CA1115284A - Derivatives of 3,3,7,8-tetramethyl-2-oxabicyclo-¬4, 4,0|-decane and their use in perfumery - Google Patents
Derivatives of 3,3,7,8-tetramethyl-2-oxabicyclo-¬4, 4,0|-decane and their use in perfumeryInfo
- Publication number
- CA1115284A CA1115284A CA305,619A CA305619A CA1115284A CA 1115284 A CA1115284 A CA 1115284A CA 305619 A CA305619 A CA 305619A CA 1115284 A CA1115284 A CA 1115284A
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- acetate
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/38—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
- C07C47/45—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings having unsaturation outside the rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/76—Benzo[c]pyrans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Abstract
A B S T R A C T
Compounds having the formula:-
Compounds having the formula:-
Description
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~
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) ====
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~
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) ====
Claims (15)
1. A compound having the formula:
wherein X represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, m has a value of 0 or 1, n has a value of 1 or 2, n+m = 2 and the dashed line indicates alter-native positions for a unit of unsaturation.
wherein X represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, m has a value of 0 or 1, n has a value of 1 or 2, n+m = 2 and the dashed line indicates alter-native positions for a unit of unsaturation.
2. A compound according to Claim 1 wherein X represents a methyl group.
3. A compound according to Claim 1 wherein X represents a hydrogen atom.
4. A compound according to any of Claims 1, 2 and 3 wherein n and m each have a value of 1.
5. A compounded perfumery composition which comprises a plurality of odiferous ingredients characterised in that it further comprises at least one compound having the formula I:
I
wherein X represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, m has a value of 0 or 1, n has a value of 1 or 2, n+m = 2 and the dashed line indicates alterna-tive positions for a unit of unsaturation.
I
wherein X represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, m has a value of 0 or 1, n has a value of 1 or 2, n+m = 2 and the dashed line indicates alterna-tive positions for a unit of unsaturation.
6. A composition according to Claim 5 characterised in that X represents a hydrogen atom.
7. A composition according to Claim 5 characterised in that n and m each have a value of 1.
8. A composition according to any of Claims 5, 6 and 7 characterised in that the composition further comprises one or more odoriferous chemicals selected from the group com-prising linalol, linalylacetate, bergamot oil, grapefruit oil, lemon oil, orange oil, petit grain oil, hexylcinnamic aldehyde, benzylsalicylate, methyl ionones, 2-alkoxy-2,6 dimethyl-octan-7-ols, methylanthranilate, geraniol and nerol and esters thereof, neroli oil, famesol, nerolidol, eugenol, isoeugenol, patchouli oil, vetiveryl acetate, cedryl acetate, p tertiary butyl cyclohexyl acetate and terpineol.
9. A composition according to any of Claims 5, 6 or 7 characterised in that the compounds of formula I comprise from 2 to 15 parts by weight thereof and that the composition further comprises one or more odoriferous chemicals selected from the group comprising linaol , linalylacetate, bergamot oil, grapefruit oil, lemon oil, orange oil, petit grain oil, hexylcinnamic aldehyde, benzylsalicylate, methyl ionones, 2-alkoxy-2, 6 dimethyl-octan-7-ols, methylanthrani-late, geraniol and nerol and esters thereof, neroli oil, famesol, nerolidol, eugenol, isoeugenol, patchouli oil, vetiveryl acetate, cedryl acetate, p tertiary butyl cyclohexyl acetate and terpineol.
10. A composition according to any of Claims 5, 6 or 7 characterised in that the compounds of formula I comprise from 3 to 7 parts by weight thereof and that the composition further comprises one or more odoriferous chemicals selected from the group comprising linaol , linalylacetate, bergamot oil, grapefruit oil, lemon oil, orange oil, petit grain oil, hexylcinnamic aldehyde, benzylsalicylate, methyl ionones, 2-alkoxy-2, 6 dimethyl-octan-7-ols, methylanthrani-late, geraniol and nerol and esters thereof, neroli oil, famesol, nerolidol, eugenol, isoeugenol, patchouli oil, vetiveryl acetate, cedryl acetate, p tertiary butyl cyclohexyl acetate and terpineol.
11. A process for the preparation of a compound having the formula:
wherein X represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, m has a value of 0 or 1, n has a value of 1 or 2, n + m = 2 and the dashed line in-dicates alternative positions for a unit of unsaturation characterised in that an alcohol having the formula:
is cyclised by heating in the presence of an acid.
wherein X represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, m has a value of 0 or 1, n has a value of 1 or 2, n + m = 2 and the dashed line in-dicates alternative positions for a unit of unsaturation characterised in that an alcohol having the formula:
is cyclised by heating in the presence of an acid.
12. A process according to Claim 11 characterised in that the acid is phosphoric acid.
13. A process according to Claim 12 characterised in that an acid solution comprising 15 to 35% by weight of acid is employed in a volume at least equal to that of the organic phase.
14. A process according to Claim 11 characterised in that the acid is present in the form of a solution of a sulphonic acid in an organic solvent.
15. A process according to Claim 14 wherein the acid is para toluene sulphonic acid.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2586377 | 1977-06-21 | ||
| GB25863/77 | 1977-06-21 | ||
| GB1333878 | 1978-04-05 | ||
| GB13338/78 | 1978-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1115284A true CA1115284A (en) | 1981-12-29 |
Family
ID=26249725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA305,619A Expired CA1115284A (en) | 1977-06-21 | 1978-06-16 | Derivatives of 3,3,7,8-tetramethyl-2-oxabicyclo-¬4, 4,0|-decane and their use in perfumery |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0000257B1 (en) |
| JP (1) | JPS549276A (en) |
| AU (1) | AU517033B2 (en) |
| CA (1) | CA1115284A (en) |
| DE (1) | DE2861629D1 (en) |
| GB (1) | GB2002358B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3302000A1 (en) * | 1983-01-21 | 1984-07-26 | Danfoss A/S, Nordborg | HYDRAULIC VALVE |
| JPS6174904A (en) * | 1984-09-17 | 1986-04-17 | Daikin Ind Ltd | Hydraulic device |
| JP4746684B2 (en) * | 2009-03-24 | 2011-08-10 | 有限会社長州電気 | Telescopic device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2483824A (en) * | 1947-07-29 | 1949-10-04 | Shell Dev | Derivatives of 2, 1-benzopyran |
-
1978
- 1978-06-16 CA CA305,619A patent/CA1115284A/en not_active Expired
- 1978-06-20 DE DE7878300056T patent/DE2861629D1/en not_active Expired
- 1978-06-20 EP EP78300056A patent/EP0000257B1/en not_active Expired
- 1978-06-21 JP JP7429778A patent/JPS549276A/en active Pending
- 1978-06-21 AU AU37336/78A patent/AU517033B2/en not_active Expired
- 1978-07-18 GB GB7830148A patent/GB2002358B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2861629D1 (en) | 1982-03-25 |
| GB2002358A (en) | 1979-02-21 |
| JPS549276A (en) | 1979-01-24 |
| EP0000257B1 (en) | 1982-02-17 |
| GB2002358B (en) | 1982-04-15 |
| AU517033B2 (en) | 1981-07-02 |
| EP0000257A1 (en) | 1979-01-10 |
| AU3733678A (en) | 1980-01-03 |
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