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WO1993003001A1 - Derives de trimethylhexanal, leur preparation et leur utilisation - Google Patents

Derives de trimethylhexanal, leur preparation et leur utilisation Download PDF

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Publication number
WO1993003001A1
WO1993003001A1 PCT/EP1992/001703 EP9201703W WO9303001A1 WO 1993003001 A1 WO1993003001 A1 WO 1993003001A1 EP 9201703 W EP9201703 W EP 9201703W WO 9303001 A1 WO9303001 A1 WO 9303001A1
Authority
WO
WIPO (PCT)
Prior art keywords
trimethylhexanal
derivatives
atoms
compounds
alkyl
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.)
Ceased
Application number
PCT/EP1992/001703
Other languages
German (de)
English (en)
Inventor
Thomas Markert
Volker Porrmann
Dirk Merkel
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1993003001A1 publication Critical patent/WO1993003001A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
    • C11B9/0019—Aliphatic compounds containing oxygen as the only heteroatom carbocylic acids; Salts or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double 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
    • C07C45/68—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
    • C07C45/72—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 reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—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 reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/007—Esters of unsaturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
    • C07C69/26—Synthetic waxes
    • 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
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom

Definitions

  • the invention relates to new trimethylhexanal derivatives, a process for their preparation and their use as fragrances.
  • radicals R 1 and R 2 independently of one another are an alkyl group having 1 to 3 C atoms and R 3 is an alkyl, acyl or alkoxycarbonyl group having 1 to 3 C atoms.
  • Another object of the invention is a process for the preparation of trimethylhexanal derivatives of the general formula (I), wherein Rl, R 2 and R3 have the meaning given above, by dehydrating, base-catalyzed aldol condensation of 3,5,5-trimethylhexanal with the with the corresponding short-chain aliphatic ketones, their reduction e.g. with complex hydrides or according to the method of Meerwein-Ponndorf with aluminum alcoholates to the corresponding alcohols and finally their derivatization to the corresponding esters (Ia), carbonates (Ib) or allyl ethers (Ic).
  • the new compounds (I) are prepared by conventional synthetic methods of organic chemistry.
  • Commercially available 3,5,5-trimethylhexanal serves as the starting material and can be reacted in the presence of conventional catalysts with corresponding short-chain ketones, for example 2-butanone or 3-pentanone, in a mixed aldol condensation, with intermediate aldol condensation products being used Elimination of water directly gives the corresponding ⁇ , ⁇ -unsaturated aldol condensation products (ZI).
  • the reaction is expediently carried out with a Excess of the more reactive and volatile component.
  • suitable catalysts are sodium hydroxide, sodium ethanolate, sodium amide, potassium tert-butoxide or heterogeneous catalysts such as potassium fluoride on aluminum oxide.
  • the carbonyl function of the aldol condensation products (ZI) can be reduced to the OH group in a further reaction, e.g. using complex hydrides such as lithium aluminum hydride or lithium or sodium borohydride.
  • the alcohols (Z2) are obtained in this way.
  • the alcohols (Z2) are then converted into the esters (Ia) by esterification with short-chain carboxylic acids or by reaction with e.g. Dimethyl carbonate or diethyl carbonate is converted into the carbonates (Ib) or by etherification according to Williamson, if desired in the presence of a phase transfer catalyst, into the allyl ethers (Ic).
  • the compounds (I) can then be purified by customary methods, for example by distillation.
  • the compounds (I) according to the invention have remarkable olfactory properties, such as are very sought after in the fragrance industry, namely sandalwood-like or green with very complex shades and great charisma.
  • the compounds of type (Ia) are characterized by their sandal scent, while the compounds of type (Ib) have fresh green notes.
  • Another object of the invention is therefore the use of the compounds of general formula (I) as fragrances.
  • sandalwood oil is particularly valued and valuable. It is obtained by steam distillation from the heartwood of sandalwood, a tropical semi-parasite that occurs in India and Malysia. Heartwood appears after about ten years and only begins to develop more quickly in twenty-year-old trees. Fully grown trees are cleared at the age of 30 to 60 years because the roots are particularly rich in fragrant heartwood [cf. E. T. Morris, Dragoco Report 1983 (30) 40]. It is therefore understandable that fragrance research is constantly striving to develop suitable substitutes for natural sapwood oil.
  • Substituted mono-, bi- or tricyclic systems represent the large number of fragrances known from the state of the art with a scent of soft wood. This also applies to ⁇ - and ⁇ -santalol, the main constituents of natural sandalwood oil.
  • the applicant is only aware of one example of a commercially available non-cyclic sand fragrance which is marketed under the trade name 0syrol ( TR ) and which is a 2,6-dimethyl-2-methoxy-6-hydroxy-octane (US Pat. No. 3,963,648).
  • Japanese patent application JP 90/282339 describes noncyclic alcohols with a sandal scent, for example tetramethyldecan-4-en-3-ol.
  • German patent application DE 3245047 describes aliphatic alcohols and esters which have fruity and in particular pear-like fragrance notes or ambrette-woody, flowery and balm-like fragrance notes. Particular emphasis is placed on 5,7,7-trimethyloctyl propionate, whose fruity, pear-like note is particularly emphasized.
  • the odor profile of the compounds (I) is original and novel. In perfume compositions, the compounds (I) enhance the harmony and charisma as well as the adhesion, the dosage being matched to the desired fragrance note taking into account the other constituents of the composition.
  • the compounds of the formula (I) are particularly suitable for modifying and enhancing known compositions. Particularly to be emphasized is their extraordinary olfactory strength, which generally contributes to the refinement of the composition.
  • the compounds of formula (I) can be combined with numerous known fragrance ingredients, for example other fragrances of natural, synthetic or partially synthetic origin, essential oils and plant extracts.
  • the range of natural fragrances can include both volatile, medium and low volatile components and that of synthetic fragrances includes representatives from practically all classes of substances. Examples are:
  • Natural products such as tree moss absolute, basil oil, agricultural oils such as bergamot oil, mandarin oil, etc., mastic absolute, myrtle oil, pal arosa oil, patchouli oil, petitgrain oil, wormwood oil, myrrh oil, olibanum oil
  • ketones such as allyl ionone, ionone, ⁇ -ionone, isoraldein, methyl ionone,
  • esters such as allylphenoxyacetate, benzyl salicylate, cinna yl propionate, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzylcarbyl acetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasyl acetate, cyclohexyl acetate, vetiver hexyl acetate
  • Lactones such as f-undecalactone, l-0xaspiro [4.4] nonan-2-one, as well as various other components often used in perfumery such as ketone musk, indole, p-menthan-8-thiol-3-one, methyleugenol, A broxan.
  • the compounds according to the invention contain chiral centers, so that these compounds can exist in different spatial forms.
  • the compounds according to the invention are obtained as mixtures of the corresponding isomers and are used as such as fragrances.
  • the usable proportions of the compounds according to the invention or their mixtures in fragrance compositions range from 1 to 70 percent by weight, based on the mixture as a whole.
  • Mixtures of the compounds (I) according to the invention and compositions of this type can be used for perfuming cosmetic preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants as well as in alcoholic perfumery (eg Eaux de Cologne , Eau de toilette, extras) can be used.
  • perfuming technical products such as detergents and cleaning agents, fabric softeners and textile treatment agents or tobacco.
  • compositions are added to them in an olfactory effective amount, in particular in a concentration of 0.05 to 2 percent by weight, based on the entire product.
  • Smell fruity, woody, balsamic, sandal note

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

Abstract

Des dérivés de triméthylhexanal répondent à la formule générale (I), dans laquelle les restes R1 et R2 désignent indépendamment l'un de l'autre un groupe alkyle ayant 1 à 3 atomes de C et R3 désigne un groupe alkyle, acyle ou alcoxycarbonyle ayant 1 à 3 atomes de C. Ces composés se caractérisent par des odeurs de type complexe apparentées au santal ou à la verdure, qui se répandent rapidement, et peuvent être mélangés avec des composés similaires ou avec d'autres parfums dans des proportions diverses afin d'obtenir de nouvelles compositions odoriférantes. La proportion de ces composés est en général comprise entre 1 et 70 % en poids, par rapport à l'ensemble de la composition. Ces compositions peuvent être utilisées pour parfumer des produits cosmétiques et techniques, ainsi que pour produire des parfums à base d'alcool.
PCT/EP1992/001703 1991-08-03 1992-07-27 Derives de trimethylhexanal, leur preparation et leur utilisation Ceased WO1993003001A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19914125765 DE4125765A1 (de) 1991-08-03 1991-08-03 Trimethylhexanal-derivate, deren herstellung und verwendung
DEP4125765.0 1991-08-03

Publications (1)

Publication Number Publication Date
WO1993003001A1 true WO1993003001A1 (fr) 1993-02-18

Family

ID=6437641

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/001703 Ceased WO1993003001A1 (fr) 1991-08-03 1992-07-27 Derives de trimethylhexanal, leur preparation et leur utilisation

Country Status (2)

Country Link
DE (1) DE4125765A1 (fr)
WO (1) WO1993003001A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19505003C1 (de) * 1995-02-15 1996-06-13 Henkel Kgaa Kondensationsprodukt und dessen Verwendung
EP1930311A1 (fr) * 2006-12-08 2008-06-11 Cognis IP Management GmbH Carbonates dialkylés d'alcools ramifiés et leur utilisation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3245047A1 (de) * 1981-12-07 1983-06-09 Firmenich S.A., 1211 Genève Aliphatische alkohole und ester und ihre verwendung als parfumbestandteile
EP0269999A2 (fr) * 1986-12-03 1988-06-08 BASF Aktiengesellschaft Alcools et esters aliphatiques, leur préparation et utilisations comme substances parfumantes
JPH02282339A (ja) * 1989-04-25 1990-11-19 T Hasegawa Co Ltd ケトン類およびアルコール類

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3245047A1 (de) * 1981-12-07 1983-06-09 Firmenich S.A., 1211 Genève Aliphatische alkohole und ester und ihre verwendung als parfumbestandteile
EP0269999A2 (fr) * 1986-12-03 1988-06-08 BASF Aktiengesellschaft Alcools et esters aliphatiques, leur préparation et utilisations comme substances parfumantes
JPH02282339A (ja) * 1989-04-25 1990-11-19 T Hasegawa Co Ltd ケトン類およびアルコール類

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Week 9101, Derwent Publications Ltd., London, GB; & JP,A,2 282 339 (HASEGAWA) 19. November 1990 in der Anmeldung erwähnt *

Also Published As

Publication number Publication date
DE4125765A1 (de) 1993-02-04

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