, there is used as the starting
material an isomer mixture of the formula
'
.~,
-- 4 --

1039305
CH~OH (IIa~
, wherein the hydroxymethyl group is present
in the 3- or 4-position,
since this is accessible by reduction of the corresponding
aldehyde mixture. The exocyclically-unsaturated esters of
formula I which are likewise obtained as an isomer mixture
after the alkanoylation can, if desired, be separated into the
individual components; for example, by preparative gas
- chromatogra~hy or distillation on a spinning~band column.
This separation is, however, not necessary.
-~he cyclohexene derivatives provided by the present
invention (i.e. the compounds of formula I and isomer ~ixtures
thereof) possess particular odorant properties. They can
accordingly be used in the perfume industry for the manufacture
of perfumes and perfumed products. For example, they can be
used for the perfuming of soaps, sclid and liquid detergents,
aerosols and cosmetic products of all kinds such as toilet
waters, salves, face milks, make-up, lipsticks, bath salts and
bath oils. In perfumes or perfumed products~ the conte~t of-
the present cyclohexene derivatives lies within wide limits;for example, between about 1%o (detergents) and about 2~/o
(alcoholic solution). In perfume bases or concentrates, the
`content can, of course, also lie above 2~/o.
The cyclohexene derivatives provided by this invention
make available, in ~eneral, a fruity, flowery, ~reen,

103930S
especially rose-like, odour having very good tenacity. The cyclohexene
derivatives in which R represents an acetyloxymethyl group and in which an
exocyclic double-bond is present are of particular value by virtue of their
particular fragrance qualities.
The cyclohexene derivatives provided by this invention can be
advantageously incorporated into odorant compositions of the flowery type.
Such compositions are thereby modified in an advantageous manner in that
their flowery character is intensified in a remarkable manner and, in
particular, fresh, rose-like, muguet-like notes are emphasized in a desirable
manner.
The high stability of the present cyclohexene derivatives in
odorant compositions of the most diverse types and their pronounced tenacity
; predestinates them as components of such compositions.
:
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,:
,
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103930S
~ he fo]lo,/ing ~xamples illustrate the p ocess proviGed
by the present invention:
~ample 1
.~
77.7 g (0.4 mol) of the alcohol mix~lre of formula IIa
hereinbefore ~ 5-t3- and 4-(hydro~methyl)-1-cyclohexenyl]-2-
-methyl-2-pentene ~ , 120.1 g (1.2 mol) o~ freshly distilled
isopropenyl acetate and 0.1 g of p-toluenesulphonic acid are
added to a round-bottomed flask which is provided with a
stirrer, thermometer, condenser and dropping funnel. The
mixture is maintained at reflux temperature for 3 hours, then
taken up in hexane, washed ~ith water, then with a sodium
bicarbonate solution and finally to neutrality with water.
After evaporation of the solvent, the cxude product is
;s distilled. ~here are obtained 71 g (75% yield) of 5-t3- and
4-(acetoxymethyl)-1-cyclohexenyl]-2-methyl-2-pentene ao an
isomer mixture; boiling point o 01 = 84-85C; ~ = 1.4800;
- ~4 - 0.958.
Example 2
255.5 g Or acetic anhydride and 2.5 g of 85% ortho-
phosphoric acid are added to a round-bottomed flask which is -
provided with a stirrer, thermometer, condenser and dropping
funnel. The contents of the flask are warmed to 40C and
- at this temperature, with coolin~, there are added over a
period of 30 minutes 388.6 g (2 mol) of the alcohol mixture
of formula IIa hereinbefore. The mixture is stirred at 40C
for a further 1 hour and then the contents of the flask are
- 7-

10393(~5
poured on to 1.25 kg of crushed ice. ~he mixture is extracteG
with toluene, the toluene extract ~ashed with wate~, a 1
sodium carbonate solution and then a~ain llith water. ~he
solvent is removed under a vacuum ~nd then the produc~ is
subjected to a fraction~l distillation. There are obt~ined
435,5 g (92% yield) of the ester mixture obtained according ~o
Example 1.
.' ,' ' .
Example ~
15 g of 98% formic acid are slo~ly added dropwise at a
temperature of 45C to 30 g of acetic anhydride. This
mixture is left for 2 hours at 45C.
.. . .
26.4 g of the mixed anhydride are added to a flas~
provided with a stirrer, thermometer, dropping funnel and
condenser and cooled to 10C. 38.9 g of the alcohol mixture
- 15 of formula IIa hereinbefore are slo~ly added dropwise at this
temperatur~. The mixture is then left to stand for 12 hours
at room temperature. It is then taken up in ether~ the
ethereal solution is washed with water, saturated sodium
carbonate solution and again with water to neutrality. The
ethereal solution is dried over sodium sulphate and the solvent
distilled off. The crude product is distilled, there bein~
obtained 27.4 g of 5~ and 4-(formyloxymethyl)-1-cyclo-
hexenyl]-2-methyl-2-pentene as an isomer mixture; boiling
point 0 07 = 81C; ~ = 1.48~8; yield: 61% of theory.
~xamPle 4
A solution consisting of 64.8 g (1/3 mol) of tne alcohol
-
",
r-
- r

: 1039~0S
mixture of formula IIa hereinbefore, 37.0 g o~ propiGnic acid
and 0.1 g of p-toluenesu],phonic acid irl 150 ml of toluene i5
, maintained at reflux temperature in a flask provided with a
condenser and water sep~rator until 6 g of water have separated.
~he mixture is washed firstly with a saturated sodium car~onate
' solution and then with water up to neutrality. The solvent
is distilled off and the crude product fractionally distilled
, in a vacuum. There are obtained 57 g of 5-[3- and 4-
-(propionylox~methyl)-l-cyclohexen~1]~2~methyl-2-pentene as
an isomer mixture; boiling point 0 04 = 86C; n20 = 1.4800;
yield: 65% of theory.
.,
Example 5
, A solution consisting of 47.3 g (0.2 mol) of the ester
mixture prepared according to Example ls 300 ml of ethanol
... .
, 15 and 4.7 g of Raney-nickel is added to a hydro~enator. ~he
', ' hydrogenation is carried out at a~mospheric pressure ~nd room
temperature. The hydrogen absorption is interrupted after - '
4.5 1. The catalyst is filtered off and the ethanol is
,
distilled off. ~he crude product is fractionally distilled.
There are obtained 28 g of 5-[3- and 4-(acetoxymethy,l)-1-
-cyclohexenyl]-2-methyl-pentane as ~n isomer mixture; boiling
point o 15 = 84C; ~ = 1.4668; yield: 5~o of theory.
~he following ~xample illustrates typic~l odorant
compositions containing the cyclohexene derivatives provided
by the present invention: ,
" ' .
,, .
_ 9 _

103930S
~) "Mv.f~let fant~s,y" compo~i.tion
Ester mixture of Example 1 300
Phenylethyl acetate 5
Citral 5
Bergamotte oil 20
- Inaole 10% (in diethyl phthalate) 30
Rhodinol 5o
~antalol 50
~inalool 60
Phenylethyl alcohol 80
-. a-Hexyl-cinnamaldehyde 200
. ` 800
,-,.......................... .
B) "Rose" composition
Parts b~ wei~ht
Ester ~ixture o Example 1 100
- C8-~!Lldehyde 10% - 5
~cetaldehyde-propyl-phenylethylacetal 5
Cg~Aldehyde 10~/o 10
Patchouli oil 10
: Pepper essence ~West Indian) 10
Phenylethyl acetate 15
Guayl acetate 15
Geranium oil Bourbon 20
Eugenol 30
~richloromethylphenylcar.binyl acetate. 60
a-Hexylcinn~maldehyde 60
Linalool 60
Citronellol G0
, -- 10 -- ,
, ', ' ' .
`~` :`` ` i ` - - - ~- r--

. Benzyl salicylate 1039305 g~
.: ~eth~Jlionone 80
Rhodinol pure 90
Geraniol 120
Phenyleth~Jl alcohol 170
Total 1000
. .
C) "Ch~pre" composition
Parts b~ weight
` Ester mixture of Example 1 - 50
Methyl-phenyl-carbinyl acetate 10
Civette abs. 10% 10
Coumarin 10
Amyl salicylate - 10
Resinoid Ciste ~abdanum 10
I~obutyl~uinoline 10% 15
Benzyl acetate 20
: Linalool 20
Y-Undecalac-tone 1~/~ 20
Oak moss abs. Yugosl. 20
Ylang ylang Bourbon 25 :-
Sandalwood oil 30
Musk ambrette 30
Cll-Aldehyde 10% 30
Rhodinol pure 40
Phenylethyl alcohol 40
Patchouli oil 40
Orange essence (Guinea) 40
a-Hexylcinnamaldehyde 50
Hydroxycit~onellal 60
', ' - 11 ~
, .. , .,, ,, , , ,, . ~ .,.,, .. , . " .. . . .. ... . .. ........ ....... ... ........ . .. .. .. .. ... . . . ...... .. .. . . .
. .
,. ~

1039305
Vetiven~l ace~ate Bourbon 6~
Y-Methylionone Coeur SS~ -
Le~on essence (Messina) SJO
Bergamotte oil lCO
Total 900
, ,
.. . .
'
.
- 12 -
., ,: