HU200586B - Process for producing beta-hydroxyacrylic acid esters - Google Patents

Abstract

The invention relates as fungicides useful derivatives of acrylic acid and processes for their preparation. The invention provides fungicides which penetrate the plant tissue and may be so volatile that they are effective in the vapor phase against fungi found on the plants. They can be used both in agriculture and in industry. The object of the invention is to provide as fungicides useful compounds and their preparation processes available, which are versatile. The compounds of the invention have the general formula and stereoisomers thereof, wherein X, Y and Z, which may be the same or different, are hydrogen or halogen atoms, or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl , Haloalkyl, alkoxy, haloalkoxy, optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, acylamino, nitro, nitrile, CO2R3, CONR4R5, COR6 -, CR7NR8 or NCR9R10 groups are; or the groups X and Y, when in adjacent positions on the phenyl ring, can combine to form a fused ring which is either aromatic or aliphatic and optionally contains one or more heteroatoms; and R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10, which may be the same or different, are hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl or cycloalkylalkyl groups; and metal complexes thereof. formula

Description

The present invention relates to a process for the preparation of novel β-hydroxyacrylic acid esters of the formula (I). The novel compounds of the present invention may be used as starting materials or intermediates for the preparation of fungicidal active ingredients.

Derivatives structurally similar to compounds of formula I are described in J. ORg. Chem. 41. 1570-4. _I 333-334 (1977). A common structural feature of the known compounds described herein is that they carry an alkoxy substituent at the β-position. Derivatives having structural similarities to those of Formula D but having substituent X at the benzene plant to be determined at a later date are described in U.S. Patent Nos. 2,908,324 and 3,219,1915.

The general formula (I) according to the invention represents the group "D" and

Ah ^! halogen phenoxy- ^f '. alkyl (phenoxy) phenoxy; so, xa ', (C 1 -C 4 alkoxy) benzyl, benzyl xxd, benzoyl, (C 1 -C 4 aSroxy) benzoyl, pyridyloxy or pyrid (C 1 -C 4 alkyl) - group.

The compounds of formula (I) according to the invention are prepared by reacting the ester of the acetic acid of formula (Π), wherein R 1 and X are the fend base and the formic acid of formula (III): R ¹ is the above reaction, the reaction mixture is acidified.

The formulas (H) and (Ifi) The reaction of the compounds is conveniently carried out in anhydrous solvent at a low temperature (e.g. 0 ° C to 5 ° C).

The following Examples illustrate the process of the invention in more detail.

Ϊ. example

Preparation of 2- (2-Phenoxy-phenyl) -3-hydroxy-propenecarboxylic acid methyl ester

To a stirred solution of 2-phenoxybenzoic acid (535 g) in anhydrous tetrahydrofuran (50 mL) was added dropwise 1 mL of a 1 M solution of borane-tetrahydrofuran in 50 mL of stirring. After the addition of the reagent, the mixture was stirred at 0 ° C for 15 minutes and then at room temperature for 1.5 hours. The mixture was poured into water and extracted with ether. The extracts were combined, washed with water, aqueous sodium bicarbonate solution and then aqueous sodium carbonate solution, dried and concentrated under reduced pressure. Obtained as a colorless oily 2-phenoxybenzyl alcohol (4.83 g, 97%).

To a solution of 2-phenoxybenzyl alcohol (4.8C) in anhydrous dichloromethane (50 mL) was added thionyl chloride (92 mL) in one portion. The resulting mixture was stirred at room temperature for 2 hours, then washed twice with water, twice with aqueous sodium bicarbonate solution and once with aqueous sodium chloride solution. The solution was dried and concentrated under reduced pressure. Obtained as a colorless oily 2-phenoxybenzyl chloride (4.87 g, 93%).

A solution of 2.80 g of 2-phenoxybenzyl chloride and 0.64 g of magnesium turnings in 15 ml of anhydrous ether is dissolved in 2-phenoxyblyryl magnesium chloride and carbon dioxide gas is introduced at 0 'C. Anhydrous tetrahydrofuran was added to ensure solubility. When the exothermic reaction subsided, the carbon dioxide supply was stopped and the mixture was allowed to warm to room temperature. The mixture was quenched with water. The reaction mixture was poured into water, washed with ether, treated with hydrochloric acid and extracted with ether. The extracts were combined, washed with water, dried and evaporated under reduced pressure. 3.06 g (61%) of solid 2-phenoxyphenylacetic acid melting at 82-85 'c are obtained. An analytically pure product recrystallized from a mixture of ether and gasoline melts at 85-86 ° C.

To a solution of 2.75 g of 2-phenoxyphenylacetic acid in 30 ml of anhydrous methanol 03 ml of concentrated sulfuric acid? We are added. The mixture was refluxed for 2 hours, then allowed to cool, poured into water and extracted with ether. The extracts were combined, washed with water, dried and finally concentrated under reduced pressure. 2.56 g (91%) of methyl 2- (phenoxyphenyl) acetic acid methyl ester are pale yellow oil.

To a suspension of 0.95 g of sodium hydride in 30 ml of anhydrous dimethylformamide at 0-5 ° C was added 24.4 ml of methyl formate, 5 g of (2-phenoxyphenyl) acetic acid methyl ester and 30 ml of anhydrous dimethylformamide mixture was added dropwise. Violent gas evolution begins. The reaction mixture was stirred at room temperature for 3.5 hours and then poured into a mixture of ice and aqueous sodium carbonate. The resulting aqueous solution was washed three times with ether, then acidified with concentrated aqueous hydrochloric acid and extracted with ether. The extracts were combined, washed with water, dried and evaporated. 2- (2-Phenoxyphenyl) -3-hydroxy-pro-pentecarboxylic acid methyl ester is obtained.

Infrared Spectrum (Liquid Film): 1711, 1655, 1590, 1478, 1435, 1370, 1344, 1270, 1225, 1190, 1160, 749 cm ^-1 .

Example 2

Preparation of 2- (2- (Benzyloxy) phenyl) -3-hydroxyacrylic acid methyl ester

To a suspension of 0.95 g of sodium hydride in 30 ml of anhydrous dimethylformamide, at 0-5 ° C, 24.4 ml of methyl formate, 5.10 g of o-benzyloxy-phenylacetic acid methyl ester and 30 ml of anhydrous dimethylformamide are added dropwise. Violent gas evolution begins. The reaction mixture was stirred at room temperature for 33 hours and then poured into a mixture of ice and aqueous sodium carbonate. The resulting aqueous solution was washed three times with ether, then acidified with concentrated aqueous hydrochloric acid and extracted with ether. The extracts were combined, washed with water, dried and evaporated. There was obtained 4.38 g of 2- (2-benzyloxy-phenyl) -3-hydroxy-acrylic acid methyl ester as a yellow oil.

Infrared spectrum (liquid film): 1716, 165, 1597, 1486, 1438, 1372, 1346, 1272, 1156, 7550 cm.

3- 1Q. example

By following the procedure described in Example 2, the compounds of formula (I) listed in Table I are prepared from the appropriate starting materials. In each of the compounds of Formula I listed in Table I, R ^{1 is} methyl. The physical constants of the products are listed in Table I.

-2HU 200586 Β

3 4 Uábtóat Apélda number X Physical constants 3 benzoyl mp 101.5-103'C 4th benzyl IR (film): 3040,3000,1690,1640,1460, 1400,1360,1330,1260,1175, 1140,1090,730,680 ^cm-1 5th 4-methoxybenzoyl NMR (90 MHz, CDCl3) 3.37 (3H, s), 3.87 (3H, s), 6.8-7.8 (9H, m), 11.8 (1H, broad s) ppm 6th 4-methoxybenzyl NMR spectral lines (90 MHz, CDCl 3): 3.54 (3H, s), 3.71 (3H, s), 3.82 (2H, s), 6.6-73 (8H, m), 11.8 (1H, broad d) ppm 7th 2- (pyrid-2-yl) ethyl NMR spectral lines (270 MHz, CDCl 3): 2.98 (4H, m), 3.72 (3H, s), 8.53 (1H, m) ppm 8th pyrid-2-yloxy IR (film): 2800-2100,1695,1625,1595,1470,1400, 1310,1255,1180,1145,880,765 cm ^-1 9th 3-iodo-phenoxy phenoxy IR (film): 3390,1727,1664,1610,1600,1579, 1483,1439,1373,1359,1270,1250, 1207,1190,1160 ^cm-1

PATENT CLAIMS

Claims (5)

PATENT CLAIMS A process for the preparation of β-hydroxyacrylic acid esters of the formula I: R ^{1 is C} 1 -C 4 alkyl, and X is phenoxy, halophenoxy, hydroxy (C 1-4 alkyl) phenoxy, benzyl, (C 1-4 alkoxy) benzyl, benzyloxy, benzoyl, (1-4). (C 1 -C 4) alkoxy) benzoyl, pyridyloxy or pyridyl (C 1 -C 4) alkyl, wherein the phenylacetic acid esters of formula (Π) are those wherein R ¹ and X are with the base and the formic acid ester of formula (R) in which R is as defined in the scope, and then the reaction mixture is acidified (Priority: 16.10.1985) A process according to claim 1, characterized by. and reacting the compounds of formula (Π) and (ΠΓ) in anhydrous solvent at a temperature of 0 ° C to 5 ° C. (Priority: 16.10.1985) 3. Process for the preparation of β-hydroxyacrylic acid esters of the formula I: R ^{l represents a C} 1 -C 4 fake lump group, and X is phenoxy, halophenoxy, hydroxy (C 1-4 alkyl) phenoxy, benzyl, (C 1-4 alkoxy) benzyl, benzyloxy, benzoyl or (1-4). alkoxy) benzo, H, wherein the phenylacetic acid esters of formula II are wherein R and X are as defined above with a base and a formic acid ester of formula QI wherein R * is as defined in the invention, then acidifying the reaction mixture (Priority 19.10.1984) A process according to claim 3, wherein the reaction of the compounds of formula (II) and (ΙΠ) in anhydrous solvent at 0 ° C and 5 ° C. (Priority: 19.10.1984)