SU269817A1 - METHOD OF OBTAINING FURYLMETHYL ALCOHOLS - Google Patents

Description

The invention relates to the field of the preparation of compounds which can be used in the synthesis of insecticidal esters. A method is proposed for preparing furylmethyl alcohols of the general formula -g-CHzOH Y-CH2 0 Rj where Y is an alkyl, alkoyl, alkodienyl, aryl or heterocyclic alkyl group, which may be substituted, in the ring with an alkyl, alkenyl, alkoxy, alkydienic, alkydienic, alkydienic, alkyl, alkenyl, alkoxylic, alkyl, alkenyl, alkoxylic, alkyl or alkyloxy group. RI and R2 may be the same or different and represent a hydrogen atom or alkyl, alkenyl or alkadienyl groups. The method consists in that the substituted 3-furancarboxylic acid ester is reacted with a metal hydride, for example lithium aluminum hydride, at a temperature e above the boiling point of the solvent in a low boiling point organic solvent, for example ether, followed by separation of the alcohol obtained in a known manner. 19 g of bromine in chloroform are added to 175 g of ethyl ester of sodium acetic acid, 400 ml of chloroform at O-10 ° C for more than 1 hour. After washing with water (4X300 ml), the chloroform solution is dissolved (Na2SO4) and evaporated. After recrystallization from ethanol (800 ml) of residues from the experiment at -20 ° C, 317 g of the desired product is obtained. After concentrating the mother liquor and cooling to -20 ° C, another 80 g of product is obtained. Total yield 397 g (63%); t. mp 79 ° C. 100 g of tetracarboxylate are added over 300 minutes with stirring to 300 ml of sulfuric acid. After heating for 5 minutes at 50 ° C, the product is cooled to room temperature and poured into ice (100 g). the product of these four experiments is extracted with ether (2-J-1 l). The ether solution is washed twice with a solution of chloride dry, (NajSO4) and evaporate. The residue is heated for 5 hours under reflux with glacial acetic acid (600 ml), constantly boiling hydrobromic acid (400 ml) and water (200 ml) and then evaporated. The residue is recrystallized from acetic acid acids (350 ml) and chloroform (600 ml), then washed with chloroform and dried, in vacuo, Yield 216 g, mp 233-238 ° C (cF-Furancarboxylic acid.

Tegracarboxyfuray is heated with 1 g of copper powder in a molten salt bath. The release of carbon dioxide is regulated, when necessary, by the heating of the bath (temperature 250-290 ° C). At 290 ° C, this product (5.8 g) is distilled. Repetition gives a total of 40 g of the product, which is recrystallized from water and obtain 30 g of pure acid with m.p. 114-118 ° C.

Methyl 3-furancarboxylic ester.

41.5 g of 3-furancarboxylic acid with 190 ml of methanol and 3.75 ml of sulfuric acid are boiled under reflux for 4 hours. Most of the methanol is evaporated, the residue is poured into water and the ester is recovered by ether. After washing (saturated solution of potassium bicarbonate and sodium chloride) drying (Na2SO4), the solvent is evaporated: and the product is distilled, i.e. 80 ° C / 30 mmHg Art. P

1.4640 (33 g).

Methyl ester of B-chlormethyl-3-furancarboxylic acid.

In a mixture of 15 g of methyl 3-furancarbonic acid ester, 4.2 g of paraformaldehyde and 4.2 g of zinc chloride in 90 g of chloroform, and 20-25 ° C, dry chloride: hydrogen is passed through for 1.5 hours. The pre-product was shaken with water, more chloroform was added and the combined organic layers were washed (3 x H 2 O), dried (Na 2 SO 4) and evaporated. After distillation of the residue, 5-chloromethyl-3-furancarboxylic acid methyl ester (9.4 g) is obtained; m.p. 80-108 ° C; 1,5003-1,5072; m.p. 42-51 ° C.

Methyl ester of 5-benzyl-3-furancarbo; new acid;

To 10.9 g of methyl ester of 5-chloromethyl-Zfurancarb-oic acid, dissolved in benzole, are added, within 50 minutes at a temperature below 20 ° C, 9.84 g of fresh-fire aluminum trichloride. With cooling (below 30 ° C), 100 ml of water is added dropwise. The product is taken up in ether, washed twice with 10% sodium hydroxide and twice with sodium chloride, and finally dried (Na 2 SO 4), extracted and distilled. Methyl ester of 5-benzyl-3-furancarboxylic acid (8.7 g) has t.: Kip. 127-135 ° C / 0.4 mm. v; t square 52-53 ° C.

5-Benzyl-3-furfuryl; second alcohol.

6.4 g of 5-benzyl-3-furancarboxylic acid methyl ester, dissolved in 90 ml of dry ether, are added dropwise to 1.35 g of lithium aluminum hydride in 135 ml of ether. Then the mixture is heated with steam, cooled, and decomposed by adding water. The ether solution was dried (Na.2SO4) and evaporated. -The residue is distilled and 5-benzyl-3-fur-furyl alcohol (4.84 g) is obtained with the bale. 151 - 156 ° С / 1.5 mmHg; m.p. 36-39 ° C.

a) Delta-phenyllevulin ki-slot.

60 g of pure sodium is dissolved in 750 ml of dry ethanol, warmed as needed, and then cooled to room temperature. After that, 234 ml of benzyl cyanide and 592 ml of diethyl succinate are kneaded into the solution. The mixture was left overnight at room temperature and then poured into 2 liters of ice water and washed with two portions of benzene (500 ml) to remove unreacted diethyl succinate and benzyl cyanide. The aqueous solution is acidified with 500 ml of dilute sulfuric acid. The precipitated oil is diluted with the ether extract.

aqueous layer, washed with a saturated solution of sodium chloride, dried over sodium sulfate, evaporated and 459 g of crude condensation product are obtained. This residue was refluxed overnight with 2 liters of glacial acetic acid, 600 ml of concentrated hydrochloric acid and 600 ml of water. The mixture is then concentrated under reduced pressure, diluted with 1 l of benzene, washed with water (2 x 500 ml), concentrated and delta-phenyllevulic acid is obtained (325 g, total yield 85%).

b) Ethyl delta phenyllevulinate.

200 g of the acid from step a) are refluxed overnight under reflux in a 1.5 l standard containing 5 wt. % sulfuric acid The volume of the mixture is reduced by distillation under reduced pressure at 50 ° C. The residue was poured into saturated sodium bicarbonate solution (1 L) and extracted with 1 L of ether. Ethereal

the extract is washed, dried, evaporated, the residue is distilled under reduced pressure, and 199 g (87%) of ethyl delta-phenyl levulinate are obtained with m.p. 134-136 ° C / 0.1 mmHg v .; ng 1,5002-1,5032.

c) Ethyl-gamma, gamma-ethylenedioxy-deltaleulinate.

200 g of ethyl ester from b), 102 g (1.65 mol) of ethylene glycol, 1 l of benzene and 1 g of t-oluol-4-sulfonic acid are boiled in the instrument

Dean and Stark until the water stops. Then the solution is washed with a saturated solution of sodium carbonate, with a saturated solution of nptri chloride and dried. The solvent is evaporated, the residue is distilled and 195 g (81%) of ketal is obtained with m.p. 146-150 ° C / 0.1 mmHg v .; 1.5010.

The residue from the distillation can be hydrolyzed with a good yield of delta-phenylVULINIC ACID-OTA.

d) Sodium salt of ethyl alpha-hydroxymethylene-gamma .a, gamma-ethylene-dioxy-delta-phenyl-levulinate.

26.4 g of ethylene ketal from step c), 14.8 g of ethyl formate, 5.2 g of 50% sodium hydride dispersion in oil and 400 ml of dry ether are mechanically stirred in a dry machine and maintained at room temperature for two to three days. The enol is precipitated in washed with ether, dried in vacuo at room temperature. 23.5 g (75%) of sodium salt are obtained. e) 5-Benzyl-3-furancarbenic acid ethyl ester.5. 5.5 g of sodium salt from step e). Start for 4 hours with 600 ml of concentrated hydrochloric acid, first at -20 ° C, then at room temperature. The product is extracted with ether; The ether solution is washed with a saturated sodium bicarbonate solution, a saturated sodium chloride solution and dried. The solvent is evaporated, and the residue is distilled and 1.9 g (47%) of 5-benzyl-3-furancarboxylic acid ethyl ester are obtained. 15 e) 5-benzyl-3-furylmethyl alcohol. 23 g of ethyl-5-benzyl-3-furyl in 100 ml of dry ether are added with stirring and at room temperature, to a mixture of 4 g of alyumo-HfTa ;; 2 e. J Vod, EF2R "layer washing with TSHG (G.ZO) n" G:., "Torgish osgatka receive 12.1 g (62%) of 5-benzyl-3 f-25 rlmethyl alcohol with t, kip. 129-132 C / 0.1 M M.Hg. Art. Identical in all respects with the sample prepared in Example 1. f g Ll-Grtv G- - ogG Gp °, l:; ™ 5-Benzyl-2-methyl-8-furyl-methyl alcohol with t. kip. 155-160 ° C / 0.1 mmHg v .; ng 1.5510. The subject of the invention. A method for producing furylmethyl alcohols of the general formula Y-CH2, where Y is alkyl. an alkenyl, alkodienyl group, an aryl OR heterocyclic alkyl group that may be substituted in the ring by an alkyl, alkenyl, alkoxy, alkodienyl group or a halo; -A-, ,, odd „„ aktm, m „,, l„ ras- ™ - al, „d„ en „., 1n„ „gr,„ „,„ „„ „„ The substituted complex eff. p of the 3-furaniearboxylic acid is subjected to —yr of f - p to interaction with a metal hydroxide, for example lithium aluminum hydride, at a temperature of -; - “P -. -P - P follow ™; the selection of the obtained alcohol in a known manner.