WO1980000915A1 - Substituted cyclic alcohols,methods of preparing and compositions containing same - Google Patents

Substituted cyclic alcohols,methods of preparing and compositions containing same Download PDF

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Publication number
WO1980000915A1
WO1980000915A1 PCT/US1979/000542 US7900542W WO8000915A1 WO 1980000915 A1 WO1980000915 A1 WO 1980000915A1 US 7900542 W US7900542 W US 7900542W WO 8000915 A1 WO8000915 A1 WO 8000915A1
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WO
WIPO (PCT)
Prior art keywords
compound
fragrance
carbon
mixture
preparing
Prior art date
Application number
PCT/US1979/000542
Other languages
English (en)
French (fr)
Inventor
B Willis
J Yureiko
Original Assignee
Fritzsche Dodge & Olcott Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US05/957,047 external-priority patent/US4188310A/en
Application filed by Fritzsche Dodge & Olcott Inc filed Critical Fritzsche Dodge & Olcott Inc
Publication of WO1980000915A1 publication Critical patent/WO1980000915A1/en

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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
    • C11B9/0026—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
    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a non-condensed ring
    • 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
    • C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
    • 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
    • C07C45/673—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 change of size of the carbon skeleton
    • C07C45/676—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 change of size of the carbon skeleton by elimination of carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
    • 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
    • C11B9/003—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing less than six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • 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
    • C07C2601/14—The ring being saturated
    • 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

  • alkyl-substituted cyclohexenols and cyclohexanols as fragrance and flavoring materials is well known.
  • carveol which has the general structure
  • (+) -carveol is a natural component of spearmint oil (+) - carveol has been found in the oils of Fortunella margarita, Anethum graveolens and Heracleum canescens. Further examples may be found in Actander, Perfume and Flavor Chemicals (1969). For example, trimethylcyclohexanol which has the structure
  • Actander compound no. 432 is ortho-tertiary-butylcyclohexanol which has the structure
  • This compound has a very tenacious, mild Sandalwood-type odor that is not as sweet and balsamic as Sandalwood oil and not nearly as powerful in active use.
  • This material is used in perfume, compositions for its Sandalwood character and economical stability.
  • U.S. Patent No. 4,052,341 discloses the use in fragrance compositions of 3-methyl-5-(2,2,3-trimethylcyclopent-3-en-l-yl)-pentan-2-ol which has the structure
  • This compound is described as possessing a strong, precious woody odor reminiscent of Sandalwood oil.
  • the present invention also provides efficient and economical processes for preparing these compounds.
  • the compound having the structure having the structure
  • R is lower alkyl and 2,2,3-trimethyl-3-cyclopenten-1-acetaldehyde having the structure
  • an admixture of Compounds 1 and2 is also useful as a fragrance material in place of either of the individual compounds.
  • Such a mixture can be prepared directly by reacting an acetoacetic ester (3) and 2,2, 3-trimethyl-3-cyclopenten-1-acetaldehyde (4) in the presence of an organic base to produce Compound 7.
  • Decarboxylation of Compound 7 by treatment with a base yields Compound 8 which upon reduction with a reagent such as sodium borohydride yields after workup a mixture of Compounds 1 and 2.
  • fragrance compositions can be prepared by incorporating in these compositions Compound 1 or Compound 2 or a mixture thereof in amounts effective to impart fragrance to the composition.
  • the dashed line may be either a carbon-carbon single bond or a carbon-carbon double bond have been prepared.
  • compounds exhibit soft, warm woody notes with powdery nuances rendering these compounds useful as fragrance materials. These compounds exhibit similar odor characteristics and may be used individually or as mixtures in fragrance applications.
  • Geometrical and optical isomers of these compounds may be separated by techniques known to the art. However, such separation is not necessary, since such mixtures of isomers can be employed directly without further separation. Additionally, mixture of these compounds wherein the dashed line may be either a carbon-carbon single bond or a carbon-carbon double bond exhibit fragrance properties similar to those of the individual compounds.
  • Compound 1. can be prepared by reacting an acetoacetic ester (3) wherein R is lower alkyl, that is,
  • R is C 1 to C 5 , preferably methyl or ethyl and 2,2,3-trimethyl-3-cyclopenten-1-acetaldehyde (4) in the presence of amines such as piperidine, morpholine, and pyrolidine.
  • This reaction proceeds through intermediate Compounds 5 and 6 to yield Compound 7.
  • intermediate Compounds 5 and 6 can be separately isolated, it is preferable in the practices of the present invention that the reaction proceed directly to the formation of Compound 7.
  • Compound 7 is then decarboxylated by conventional procedures, e.g.
  • Compound 2 may be prepared in an analogous manner. First, an acetoacetic ester (3) is reacted with 2 ,2, 3-trimethyl-3-cyclopenten-1-acetaldehyde (4) to produce 7. Compound 7 is decarboxylated to produce Compound 8 which is hydrogenated by a conventional technique such as by treatment with hydrogen gas in the presence of a catalyst such as a palladium on-carbon catalyst to produce Compound 9. Reduction of 9 bytreatment with a suitable metal hydride, e.g. lithium aluminum hydride, yields Compound 2.
  • base such as sodium hydroxide or potassium hydroxide or other known systems
  • a metal hydride such as di-isobutyl aluminum hydride
  • Compound 2 can be produced directly from Compound 8 by reducing the double bond and the carbonyl group of the six-membered ring with hydrogen at an elevated temperature and pressure in the presence of a catalyst and a solvent such as butyl- or isopropyl-alcohol.
  • mixtures of Compounds 1 and 2. exhibit fragrance properties similar to those of either of the individual compounds. Therefore, such a mixture can be readily substituted for either compound in fragrance ap plications.
  • Such a mixture can be prepared by mixing the separately prepared compounds in desired amounts. Additionally, the mixture can be prepared directly from Compound 8 by reacting 8 with a reducing agent such as sodium borohydride.
  • Compound 1, Compound 2 or a mixture thereof are readily incorporated into fragrance compositions for use in detergents,soaps, perfumes, bath preparations, hair preparations, cosmetic preparations and the like.
  • the compound or mixture should desirably be present in an amount from about 0.1% to about 80% by weight based upon the weight of the composition.
  • Piperidine (0.8 g) in ethanol (3.0 ml) was added over 0.5 hr to a stirred mixture of ethyl acetoacetate (143 g, 1.1 mol) and 2,2,3-trimethyl-3-cyclopenten-1-acetaldehyde (81.3 g, ca. 0.5 mol), maintaining the reaction temperature -5 to -10°C.
  • the reac tion mixture was then kept at 0° for 15 hr.
  • a further quan tity of piperidine (0.3 g) in ethanol (3.0 ml) was added, with agitation, and the mixture kept at 0° for a further 24 hr.
  • Example 2 The product of Example 1 (147 g) was dissolved in methanol (400 ml), and a solution of sodium hydroxide (21.3 g, 0.53 mol) in water (400 ml) added in one portion, with agitation. The mixture was heated at gentle reflux for 19 hr, then cooled, and poured into 5% sodium bicarbonate solution (800 ml). The organic product was extracted with benzene (3 x 200 ml), and the combined extracts washed with brine (3 x 200 ml). Solvent was evaporated and the residue distilled to provide. the desired product, b 1.5 126-133° (80.9 g).
  • Example 2 The product of Example 2 (116 g, 0.5 mol), butyl alcohol (73 ml), potassium hydroxide (0.05 g) and copper chromite (7.0 were charged to a 500 ml autoclave, and the stirred mixture heated at 155-160° under 300 psi of hydrogen. When the uptake of hydrogen gas had stopped the mixture was cooled (20°) and the autoclave evacuated before purging with nitrogen. The reaction mixture was filtered, the solvent evaporated and the residue immediately distilled to provide an oil (103 g),which was shown by GLC and spectral analysis to be the desired product.
  • oil 103 g
  • the organic product was extracted with diethyl ether (3 x 100 ml) and the combined organic extracts washed successively with water (3 x 100 ml), 5% sodium bicarbonate solution (100 ml) and water (3 x 100 ml).
  • the organic layer was dried, the solvent evaporated, and the residue distilled to provide an oil b 2.0 129-130° (43.0 g), which was shown by GLC and spectral analysis to be a mixture of alcohols 1 and 2.
  • Compound 1 is the novel compound of this invention as previously defined.
  • Compound 2 is a novel compound in accordance with the present invention as previously defined.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
PCT/US1979/000542 1978-11-02 1979-07-26 Substituted cyclic alcohols,methods of preparing and compositions containing same WO1980000915A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/957,047 US4188310A (en) 1977-09-30 1978-11-02 Substituted cyclic alcohols, methods of preparing and compositions containing same
US957047 1992-10-05

Publications (1)

Publication Number Publication Date
WO1980000915A1 true WO1980000915A1 (en) 1980-05-15

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Application Number Title Priority Date Filing Date
PCT/US1979/000542 WO1980000915A1 (en) 1978-11-02 1979-07-26 Substituted cyclic alcohols,methods of preparing and compositions containing same

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EP (1) EP0023485A1 (enrdf_load_html_response)
JP (1) JPH0222052B2 (enrdf_load_html_response)
WO (1) WO1980000915A1 (enrdf_load_html_response)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0026344A1 (de) * 1979-09-04 1981-04-08 Dragoco Gerberding & Co. GmbH 2,2,3-Trimethylcyclopent-3-en-ylmethyl-substituierte alicyclische Ketone und Alkohole, Herstellungsverfahren und deren Verwendung als Riechstoffe
EP0504592A1 (fr) * 1991-03-22 1992-09-23 Firmenich Sa Alcool tertiare à sous-structure campholénique et son utilisation à titre d'ingrédient parfumant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2283437A (en) * 1942-05-19 x c chacl
US2576078A (en) * 1949-01-03 1951-11-20 Dow Chemical Co Method for the preparation of 2-(2-cycloalkenyl) cycloalkanols
US2985635A (en) * 1957-01-15 1961-05-23 Wassermann Albert Reaction products of cyclopentadiene and trichloroacetic acid
US3962147A (en) * 1972-05-29 1976-06-08 Firmenich S.A. Perfume composition containing 6,10 dimethyl - spiro [4.5]decane-type compounds
US3984354A (en) * 1971-12-27 1976-10-05 Monsanto Company 1-(3'-Hexenyl)-1-cycloalkanols and their esters

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1084235A (enrdf_load_html_response) * 1963-09-03
US4052341A (en) * 1976-04-29 1977-10-04 Givaudan Corporation 3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol compound and perfume compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2283437A (en) * 1942-05-19 x c chacl
US2576078A (en) * 1949-01-03 1951-11-20 Dow Chemical Co Method for the preparation of 2-(2-cycloalkenyl) cycloalkanols
US2985635A (en) * 1957-01-15 1961-05-23 Wassermann Albert Reaction products of cyclopentadiene and trichloroacetic acid
US3984354A (en) * 1971-12-27 1976-10-05 Monsanto Company 1-(3'-Hexenyl)-1-cycloalkanols and their esters
US3962147A (en) * 1972-05-29 1976-06-08 Firmenich S.A. Perfume composition containing 6,10 dimethyl - spiro [4.5]decane-type compounds

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J. American Chemical Society, Vol. 97, #6, pp 1622 to 3,1975. *
See also references of EP0023485A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0026344A1 (de) * 1979-09-04 1981-04-08 Dragoco Gerberding & Co. GmbH 2,2,3-Trimethylcyclopent-3-en-ylmethyl-substituierte alicyclische Ketone und Alkohole, Herstellungsverfahren und deren Verwendung als Riechstoffe
EP0504592A1 (fr) * 1991-03-22 1992-09-23 Firmenich Sa Alcool tertiare à sous-structure campholénique et son utilisation à titre d'ingrédient parfumant

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JPH0222052B2 (enrdf_load_html_response) 1990-05-17
EP0023485A4 (en) 1981-02-06
EP0023485A1 (en) 1981-02-11
JPS56500014A (enrdf_load_html_response) 1981-01-08

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