DE2461593C3 - 1,2,6-trimethyltricyclo [53.2, 02'7! -dodeca-5-on, process for its production and its use as a fragrance - Google Patents

Description

is reacted with a Lewis acid in a mixture with an inert solvent at -10 to +30 ⁰ C.

3. The method according to claim 2, characterized in that the Lewis acid is an aluminum, Zinc or magnesium halide of the general formula

AlX ₃ , ZnX ₂ or MgX ₂ ,

in which X represents a chlorine, bromine or iodine atom, or a boron trifluoride-diethyl ether complex is used

4. The method of claim 2 and 3, characterized in that one carries out the reaction at temperatures of 5 to 10 ^0. C.

5. The method according to claim 3, characterized in that 1/20 to 1/30 mol of the boron trifluoride-diethyl ether complex per mole of 5,6-epoxy-I ^, ö-trimethyltricyclofS.S ^ .O ^ j-dodecane used.

6. The method according to claim 3, characterized in that 1/10 to 1.2MoI aluminum, zinc or Magnesium halide per mole of 5,6-epoxy-1,2,6-trimethyltricyclofS ^ .O ^ J-dodecane used.

7. The method according to claim 2 to 6, characterized in that the reaction under anhydrous air or anhydrous nitrogen as protective gas.

8. The method according to claim, characterized in that the reaction is carried out for 4 to 5 Hours.

9. Use of 1,2,6-trimethyltricyclorjj ^ .O ^ -dodeca-S-one according to claim 1 as a fragrance.

men. Some of these synthetic fragrances can be used as a substitute for the expensive ambergrisea. For example, Manool derivatives, i. H. Diterpenes obtained from certain conifers are widely used as a substitute for ambergris.

In general, however, fragrances are only ambergris It is difficult to produce a similar odor and there are special starting compounds for their production Natural substances required. Therefore, the synthesis of fragrances with an amber-like odor is expensive.

The invention is based on the object of creating a new, easy-to-manufacture connection that turns out to be Fragrance with an amber-like odor is suitable. This object is achieved by the invention.

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

F i g. 1 shows the 1R 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 the compound (1).

The compound of the formula (I) is a sesquiterpene of the empirical formula Ci ₅ H ^ O and the formula I.

35

40

45

Fragrances similar to ambergris are valuable starting compounds for fragrance compositions and perfumes, Ambergris, an intestinal excretion from the sperm whales, is particularly expensive is found or is washed ashore and collected on the coasts, especially of the Atlantic. The main ingredient Ambra grisea is Ambrein, a tricyclic triterpene alcohol; see progress of the Chemistry org. Naturstoffe, Vol. 6, Springer Verlag; E .. Led er er, Odeurs et parfums des animaux, Paris (50), pages 120 to 129, and E. Lederer, Ind. Perfume. Cosmet, Vol. 12 (1957), page 231.

Numerous attempts have been made to synthesize fragrances with amber-like genes.

CH,

The compound of the formula (I) can be produced more cheaply than conventional fragrances with an ambergris odor, and the compound is valuable for its excellent amber odor.

According to the invention, the compound (I) can be prepared by adding 5,6-epoxy-1,2,6-trimethyltricyclododecane to a mixture of a Lewis acid, such as AlX ₃ , ZnX: or MgX ₂ , in which X is a chlorine , Bromine or iodine atom, or a boron trifluoride-diethyl ether-K complex and a solvent inert to the Lewis acid, such as an ether, for example diethyl ether or dipropyl ether, a hydrocarbon such as η-hexane, n-octane, benzene or toluene , a halogenated hydrocarbon such as dichloromethane or chloroform, or an ester such as ethyl acetate or butyl acetate, at temperatures of -10 to + 30 ⁰ C is added dropwise. During this process, the 5,6-epoxy compound, which is referred to as compound (II), is isomerized. The reaction can also be carried out in the absence of an inert solvent. However, if an inert solvent is used, the reaction is smoother.

When using the boron trifluoride-diethyl ether complex as a Lewis acid, this catalyst is in in an amount of about 1/20 to 1/30 mole per mole of the compound (II). When using other Lewis acids are used about 0.1 to 1.2 moles per mole of the compound (II). A 1: 1 molar ratio is preferred because the reaction proceeds more smoothly and better results are obtained.

The preferred isomerization temperature is from 5 to 10 ^° C. At an isomerization ^{temperature above 30 °} C., larger amounts of polymeric products are formed. The isomerization is sensitive to moisture. Therefore, the invention

<i

Procedure carried out under anhydrous conditions and in dry air or dry nitrogen. The reaction time for isomerization is preferably 4 to 5 hours.

When the isomerization is complete, the solution is acidified, for example with cold, dilute hydrochloric acid or sulfuric acid, and then extracted with a solvent such as diethyl ether or benzene. The organic extract is evaporated under reduced pressure. It is the compound (I) in crystalline κ form If- a yield of at least 75% of theory. Th. Received.

The compound (11) used according to the process is obtained by reacting LS ^ -trimethylcyclododecatriene-1,5,9 (hereinafter referred to as 1,5,9-TMCDT ι; the cyclic trimer of isoprene) with a acidic catalyst and subsequent treatment of the 1 £ 6-trimethyltricyclo [5,3,2,0W] -dodeca-5-ene formed (Compound III) prepared with a peracid. When treating 1,5,9-TMCDT with an acid An intramolecular ring closure

The compound (I) is a fragrance with a strong odor of natural ambergris, a peculiar wood-like odor and a so-called "natural odor" that is reminiscent of damp earth or forest odor. When the compound (1) is absorbed on filter paper and when left to stand at room temperature ( for example at 20 to 30 ⁰ C) the residual odor is very strong and lasts at least a week. The scent of the compound (I) is strong. Even when the compound (I) is diluted in ethanol, this odor can still be perceived at a dilution of 1/10 000

From DT-OS 18 11 289 the cis-l, 7,7-trimethylbicyclo [4,4,0] -decanon- (3) and the corresponding trans connection known. It is described there that both Isomers develop an intense fine wood-like odor with an amber-like scent note. A review found that both isomers had a camphor-like amber-like odor. The connection (1) is characterized by a higher fixing power and a characteristic woody-amber-like appearance compared to these isomers Odor note off.

Due to its olfactory properties, the compound (I) can be used as a fragrance for the most varied of substances Purposes are used, for example as a component of perfumes and for perfuming cosmetic Preparations and soaps. Furthermore, the compound (I) can be used together with natural ambergris, musk or Civet, or along with natural sandalwood oil, vetiver oil, patchouli oil or cedar oil on the basis of theirs wood-like odor can be used for the production of men's perfumes.

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

Preparation of 1,2,6-trimethyltricyclo [5,3,2,0 ²⁷ ] -dodeca-5-en (compound III) from 1,5,9-trimethylcyclododecatriene-1,5,9 (1,5,9-TMCDT) .

150 g of 1,59-TMCDT with a temperature of 91 to 92 ° C., 260 ml of formic acid and 150 ml of dichloromethane are placed in a three-necked flask with a capacity of 11. 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. The mixture is then reacted for 3 hours at this temperature and for a further 3 hours at 20 to 30 ° C. with stirring. When 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. Yield 135 gl ^ ö -trimethyltncyclo-dodeca-S-ene with a bp of 75 to 80 ° C / 0.05 torr. .

Production of the compound (Ii) from the compound

! o 100 ml of dichloromethane are mixed with 20.4 g (0.1 mol) li.e-TrimethyltricyclofS ^ AOiT-dodeca-S-en and 17 g Sodium carbonate is added and the mixture is cooled to 0 to 5 ° C. while stirring. Then be at this temperature within 2 hours 20.8 g (0.11 mol) of a 40 percent Solution of peracetic acid in glacial acetic acid was added. The mixture is at this temperature for 2 hours and Stirred for a further 3 hours at room temperature. Then 200 ml of water are added, and the resulting solution is extracted twice with dichloromethane ^ o. The dichloromethane extract is saturated with washed neutral aqueous sodium chloride solution and then dried over sodium sulfate. After that the dichloromethane is distilled off and the residue is distilled in vacuo. Yield 21 g of the compound (II) from bp 85 to 90 ° C / 0.03 Torr.

example 1

13.4 g (0.1 mol) of anhydrous aluminum chloride and 100 ml of η-hexane are mixed with one another under anhydrous nitrogen as protective gas and ^{cooled to 0 to 10 °} C., within one hour 22 g (0.1 mol) of the compound ( H) dropped in. The mixture is 1

Stirred hour at 0 to 10 ⁰ C and 2 more hours at room temperature. The reaction mixture is then poured into 100 ml of cold 6 η-hydrochloric acid and the solution is extracted with η-hexane. The hexane extract is dried over sodium sulfate and evaporated. the

The residue is distilled under reduced pressure. Yield 20 g of compound (I) with a boiling point of 105 ° to 11 ° C./0.05 torr. After recrystallization from methanol 17.6 g (80% d. Th.) Prisms are obtained, melting at 99.5 to 100.5 ⁰ C.

IR absorption spectrum: 1710 cm- ¹ (C = O) mass spectrum: M ⁺ 220 (molecular ion)

M ⁺ -CH ₃ 205 M + -CO 192

50 NMR spectrum:

CH ₃ (a)

CH ₃ (C)

(a) 0.95 ppm (3H, s)

(b) 1.20 ppm (3H, s)

(c) 0.89 ppm (3H, d,] = 7cps)

(d) 2.77 ppm (lH, q, J = 7cps)

(e) 2.37 ppm (2H, m)

Analysis of the X-ray diffraction diagram (direct method):

Lattice constant ·. a = 7.975 Å, b = 13.225 Å, c = 7.147 Å;

«= 95.7 °, 0 = 60.0 °, γ = 104.2 °. Space group: PT, Z = The ketone has the empirical formula C15H24O. The ketone thus has the stereochemical structural formula

Values (Ä) of X, Y and ZaIs fixed coordinates:

RX

RY

RZ

0.9791 5.7703 1.7584 Cl 2.3424 5.6967 2.4672 C2 3.1955 4.4961 2.0121 C3 2.3586 3.2151 1.9691 C4 3.0098 1.9672 1.2955 C5 3.6074 2.3334 -0.0927 C6 2.4712 2.8519 -1.0345 C7 1.5720 3.8637 -0.3559 C8 1.1293 3.4170 1.0436 C9 02013 4.4893 1.6283 C 10 0.5477 1.9829 0.9738 CIl 1.7833 1.0214 1.1082 C12 -1.1340 4.7008 0.8295 C13 1.9438 2.8689 3.4240 C 14 4.1078 1.2928 2.1657 C15 0.5492 6.8548 1.4110 OI

C2-C1-C1-C2- C3-C4-C5-C4- C4-C5-C6-C5- C6-C7-C4-C9- C8-C9-Cl-ClO- C5-C12-C2-C1- C2-C3-C3-C4- C9-C4-C4-C5- C12-C5-C7-C8- C4-C9-C10-C9 C9-C10 ClO-Cl C3-C4-C5-C4-C4-C5-C6-C5-C5-C6-C4-C9-C8-C9-CI-C 10 C9-C11

ClO C3 C9 C C C C8 ClO CH -C -ClI Ol C4 C C C -C C9 -CIl -CIl -C -OI C5 C9 -C6 -C12 -C7 -C8 -C -C9 -C

117.21 113.06 109.94 109.74 102.04 109.29 112.52 110.05 109.68 111.65 104.92 119.15 110.94 107.85 112.11 113.57 111.06 112.68 101.76 115.93 114.50 173.46 116.95 100.20 110.94 109.74 109.65 110.69 108.58 108.39 105.50

Example 2

Example 1 is repeated, but 0.57 g (0.004 mol) of the boron trifluoride-diethyl ether complex Yield 17.2 g (78% of theory) of the compound (I) used instead of the aluminum chloride.

Example 3

Below is a recipe for a perfume or given a cologne:

Formation angle of the atoms from the fixed coordinates:

Three atoms bond angle.

Degree

Civetone Absolutely

Muskon Absolutely

Oak moss Absolutely

Vanilla Absolutely

Ambrette musk

Sandalwood oil

Patchouli oil

Methylionone

Vetiver oil

Eugenol

Phenylethyl alcohol

Geraniol

Benzyl acetate

Jasmine Absolutely

Hexyl cinnamaldehyde

Linalool

Linalyl acetate

Bergamot oil

Connection (I)

10 g 5g 30 g 10g 80 g 50g 80 g 30 g

100g 20g 30g 30g 30g 20g 50g 50g 50g

125g 50g

850g Example 4 gende composition is suitable for the f
tire: 'arfumie Ethylene brassylate 90 g Sandalwood oil 50g Resinoid oak moss 10g Patchouli oil 50g Coumarin 30 g Bornyl acetate 15g Citronellol 60g Tetrahydrogeraniol 5g Petitgrain oils 30 g Lavender oil 80 g Stearyl acetate 15g Spruce needle oil 10g Linalool 185 g Linalylacclate 120 g Connection (I) 50 g

800 g

For this purpose 3 NIiUl drawings

Claims (2)

of formula I. Patent claims: 1,2,6-trimethyltricyclo [5,3,2,0 "] - dodeca-5-one (D 2. Process for the preparation of 1,2,6-trimethyltricyclo [5,3,2,0 ²⁷ ] -dodeca-5-one according to claim 1, characterized in that one