DE2461594C3 - 5,6-epoxy-1,2,6-trimethyltrlcyclo square bracket to 5,3,2,0 to the 2,7 square bracket to dodecane, process for its preparation and its use as a fragrance - Google Patents

Description

Ambergris-like fragrances are valuable starting compounds for fragrance compositions and Perfumes. Ambergris, an intestinal excretion, is particularly expensive the sperm whales found in the intestines of killed whales or on the coasts, especially of the Atlantic, is washed ashore or collected. The main component of the ambergris grisea is the ambergrine, a tricyclic triterpene alcohol; See Advances in Chemistry org. Naturstoffe, Vol. 6, Springer Verlag; E. Led he er, Odeurs et parfums des animaux, Paris (1950), pp. 120 to 129 and E. Lederer, Ind. Perfume. Cosmet, Vol. 12 (1957), p. 231. There have been numerous attempts to synthesize fragrances with amber-like substances Smell undertaken. Some of these synthetic fragrances can be used as replacements for the expensive one Ambra grisea can be used. For example, Manool derivatives, i. H. Diterpenes made from certain Conifers obtained are used extensively as a substitute for ambergris

In general, however, fragrances with an amber-like odor are difficult to manufacture, and they are special natural substances are required as starting compounds for their production. That is why the synthesis of Fragrances with an amber-like odor are expensive.

The invention is based on the object of creating a new compound that can be used as a fragrance an amber-like and wood-like smell. This object is achieved by the invention

The invention thus relates to the subject matter characterized in the claims.

Fig. 1 shows the infrared absorption spectrum of the compound (I);

F i g. 2 shows the mass spectrum of the compound (I); F i g. 3 shows the NMR spectrum of Compound (I); F i g. 4 shows the stereochemical formula of the ketone obtained by isomerization of the compound (I) has been

The compound of the formula I is a sesquiterpene hydrocarbon with the empirical formula C15H24O and the structural formula I.

The compound (1) can be produced more cheaply than

common odoriferous substances with an amber-like odor, and it is one because of its olfactory properties valuable fragrance.

According to the invention, the compound (I) can be obtained by reacting 1 mole of U, 6-trimethyltricyclic 53 ^, 0 ² · ⁷ ] -dodeca-5-ene (hereinafter referred to as compound II) with 1 to 1.2 moles of a peracid can be produced in a known manner. Examples of usable peracids are peracetic acid, perbenzoic acid, perpropionic acid, performic acid, monoperphthalic acid and trifluoroperacetic acid.

The reaction is carried out in the presence of a solvent which is inert towards the peracid Examples of solvents that can be used are dichloromethane, chloroform, acetone, methyl ethyl ketone and ethyl acetate and ethyl propionate. Since acid is formed in the course of the epoxidation reaction, the Reaction system from the beginning or during the reaction or after completion of the reaction Acid acceptor added to the resulting acid

neutralize. Examples of acid acceptors that can be used are sodium and potassium carbonate or acetate and alkaline earth metal hydroxides, such as calcium and barium hydroxide. The reaction can be carried out at temperatures of - are conducted from 0 to 5 ° C 5 to 1O ⁰ C, preferably. The reaction is completed in the temperature range from -5 to 10 ^0. C within about 8 hours and at temperatures of 0 to 5 ° C over about 5 hours. After completion of the reaction, the compound (I) is extracted with a solvent such as dichloromethane or chloroform, and the organic extract is distilled under reduced pressure. The compound (1) can be obtained in a high yield.

The compound (U] used according to the process is obtained by reacting!, S ^ -trimethylcyclododecatriene-1,5,9 (hereinafter referred to as 1,5,9-TMCDT is the cyclic trimer of isoprene) with an acidic one Receive catalyst. This conversion is an intramolecular ring closure reaction.

The compound (I) is a fragrance with a strong odor of natural ambergris, a peculiar one wood-like odor, a camphor-like diffusibility and a so-called »natural Ge odor «, which is reminiscent of damp earth or forest odor When the compound (I) is absorbed on filter paper

6s and upon standing at room temperature (example, at 20 to 3O ⁰ C) of the residual odor is very strong to keep at least one week. The scent of compound (I) is strong. Even when diluted de

15th

Compound (I) in ethanol, this odor can still be perceived in a dilution of 1/10 000.

The compound (I) can be olfactory on Gi and its Properties as a fragrance can be used for a wide variety of purposes, for example as a component of perfumes and for perfuming cosmetic preparations and of soaps. Furthermore you can; connection

(I) together with natural ambergris, musk or cifett, or together with natural sandalwood oil, Yetiver oil, patchouli oil or cedar oil due to their wood-like odor can be used for the production of men's perfume.

The examples illustrate the invention. Parts, percentages and proportions relate to the Weight unless otherwise stated

Production of 1,2,6-trimethyl
dodeca-5-en

(Compound II)

20th

150 g of 1Ä9-TMCDT with a temperature of 91 to 92 ° C, 260 ml of formic acid and 150 ml of dichloromethane are placed in a 1 liter three-necked flask. The mixture is cooled to 5 to 10 ° C. and a solution of 7.5 ml of sulfuric acid in 40 ml of formic acid is added dropwise at this temperature over the course of 30 minutes. 30 ^° C. reacted with stirring. After the reaction has ended, the dichloromethane is distilled off at normal pressure and the formic acid is distilled off under reduced pressure. The residue is then neutralized, washed with 3 percent aqueous sodium bicarbonate solution and water, dried over sodium sulfate and distilled B.p. 75 to 80 ° C / 0.05 torr. The yield is 90.0% of theory η S ⁵ = 1.5111. IR absorption spectrum: 802 and 1660 cm- '.

Based on the IR absorption spectrum, the NMR spectrum and the mass spectrum of the compound

(II) and based on the X-ray diffraction analysis of the crystalline produced from the compound (II) Ketone, the compound (II) has the following structural formula

45 Sodium chloride solution washed neutral, dried over sodium sulfate and evaporated. The residue is distilled under reduced pressure. Yield 21 g (95% of theory) of compound (1) as an oil with a boiling point of 85 to 90 ° C / 0.03 Torr, η ¥ = 1, 5063

IR absorption spectrum: characteristic epoxy absorption at 802,880 and 1240 cm- '.

Mass spectrum: M ⁺ 220 (molecular ion).

NMR spectrum:

h-H (d)

CH ₃ (C)

(a) 0.72 ppm (3H, s).

(b) 0.75 ppm (3H, s).

(c) 1.18 ppm (3H, s).

(d) 2.87 ppm (1H, t).

The compound (I) is reacted with a Lewis acid. It is a crystalline ketone, mp 99.5 bi: obtain 100.5 ⁰ C. The structure of the ketone is determined by X-ray diffraction analysis.

The stereochemical shown in Fig.4 Formula can be derived from these values. Da ketone has the molecular formula C15H24O. The ketone ha thus the stereochemical structural formula III

Thus, compound (I) has structural formula IV

55

A mixture of 20.4 g (0.1 mol) of the compound (II) and 17 g of sodium carbonate is introduced into 100 ml of dichloromethane with stirring. 20.8 g (0.11 mol) of a 40 percent solution of peracetic acid in acetic acid are then added dropwise at a temperature of 0 to 5 ° C. over the course of 2 hours. The solution is then stirred for 2 hours at this temperature and for a further 3 hours at room temperature. 200 ml of water are then added to the solution and the mixture is extracted twice with dichloromethane. The dichloromethane extract is mixed with saturated aqueous solution

Example 2

The reaction is carried out according to Example 1 however, instead of the 40 percent peracetic acid solution, 15 g (0.11 mol) of perbenzoic acid will be used Dichloromethane solution used. Furthermore, 5.8 sodium carbonate are used. The compound (1) is 93 percent yield obtained.

Example 3

Below is a recipe for a perfume or eau de Cologne:

Vetiveryl acetate patchouli oil Oakmoss Musk Ketone Coumarin Methyljonon

Hydroxycitronellal cinnamon alcohol stearyl acetate phenylethyl alcohol Geraniol Terpineol Galbanum oil Lavender oil Bergamot oil

Ylang-ylang oil compound (Γ)

24 61594 J. 6th 5 Resinoid oak moss Perfume Example 4 Cabdanum 80 g
150 g The following composition is suitable for Patchouli oil 50 g of soaps: Heliotropin 50 y 20 g ίο Ambrette musk 20 y 10g Vanillin 5Of 80 g Benzyl salicylate 120 § 10g Amyl salicylate 1501 90 g Geranium oil 50 g 30 g 15 geraniol 60 g 25 g Anisaldehyde 240 g 40 g Lavender oil 70 g 50 g Connection (I) 30 g 15g 60 g 10g Sheet drawings 60 g 20 g 40 g 30 g 1000g 20 g 70 g 800 g For this 4

Claims (3)

Patent claims: ί 1.
can the formula 2. A process for the preparation of 5,6-epoxy-1,2,6-trimethyltricyclo [53A0 ⁱ⁷ ] dodecane, characterized in that lAe-trimethyltricyclofS ^ ÄO ^ Tdodeca-S-ene with a peracid im Molar ratio 1: 1 to 1.2: 1 in the presence of a solvent which is inert towards the peracid and an acid acceptor at temperatures of -5 to 10 ⁰ C 3. Use of 5,6-epoxy-1,2,6-trimethyltricyclo [53A0 ² - ^r ] dodecane according to claim 1 as a fragrance.