Note: Descriptions are shown in the official language in which they were submitted.
This invention is concerned with certain novel organic compounds a~d
with perfumery compositions containing the compounds. It has been discover-
ed that these compounds exhibit unique, attractive odours which render them
useful in ingredients of perfumery compos;tions which compositions find use
in a wide variety of applications.
From our aspect our invention provides compounds of the formula:-
~ X
Hn ~ ~
~0
/\
wherein X represents a hydrogen atom or an alkyl group having from 1 to 4carbon atoms and m has a valuè 0 or 1, n has a value 1 or 2 and n + m = 2
the dashed lines indicating alternative positions for a unit of unsatura-
tion. Such compounds may be individual stereoisomers or mixtures of thepossible stereoisomers of compounds having the above formula.
These compounds have been discovered to have a fresh floral type of
odour, with a blend of prominent neroili~ bitter orange notes. Further-
more, the odours of these compounds blend harmoniously with those of other
known odiferous chemicals to produce useful compounded perfumery composi-
tions.
The novel compounds of this invention are derivatives of 3, 3, 7, 8
- tetramethyl - 2 ~ oxabicyclo - ~4,4,0] - decane which will hereinafter
be referred to for convenience as bigarade-oxides. They may be employed -
as a major ingredient of these compos;tions depending upon the desired
overallodour required. In general the bigarade-oxides will constitute
from 2 to 15~ preferably 3 to 7 parts by weight of the composition. The
perfumery compositions of this invention may ftnd use as 5UC~ or after
dilution, but more usually they are added in small proporti`ons to other
' -,
; '~' ':
'
:, , ,......... , . ,, -. . ~ .. . . . .. . .
. -. - . : ,. , . :. .
- , ~ , . ::. . ;
- 3 - ~L~L~LS ~
materials such as space sprays or to soap cosmetic or deodorant composi-
tions or to substrates such as fibre fabric or paper products in order to
provide them with agreeable olfactory properties. Such compositions are
products of commerce and they may comprise a simple or complex mixture of
individual perfumery compounds.
Thus, from a second aspect our invention provides a compounded per-
fumery composition comprising a plurality of odiferous chemicals to~ether
with at least one compound having the formula:-
~ Hm
~X
~
/ \
wherein X and m and n are as hereinbefore defined.
The unique fruity floral odours of the novel bigarade-oxides of our
invention find special use in compositions designed for use in various per-
fumed bath preparations such as bath salts etc.
These novel perfumery compositions may be compounded accordin~ to
recognised techniques of the perfumery arts employing known odoriferous
perfumery ingredients such as those described in the standard textbooks
of the art, e.g. "Soap, Perfumery and Cosmetics" by W.A. Poucher, 8th
Edition, published by Chapman and Hall (London) 1974; "Perfume and Flavour
Chemicals" by S. Arctander published by the author (Montcla;r) 1969
"Perfume and Flavour Materials of Natural Origin" also by S. Arctander
self-published Elizabeth New Jersey (1960) and "Perfume Technology" by
M. Billot and F.V. Wells published by Ellis Horwood Ltd. 1975. The re-
levant disclosures of these aforesaid textbooks are hereby incorporated
by reference herein. Specific odoriferous ingredien~s which may be blended
with the bigarade-oxides in a compounded perfumery composition are the
derivatives of 2, 6-dimethyl-2-alkoxy octan-7-ol (as claimed in our Dutch
Patent Application No. 72. 15238), vetivert oil, vetiverol, vetiveryl acetate
:.
..
., . . -
.
- 4 - ~L~i~L5 ~ g
guaic wood oil, esters of anthranilic acid such as the methyl, N methyl
methyl, ethyl, phenyl-ethyl, cinnamyl, linalyl, methyl and geranyl esters,
benzyl acetate, lemon oil, dimethyl benzyl carbinol~ dimethyl benz~l car-
binyl acetate, rose absolute, jasmin absolute, ionones, iso-nonyl acetate,
methyl phenyl acetate, styrallyl acetate, B. phenyl ethanol, citronellol,
citronellal, hydroxy citronnelal,geranium oil, geraniol, linalol, nerol,
lavandin oil, 1inalyl acetate, patchouli oil, petitgrain oil, bergamot oil,
heliotropin, ethylene brassylate, undecy1 aldehyele, cinnamaldehyde, benzyl
salicylate, cinnamyl alcohol, clove bud oil, bay oil, nutmeg oil, pimento
lC berry oil, terpineol, ylang oil, benzyl benzoate~ sandal-wood oil, clary
sage oil, amyl salicylate, labdanum resin, methyl ionones, dihydro-myr-
cenol, orange oil, vanillin, ethylvanillin, olibanum resin, musk ambrette,
rhodinol, mandarin oil, methylnonyl acetaldehyde, neroli oil, cedrol, oak-
moss, isovalanone, eugenol, iso-eugenol, cedar.~ood oil, p-tert-butyl cyclo-
lS hexyl acetate.
Typically the novel bigarde-oxides are blended with at least two, us-
ually at least five and preFerably at least ten of the foregoin~ ingredients.
Preferred compounds for present use are those wherein X represents a
methyl group or a hydrogen atom. Most preferably the isomers wherein n and
m have a value of l are used.
Particularly preferred odoriferous ingredients for blending with the
bi~arade-oxides are linalol, linalylacetate, bergamot oil, grapefruit oil,
lemon oil, orange oil, petitgrain oil~ hexycinnamic aldehyde, benzylsalicy-
late, methyl ionones, 2-alkoxy-2, 6 dimethyl-octan-7-ols, methylanthranilate,
geraniol and nerol and esters thereof, neroli oil, farnesol, nerolidolg
eugenol, isoeugenol, patchouli oil, vetiveryl acetate, cedryl acetate, p-ter-
tiary butyl cyclohexyl acetate and terpineol.
The novel bigarade-oxides may conveniently be made by a multi-step syn-
thesis which uses the triene known as allo ocimene as its starting material.
Allo acimene is readily available as a product of the thermal isomerisation
of ocimene, a triene found as a constituent of several essential oils or
more usually from the thermal isomerisation of a pinene.
As a f;rst step in this synthesis allo-ocimene is reacted with an unsat-
urated dienophile ha~ing the formula: CH2 = CXY the reactiGn being an example
'
.
. ~ . ' , . .
.. . . . .
,, , ,. . .:
.. . . . ..
of a Diels-Alder addition. The reaction proceeds according to the follow-
;ng equation:-
~`J Y J \~ ~ Y
The desired intermediate for the production of the novel c~mpounds ~fthe invention is the compound of formula:~
I
.'` . ~ '. .
IU< CH2H ''
which can be produced directly by using an unsaturated alcohol as the dieno-
phile in the above reaction, e.g. where X represents a hydrogen atom all~l
alcohol can be used. Other dienophiles which yield adducts which can be
converted to an alcohol having the above formula may also be employed and
the nature of the substituent ~ will vary accordingly. Thus acrolein, acry-
lic acid, acrylate esters and acrylic acid chloride can be employed. Pre-
ferably an unsaturated aldehyde is employed as the dienophile because of
its properties as a dienophile and the ease with which the adduct ~lde~yde
can be converted to the desired alcohol intermediate. Thus in this case of
lS the preferred compounds where X represents a hydrogen atom acrolein is addedto allo-ocimene. The Diels Alder addition can be carried out at elevated
temperatures and pressures e.g. 120 to 180C and 50 to 150 psi or at am6ient
temperatures in the presence of a suitable electrophilic catal~st such as
aluminium chloride; The Diels-Alder addition of acrolein and allyl alcohol
~q all ocimene has been reported in The Journal of the Chemical sOcei.ty of
Japan Volume 5 (1973 pages 1064 to 1066~. This discloswre describes the
, -
- , . . .
s~
--6--
addition to a mixture of trans-trans and trans-cis allo-
ocimene. When using a mixture of these two stereoisomers
we prefer to carry out the reaction under elevated tempera-
tures and pressures. When the low temperature catalysed
reaction is employed the trans-cis isomer reacts extremely
slowly. The Diels-Alder addition is probably stereo-
specific and the product which is preferably separated ~y
fractional distillation comprises a mixture of the four
stereoisomeric adducts having the above formula. These
adducts are then converted to the corresponding alcohols.
In the preferred case the aldehydes are reduced using the
conventional technique of synthetic organic chemistry.
Where other dienophiles are employed in the addition step
such as an unsaturated carboxylic acid, carboxylic acid
lS Qster and carboxylic acid chloride the adducts are :Likewise
converted to the corresponding alcohols using conventional
techniques.
The conversion of the aldehyde to the correspond-
ing alcohol may conveniently be achieved using catalytic
hydrogenation i.e. heating the aldehyde adduct(s) at an
elevated temperature of from 150C to 170C under superat-
mospheric pressure say 180 to 200 psi in an atmosphere of
hydrogen gas and in the presence of a suitable catalyst.
Preferably the catalyst employed is copper chromite but
other conventional catalysts such as nickel, copper and
palladium may be employed. Alternatively the reduction
can be achieved using chemical methods in particular
reduction with metal hydrides such as lithium aluminium
hydride or sodium borohydride which reagents are normally
added to the aldeh~de as a solution in ether or water
respectively, the reaction proceeding smoothly at ambient
temperature. In conducting this reduction care should be
taken to ensure that the ethylenic units of unsaturation
present in the molecule are not attacked. The alcohols
may be separated from the mixture of products formed
using conventional techniques e.g. fractional distillation
or used directly in the next stage in the synthesis.
. , :: - . , . ... .. . . : ~. . .
. ~ . . . : . . . '
' ' ' ' , " ~ : ' .' ' ' .
' '' ', ,, ~, ' . ' .'. ~ ,, " . '' ' , , ' ' ,
... . . . . . . . .. . .
-6a- ~5%84
The alcohol thus obtained may be cyclised to the
bigarade-oxide by heating preferably under reflux in
the presence of a protonic acid catalyst. Conveniently
an aqueous solution of a mineral acid or phosphoric acid
or an organic solution of a sulphonic acid. The reaction
will usually go to completion under reflux within a period
of a few hours e.g. 6 to 20 hours. Preferably an aqueous
acid solution is employed as the catalyst. In order to
speed the reaction a relatively concentrated solution
e.g. 15 to 35~ by weight is preferably employed in such a
quantity that the volume of the aqueous phase is at least
.j~ '.
:. . . . . . . . .
.. . ..
- 7 - ~L~L~S 2~
eqùal to and preferably at least twice the volume of the organic phase.
The use of more concentrated acid solutions gives a desirably high yield
in a relatively short time e.g. 6 to 10 hours. The oil layer may be separa-
ted from the aqueous layer and fractionated to give the desired bigarade-
oxide product.
The use of organic solutions of sulphonic acids e.g. para-toluene
sulphonic acids in benzene or in an alkyl benzene speeds the reaction and
favours the production of these nove1 compounds wherein n and m have a value
of 1. The organic layer is preferably washed with a dilute aqueous solution
of a caustic alkali and the bigarade-oxides are then separated by ~ractional
distillation.
The product normally comprises a mixture of the various stereoisomers
of compounds having the appropriate molecular formula as defined above. It
will normally comprise a mixture of the compounds wherein n has a value of
I with those wherein n has a value of 2. This mixture can be fractionated
to separate those compounds having the above formula wherein n = 1 from
these where n = 2. In the former the novel odoriferous character is more
pronounced~ However, the presence of the làtter complements this odour
in a desirable mannor and preferably this separation step is omitted. Forma- -
tion of the compounds wherein n has a value of 2 is fa~oured by the treat-
ment of the alcohol with acid for a longer period or by using a stronger
acid.
The invention is illustrated by the following examples:- -
EXAMPLE 1: Preparation of 1, 6-dimethyl 3- isobutenyl-4- formyl
cyclohexene
55~g of allo-ocimene (85% 4E, 6Z, 15% 4E, 6E) and 224 g of acrolein
were placed in a stainless steel vessel which is equipped to withstand a
high internal pressure at elevated temperatures. 1 gm of embanox, a poly-
merisat;on inhibitor, was added. The air in the vessel was displaced with
nitrogen and the vessel was closed. The temperature was raised to 165-170C
and maintained in the range for 6 hours. The maximum pressure recorde.~was
150 psi. The reaction mixture was then distilled and a mixture of four
isomeric aldehydes collected which represented a 70~ yi~èld of the desired
pr~duct. The percentages of adducts were determined by GLC ~o be as follo~ls:
... , . . , ~
... .. ,. ~ , ., ... ; . ;... ,. ,. . . ,. ., , , . ', ' . . ~.: ' '... ..:
... . .. .. .. . . . .. ..- .
. :: '' - ' . ~ .. . . . . .
- 8 - ~3L~L5 Z~4
,CH0 ,CH0 ~ CH0 ~ CH0
A 4% B 11% C 72% D 13%
.. . . . . .
EXAMPLE 2: Preparation of 1, 6-dimethyl 3-;sobutenyl-4-formylcyclo-
hexene.
408 g of allo-ocimene (85% 4E 6Z, 15% 4E 6E) and 202 9 of acrolein were
placed in a stainless steel vessel which is equipped to withstand a high
internal pressure at elevated temperatures. 1 gm of hydroquinone, a poly-
S merisation inhibitor, was added. The air in the vessel was displaced withnitrogen and the vessel closed. The temperature was raised to 145--150C
and maintained in the range for 7.5 hours. The maximum pressure recorded
was 105 psi. The reaction mixture was then distilled and a mix~ure of four
aldehydes collected which represented a 66% yield of the desired product.
The percentages of adducts were A 4%, B 11%, C 74% and D 11~ where the letters
A, B, C, D represent the isomers denoted as such in Example 1.
EXAMPLE 3: Preparation of 1, 6 dimethyl-3-isobutenyl 4-hydroxymethyl-cyclohexene.
400 gm of the mixed aldehyde product obtained from 1 above was mixed with
200 mls of methanol and 8 gms of copper chromite and shaken in an atmosphere
of hydrogen at a temperature of 180C and a pressure of 180-200 psi for a
period of six hours. The product was filtered and distilled to aive a mixture
of four isomeric alcohols in 85% yield.
EXAMPLE 4: Preparation of 1, 6-dimethyl-3-isobutenyl-~-hydroxy-
methyl cyclohexene.
443 g of the mixed aldehyde product obtained from 2 abo~e was mixed with
' 20 5g copper chromite and shaken ;n an atmosphere of hydrogen at a temperature of
150C and a pressure of 130-150 psi for 14 hours. The product was filtered
and distilled to give a mixture of four isomeric alcohols in 85% yield.
- .,, , - . . - , , ,- . ~ ~ ........................ . ... . .
.. .. ,.... . ~ ..................... . . . ..... ..... . .....
, , :: , ., ,- . -
.. ,. , ~. . ... . . . . ~ .. -:, ,
.SL5Z8~
g
EX~MPLE 5: Preparation of 3, 3, 7, 8 - tetramethyl-2-oxabicyclo-
[4,4,0~ dec-6-en. -
1500 mls of a 10% aqueous solution of phosphoric acid were added to
500 gm of the alcohol mixture obtained in (3) above and the solution reflux-
ed gently with stirring for a period of 8 hours. The oil layer was separat-
ed and washed with dilute aqueous caustic alkali, dried over magnesium sui-
phate and distilled to yield the desired product.
EXAMPLE 6: Preparation of 3, 3, 7, 8-tetramethyl-2-oxabicyclo-
[4,4,0~ dec-6-enes and 3,3,7, 8-tetramethyl-2-
oxabicyclo- ~4,4,0~ dec-7-enes.
3000 mls of a 30% aqueous solution of phosphoric acid were added to
1160 g of the alcohol mixture obtained in 3 above and the solution refluxed
gently with stirring for a period of 12 hours. The oil layer was separated
and washed with dilute aqueous caustic alkali and then water. The crude
product was distilled to give a 74% yield of the six possible oxide isomers.
EXAMPLE 7: Preparation o~ 3,3,7, 8-tetramethyl-2-oxabicyclo-
~4,4,0] dec-6-enes and 3,3,7, 8-tetramethyl-2-
oxabicyclo- [4,4,0~ dec-7-enes.
! 20 20g of para-toluene sulphonic acid in 384g of ethylbenzene were added
to 384g of the alcohol mixture obtained in 3 above and the solution was stir-
red at 70-80C ~or 7.5 h. The react~on mixture was washed with dilute
aqueous caustic alkali and then water. The crude product was distilled to
give a 77% yield of the six possible oxide isomers.
EXAMPLE 8:
.
A compounded perfumery composition was made up as follow (all parts
~ by weight):
; Bergamot oil 20
B pinene 100
Limonene 140
Trans ocimene 20
Linalol 300
Linalylacetate 80
. ! ,
, . ' ,. ' ' ' ' ' , ".. ' ' . ' . " ' ."' , ' ' . ' . ., ' ~.,, . ' ' '' " '. ' ' ,. '
., ' ' . ' . ' '', ' ' .,:.. '' ' ,', ' . ' ' ' , '' ' .' ' ' '. . " '''
lo~ 5~
Petitgrain oil 40
Terpineol 30
Geraniol 30
Nerol 10
Neryl acetate 20
Geranyl acetate 30
Nerolidol 50
Farnesol 20
Indole
(10% solution ) 25
in linalol)
Bigarade-oxide )
(Product o~ ) 80
Example 3)
1000
====
