US3875241A - Bis-enolethers of substituted acetyl cyclohexanones - Google Patents

Bis-enolethers of substituted acetyl cyclohexanones Download PDF

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US3875241A
US3875241A US110652A US11065271A US3875241A US 3875241 A US3875241 A US 3875241A US 110652 A US110652 A US 110652A US 11065271 A US11065271 A US 11065271A US 3875241 A US3875241 A US 3875241A
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enolethers
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acetyl
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hexene
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Bernard Pierre Corbier
Paul Jose Teisseire
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Roure SA
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Roure Bertrand Dupont SA
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Priority to US05/546,533 priority patent/US3953516A/en
Priority to US05/546,531 priority patent/US3953515A/en
Priority to US05/546,564 priority patent/US3948815A/en
Priority to US05/546,532 priority patent/US3953471A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/188—Unsaturated ethers
    • 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
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
    • 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
    • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
    • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
    • C11B9/0057—Spiro compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • 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

Definitions

  • ABSTRACT Novel diketones illustrative of which is that having the formula and derivatives thereof, illustrative of which are lower enolethers such as those of the formula where R represents a lower alkyl group. These compounds possess useful perfume properties.
  • the enolethers of said earlier related application will be clarified as side-chain lower enolethers whereas the enolethers of the present invention will be referred to as ring-substituted lower enolethers.
  • R and R represent lower alkyl or cyclo lower alkyl groups, preferably containing up to 5 carbon atoms, such as methyl, ethyl, propyl, bu-
  • ring-substituted lower enolethers, enolesters or ketals of said diketones may, for example contain 1 to 5 carbon atoms in the ether or ester or ketal groups.
  • the compounds of formula 1, their ring-substituted enolethers, enolesters and ketals have interesting and pleasant odors, in particular, they possess woody odors, and accordingly are useful as odorants and can be employed as such in, for example, perfumes, soaps, detergents, cleansing agents and other scented compositions.
  • the invention comprises compounds in accordance with the formula and also the corresponding ring-substituted lower enolethers lower enolesters and ketals.
  • R, and R represent lower alkyl or cyclo lower alkyl groups.
  • R represents a lower alkyl group, R, and R which may be the same or different, represent lower alkyl or cycloloweralkyl groups and the symbols R each represent a lower alkyl group or, taken together, a lower alkylene group.
  • the compounds of the invention of formulae II, III, IV and V posesses interesting and useful odoriferous properties. These compounds may accordingly be used alone or, more normally, in admixture with other perfume ingredients and carriers used in perfumes or odorants, in such odoriferous compositions as perfumes, soaps, detergents, cleansing agents and other scented compositions.
  • the compounds of the invention are of particular interest in that they possess pleasant woody odors.
  • the monoethylenolether having the formula VII i.e. l-ethoxy-4-acetyl-3,3,5,5-tetramethylcyclo-1- hexene has a highly refined, woody smell, as has the ethylene ketal having the formula o 11 0 VIII
  • the a,B-unsaturated ketones of formula IX used as starting materials are to a large extent known compounds such as, for example, mesityl oxide, and can be prepared by methods known per se by condensing two ketones which may be the same or different.
  • mesityl oxide can be obtained from acetone by auto-condensation.
  • Other typical starting compounds of formula IX are, for example, those in which R and R represent ethyl groups Whilst R represents hydrogen, and those in which R is ethyl, R methyl, and R hydrogen.
  • the alkyl group of the aforementioned alkyl orthoformate is preferably a lower primary alkyl group with l to 5 carbon atoms, such as methyl, ethyl, n-propyl, butyl, isobutyl, amyl or isoamyl.
  • Suitable acid catalysts are, for example, Lewis acids such as boron trifluoride etherate.
  • Reaction of the ketone corresponding to formula IX with the alkylorthoformate generally yields a mixture of several enolethers which are distinguished by the different positions of the enolether group.
  • the enolether group can be present in the side chain, as is the case with monoenolethers having the general formula in which R represents a lower alkyl group, in particular a primary alkyl group with l to 5 carbon atoms, and R and R are lower alkyl groups.
  • R represents a lower alkyl group, in particular a primary alkyl group with l to 5 carbon atoms
  • R and R are lower alkyl groups.
  • the enolether group may be present in the ring, as is the case with monoenolethers having the general formula in which R, R and R are as defined above.
  • enolether groups may be present both in the side chain and in the ring, as is the case with bisenolethers having the general formula in which R, R and R are as defined above.
  • reaction products can be isolated from the reaction mixture by conventional methods, for example by repeated fractional distillation. Completely pure products can be obtained by methods such as chromatography.
  • the resulting enolethers of formulae X, III or IV can be converted into the corresonding diketones of formula II by hydrolysis, preferably acid hydrolysis.
  • enolethers corresponding to the formulae XIII in which R is as defined above are subjected to the action of dilute hydrochloric acid at room temperature, 4-acetyl-3,3,5,5-tetramethylcyclohexanone is formed, i.e. the diketone having the formula
  • the diketones thus obtained can be ketalized by methods known per se, for example by reaction with a lower alkylene glycol such as ethylene or propylene glycol, in the presence of an acid agent.
  • a lower alkylene glycol such as ethylene or propylene glycol
  • ketals of the general formula 3o XV in which R is as defined above for example, 4-acetyl- 1,l-dimethoxy-3,3,5,5-tetramethylcyc1ohexane or 4- acetyl-l ,1-ethylenedihydroxy-3,3,5,5-tetramethylcyclohexane.
  • the diketones of formula 11 can also be converted by methods known per se into the corresponding enolethers are enolesters.
  • conversion into an enolether can be effected by reaction with a lower alkylorthoformate such as methylor ethylorthoformate, in the presence of a Lewis acid such as boron trifluoride etherate.
  • the aforementioned diketone can be reacted with a conventional esterifying agent, for instance with a functional derivative of a lower alkane carboxylic acid, illustratively with an anhydride or an ester of such an acid, such as isopropenyl acetate.
  • a conventional esterifying agent for instance with a functional derivative of a lower alkane carboxylic acid, illustratively with an anhydride or an ester of such an acid, such as isopropenyl acetate.
  • EXAMPLE 1 1 ml. of boron trifluoride etherate is added to 117.6 g. (1.2 mols) of mesityl oxide. The temperature of the reaction mixture is increased to 50, 148 g. (1 mol) of ethylorthoformate being added to it over a period of 2 hours. The temperature is kept at 30 for 24 hours, after which 5 g. of powdered sodium carbonate are added and the mixture stirred for 30 minutes. The resulting product is washed once with 100 ml. of a 10% sodium carbonate solution and twice with 100 ml. of a 30% brine solution. A mixture of ethyl alcohol, ethyl formate and excess mesityl oxide is obtained by distillation at normal pressure. The following compounds are obtained as the main products in practically the same quantities:
  • EXAMPLE 2 Either of the enolethers obtained in accordance with Example 1 or a mixture thereof is hydrolyzed with 10 times its weight of 0.5% aqueous hydrochloric acid by stirring the mixture for 24 hours at room temperature (approx. 2025). In this way, 75 g. of crude product are obtained from 100 g. of starting product. It is purified by fractional distillation yielding 4-acetyl-3,3,5,5- tetramethylcyclohexanone. Boiling point: 108/2 mm.; n 1.4786.
  • EXAMPLE 3 1 mol of 4-acetyl-3,3,5,5-tetramethylcyc1ohexanone is reacted in benzene solution with 1 mo] of ethylene glycol in the presence of p-toluene sulphonic acid. On completion of the reaction, the benzene solution is washed, 4-acety1-1,1-ethylenedihydroxy-3 ,3 ,5 ,5- tetramethylcyclohexanone being obtained in crystallized form following removal of the benzene. Melting point: 113113.5.
  • EXAMPLE 6 l-acetoxy-4-acetyl-3 ,3 ,5 ,5 -tetramethylcyclo- 1 hexene (b.p. 9294/0.3 mm.; n 1.4785) is obtained by reacting 4-acetyl-3,3,5,5-tetramethylcyclohexanone with isopropenyl acetate. This compound is distinguished by its very refined, but slightly woody and amber-like odor.
  • EXAMPLE 7 Starting from mesityl oxide and methylorthoformate, the procedure described in Example 1 yields a mixture from which the bis-enolether, 1-methoxy-4-( 1- methoxyvinyl)-3,3,5 ,5-tetramethylcyclo-1-hexer1e is isolated; boiling point 1 -84/l mm., n 1.4872.
  • EXAMPLE 8 Starting from mesityl oxide and npropylorthoformate, the procedure described in Example 1 yields a mixture of the corresponding npropylenolethers boiling at 100/1 mm., n 1.4795. Its odor is similar to that of the corresponding mixture of Example 1.
  • EXAMPLE 10 Starting from mesityl oxide and isoamylorthoformate, the procedure described in Example 1 yields a mixture of the corresponding isoamylenolethers boiling at 110-120/1 mm.; n 1.4780. lts odor is similar to that of the corresponding mixture of Example 1, although slightly weaker.
  • EXAMPLE 1 1 0.8 ml of etherate of boron trifluoride are added to 496 g (4 moles) of cyclopropy1-4-pentene-3-one-2. The temperature of the mixture is brought up to 50C and after 4 hours 1 18.4 g (0,8 mole) of ethyl orthoformiate is added. The temperature is maintained at 50C for 4 hours. The solvent is then removed in a boiling water bath under reduced pressure (20 mm of Hg). There is obtained 550 g of crude product containing excess cyclopropyl-4-pentene-3-one-2 which is recovered by distillation.
  • the crude product thus obtained can be used directly in this condition in the preparation of perfume compositions.
  • the crude product had a strong ambergris/timber smell.
  • EXAMPLE 12 Some odorant compositions containing a mixture of 4-(1-ethoxyvinyl)-3,3,5 ,5-tetramethylcyclohexanone (substance A) and 1-ethoxy-4-(1-ethoxyvinyl)-3,3,5,5- cyclo-l-hexene (substance B), are described in the following:
  • a compound as claimed in claim 1 which is lethoxy-4-( l-ethoxyvinyl)-3 ,3,5 ,S-tetramethyl-cyclo-l hexene.

Abstract

Novel diketones, illustrative of which is that having the formula

AND DERIVATIVES THEREOF, ILLUSTRATIVE OF WHICH ARE LOWER ENOLETHERS SUCH AS THOSE OF THE FORMULA

WHERE R represents a lower alkyl group. These compounds possess useful perfume properties.

Description

United States Patent [1 1 Corbier et al.
[451 Apr. 1, 1975 1 BIS-ENOLETHERS OF SUBSTITUTED ACETYL CYCLOHEXANONES [75] Inventors: Bernard Pierre Corbier; Paul Jose Teisseire, both of Grasse, France 173 Assignee: S.A. des Establissements Rowre- Bertrand Fils & Justin Dupont. Grasse. France [22] Filed: Jan. 28, 1971 [21] Appl. No.: 110,652
Related U.S. Application Data [63] Continuation-impart of Scr. No. 585.259, Oct. 10,
I966. Pat. NO. 3578.715.
Primary Iixuminor-Bernard Helfin :lsxislanl E.\'umin0rNorman Morgenstern Almrncy, Agent. or FirmWallenstein, Spangenberg. Hattis & Strampel [57] ABSTRACT Novel diketones, illustrative of which is that having the formula and derivatives thereof, illustrative of which are lower enolethers such as those of the formula where R represents a lower alkyl group. These compounds possess useful perfume properties.
4 Claims, No Drawings BIS-ENOLETHERS OF SUBSTITUTED ACETYL CYCLOHEXANONES CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of application Ser. No. 585,259 filed Oct. 10, 1966, now US. Pat. No. 3,578,715, patented May 11, 1971. Said earlier application relates to novel lower enolethers illustrative of which are those of the formula wherein R represents a lower alkyl group. For the sake of clarity, the enolethers of said earlier related application will be clarified as side-chain lower enolethers whereas the enolethers of the present invention will be referred to as ring-substituted lower enolethers.
BRIEF SUMMARY OF THE INVENTION This invention relates to novel diketones of the general formula and also to the corresponding ring-substituted lower enolethers, lower enolesters and ketals of said diketones. In general formula I, R and R represent lower alkyl or cyclo lower alkyl groups, preferably containing up to 5 carbon atoms, such as methyl, ethyl, propyl, bu-
tyl, cyclo propyl or cyclo butyl. The aforementioned ring-substituted lower enolethers, enolesters or ketals of said diketones may, for example contain 1 to 5 carbon atoms in the ether or ester or ketal groups.
The compounds of formula 1, their ring-substituted enolethers, enolesters and ketals have interesting and pleasant odors, in particular, they possess woody odors, and accordingly are useful as odorants and can be employed as such in, for example, perfumes, soaps, detergents, cleansing agents and other scented compositions.
DETAILED DESCRIPTION OF THE INVENTION The invention comprises compounds in accordance with the formula and also the corresponding ring-substituted lower enolethers lower enolesters and ketals. In these compounds R, and R represent lower alkyl or cyclo lower alkyl groups.
Thus, the invention comprises compounds in accordance with any of the following formulae:
R 0 /R2 3 2 /R l l \/\CH MR2 3 B0 (II) 1 (III) 0 R2 ll CH R m 3 wherein in each of formulae II to V, R represents a lower alkyl group, R, and R which may be the same or different, represent lower alkyl or cycloloweralkyl groups and the symbols R each represent a lower alkyl group or, taken together, a lower alkylene group.
The compounds of the invention of formulae II, III, IV and V posesses interesting and useful odoriferous properties. These compounds may accordingly be used alone or, more normally, in admixture with other perfume ingredients and carriers used in perfumes or odorants, in such odoriferous compositions as perfumes, soaps, detergents, cleansing agents and other scented compositions.
The compounds of the invention are of particular interest in that they possess pleasant woody odors.
Special examples of compounds of this invention and their odors are:
The bis-ethylenolether having the formula H 6 0 VI Le. l-ethoxy-4-( 1ethoxyvinyl )-3 ,3 ,5 ,S-tetramethylcyclo-l-hexene, has a pleasant woody smell.
The monoethylenolether having the formula VII i.e. l-ethoxy-4-acetyl-3,3,5,5-tetramethylcyclo-1- hexene has a highly refined, woody smell, as has the ethylene ketal having the formula o 11 0 VIII The compounds of the invention may be prepared by reacting a ketone of the general formula c=p-co-cn IX R J R in which R R are as defined above, with a lower alkyl orthoformate in the presence of an acid catalyst and, if desired, subjecting the reaction product to hydrolysis, ketalization, enol etherification or enol esterification.
The a,B-unsaturated ketones of formula IX used as starting materials are to a large extent known compounds such as, for example, mesityl oxide, and can be prepared by methods known per se by condensing two ketones which may be the same or different. For example, mesityl oxide can be obtained from acetone by auto-condensation. Other typical starting compounds of formula IX are, for example, those in which R and R represent ethyl groups Whilst R represents hydrogen, and those in which R is ethyl, R methyl, and R hydrogen.
The alkyl group of the aforementioned alkyl orthoformate is preferably a lower primary alkyl group with l to 5 carbon atoms, such as methyl, ethyl, n-propyl, butyl, isobutyl, amyl or isoamyl. Suitable acid catalysts are, for example, Lewis acids such as boron trifluoride etherate.
Reaction of the ketone corresponding to formula IX with the alkylorthoformate generally yields a mixture of several enolethers which are distinguished by the different positions of the enolether group. For example, the enolether group can be present in the side chain, as is the case with monoenolethers having the general formula in which R represents a lower alkyl group, in particular a primary alkyl group with l to 5 carbon atoms, and R and R are lower alkyl groups. The compounds of formula X are claimed in our aforesaid copending application Ser. No. 565,259, now US. Pat. No. 3,578,715.
On the other hand, the enolether group may be present in the ring, as is the case with monoenolethers having the general formula in which R, R and R are as defined above.
Finally, enolether groups may be present both in the side chain and in the ring, as is the case with bisenolethers having the general formula in which R, R and R are as defined above.
The quantitative proportion of these various enolethers is governed both by the reaction conditions components and above all by the quantities in which the two starting components are used. In cases where a ketone of formula IX is used in a large excess in relation to the alkylorthoformate, the monoenolethers of formula X will mostly be obtained. If, on the other hand, the two starting components are used in approximately equimolar quantities, the bis-enolethers of formula IX will predominate in the product.
The reaction products can be isolated from the reaction mixture by conventional methods, for example by repeated fractional distillation. Completely pure products can be obtained by methods such as chromatography.
The resulting enolethers of formulae X, III or IV can be converted into the corresonding diketones of formula II by hydrolysis, preferably acid hydrolysis.
If, for example, enolethers corresponding to the formulae XIII in which R is as defined above, are subjected to the action of dilute hydrochloric acid at room temperature, 4-acetyl-3,3,5,5-tetramethylcyclohexanone is formed, i.e. the diketone having the formula The diketones thus obtained can be ketalized by methods known per se, for example by reaction with a lower alkylene glycol such as ethylene or propylene glycol, in the presence of an acid agent. There are obtained in this way monoketals corresponding to the general formula in which the two symbols R each represent a lower alkyl group, preferably containing 1 to 4 carbon atoms,
or together represent a lower alkylene group, preferably containing 2 to 4 carbon atoms, whilst the symbols R and R are as defined above.
For example, one obtains from the diketone of formula XIV ketals of the general formula 3o XV in which R is as defined above, for example, 4-acetyl- 1,l-dimethoxy-3,3,5,5-tetramethylcyc1ohexane or 4- acetyl-l ,1-ethylenedihydroxy-3,3,5,5-tetramethylcyclohexane.
The diketones of formula 11 can also be converted by methods known per se into the corresponding enolethers are enolesters. For example, conversion into an enolether can be effected by reaction with a lower alkylorthoformate such as methylor ethylorthoformate, in the presence of a Lewis acid such as boron trifluoride etherate. For conversion into an enol ester, for example into 1-acetoxy-4-acety1-3,3,5,5- tetramethylcyclo-l-hexene, the aforementioned diketone can be reacted with a conventional esterifying agent, for instance with a functional derivative of a lower alkane carboxylic acid, illustratively with an anhydride or an ester of such an acid, such as isopropenyl acetate.
In the following Examples, the temperatures are given in degrees Centigrade (C).
EXAMPLE 1 1 ml. of boron trifluoride etherate is added to 117.6 g. (1.2 mols) of mesityl oxide. The temperature of the reaction mixture is increased to 50, 148 g. (1 mol) of ethylorthoformate being added to it over a period of 2 hours. The temperature is kept at 30 for 24 hours, after which 5 g. of powdered sodium carbonate are added and the mixture stirred for 30 minutes. The resulting product is washed once with 100 ml. of a 10% sodium carbonate solution and twice with 100 ml. of a 30% brine solution. A mixture of ethyl alcohol, ethyl formate and excess mesityl oxide is obtained by distillation at normal pressure. The following compounds are obtained as the main products in practically the same quantities:
a. 1-ethoxy-4-( 1-ethoxyvinyl)-3,3,5,5-tetramethylcyclo-l-hexene; boiling point: 7476/2 mm; n 1.4744; carbonyl index: 220 (theoretical value for one function 222).
b. 4-( 1-ethoxyvinyl)-3 ,3 ,5 ,S-tetramethylcyclohexanone (said (b) compound being described in Example 1 of our aforesaid copending Application and being covered in claims thereof).
EXAMPLE 2 Either of the enolethers obtained in accordance with Example 1 or a mixture thereof is hydrolyzed with 10 times its weight of 0.5% aqueous hydrochloric acid by stirring the mixture for 24 hours at room temperature (approx. 2025). In this way, 75 g. of crude product are obtained from 100 g. of starting product. It is purified by fractional distillation yielding 4-acetyl-3,3,5,5- tetramethylcyclohexanone. Boiling point: 108/2 mm.; n 1.4786.
EXAMPLE 3 1 mol of 4-acetyl-3,3,5,5-tetramethylcyc1ohexanone is reacted in benzene solution with 1 mo] of ethylene glycol in the presence of p-toluene sulphonic acid. On completion of the reaction, the benzene solution is washed, 4-acety1-1,1-ethylenedihydroxy-3 ,3 ,5 ,5- tetramethylcyclohexanone being obtained in crystallized form following removal of the benzene. Melting point: 113113.5.
EXAMPLE 4 132.5 g. (1.25 mols) of methylorthoformate are added dropwise at 35 i 5 over a period of 1 hour to 196 g. (1 mol) of 4-acetyl-3,3,5,5-tetramethylcyclohexanone containing 1 ml. of boron trifluoride etherate. On completion of the addition, the reaction mixture is kept for another 24 hours at the aforementioned temperature. 8 g. of sodium carbonate are then added and the mixture stirred for 15 minutes, after which it is diluted with 1 litre of petroleum ether and washed in the usual way. Following repeated distillations, the following two compounds are obtained in a ratio of 1:4 in a total yield of approximately a. 4-acetyl-1-methoxy-3 ,3 ,5 ,S-tetramethylcyclo- 1 hexene: Boiling point: 7880/1 mm.; n 1.4780.
7 b. 4-acetyl-1 ,1-dimethoxy-3 ,3 ,5 ,S-tetramethylcyclohexane; Boiling point: 9093/1 mm.; Melting point: 5960. Both these compounds have a pungent cork odor accompanied in the case of b) by a distinct suggestion of carbophyllenol.
EXAMPLE 5 The following monoenolethers are similarly obtained:
4-acetyll -ethoxy-3 ,3 ,5 ,S-tetramethylcyclo- 1 hexene; Boiling point: 90/1 by mm.; nD 1.4745; this compound smells of cork and camations, with a trace of geranium.
4-acetyl-1-n-propoxy-3 ,3 ,5 ,S-tetramethylcyclo-l hexene; Boiling point: 92/O.4 mm.; n 1.4749; this compound has a musty odor, reminiscent of patchouli.
4-acetyl- 1 -n-butoxy-3 ,3,5 ,S-tetramethylcyclo- 1 hexene; Boiling point 97-99/0.44 mm.; n 1.4735; this compound has a pungent, woody odor reminiscent of sandalwood, accompanied by a musty flavor.
4-acetyl-1-isobutoxy-3 ,3 ,5 ,S-tetramethylcyclo- 1 hexene; Boiling point 107-109/O.5 mm.; n 1.4712; this compound has a pungent, musty odor, reminiscent of patchouli.
4-acetyl-1-n-amyloxy-3 ,3 ,5 ,5 -tetramethylcyclo- 1 hexene; Boiling point 101104/0.3 mm.; n 1.4630; odor weaker than in the preceding examples, but of the same woody, musty flavor.
4-acetyl-1-isoamyloxy-3 ,3 ,5 ,S-tetramethylcyclo- 1 hexene; Boiling point 106-108/0.2 mm.; n 1.4658; this compound has the same type of odor as the substances described above.
4-acetyll -allyloxy-3 ,3 ,5 ,S-tetramethylcyclo-l hexene; Boiling point 95-100/0.5 mm.; n 1.4846; woody smell with a trace of carnations.
In addition, the corresponding ketals can be obtained, such as for example:
4-acetyl-1,1-diethoxy-3 ,3 ,5 ,S-tetramethylcyclohexane; Boiling point 104/1 mm.; n 1.4676.
4-acetyl-1,1-di-n-propoxy-3 ,3 ,5 ,5 -tetramethylcyclohexane; Boiling point 1 18/0.4 mm.; n 1.4676.
4-acetyl-1,1-di-n-butoxy-3 ,3 ,5 ,S-tetramethylcyclohexane; Boiling point 125l27/0.4 mm.; n 1.4662; weak, woody flavor.
4-acetyl-1,l-di-isobutoxy-3 ,3 ,5 ,S-tetramethylcyclohexane; Boiling point l25128/0.5 mm.; Melting point 48.
EXAMPLE 6 l-acetoxy-4-acetyl-3 ,3 ,5 ,5 -tetramethylcyclo- 1 hexene (b.p. 9294/0.3 mm.; n 1.4785) is obtained by reacting 4-acetyl-3,3,5,5-tetramethylcyclohexanone with isopropenyl acetate. This compound is distinguished by its very refined, but slightly woody and amber-like odor.
EXAMPLE 7 Starting from mesityl oxide and methylorthoformate, the procedure described in Example 1 yields a mixture from which the bis-enolether, 1-methoxy-4-( 1- methoxyvinyl)-3,3,5 ,5-tetramethylcyclo-1-hexer1e is isolated; boiling point 1 -84/l mm., n 1.4872.
EXAMPLE 8 Starting from mesityl oxide and npropylorthoformate, the procedure described in Example 1 yields a mixture of the corresponding npropylenolethers boiling at 100/1 mm., n 1.4795. Its odor is similar to that of the corresponding mixture of Example 1.
EXAMPLE 9 Starting from mesityl oxide and isobutylorthoformate, the procedure described in Example 1 yields a mixture of the corresponding isobutylenolethers boiling at 1l0-120/1 mm.; n 1.4775. lts odor is similar to that of the corresponding mixture of Example 1, although somewhat stronger.
EXAMPLE 10 Starting from mesityl oxide and isoamylorthoformate, the procedure described in Example 1 yields a mixture of the corresponding isoamylenolethers boiling at 110-120/1 mm.; n 1.4780. lts odor is similar to that of the corresponding mixture of Example 1, although slightly weaker.
EXAMPLE 1 1 0.8 ml of etherate of boron trifluoride are added to 496 g (4 moles) of cyclopropy1-4-pentene-3-one-2. The temperature of the mixture is brought up to 50C and after 4 hours 1 18.4 g (0,8 mole) of ethyl orthoformiate is added. The temperature is maintained at 50C for 4 hours. The solvent is then removed in a boiling water bath under reduced pressure (20 mm of Hg). There is obtained 550 g of crude product containing excess cyclopropyl-4-pentene-3-one-2 which is recovered by distillation.
The residue remaining after the distillation (121,5 g) is distilled under a pressure of 0,5 mm of Hg. g of product distills over in the range from 1 10-124C. The product shows Chromatographic analysis of the vapour phase indicates the presence of 4-acetyl-3,5-dimethyl-3,S-dicyclopropylcyclohexanone;
4-(ethoxy-vinyl)-3,5-dimethyl-3,5-dicyclopropylcyclohex-l-ene and 1-ethoxy-4-( l-ethoxy-vinyl )-3 ,5-dimethyl-3 ,5- dicyclopropyl-cyclohex- 1 -ene.
The infra-red spectrum of the product is as follows:
(Cl-l 3000, 3078 and 3110 cm; (CH 1010 cm; (CO) 1705 cm (strong band); (C=) 1660 and 1642 cm (2 strong bands); (C-O) 1235 and 1295 cm; (CH) 3078 cm; (C=C) 1640 cm"; (H) 820 cm and (CH 795 cm".
The crude product thus obtained can be used directly in this condition in the preparation of perfume compositions. The crude product had a strong ambergris/timber smell.
EXAMPLE 12 Some odorant compositions containing a mixture of 4-(1-ethoxyvinyl)-3,3,5 ,5-tetramethylcyclohexanone (substance A) and 1-ethoxy-4-(1-ethoxyvinyl)-3,3,5,5- cyclo-l-hexene (substance B), are described in the following:
PARTS BY WEIGHT We claim: 1. Compounds having the general formula CH 2 IV wherein R represents a lower alkyl group and R and R represent lower alkyl groups.
2. Compounds as claimed in claim 1 wherein R and R represent methyl groups.
3. A compound as claimed in claim 1 which is lethoxy-4-( l-ethoxyvinyl)-3 ,3,5 ,S-tetramethyl-cyclo-l hexene.
4. A compound which is l-ethoxy-4-(1-ethoxyvinyl)- 3 ,5-dimethyl-3,5-dicyclopropyl-cyclo- 1 -hexene.

Claims (4)

1. COMPOUNDS HAVING THE GENERAL FORMULA
2. Compounds as claimed in claim 1 wherein R1 and R2 represent methyl groups.
3. A compound as claimed in claim 1 which is 1-ethoxy-4-(1-ethoxyvinyl)-3,3,5,5-tetramethyl-cyclo-1-hexene.
4. A compound which is 1-ethoxy-4-(1-ethoxyvinyl)-3,5-dimethyl-3,5-dicyclopropyl-cyclo-1-hexene.
US110652A 1965-10-14 1971-01-28 Bis-enolethers of substituted acetyl cyclohexanones Expired - Lifetime US3875241A (en)

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US110652A US3875241A (en) 1965-10-14 1971-01-28 Bis-enolethers of substituted acetyl cyclohexanones
US05/546,533 US3953516A (en) 1965-10-14 1975-02-03 Mono-enol ethers of 4-acetyl-3,3,5,5-tetramethylcyclohexanone
US05/546,531 US3953515A (en) 1965-10-14 1975-02-03 4-Acetyl-3,3,5,5 tetraalkylcyclohexanones
US05/546,564 US3948815A (en) 1965-10-14 1975-02-03 Perfume compositions
US05/546,532 US3953471A (en) 1965-10-14 1975-02-03 Ketals of 4-acetyl-3,3,5,5-tetramethylcyclohexanone

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CH1421665A CH467333A (en) 1965-10-14 1965-10-14 Use of diketones as odorants in the preparation of perfume compositions
US58525966A 1966-10-10 1966-10-10
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US05/546,564 Division US3948815A (en) 1965-10-14 1975-02-03 Perfume compositions
US05/546,532 Division US3953471A (en) 1965-10-14 1975-02-03 Ketals of 4-acetyl-3,3,5,5-tetramethylcyclohexanone
US05/546,531 Division US3953515A (en) 1965-10-14 1975-02-03 4-Acetyl-3,3,5,5 tetraalkylcyclohexanones

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957877A (en) * 1972-10-26 1976-05-18 Firmenich S.A. Butenoyl-cyclohexanones
US3974181A (en) * 1967-02-23 1976-08-10 Hoffmann-La Roche Inc. Trimethyl-1,4-dioxaspiro[4,5]dec-7-en-8-methanol
US4021488A (en) * 1976-08-11 1977-05-03 International Flavors & Fragrances Inc. 1-Acetyl-3,3-dimethyl-(2-propenyl)cyclohexane
US4123393A (en) * 1977-02-04 1978-10-31 International Flavors & Fragrances Inc. Substituted-norbornane perfume compositions
US4153615A (en) * 1978-03-27 1979-05-08 Hoffmann-La Roche Inc. Method of producing coloring agents
US4175569A (en) * 1976-08-11 1979-11-27 International Flavors & Fragrances Inc. Substituted-1-ocetyl-3,3-dimethylcyclohexane employed in flavoring tobacco compositions
US4202840A (en) * 1978-09-29 1980-05-13 Stauffer Chemical Company 1-Hydroxy-2-(alkylketo)-4,4,6,6-tetramethyl cyclohexen-3,5-diones
US4506102A (en) * 1982-05-27 1985-03-19 Chemische Werke Huls Ag 2-Methoxyethyl cyclododecenyl ether and processes for its preparation and conversion to 2-methoxyethyl cyclododecyl ether

Citations (1)

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GB1141910A (en) * 1965-10-14 1969-02-05 Roure Bertrand Dupont Sa Cyclic compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1141910A (en) * 1965-10-14 1969-02-05 Roure Bertrand Dupont Sa Cyclic compounds

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3974181A (en) * 1967-02-23 1976-08-10 Hoffmann-La Roche Inc. Trimethyl-1,4-dioxaspiro[4,5]dec-7-en-8-methanol
US3957877A (en) * 1972-10-26 1976-05-18 Firmenich S.A. Butenoyl-cyclohexanones
US4021488A (en) * 1976-08-11 1977-05-03 International Flavors & Fragrances Inc. 1-Acetyl-3,3-dimethyl-(2-propenyl)cyclohexane
US4081479A (en) * 1976-08-11 1978-03-28 International Flavors & Fragrances Inc. Substituted-1-acetyl-3,3-dimethylcyclohexane
US4175569A (en) * 1976-08-11 1979-11-27 International Flavors & Fragrances Inc. Substituted-1-ocetyl-3,3-dimethylcyclohexane employed in flavoring tobacco compositions
US4123393A (en) * 1977-02-04 1978-10-31 International Flavors & Fragrances Inc. Substituted-norbornane perfume compositions
US4153615A (en) * 1978-03-27 1979-05-08 Hoffmann-La Roche Inc. Method of producing coloring agents
US4202840A (en) * 1978-09-29 1980-05-13 Stauffer Chemical Company 1-Hydroxy-2-(alkylketo)-4,4,6,6-tetramethyl cyclohexen-3,5-diones
US4506102A (en) * 1982-05-27 1985-03-19 Chemische Werke Huls Ag 2-Methoxyethyl cyclododecenyl ether and processes for its preparation and conversion to 2-methoxyethyl cyclododecyl ether

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