DE3208203C1 - Mixture of dimethyl-tricyclo [5.2.1.0?] Decyl-methyl-ethers and mixture of dimethyl-tricyclo [5.2.1.0?] Decenyl-methyl-ethers, process for their preparation and their use as fragrances or flavorings - Google Patents

Abstract

The mixture has the general formula A wherein a methyl group is present in C-1 or C-9, a methoxy group is present at C-8 or C-9, R<1>, R<2>, R<3> are a methyl group or hydrogen atoms, one of the substituents being a methyl rest and the other two being hydrogen atoms, the dotted line representing a simple bond C-C and a double bond (optional at C-3 or C-4) for the decenyl-ether mixture or two simple bonds C-C for the decyl-ether mixtures. The mixture having the formula A may be prepared by addition of methanol to methylcyclopentadien dimer and optionally, by catalytic hydrogenation of the mixture obtained. The mixture is used as a perfume or aroma.

Description

The dicyclopentadiene (1) is an important starting material for the production of fragrances. The esters 2b-c obtained by addition of carboxylic acids (e.g. acetic acid, propionic acid) (illustration: Zeilanov et al., Chem. Abstracts, 68, 49 319d) are fragrances used in large quantities worldwide. Formate -2a is described in GB-PS 8 15 232 (June 24, 1959) and dimethylacrylate 2d in US-PS 35 93 745 (August 10, 1971). In DE-OS 27 42 519 (March 23, 1978) the ethers of formula 3 are claimed as fragrances. Further secondary products from dicyclopentadiene, which due to their constitution can be assigned to completely different substance groups, are summarized by Ohloff and Rode-Gawal (in: H. Aebi, E. Baumgartner, HP Fiedler and G. Ohloff, "Cosmetics, fragrances and food additives") , G. Thieme Verlag, Stuttgart 1978,5.55-57) 2 /, 2 a: R = H RCO R | 2 b: R = Me 7 RCO 2 R = El iW \ 4 2 2 dR = RO 3 3 (R = Cl - C-alkyl, Cl - C7-alkenyl) RO R1, R2 = H, CH3 / CH3, II R3 = H, C1-C3-acyl, G3- or C4-alkyl, C3- or C4-alkenyl R4, R5, R6 = = CH3, H 'HI'H, CH3, High, H, CH3 Little was known about the use of products made from Metliyicyclopentadiene as fragrances. In EP-PS Al 0039 232, the dimethyl-tricyclodecane derivatives of the general formula 5 obtained from the dimeric methylcyclopentadiene 4 are claimed as fragrances, the dashed line denoting an optional double bond. The methyl group in the norbornane part should alternatively be contained in the radicals R1 or R2 and the methyl group in the cyclopentene part alternatively in the radicals R4, R5 or R6. The unsubstituted positions R3, R2, R4-R6 should be occupied by hydrogen. Part of the molecule Y is intended to mean a carbonyl, hydroxyl, acetate, propionate or a C3 or C4 ether group. The products exist as mixtures of constitutional isomers.

For the ketones, alcohols and esters of general formula 5 are used spicy-camphor-like (ketone mixture), woody-camphor-like (alcohol mixture) and fruity (Ester mixture) odor notes described. The unsaturated ethers (allyl) are said to strongly herbaceous and the saturated (R3 = n-propyl or i-propyl) fruity (banana), spicy (cinnamon), green or bitter, sweet, herbaceous (petitgrain, lavender, bergamot) Olfactory have aspects.

The methyl ethers are not described in EP-PS Al 0039232 and also not claimed. Hence it was also about the olfactory qualities of these ethers nothing known.

We have now surprisingly found that especially the obtained from the dimeric methylcyclopentadiene 4 by formal addition of methanol Methyl ether of the general formula A (9a-c) with strong and original fragrances radiating light-flowery and fruity notes, which are in the olfactory type of the C3- / C4-alkyl and alkenyl ethers mentioned in EP-PS Al 0039232 of the general Formula 5 clearly distinguish them in terms of smell intensity and appearance surpass.

The methylcyclopentadiene [representation: overview in W. T. Ford, J. Org. Chem. 25, 3979 (1971)] is a mixture of the three double bond isomers 6a, b, c before.

According to S. McLean and.P. Haynes [Tetrahedron, 21, 2313 (1965)], 44.5% of the 1-methyl isomer 6a, 54.5% of the C-2 isomer 6b and only about 1% of the C-5 isomer 6c are in equilibrium before.

6a 6b 6c (44.5%) (54.5%) (<1%) (6a + 6a) (6a + 6b) 7a 7b 7c (6b + 6a) (6b + 6b) 8a 8b 8c In the dimerization of an equilibrium mixture of methylcyclopentadiene, theoretically a number of compounds can be formed, assuming that iProNs with angular methyl groups are sterically unfavorable and do not erode in any appreciable amount , and that the products to be derived from 6c (<1%) can be neglected, the dimeric Metüylcy: lopentadiene (gas chromatogram: abbr. l) should consist of the constitutional isomers 7a-c and 8a-c. The WNMR spectrum (Fig. 2) shows in the area olelinic protons (5-6 ppm) signal groups whose integral corresponds to 2.2 protons.

The signals at 1.25 and 1.50 ppm can be analogous to dicyclopentadiene (Sadtler NMR spectra collection, No. 6494 M) assigned to the protons of the C1 bridge will. Only the signals of relatively low intensity at 1.23 and 1.35 ppm can assigned to the bridgehead methyl groups of 7a - c.

This finding and the intensity of the olefinic signals show this predominant presence of the isomers 8a-c (approx. 85%), while 7a-c only for approx.

15% are included.

The compounds of general formula A claimed here can be are represented by acid-catalyzed addition of methanol to 4, preferably using sulfuric acid or strongly acidic ion exchange resins or of Lewis acids such as BF3 etherate. The addition takes place in analogy to dicyclopentadiene only on the double bond of the norbornene part. From the 'H-NMR spectra of Reaction mixtures it can be seen that anti-Markovnikoff addition has occurred preferentially. The secondary Ethers with the constitutions 9a, b are the main products. In analogy to Dicyclopentadiene partial skeletal rearrangements are also conceivable [overview in E. M. Engler, M. Farasin, A. Sevin, J. M.

Cense and P. v. R. Schleyer, J. Amer. Chem. Soc., 95, 5769 (1973) 1.

The ethers of the general formula A were represented by Reaction of dimeric methylcyclopentadiene (4 or 8a-c + 7a-c with methanol in the presence strong protic acids, e.g. B. sulfuric acid, or strongly acidic ion exchange resins, z. B.

Lewatit SC 104 (Bayer AG), or Lewis acids, e.g. B.

Boron trifluoride). The addition of methanol produced a mixture of methyl ethers 9a - c (gas chromatogram: A b b.3, tH-NMR: A b b.4) obtained from two main isomers as well as several minor isomers. The tH-NMR data indicate the preferred one Presence of isomers 9a, b, which are due to the isomer distribution of the dimeric methylcyclopentadiene are to be expected as secondary products of 8a - c.

That from dimeric methylcyclopentadiene (4 resp.

8a-c + 7a-c) methyl ether mixture obtained by addition of methanol 9a -c has bright, radiant, but also flowery, sweet and fruity olfactory aspects, reminiscent of tropical fruits.

By catalytic hydrogenation using Raney nickel or Precious metal catalysts (e.g.

Palladium-carbon) and neutral solvents at normal pressure or elevated pressure, preferably up to 20 ° and 60 ° C., became the isomer mixture from 9a-c 10a-c (MS: A b b. 5). The mixture of saturated methyl ethers 10a-c is similar in the odor type 9a - c, but looks finer and less sweet and is somewhat reminiscent of apricot and peach.

The isomer mixtures 9a-c and 10a-c are due to their odor properties usable as fragrances or as a component of perfume compositions for cosmetic and use technical purposes.

Example 1 Reaction of dimeric methylcyclopentadiene (4) with methanol using H2SO4 A solution of 30 g sulfuric acid (80%) in 1440 g Methanol were stirred at 50 ° C with 720 g (4.5 mol) of methylcyclopentadiene, dimer, added dropwise (30 min). After 8 hours of stirring at boiling temp. and cooling became 60 ml total Na2CO3 solution added dropwise.

After concentration, 100 ml of water were added. One extracted with Gasoline, concentrated, distilled over a 50 cm Vigreux column and received 420 g (48%) of a mixture of 4 (5), 9-dimethyl-8-methoxy-tricyclo- [5.2.1.02,6] decene-4 (9a) + 3 (4), 9-dimethyl-8-methoxy-tricyclo [5.2.1.02,6] decene-3 (9b) + 1,5-dimethyl-8-methoxy-tricyclo- [5.2.1.02.6 ] decen-4 (9c) [cp. (1.3 mbar) = 660 Cj as a colorless oil; Gas chromatogram: A b b. 3, 1 H-NMR: Fig.4, MS: Fig.5.

C13H20O (192.4) Example 2 Conversion of dimeric methylcyclopentadiene (4) with methanol using Lewatit SC 104 A solution of 240 g (15 mol) Methylcyclopentadiene, dimer, in 480 g of methanol was mixed with 220 ml of ion exchange resin Lewatit SC 104 (Bayer AG) added and 9 hours at boiling temp. touched. After filtration the cooled solution was concentrated and distilled. 150 g (52%) of 9a were obtained - c.

Example 3 Hydrogenation of 9a-c A solution of 57.6 g of 9a-c (product mixture from Example 1) in 400 ml of dry methanol was mixed with 0.5 g of palladium / activated carbon added and stirred in a hydrogen atmosphere (20 at) for 3 hours. After relaxing of the autoclave, filtration and concentration left 58 g of crude product. distillation over a 30 cm Vigreux column gave 49 g (83%) iOa-c; Kp.

(0.8 mbar) = 54 ° C; MS; MS: A b 5.

Ct3H22O (194.4) Example 4 Perfume oil with a sweet and herbaceous note a b Orange oil, Brazilian 150 150 (Florida type) Isobornyl acetate 300 300 Cyclohexyloxcessetic acid allyl ester 10 10 Bergamot oil 100 100 Rosemary oil, Tunisian 30 30 Mugwort oil 10 10 Dimethyltetrahydrobenzaldehyde 5 5 styrene acetate 20 2ü hexyl cinnamaldehyde, alpha 100 100 geranium oil, bourbon synth. 10 s 10 phenylethyl alcohol 30 30 citronellol 30 30 4-tert-butyl-cyclohexyl acetate 100 100 Acetylcedren / Acetylthujopssen 30 30 Patchouiy Oil, Singapore 20 20 Galbanum Oil 5 5 Galbanum Resinoid 10 10 Musk Ambrette 20 20 Attractolide 20 20 Dipropylene Glycol 100 -Methylether 9a-c - 100 11.00 1100 The perfume oil of the above composition a has a harmonious, sweet and herbaceous fragrance complex, which when 100 g of the methyl ether mixture sches 9a - c is gaining a lot of charisma, while at the same time Emphasis on sweet and fruity aspects. After 6 hours of ventilation on the olfactory strip, it works Mixture a is significantly weaker and has changed the fragrance complex, while b has changed the fragrance complex has largely retained and also has a higher odor intensity; 9a - c have thus also fixing properties.

Example S Perfume oil with a fresh, floral-fruity note of methyl ether 9a-c 300 Hydroxycitronelial 220 Jasmine Base, synth. 140 Attractolide 120 Citronenoel 80 spruce needle oil, Siberian 50 oak moss extract, 50% in DEP 40 galbanum extract, 50% in DEP 20 Methylchavicol 20 Dimethyltetrahydrobenzaldehyde 10 1000 This perfume oil, which contains a relatively high dosage of the ethyl ether mixture 9a-c, has one harmonious, fresh and radiant fragrance with a flowery-fruity direction and bitter Fund.

Example 6 Perfume oil with tart herbaceous notes a b cedar leaf oil 150 150 Bergamot oil 100 1 «8S phenylethyl alcohol 100 100 Terpineol, pure 100 100 Acetylcedren / Acetylthujopsen 100 100 Amyl salicylate 70 Linalyl acetate 60 60 Linaiool 50 50 MethyUonon, gamma 50 50 4-tert-butylcyclohexyl acetate 50 5u anisaldehyde 50 Benzyl salicylate 50 50 Coumarin 50 50 Rosemary oil, Tunisian 45 45 Wormwood oil 30 30 Citronellol 30 30 Ylang-YIang-Oil 30 30 Attractolide 30 30 Spik Oil, Spanish 20 20 Clary Sage Oil 10 10 PEeffenninzöl? Brazilian 5 5 ltmenoxid, inactive, 10% in DPG 5 5 galbanum extract 5 5 Dipropylene glycol 11u -Methylether IOa-c - 110 1300 1300 The perfume oil a has a harmonious herbaceous fragrance complex, which when the methyl ethers 10a-c (Mixture b) has an interesting olfactory aspect that is reminiscent of tropical fruits remind.

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Claims (4)

Claims: 1. Mixture of dimethyl tricyclo [5.2.1.02; qdecylmethyl ethers and mixture of dimethyl tricyclo [5.2.1.026] decenyl methyl ethers of the general formula A, in which - a methyl group on (1 or C- 9 is, - the methoxy group is at C-8 or C-9, - R1, R2, R3 are methyl or hydrogen radicals, one of the substituents being a methyl radical and the other two hydrogen radicals and - the dashed line for the mixture of decenyl -ether means a C - C single bond and a double bond (optionally at C-3 or C-4) and for the mixture of decyl ethers two C - C single bonds. 2. Preparation of the mixtures according to claim 1, characterized in that that methanol to dimeric methylcyclopentadiene using protic acids or Lewis acids is added at the boiling point and, if necessary, the d3 or 214 double bond is catalytically hydrogenated. 3. Use of the mixtures according to claim 1 as Fragrances or ingredients of fragrance mixtures or perfume oils for cosmetic and technical perfuming. 4. Use of the mixtures according to claim 1 as flavorings for flavoring of food or tobacco products.