WO1984002338A1 - Derives de tricyclo ad5,2,1,02,6 bddecane avec chaine laterale fonctionnalisee, leur fabrication et leur utilisation en tant que parfums - Google Patents

Derives de tricyclo ad5,2,1,02,6 bddecane avec chaine laterale fonctionnalisee, leur fabrication et leur utilisation en tant que parfums Download PDF

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Publication number
WO1984002338A1
WO1984002338A1 PCT/EP1983/000330 EP8300330W WO8402338A1 WO 1984002338 A1 WO1984002338 A1 WO 1984002338A1 EP 8300330 W EP8300330 W EP 8300330W WO 8402338 A1 WO8402338 A1 WO 8402338A1
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Prior art keywords
tricyclo
optionally
double bond
derivatives
hydrogen
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PCT/EP1983/000330
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German (de)
English (en)
Inventor
Ernst-Joachim Brunke
Hartmut Struwe
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Dragoco Gerberding Co Gmbh
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Publication of WO1984002338A1 publication Critical patent/WO1984002338A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • 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
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/13—Monohydroxylic alcohols containing saturated rings
    • C07C31/137—Monohydroxylic alcohols containing saturated rings polycyclic with condensed ring systems
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/29—Saturated compounds containing keto groups bound to rings
    • C07C49/313—Saturated compounds containing keto groups bound to rings polycyclic
    • C07C49/323—Saturated compounds containing keto groups bound to rings polycyclic having keto groups bound to condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
    • C07C49/553—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings 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
    • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C11/00—Fermentation processes for beer
    • C12C11/02—Pitching yeast
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes

Definitions

  • Tricyclo [5.2.1.0 2.6 ] decane derivatives with a functionalized side chain their production and use as fragrances
  • Dicyclopentadiene (1) is an important raw material for fragrance production.
  • the esters 2b-c obtained by adding carboxylic acids e.g. acetic acid, propionic acid
  • carboxylic acids e.g. acetic acid, propionic acid
  • Formate 2a has been described in UK Pat. No. 815,232 (June 6, 1959) and dimethylacrylate 2d in US Pat. No. 3,598,745 (Aug. 10, 1971).
  • Other products from dicyclopentadiene are described in summary by Ohloff and R ⁇ dé-Gawal (in: H. Aebi, E. Baumgartner, HP Fiedler and G.
  • DOS 3 120700 A1 (February 25, 1982) describes the tricyclodecane derivatives of the general formula 6 and their use as fragrances.
  • the present invention relates to the new tricyclo [5.2.1.0 2.6 ] decane derivatives of the general formula A, in which R 1 , R 2 are each hydrogen radicals or alternatively a substituent of the pairs of substituents R 1 and R 2 are a methyl group and the other is a hydrogen radical,
  • R 4 is a straight-chain or branched C 1 -C 4 alkyl radical or a C 2 -C 4 alkenyl radical and - one of the dashed lines Lines one CC single bond and the other one
  • the new tricyclo [5.2.1.0 2,6 ] decane derivatives of the formula A surprisingly have very pleasant woody and herbaceous odor notes with great adhesive strength and a natural effect; some derivatives surprisingly have the scent of cedarwood oil and others the muscatel sage.
  • tricyclodecane derivatives with a functionalized side chain on the cyclopentane part of the molecule have hitherto not been known.
  • the (dimethyl) tricyclcdecane derivatives of the formula A according to the invention were prepared from dimeric (methyl) cyclopentadiene by selective hydrogenation in the norborn fraction, subsequent Friedel craft acylation and - optionally - subsequent reactions.
  • Methylcyclopentadiene (presentation: overview by WT Ford, J. Org. Chem. 25, 3979 (1971)) is a mixture of the three double bond isomers 3a, b, c. According to S. McLean and P. Haynes (Tetrahedron 21 2313 (1965)), 44.5% of the 1-methyl isomer 3a, 54.5% of the C-2 isomer 3b and only approx -5- isomers 3c. Theoretically, a multitude of products can be formed in the dimerization of an equilibrium mixture of methylcyclopentadiene. Assuming that products with an angular methyl group are sterically favorable and do not result in a significant amount, and that those of 3c ( ⁇ 1%)
  • the dimeric methylcyclopentadiene (gas chromatogram: Fig. 1) should consist essentially of the constitutional isomers 7a-f.
  • the 1 H-NMR spectrum (Fig. 2) shows in the range of olefinic protons (5-6 ppm) signal groups whose integral corresponds to 2.2 protons.
  • the signals at 1.25 and 1.50 ppm can be assigned to the protons of the C 1 bridge in analogy to dicyclopentadiene (Sadtler NMR spectra collection, No. 6494 M).
  • Only the signals of relatively low intensity at 1.23 and 1.35 ppm can be assigned to the bridgehead methyl groups of 7a-c. This finding and the intensity of the olefinic signals show the predominance of the isomers 7d-f (approx. 85%), while only approx. 15% of 7a-c are present.
  • the new mono-enes 8a-f obtained in this way are, according to GC (Fig. 3), a mixture of three main isomers (approx. 16, 24 and 37%) as well as further secondary isomers, which, however, like 7a-f, are constitutional isomers can also act stereoisomers. All of these isomers show a very similar mass spectrometric fragmentation pattern, which by opening the norbornane system to form a methylcyclopentadienyl radical cation (m / z 80) and one Methylcyclopentans can be explained. In the 1 H-NMR spectrum (Fig.
  • the new compounds of general formula A are unsaturated and saturated acylation products of 8a-f as well as hydroxyl, acetoxy, propoxy and desmethyl derivatives derived therefrom.
  • the structure of the 1st main isomer (9a or 9b) is shown by the 1 H-NMR spectrum.
  • the 2nd main peak of the gas chromatogram (Fig. 5) consists of two isomers.
  • a singlet appears at 1.30 ppm for the bridgehead methyl group in 10c and a doublet at 1.29 ppm for the C-9 methyl group of 10a.
  • the signals at 1.95 ppm for the olefinic methyl group and at 2.12 ppm for the acetyl group characterize the ⁇ , ⁇ -unsaturated carbonyl system as do the IR bands at 1650 and 1675 cm -1 .
  • the mixture of the new saturated alcohols 11a-d + 12a-d was obtained from the ketone mixture 9a-d + 10a-d by exhaustive catalytic hydrogenation (Example 5).
  • the isomers of shorter gas chromatographic retention time (11a-d) belong to the same structure type as 9a-d and the alcohols of higher retention time (12a-d) belong to the same structure type as 10a-d. This is particularly evident from the mass spectrometric fragmentation behavior.
  • dehydration occurs to form a vinyl side chain, which then eliminates C 3 H 6 from the. Cyclopentene part leads.
  • the new saturated Laces 13a-d + 14a-d were prepared by selective catalytic hydrogenation of the ketone mixture 9a-d + 10a-d or by oxidation of the alcohol mixture 11a-d + 12a-d (Example 6).
  • the isomers with a shorter gas chromatographic retention time (here main peak 1) are assigned to the same structure type as 9a-d, or the ketones with a higher retention time (here main peak 2) to the structure type of 10a-d.
  • the saturated ketones 13a-d + 14a-d smell pleasantly woody and somewhat herbaceous-fruity.
  • the unsaturated alcohols 15a-d + 16a-d were prepared by reducing the unsaturated ketones 9a-d + 10a-d. Usual esterification gave 11a-c + 12a-d the mixture of acetates 17a-d + 18a-d, or propionates 18a-d + 20a-d, and acetates 21a-d + 22a-d from unsaturated alcohols. or the propionates 23a-d + 24a-d. These ester mixtures have woody smell properties, each with slightly different nuances.
  • the higher homologs 25 / 26-31 / 32 have been shown from 8a-f, namely 25/26 with propionic anhydride, 27/28 with butyric anhydride, 29/30 with isobutyric anhydride and 31/32 with crotonic anhydride.
  • the smell of the ketone mixture 25/26 is woody and somewhat resinous, while that of the mixture 27/28 is woody with a clear touch of lovage.
  • the crotonylation product mixture 31/32 smells soft woody-herbaceous with pleasant, herbaceous-greasy notes that are pronounced of cis-jasmon.
  • the corresponding ketones 45/46, 47/48, 49/50 were obtained by oxidation of the alcohols 33/34, 35/36, 37/38, the woody-sweet and with a higher molecular weight, there are also herbaceous scent notes.
  • Dimer cyclopentadiene (1) was prepared according to the method described by Ch.A. Brown given the protocol (Ch.A. Brown, Chem. Comm. 1969, 952) selectively hydrogenated to 51, which was acylated to the unsaturated ketones 52a, b under the conditions used for the preparation of the new compounds 9a + d + 10a-d ; the compounds 52a, b have a sweet-herbaceous fragrance (type: caraway). Selective hydrogenation gave the saturated ketones 53a, b with a long-lasting spicy-herbaceous fragrance (type: cedar leaf oil) and full saturation gave the alcohols 54a, b with a mild, woody fragrance.
  • the higher homologues R 4 : C 1 -C 4 alkyl, C 2 -C 4 alkenyl
  • the new compounds of the general formula A can advantageously be used as fragrances or constituents of perfume oils for cosmetic or technical applications.
  • MS (Fig. 9): m / z (%) 204 (6, M + ), 186 (1), 161 (68), 119 (21), 105 (23), 91 (24), 81 (100 ), ..., 43 (29).
  • This perfume oil base with a high content of the new ketones 9a-d + 10a-d has a harmonious, strongly woody note with original fresh, herbaceous aspects.
  • the perfume oil of the above composition has a balanced fragrance complex of the Fougère type with sweet-herbaceous aspects.
  • new, improved fragrances were achieved.
  • the ketone mixture 9a-d + 10a-d is incorporated (according to Example 2), an interesting herbaceous-woody fragrance complex is achieved.
  • 150 parts of the saturated ketones 13a-d + 14a-d are added, a harmonious herb-herb complex with an increased radiance is created.
  • the perfume oil obtained by incorporating 11a-d + 12a-d has a fresh herb-sweet complex with great adhesive strength.
  • the new perfume oils obtained by adding the substances according to the invention are also distinguished by an increased odor constancy (fixation) compared to the original mixture.
  • Methyl ionone gamma 100 100 100
  • Mixtures a, b, c each have a balanced, original fragrance complex of the chypre type, with woody-sweet, b aldehydic-woody and c woody-sweet odor aspects being emphasized.
  • Fig. 1 Gas chromatogram [50 m, FFAP glass capillary, 40-250 ° C, 8 ° C / min] of dimeric methylcyclopentadiene
  • Fig. 2 1 H NMR spectrum [CCi 4 , 60 MHz] of dimeric methylcyclopentadiene
  • Fig. 3 Gas chromatogram [50 m, glass capillary FFAP, 40-250 ° C, 8 ° C / min] from 8a-f
  • Fig. 5 Gas chromatogram [50 m glass capillary FFAP, 40-250oC, 4oC / min] of 9a-d + 10a-d (according to example 2)
  • Fig. 6 Gas chromatogram [50 m glass capillary FFAP, 40-250 ° C, 4 C / min] of 9a-d + 10a-d (according to example 3)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
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  • Bioinformatics & Cheminformatics (AREA)
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  • Food Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Zoology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Fats And Perfumes (AREA)

Abstract

Nouveaux dérivés de tricyclo AD5,2,1,02,6 BDdécane de formule générale (A), où R1 et R2 représentent un résidu d'hydrogène ou, alternativement, l'un des substituants de la paire de substituants formée par R1 et R2 est un groupe méthyle et l'autre un résidu d'hydrogène, R3 est a) un groupe oxo ou b) un groupe hydroxy, acétoxy ou propoxy et un résidu d'hydrogène, R4 est un résidu d'alcényle comportant entre 2 et 4 atomes de carbone ou un résidu d'alcoyle comportant entre 1 et 4 atomes de carbone à chaîne droite ou ramifiée, et où l'une des lignes hachurées représente une liaison simple entre deux atomes de carbone et l'autre une liaison simple entre deux atomes de carbone ou une liaison double en position 3 ou 4, les résidus R1 et R2, les chaînes latérales en position 4, respectivement 5, et le cas échéant une double liaison en position, respectivement 4, étant contenus de telle manière que les composés de formule (A) se présentent en tant que mélanges; procédé de fabrication de ces dérivés de tricyclo AD5,2,1,02,6 BDdécane, ainsi que l'utilisation du nouveau composé deformule (A) en tant que parfums, respectivement composants de compositions de parfums pour parfumer des produits cosmétiques et techniques.
PCT/EP1983/000330 1982-12-09 1983-12-09 Derives de tricyclo ad5,2,1,02,6 bddecane avec chaine laterale fonctionnalisee, leur fabrication et leur utilisation en tant que parfums WO1984002338A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19823245524 DE3245524A1 (de) 1982-12-09 1982-12-09 Dimethyl-tricyclo(5.2.1.0(pfeil hoch)2(pfeil hoch)(pfeil hoch),(pfeil hoch)(pfeil hoch)6(pfeil hoch))decan-derivate mit funktionalisierter seitenkette, deren herstellung und verwendung als riechstoffe

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WO1984002338A1 true WO1984002338A1 (fr) 1984-06-21

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EP (1) EP0128175A1 (fr)
DE (1) DE3245524A1 (fr)
WO (1) WO1984002338A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10144816A1 (de) * 2001-09-12 2003-03-27 Dragoco Gerberding Co Ag Duft-und Aromastoff

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2334343A1 (fr) * 1975-12-08 1977-07-08 Firmenich & Cie Utilisation de derives du tricyclo-decane comme ingredients parfumants

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2334343A1 (fr) * 1975-12-08 1977-07-08 Firmenich & Cie Utilisation de derives du tricyclo-decane comme ingredients parfumants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemische Berichte, 1979, No. 112, W. KREISER et al.: 'Erste Totalsynthese von (-) -'Alben", pages 408-422, see pages 412,419,420 *

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EP0128175A1 (fr) 1984-12-19
DE3245524A1 (de) 1984-06-14

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