CH590810A5 - Organoleptic oxygenated alicyclic derivs - giving galbanum or juniper oil-like odours to perfume compsns. soaps etc. - Google Patents

Abstract

Cpds. of formula (I): (with a satd. ring or an isolated double bond in the 1-, 4- or 6-posn. or two double bonds in the 1- and 4-, 1- and 5- or 4- and 6-posns. of the rign as indicated by the dotted lines, in which n is 0 - 2, Z is bonded at the 1- or 6- posns. of the righ to a C atom and may be -CO, -SOR8 or where R8 is an acyl gp. and R9 are, singly, 1-6C alkyl, or, together 2-6C alkenylyl gps., Y is O or CH2 and R1, R2, R3, R4 and R5 are each H or one is methyl and all the others are H and R6 and R7 are each 1-3C alkyl or one is H and the other alkyl) have organoleptic props. Cpds. (I) may have fruity, green, woody and oily notes reminiscent of galbanum or juniper oil and are very powerful, pref. 0.01-2 wt.% achieving desired effects.

Description

  

  
 



  The compound of formula:
EMI1.1
 possessing a cyclic double bond in one of the positions indicated by the dotted lines is a new compound, endowed with interesting organoleptic properties. It is more particularly appreciated in the art for its original and remarkably powerful odor, of the green, herbaceous type, recalling in particular that of the galbanum resinoid.



   The invention relates to a process for the preparation of compound I above, characterized in that reacting, in the presence of a strong base and of an inert organic solvent, an allyl halide with a carbonyl compound of formula:
EMI1.2
 having a double bond in one of the positions indicated by the dotted lines, and the reaction product thus obtained is hydrolyzed.



   The reaction of the carbonyl compound II with the allyl halide, preferably allyl chloride or bromide, is carried out according to the usual techniques, such as for example those described in HO House, Modern Synthetic Reactions, WA Benjamin Inc. , New York, 1969, p. 163 and following.



   As strong base, one can in particular use an alkali metal alcoholate such as sodium or potassium for example, or alternatively the lithium salt of a secondary aliphatic amine, such as diisopropylamine for example. The above reaction is further carried out in the presence of an inert organic solvent. An ether, such as ethyl ether or tetrahydrofuran for example, is used for such purposes.



   Compound II, used as the starting material in the above process, can be obtained according to known methods. 3,3-Dimethylcyclohex-1-en-1 -yl-methyl ketone, for example, can be easily prepared from dehydrolinalool according to a method described in Z. Chem. , 9, 64 (1969).



   The following examples will illustrate the present invention in more detail. In said examples, temperatures are indicated in degrees centigrade.



  Example 1: 1- (3, 3-Diméllîyfryclohex-1-êtîe-1-yi) pent-4-en-1-oiîe
 5 g of a 12% solution of butyllithium in hexane, dissolved in 100 ml of absolute ether, were added at OC C to 7.3 g of diisopropylamine in 70 ml of anhydrous ether. 10 g of 3.3 dimethylcyclohex-1-en-1-yl-methyl ketone, prepared according to Z.



  Chem. , 9, 64 (1969), were then added to the above mixture, the latter being stirred for 60 min at 0 C before receiving 8.8 g of allyl bromide. After having been stirred overnight at room temperature, the reaction mixture was hydrolyzed using H 2 O and the organic phase separated, washed, dried and finally distilled according to the usual techniques.



   There was thus obtained 5.9 g of a mixture containing about 25% of starting material, 40% of 1- (3,3-dimethylcyclohex-1-en-1-yl) pent-4-en-1-one and 30% of a compound of formula:
EMI1.3
 according to analysis by gas chromatography.



   The desired product was then isolated in the pure state, after separation of the mixture by means of preparative gas chromatography and characterized as follows:
 nD20 = 1.4879; d420 = 0.9262.



   IR: 3080, 1680, 1640, 990, 910, 820 cm-1.



   NMR: 0.88 (6H, 2s); 1.32 (2H, t, J = 7 cPo); 4.75 to 6.20 (3H, m); 6.73 (1H, m) a ppm.



   MS: M + = 192 (7); m / e = 177 (5), 164 (3), 149 (2), 137 (100), 121 (6), 109 (45), 93 (6), 81 (13), 67 (33), 55 (28), 41 (16).



     Example 2:
 1- (3,3-DimetSzylcycloSlex-6-en-1-yl) pent-4-en-1-one
 The above compound was prepared from 5 g of 3,3 dimethylcyclohex-6-en-1-yl-methyl ketone and of allyl bromide, under the conditions described previously in Example 1. The product thus obtained, after purification by preparative gas chromatography, was characterized as follows: nu20 = 1.4891; d42 = 0.9247.



   IR: 3080, 1820, 1675, 1640, 990, 910 cm-1.



   NMR: 1.06 (6H, 2s); 4.73-6.00 (3H, m); 6.40 (1H, m) ppm.



   MS: M + = 192 (13); m / e = 177 (6), 137 (100), 109 (85), 93 (12), 81 (32), 67 (55), 55 (58), 41 (45).



   The 3,3-dimethylcyclohex-6-en-1 -yl-methyl ketone used above, as the starting material, can be prepared as follows:
 a) 467 g of methyl vinyl ketone and 480 g of isobutyraldehyde dissolved in a mixture of 700 ml of water and 350 ml of methanol were added over 3 h, under nitrogen, to a mixture maintained at 60 70 ° C of 25 g of KOH, 150 ml of methanol and 1000 ml of water.



  After being heated for 1 h at 70 C and cooled to 25 C, the mixture, diluted with H2O, was extracted with petroleum ether and finally treated as indicated above to give 325 g (40%) of 4.4 -dimethylcyclohex-2-en-1-one, eb. 7376 C / 15 torr.



   b) 124 g of the above compound were hydrogenated in the presence of 2 g of Raney nickel in 300 ml of isopropanol to finally give 120 g of 4,4-dimethylcyclohexanone.



   c) 26 g of the above compound, dissolved in 200 ml of ether, were added over 45 min, at 0 - C, to a mixture of 22 g of sodium methoxide, 30 g of ethyl formate and 100 ml of ether. The reaction mixture was then stirred overnight at room temperature, followed by the addition of 600 ml of water maintained at 0 ° C. and finally acidified with 30% HCl. After extraction with petroleum ether and treatment of the organic phase as indicated above, 26 g of a compound of formula were isolated:
EMI1.4
 eb. 29-33- C / 0.0 1 torr, yield 75%.

  After treatment at 68 ° C. for 3-5 minutes of 15 g of said compound by means of 10.5 g of ethyl orthoformate, in the presence of 0.1 g of p-toluenesulfonic acid in 20 ml of methanol, and extracting the reaction mixture with petroleum ether, 17 g of a mixture of compounds of formulas were isolated:
EMI2.1

EMI2.2

The above mixture was used for the next reaction step without further purification.



   d) 6.0 g of the above mixture, dissolved in 20 ml of ether, were added under nitrogen to 0.8 g of LiAlH4 suspended in 30 ml of ether and finally stirred overnight. After addition of H2O, extraction with petroleum ether, washing, drying and distillation as indicated above, 6.8 g of impure material was isolated.



  After heating under reflux for 90 min in the presence of 0.3 g of p-toluenesulfonic acid and distillation, 4.8 g of a product containing 78% of 1-formyl-3,3-dimethylcyclohex was finally obtained. -6-year.



   e) 1.5 g of the above compound in 20 ml of ether was added to a solution prepared from 1.3 g of CH3I, 1.25 g of Mg turnings and 50 ml of ether. After being stirred for 2 h, the mixture was poured onto ice, then extracted and finally distilled to give 1.43 g of 1- (3,3-dimethylcyclohex-6-en-1-yl) -l-hydroxyethane.



   IR: 3400 cm-1.



   NMR: 0.91 (6H, 2s); 1.18 (3H, J - "" 6Hz); 4.06 (1H, m); 5.53 (1H, m) i ppm.



   MS: M + = 154 (21), m / e: 139 (6), 121 (16), 85 (26), 69 (20), 43 (100).



   f) 1.2 g of the above compound was treated, under nitrogen and at 25C C, with 20 g of MnO2 in 50 ml of petroleum ether.



  36 h after addition of the reagents, filtration and fractional distillation of the reaction mixture, 1.08 g (85%) of (3,3dimethylcyclohex-6-en-1 -yl) methyl ketone was isolated.



      n = 1.4809; d420 = 0.9309.



   IR: 1670,1640cm-1
 g) 10 g of the above compound were added at 0 C to a mixture obtained from 5 g of a 12% solution of butyllithium in hexane, 7.3 g of isopropylamine and 70 ml of ether. One hour after addition of the reagents, a further 8.8 g of allyl bromide was added and left to stand overnight. After addition of H2O and treatment of the reaction mixture as indicated above, 6 g of a product containing 20% of 1- (3,3-dimethylcyclohex-6-en-1-yl) pent-4-ene- was isolated. 1-one. This compound was obtained in the pure state by c.p.g. preparatory.

 

   g ') 5 g of a 12% solution of butyllithium in hexane and 100 ml of ether were added, at 0 ° C. to C, to 73 g of isopropylamine dissolved in 70 ml of ether. 10 g of (3,3-dimethylcyclohex-1-en-1-yl) methyl ketone were then added, over 1 h and at OC, to the above mixture and finally 8.8 g of allyl bromide. After the treatments described above, 5.9 g of a mixture containing 40% of 1 - (3,3-dimethylcyclohex-1 -ene-1 -yl) pent-4-en-I-one were collected, finally isolated in the pure state by cpg preparatory.

 

Claims (1)

CLAIM Process for the preparation of an unsaturated alicyclic compound of the formula: EMI2.3 having a cyclic double bond in one of the positions indicated by the dotted lines, characterized in that, in the presence of a strong base and an inert organic solvent, an allyl halide is reacted with a carbonyl compound of formula: EMI2.4 having a double bond in one of the positions indicated by the dotted lines, and the reaction product thus obtained is hydrolyzed. SUB-CLAIMS 1. Method according to claim, characterized in that compound II is reacted with allyl bromide. 2. Method according to claim, characterized in that the lithium salt of diisopropylamine is used as strong base and, as inert organic solvent, diethyl ether.