EP0023485A1 - Alcools cycliques substitues, methodes de preparation et compositions les contenant - Google Patents

Alcools cycliques substitues, methodes de preparation et compositions les contenant

Info

Publication number
EP0023485A1
EP0023485A1 EP79901021A EP79901021A EP0023485A1 EP 0023485 A1 EP0023485 A1 EP 0023485A1 EP 79901021 A EP79901021 A EP 79901021A EP 79901021 A EP79901021 A EP 79901021A EP 0023485 A1 EP0023485 A1 EP 0023485A1
Authority
EP
European Patent Office
Prior art keywords
compound
carbon
fragrance
mixture
composition
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP79901021A
Other languages
German (de)
English (en)
Other versions
EP0023485A4 (fr
Inventor
Brian J. Willis
John M. Yurecko, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fritzsche Dodge and Olcott Inc
Original Assignee
Fritzsche Dodge and 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 and Olcott Inc filed Critical Fritzsche Dodge and Olcott Inc
Publication of EP0023485A4 publication Critical patent/EP0023485A4/fr
Publication of EP0023485A1 publication Critical patent/EP0023485A1/fr
Withdrawn legal-status Critical Current

Links

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.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)

Abstract

De nouveaux composes sont utiles comme materiau pour des parfums et possedent la structure (FORMULE) ou la ligne en pointille peut etre soit une liaison simple carbone-carbone ou une liaison double carbone-carbone. Des methodes sont egalement decrites pour preparer ces composes a partir de produits de reaction d'ester acetoacetiques et de 2,2,3-trimethyl-3-cyclopentene-1-acetaldehyde et les compositions de parfums qui comprennent les composes.
EP79901021A 1978-11-02 1980-05-20 Alcools cycliques substitues, methodes de preparation et compositions les contenant Withdrawn EP0023485A1 (fr)

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 (2)

Publication Number Publication Date
EP0023485A4 EP0023485A4 (fr) 1981-02-06
EP0023485A1 true EP0023485A1 (fr) 1981-02-11

Family

ID=25499004

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79901021A Withdrawn EP0023485A1 (fr) 1978-11-02 1980-05-20 Alcools cycliques substitues, methodes de preparation et compositions les contenant

Country Status (3)

Country Link
EP (1) EP0023485A1 (fr)
JP (1) JPH0222052B2 (fr)
WO (1) WO1980000915A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2935683C2 (de) * 1979-09-04 1982-03-18 Dragoco Gerberding & Co Gmbh, 3450 Holzminden 2,2,3-Trimethylcyclopent-3-en-ylmethyl-substituierte alicyclische Ketone und Alkohole, Herstellungsverfahren und deren Verwendung als Riechstoffe
EP0504592B1 (fr) * 1991-03-22 1995-05-10 Firmenich Sa Alcool tertiare à sous-structure campholénique et son utilisation à titre d'ingrédient parfumant

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1084235A (fr) * 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

Family Cites Families (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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1084235A (fr) * 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8000915A1 *

Also Published As

Publication number Publication date
JPH0222052B2 (fr) 1990-05-17
JPS56500014A (fr) 1981-01-08
EP0023485A4 (fr) 1981-02-06
WO1980000915A1 (fr) 1980-05-15

Similar Documents

Publication Publication Date Title
US4264467A (en) Cyclic C6 compounds and their use in perfumes
CA1084949A (fr) Compose odorant
EP0118809B1 (fr) Composition consistant essentiellement en trans-1-(2,6,6-triméthylcyclohexyl)-hexane-3-ol, son utilisation et son procédé de préparation; cétone et alcool cycloaliphatiques intermédiaires
JP2010506861A (ja) 匂い物質として有用な２，２，３−トリメチルシクロペンタ−３−エンカルバルデヒド誘導体
JPS627176B2 (fr)
EP0466019B1 (fr) Dérivés de l'aldéhyde dihydrocampholénique
EP0118817B1 (fr) Procédé pour la préparation d'une composition d'isomères de (triméthyl-2,6,6-cyclohexyl)-1-hexanol-3, utilisation de la composition obtenue et carbinols intermédiaires
US4188310A (en) Substituted cyclic alcohols, methods of preparing and compositions containing same
EP0023485A1 (fr) Alcools cycliques substitues, methodes de preparation et compositions les contenant
US4289658A (en) 2-[-(2'2'3'-Trimethyl-3'-cyclopenten-1'-yl)-ethyliden]-and ethyl]-cyclopentanols
US4477683A (en) 3-Methyl-1-(2,3,4-and 2,4,4-trimethyl-1-cyclopentylidene) pent-2-en-4-one and isomers, and perfume compositions thereof
US4891447A (en) Sandalwood odorants
JP2003532701A (ja) トリメチルデセン化合物
US2815386A (en) 3, 7, 9-trimethyl-2, 6-decadien-1-al
US4631147A (en) Cycloalkan-1-ol derivatives and perfume compositions comprising the same
JP6154893B2 (ja) 有機化合物
JPH05339188A (ja) ２−（２−ｔ−ブチルシクロヘキシルオキシ）−１−ブタノール及びこれを含有する香料組成物
US2849491A (en) 6, 8-dimethyl-5-nonen-2-one
JPH045656B2 (fr)
JPH0212935B2 (fr)
EP0189581A1 (fr) Bicyclo[2.2.1]heptanes et -heptènes- 2,3 disubstitués, leur préparation et leur application comme parfum
DE3443536A1 (de) Methylsubstituierte bicyclo(2.2.1)heptan-derivate und deren verwendung als riechstoffe
JP2007507563A (ja) 有機化合物
RU2035448C1 (ru) 2-ацетонил-5,5-диметил-1,2,3,4,5,6,7,8-октагидронафталин в качестве компонента парфюмерной композиции, способ его получения, 2,6-диметил-2,6,10-тридекатриен-12-он в качестве промежуточного продукта в синтезе 2-ацетонил-5,5-диметил-1,2,3,4,5,6,7,8-октагидронафталина
JPS625123B2 (fr)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19800827

AK Designated contracting states

Designated state(s): AT CH DE FR GB LU NL SE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19820811

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WILLIS, BRIAN J.

Inventor name: YURECKO, JOHN M., JR.