PL198496B1 - New compound, methyl furyl analogue of farnesol - Google Patents

Abstract

The new compound, 3,7-dimethyl-9- (5-methylphoran-2-yl) -nona-2,6-dien-1-ol of formula 1.

Description

The present invention relates to a novel compound, farnesol methylfuryl analogue, having a floral odor similar to that of farnesol.

Farnesol is an acyclic sesquiterpene alcohol found in nature, incl. in petitgrain Bigarade and ambret oil. It is widely used in flavor compositions and food flavors, and also exhibits high biological activity against pathogenic microflora.

The invention relates to a new compound, 3,7-dimethyl-9- (5-methylfuran-2-yl) -non-2,6-diene-1-ol of the formula I, which is a methylfuryl analogue of farnesol, containing farnesol isobutenyl residue methylfuryl substituent. The compound according to the invention is characterized by a pleasant, floral odor similar to that of natural farnesol, its volatility is much lower compared to that of farnesol, and moreover, it exhibits higher solubility in water / alcohol solvents than farnesol, which is a desirable property from the point of view of application in agents perfumery. The new compound is used as a component of fragrances imitating natural floral and fancy fragrances. The physicochemical and spectral properties of the new compound are as follows:

boiling point 403-408 K at a pressure of 0.08 kPa;

MS (cis / cis isomer): 230 (M ± 18.2), 147 (2), 135 (2), 108 (4), 96 (10), 95 (100), 67 (3), 77 (2) ), 67 (4), 43 (10), 41 (10);

MS (cis / trans isomer): 248 M ⁺ . 0), 135 (2), 108 (2), 96 (10), 95 (100), 79 (3), 67 (4), 53 (2), 43 (7), 41 (7);

MS (trans / cis isomer), 248M ⁺ , 0), 135 (2), 108 (3), 96 (10), 95 (100), 77 (3), 67 (4), 53 (2), 43 (10), 41 (19);

MS (trans / trans isomer), 248 (M ⁺ , 0), 135 (2), 108 (3), 96 (10), 95 (100), 77 (2), 67 (4), 53 (2) , 43 (9), 41 (10);

¹ H NMR (DCl3) δ: 5.84 (m, 2H), 5.40 (m, 1H), 5.15 (m, 1H), 4.10 (m, 2H), 2.65 (m , 2H), 2.28 m, 2H), 2.25 (s, 3H), 2.01 (m, 4H), 1.75-1.62 (6H),

3,7-Dimethyl-9- (5-methylfuran-2-yl) -nona-2,6-dien-1-ol of formula 1 can be obtained as a mixture of four cis / trans isomers from 3-methyl-5 - (5-methylfuran-2-yl) -pent-1-1n-3-ol of formula 2 by treating it in the first step with ethyl acetoacetate. The resulting ketone is subjected to a Grignard reaction with vinylmagnesium bromide and then to phosphorus tribromide (PBr3) to form a bromide derivative that is treated with potassium acetate to form 3,7-dimethyl-9- acetate. (5-methylfuran-2-yl) -nona-2,6-dien-1-ol. By alkaline hydrolysis of this acetate, 3,7-dimethyl-9- (5-methyl-furan-2-yl) -nona-2,6-diene-1-ol is obtained with a yield of about 50%, based on the starting compound of formula 2.

The following example illustrates the subject of the invention.

P r z k ł a d

A mixture of 0.1 mol of 3-methyl-5- (5-methylfuran-2-yl) -pent-1-1n-3-ol and 0.2 mol of ethyl acetoacetate was heated to 180 ° C for 3 hours. During the reaction, carbon dioxide was released and ethanol was distilled off. After completion of the reaction, excess ethyl acetoacetate was evaporated and the reaction product was distilled off at a boiling point of 383-398 K at 0.40 kPa. 0.048 mol of the obtained ketone was added dropwise over 2 hours to a solution of 0.05 mol of vinylmagnesium bromide in 50 ml of tetrahydrofuran keeping the temperature at about 35 ° C. After completion of the reaction, saturated ammonium chloride solution was added and the product was extracted three times with toluene. The product extract, after washing with water and evaporating the solvent, was distilled at a temperature of 390-393 K at a pressure of 0.13 kPa. To a mixture of 0.04 mol of the alcohol obtained in 60 cm ^{3 of} diethyl ether, cooled to -20 ° C, 0.03 mol of PBr3 was added dropwise with stirring. After completion of the dropwise addition, the contents of the flask were stirred at this temperature for 1.5 hours, then the reaction mixture was poured into 40 cm ^{3 of} water and the layers were separated. The organic layer was washed with 3 portions of 25 cm ^{3 of} water, 50 cm ^{3 of} 1% Na 2 SO ³ solution, again with water and dried. After distilling off the ether to the residue was added 70 cm ^{3 of} dimethylformamide and 0.03 mole of potassium acetate, and the mixture was heated and stirred for 1.5 hours at 95 ° C. After cooling, 70 cm ^{3 of} diethyl ether were added to the mixture, the organic layer was washed neutral with water, dried and then distilled. 0.03 mol of the resulting mixture of cis / trans acetates metylofuryloanalogów farnesol was heated for 3 hours under reflux with 0.03 mole of KOH and 25 cm ³ of methanol. After cooling, the mixture was poured into 15 cm ^{3 of} water and extracted with 5 portions of methylene chloride. The combined organic layers were washed until neutral, dried and distilled.

PL 198 496 B1

A mixture of four cis / trans methylfuryl analogs of farnesol of the formula I was obtained with a yield of 85%, with the above-mentioned physicochemical and spectral properties.

Claims (1)

The new compound, 3,7-dimethyl-9- (5-methylphoran-2-yl) -nona-2,6-dien-1-ol of formula 1.