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WO1993002998A1 - Composes bicycliques, leur preparation et leur utilisation - Google Patents

Composes bicycliques, leur preparation et leur utilisation Download PDF

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Publication number
WO1993002998A1
WO1993002998A1 PCT/EP1992/001632 EP9201632W WO9302998A1 WO 1993002998 A1 WO1993002998 A1 WO 1993002998A1 EP 9201632 W EP9201632 W EP 9201632W WO 9302998 A1 WO9302998 A1 WO 9302998A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
group
bicyclic compounds
bicyclic
radical
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/EP1992/001632
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German (de)
English (en)
Inventor
Thomas Markert
Klaus Bruns
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 WO1993002998A1 publication Critical patent/WO1993002998A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
    • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
    • C07C33/12—Alcohols containing rings other than six-membered aromatic rings containing five-membered rings
    • 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
    • C07C45/67—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
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/225—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings
    • 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
    • C07C49/21—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings

Definitions

  • the invention relates to new bicyclic compounds, a process for their preparation and their use as fragrances.
  • sandalwood oil is particularly valued and valuable. It is obtained from the heartwood of sandalwood, a tropical semi-parasite that occurs in India and Malaysia, by steam distillation. 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. ETMorris, Dragoco Report 1983 (30) 40]. It is therefore understandable that fragrance research is constantly striving to develop suitable substitutes for natural sandalwood oil.
  • DE 2833283 describes norbornane or norbornene compounds which carry a methyl group on the bicyclus and which have a 3-hydroxy-2-methylpent-1-enyl radical as the side chain. Such compounds are said to have a fragrance similar to that of ⁇ or ⁇ -Santalol. This observation is remarkable since EJBrunke had shortly before attributed compounds with camphanyl residue only very weak odor effects when trying to formulate a relationship between chemical structure and sandalwood scent [Dragoco Report 1981 (28) 251].
  • bicyclic compounds which contain a side chain with two double bonds or a saturated side chain with a hydroxyl or carbonyl function [JP 83/180443, cited from Chem. Abstr. 100, 68566c].
  • II A by G.Buchbauer et al. synthesized isocamphane derivative with a 2-methylprop-2-en-l-ol side chain, the smell of which is described as camphorous-floral-woody [monthly h. Chem. 1987 (118) 511].
  • bicyclic compounds of the general formula (I) meet the requirements for a fragrance excellently in all respects and are advantageously used as fragrances with differently nuanced odor notes, including sandalwood notes, with good adhesive strength can.
  • the invention therefore relates to bicyclic compounds of the general formula (I)
  • radicals R 1 and R 2 independently of one another are hydrogen or an alkyl group having 1 to 3 C atoms mean.
  • Another object of the invention is a process for the preparation of the bicyclic compounds of the general formula (I), in which R has the meaning given above, by dehydrating base-catalyzed aldol condensation of 3,3-dimethyl-2-norbornane-acetaldehyde with the corresponding the short-chain aliphatic ketones or aldehydes to the compounds (Ib) or (Ic) and their reduction, for example using complex hydrides to the alkyl alcohols (Ia) or (Id).
  • the cyclohexanols of the formula (Ie) are prepared by condensation of 3,3-dimethyl-2-norbornane acetaldehyde with 2 molecules of acetoacetic acid ester to give a cyclohexenone ester which, after saponification and decarboxylation, gives a cyclohexenone. This is converted to the allylic alcohols by reduction, for example using complex hydrides, or to the cyclohexanols by catalytic hydrogenation.
  • the individual steps in the preparation of the new compounds (I) are carried out according to known synthetic methods of organic chemistry.
  • the aldehyde (II) can be in the presence of conventional catalysts with corresponding short-chain aldehydes or ketones, e.g. React acet-, propion-, butyr-, isobutyraldehyde, acetone, 2-butanone or 3-pentanone in a mixed aldol condensation, the corresponding ⁇ , ⁇ -unsaturated aldol condensation products (Ib) being obtained directly via intermediate aldol condensation products with elimination of water. or (Ic) can be obtained.
  • the reaction is expediently carried out with an excess of the reactive and more volatile component.
  • catalysts are Sodium hydroxide, sodium methoxide, sodium amide, potassium tert-butanolate or heterogeneous catalysts such as potassium fluoride on aluminum oxide are possible.
  • the compounds (I) obtained in this procedure are predominantly E-configured on the double bond.
  • the carbonyl function of the aldol condensation products (Ib) or (Ic) can be reduced to the OH group in a further reaction, e.g. by means of complex hydrides such as lithium aluminum hydride or lithium or sodium borohydride or according to Meerwein-Pondorf.
  • the allyl alcohols (Ia) and (Id) are obtained in this way.
  • the new compounds (le) can be prepared by condensing (II) with 2 molecules of an acetoacetic ester, for example ethyl acetoacetate, in the presence of a base, for example pyrrolidine or piperidine, a 4-carbethoxy-3- methyl-2-cyclohexen-l-one is formed.
  • a base for example potassium hydroxide, sodium hydroxide
  • This is saponified with the addition of a base, for example potassium hydroxide, sodium hydroxide, to give the corresponding carboxylic acid salt, which is converted into the free acid by cooking with, for example, p-toluenesulfonic acid or sulfuric acid can be transferred, which decarboxylates immediately under the reaction conditions and provides the cyclohexenone.
  • the carbonyl function of the products obtained in this way can be selectively reduced to the alcohol function by means of complex hydrides such as NaBH4, LiAlH. *., KBH4, LiBH4.
  • complex hydrides such as NaBH4, LiAlH. *., KBH4, LiBH4.
  • cyclohexenols are obtained which can be converted into the corresponding cyclohexanols by catalytic hydrogenation, for example in the presence of nickel, palladium or platinum catalysts.
  • the compounds (I) can then be prepared by conventional methods, e.g. can be purified by distillation.
  • the compounds according to the invention are odoriferous substances with differently nuanced, intensely woody odor notes and exceptional adhesive strength. They differ from the bicyclic compounds described in the prior art by characteristic, qualitatively significantly different odor profiles.
  • Another object of the invention is therefore the use of the bicyclic compounds of the general formula (I) as fragrances.
  • the compounds (Ia) have remarkable odor properties, such as are very sought after in the fragrance industry, namely sandalwood-like with very complex shades and great radiance.
  • the particular smell characteristic of the compounds (Ia) of the sandalwood type according to the invention is original and novel and differs significantly from the smell characteristic of the bicyclic and tricyclic compounds known as fragrances, which is particularly surprising.
  • the compounds (Ia) enhance the harmony, naturalness 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 general formula (Ib) are notable for woody, balsamic scent notes reminiscent of Jonone, while the fragrance profile of the compounds of type Ib and Ic can be described as fruity, woody, pronounced of Damascone.
  • 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 used with numerous known fragrance ingredients, e.g. combine 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, palmarosa oil, patchouli oil, petitgrain oil, Paraguay, Wer utöl,
  • aldehydes such as citral, helional R , oc-hexylcinnamaldehyde, hydroxycitronellal , lalial R [p-tert-butyl-oc-methyldihydrocinnamaldehyde], methylnonyl acetaldehyde, tetrahydrocitral, heliotropin,
  • Ketones such as allyl ionone, ionone, ⁇ -ionone, isoraldein [methyl ionone], irone
  • esters such as allylphenoxyacetate, benzyl salicylate, cinna yl propionate, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzylcarbinylacetate, ethyl acetoacetate, hexenyl isobutyrate, linalyl acetate, methyldihydrojyl acetate, viethyl acetate, viethyl acetate, viethyl acetate,
  • lactones such as gamma-undecalactone, l-0xaspiro [4.4] nonan-2-one, as well as various other components often used in perfumery such as ketone oschus, indole, p-menthan-8-thiol-3-one, methyleugenol.
  • 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 both for perfuming cosmetic preparations such as lotions, creams, shampoos, soaps, ointments, powders, aerosols, toothpastes, mouthwashes, deodorants and in alcoholic perfumery (for example Eau 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.
  • these values should not represent any limit values, since the experienced perfume can achieve effects with even lower concentrations or can build up new complexes with even higher doses.
  • the compounds of the general formula Ia were prepared starting from 3,3-dimethyl-2-norbornane acetaldehyde II, which was obtained from camphene by known methods by hydroformylation in the presence of a rhodium or cobalt catalyst.
  • the aldehyde was obtained as a 1: 1 mixture of exo and endo product.
  • the products which are likewise possible according to the mechanism of hydroformylation and in which the aldehyde group is located directly on the bicyclus could not be detected.
  • example 3 reinforces the floral character of the composition in the top note and gives the composition a fresh, warm naturalness.
  • Mix B is much more harmonious than Mix A.
  • the lavender character is more pronounced and natural warmth.

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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)

Abstract

Des composés bicycliques répondent à la formule générale (I), dans laquelle le reste R désigne un groupe (a) -CH=CR1-CH(OH)-CH2R2, (b) -CH=CR1-CO-CH2R2, (c), (d) ou (e) un reste cyclohexyle qui porte à des positions diverses un groupe OH et un groupe méthyle et qui peut le cas échéant avoir une liaison double, alors que les restes R1 et R2 désignent indépendamment l'un de l'autre hydrogène ou un groupe alkyle ayant 1 à 3 atomes de C. Ces composés se caractérisent par des odeurs d'un type complexe apparentées à l'odeur du bois de santal, qui se répandent rapidement et qui peuvent être mélangés avec des composés similaires ou avec d'autres matières odoriférantes, 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/EP1992/001632 1991-07-26 1992-07-17 Composes bicycliques, leur preparation et leur utilisation Ceased WO1993002998A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4124886.4 1991-07-26
DE19914124886 DE4124886A1 (de) 1991-07-26 1991-07-26 Bicyclische verbindungen, deren herstellung und verwendung

Publications (1)

Publication Number Publication Date
WO1993002998A1 true WO1993002998A1 (fr) 1993-02-18

Family

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Application Number Title Priority Date Filing Date
PCT/EP1992/001632 Ceased WO1993002998A1 (fr) 1991-07-26 1992-07-17 Composes bicycliques, leur preparation et leur utilisation

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DE (1) DE4124886A1 (fr)
WO (1) WO1993002998A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2831165B1 (fr) * 2001-10-23 2005-06-17 Mane Fils V Nouveaux derives du norbornane et du norbornene, leur utilisation et produits parfumes les contenant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1192771B (de) * 1963-08-14 1965-05-13 Wolfen Filmfab Veb Riechstoffe und Riechstoffkompositionen
DE1196310B (de) * 1964-02-17 1965-07-08 Wolfen Filmfab Veb Riechstoffe und Riechstoffkompositionen
FR1415691A (fr) * 1963-09-03 1965-10-29 Firmenich & Cie Dérivé du cyclohexanol et procédé pour le préparer
DE2708048A1 (de) * 1976-02-27 1977-09-01 Shell Int Research Tertiaere alkohole, verfahren zu ihrer herstellung und ihre verwendung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1192771B (de) * 1963-08-14 1965-05-13 Wolfen Filmfab Veb Riechstoffe und Riechstoffkompositionen
FR1415691A (fr) * 1963-09-03 1965-10-29 Firmenich & Cie Dérivé du cyclohexanol et procédé pour le préparer
DE1196310B (de) * 1964-02-17 1965-07-08 Wolfen Filmfab Veb Riechstoffe und Riechstoffkompositionen
DE2708048A1 (de) * 1976-02-27 1977-09-01 Shell Int Research Tertiaere alkohole, verfahren zu ihrer herstellung und ihre verwendung

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS SERVICE REGISTRY HANDBOOK 1983 SUPPLEMENT Colombus, Ohio, US *
CHEMICAL ABSTRACTS SERVICE REGISTRY HANDBOOK 1985 SUPPLEMENT Colombus, Ohio, US *
CHEMICAL ABSTRACTS, vol. 108, 1988, Columbus, Ohio, US; abstract no. 132075m, 'Syntheses in the isocamphane series. XXVII. Analogs of delta - santalol. I.' Seite 781 ;Spalte 2 ; *
CHEMICAL ABSTRACTS, vol. 60, 1964, Columbus, Ohio, US; abstract no. 563f, L.A. KHEIFITS ET AL. 'Terpenophenols. XII. Condensation of camphene and norbornene with p-cresol and transformations of condensation products.' Spalte 1 ; *

Also Published As

Publication number Publication date
DE4124886A1 (de) 1993-01-28

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