TW383297B - Process for the preparation of phenylglyoxylic acid derivatives - Google Patents

Abstract

The present invention relates to a process for the preparation of o-chloromethylphenyl-methoximinoglyoxylic acid esters of formula (I) wherein R is C3-C8alkyl, in which process o-chloromethylphenylglyoxylic acid amide of formula (III) which is, in any order or concurrently, a) oximated with o-methylhydroxylamine and b) esterified under acid conditions with a R-OH alcohol, wherein R is C3-C8alkyl. A process for the preparation of compound III is also described.

Description

A7 B7 V. Description of the invention (/) The present invention relates to a method for preparing o-chloromethylphenylmethoxyimine dihydroxyacetate of formula I

Wherein R is (C3_C8) alkyl, in this method, o-chloromethylphenyldihydroxyacetamide of formula III --------- ^ ------ 1T (Please read first (Notes on the back then fill out this page)

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs in any order or simultaneously (a) oximation with oxymonomethylhydroxylamine, and (b) esterification with R-OH alcohol under acid conditions, where R is (C 3 -Cs) alkyl. The invention also discloses a method for preparing a compound of the formula I I I. The two reaction steps are conveniently performed at a temperature ranging from 20¾ to 70P, preferably at 40C to 7010. The oxymonomethylhydroxylamine is the same as the above -4-This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (2 丨 〇297297 mm) A7 B7 5. The description of the invention (2) is generally used, but it is preferably used as a salt . Preferred salts are suitably those containing mineral acids such as hydrohalic acid, sulfuric acid, phosphoric acid, nitric acid and similar acids, but may also contain organic acids such as sulfonic acids (methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid) Methanesulfonic acid, nitrobenzenesulfonic acid, and the like), acetic acid, trichloroacetic acid, lactic acid * maleic acid, oxalic acid, and others. Compounds of formula I can be obtained from the preparation of the methoxyimine phenylglyoxylate series E of formula IV-intermediates of configuration fungicides, of which methyl esters are particularly economical (EP-254426, EP — 4605 75, ep-463488, ep-472300, ep-299694, ep — 253213, WO-95 / l 8789, circles 0-95'21153 and others).

In one aspect of the invention, the invention relates to compounds of formula IV. The compound of the present invention is equivalent to Formula IV --------- ^ -------. 1T (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs where R is (Cs — Cs) alkyl, and A is —N = CR2R3, and R2 is hydrogen, (Ci-C *) alkyl, (C! —C4) halogen Alkyl, (C3-C6) cycloalkyl; R3 is (Ci-C6) alkyl, aryl- (Ci-C4) -5- This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) ） Industrial Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, Printed Poly A7 B7 V. Description of the Invention (3) Alkyl, heteroaryl- (C: — C4) alkyl, (C2 — ce) alkenyl, aryl-1 (C2 — C6) Alkenyl'heteroaryl- (C2-c6) alkenyl, (C3) cycloalkyl, heteroaryl, aryl, or aryl substituted with one to three halogens, (C! -C4) alkyl , (C! — C 4) haloalkyl. Particularly preferred compounds of formula IV are those wherein R2 is hydrogen or (C! -C4) alkyl and R3 is aryl or substituted with (Ci-C4) haloalkyl. Another particularly preferred compound of formula IV is one in which R2 is methyl and R3 is 3-trifluoromethylphenyl. Yet another particularly preferred compound of formula I is where R is pentyl and A is -N = (C (CΗ3) (3-trifluoromethylbenzyl). Aryl is phenyl or naphthyl, Kphenyl It is totally surprising that it has now been found that if methyl esters are not directly obtained from amidine-chloromethylphenylglyoxylic acid amine III by methylenzyme decomposition, and long amidine esters are first prepared, and When transesterification is carried out to methyl esters at a later stage of the method, each of the methoxyimine diglycolate moiety M of formula I and the chloromethyl side bonds of this intermediate becomes each additional The reaction is carried out with particularly high purity and high yield. The o-chloromethylphenylmethoxyimine diglycolate of formula I has an E configuration or a Z configuration in the desired imine double bond of the biological activity. Synthesis A special advantage of the compound of formula I is that by this method (M long-chain esters), almost only the E configuration is formed (E / Z ratio is higher than 90: -6-this paper size applies to Chinese National Standard (CNS) Α4 Specifications (210X 297mm) --------- I— (Please read the precautions on the back before filling out this page) • 1Τ Α7 Β7 i 、 Invention description Zhen) 1)) According to the above, suitable alkanes for preparing the intermediates of formula I of the present invention are n-propion, isopropion, n-butanol, secondary butanol, isobutanol and n-pentanase. Fermentation, n-heptanol, n-octanol and their corresponding isomers. Among all the isomers, M (Cs — Cs) alkanol is preferred, and M-n-pentanase is particularly preferred. Formula III or the corresponding oxime In the traditional way, the acid reaction conditions such as adding sulfuric acid or adding hydrochloric acid gas to the reaction medium are performed. (C3_Cs) Alkanol may be used in excess as an esterification, or it may only be used as a solvent or diluent. Qi It can also be reacted with one or more inert diluents. Suitable diluents are, for example, hydrocarbons or halogenated hydrocarbons, typically hexane, heptane, alkane, chloroform, dichloroethane; aromatic hydrocarbons or aromatic halogenated hydrocarbons. , Typically toluene, xylene, chlorobenzene, dichlorobenzene; or ether, such as dioxane, tetrahydrofuran, diisopropyl, such as acetone, methyl isobutyl ketone, cyclopentanone; or a mixture thereof ! IIIII 1 /. ^ III (Please read the notes on the back before filling out this page) Ministry of Economic Affairs Central Standard Consumption cooperation with employees of the quasi bureau Du printed the content of Jiadu Dentex under the solution or solution, which is more concentrated alcohol solution, water storage <% alkane alcohol before acid 5 the ο alkane halide 2 line L0} from hydrogen M to co is concentrated. o C should be stored under the condition of I, 3 or the acid in the water is more than C, and ί is in the calculation, or P is in the acid, and the water is better than sulfur 2 which has no The amount of solution is 1, which is as small as P in the water form. Ο Straight. I liquid. Can 05 be dissolved in line 1 to 1 into the water, and the amine can be converted into amine. The degree of alcohol is ο ester condition. Acid alkane degree 2 Love chlorine high temperature water hydrogen more applicable from this paper standard Chinese national standard (CNS) A4 specifications (210X297 mm) A7 B7 Printed by the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs-15th, invention description ( 1 1 I 0 0 1 1 1 Single reaction step according to the above-mentioned hydrolysis and esterification system M Μ decomposition 1 I Please 1 | Step 0 first 1 read 1 Formula III The reverse of the m group of the compound and oxygen-methylhydroxylamine or a salt thereof. I should be able to enter the note 1 or 1 before or after the fermentation and hydrolysis step of the compound of formula III, but it is preferable to perform 0 simultaneously. One of the main features of the present invention is the available items 1 1 and 1 single method steps to transform Formula III into Formula I. Fill out this% The present invention also relates to-* Preparation of o-nitromethylphenyl di-page V_ ^ 1 I Ammonium glycolate, which is produced by partially hydrolyzing o-chloromethylbenzoyl of formula II 1 1 Cyanide production This method includes > λ 0 8 to 1 5 1 1 per mole Saponification of water with 0 suitable acids are sulfonic acids such as hydrohalic acid> 1 1 1 sulfuric acid sulfuric acid phosphoric acid phosphoric acid nitric acid and the like M and mixtures of these acids and others are conveniently Hydrogenic acid can be added to concentrated acetic acid and / or 1 1 I to concentrated hydrochloric acid aqueous solution. The temperature range is 10 V to 5 0 1 1 > preferably 15 V to 30 V. The reaction is also possible. It is carried out in the presence of a solvent. Preferably, toluene dimethyl 1 I, benzoxanodioxane, tetrahydrofuran, diethyl ether, dioxan, hexane, 1 1 and others are used. The present invention is also limited to the preparation of an — Chloromethylphenylmethoxy 1 1 imide dihydroxyacetate mixing method is 1 | (a) o-chloromethyl benzamidine cyanide of formula II is partially saponified to 1 | formula III O-ammonia methylphenyldihydroxyacetic acid m amine and 1 1 (b) make the obtained o-ammonia methylphenyldihydroxyacetic acid amine M any 1 1-8- 1 1 This paper size applies Chinese national standards (CNS) A4 size (2 丨 〇 X 297 mm) A7 B7 V. Description of the invention (Heart) Reaction with oxygen monomethylhydroxylamine and R-0HK sequentially or simultaneously according to the T reaction formula, where R is (C3 — Cs) comprehensive ® ml--1 = 1 --- 1- -II nn (Please read the notes on the back before filling this page)

, 1T

The invention is also limited to a novel o-nitromethylphenylglyoxylic acid amine product of formula III, K and the novel fluorene-chloromethylphenyl of formula I A methoxyimino diglycolate, wherein R is (Cs-Ca) alkane, preferably (Cs-Cs) alkyl. The method of the present invention has a surprising advantage in that it provides the novel form III amidine of crystalline form in high yield and purity. The use of pure amidine III to prepare compounds of formula I constitutes another advantage of the present invention. The present invention also relates to the use of a compound of formula I as a reactive neighbor. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs is printed A7 B7 five ' DESCRIPTION OF THE INVENTION (η) An intermediate μ of chloromethyl prepares an insecticide. Such insecticides may be bactericides, insecticides, ACARICIDES, nematodes or herbicides, for example, as shown in EP-A-254426, EP-A-46057 5, EP-A-463488, EP-A -472300 'EP-A-299694, EP-A-253213, WO-95 / 18799, WO-95 / 21 153M and other publications. Example W-1: Preparation of o-chloromethylphenyldihydroxyacetamide

(A) 20 g of hydrochloric acid gas (0.55 mol) was formed in 1 hour by adding 1 79. 6 g of o-chloromethyl benzamidine cyanide (1 mol) in 400 g of acetic acid Puppet float. Then add 3 1.8 grams of 32% aqueous hydrochloric acid saliva (1.2 moles) to this enlightenment. The suspension was stirred at room temperature for 28 hours. The partially crystallized product was separated by filtration, washed with 2 × 5 ml of n-pentanol and 2 × 50 ml of hexane, and then dried. The yield was 89 · 2 grams (45 · 1%). The mother liquor is recovered as a diluent in the next batch. (B) 33 · 1 g of acetic acid was added to 179.6 g of o-chlorochloro-1-0-This paper is in accordance with China National Standard (CNS) A4 (2 丨 0 X 297 mm) — II III Pack III —Order I ^ ii (please read the notes on the back before filling this page) Α7 Β7 V. Description of the invention (none) Benzyl formamidine cyanide (1 mole) in the previous batch of 482 · 9 g mother liquor The resulting suspension was then added with 5 grams of hydrochloric acid gas (0.41 mole). 24.3 grams of a 32% aqueous hydrochloric acid solution (0.92 mol water) was added to the reaction mixture at room temperature, and the reaction mixture was stirred at room temperature for 2 hours, and then filtered with K. The crystals were washed with glutamate and hexane, and then dried. The yield was 172 ♦ 8 grams (87 · 4%), and the mother liquor was used as the dilution for the next batch. W — 2: Preparation of o-chloromethylphenyl monooxymonomethoxyimino dihydroxyacetic acid amyl acetate -------- pack-(Please read the precautions on the back before filling this page) ^ COOn-pentyl CH, -0 ^

CHXI Orders Consumption Cooperation with the Central Standards Bureau of the Ministry of Economic Affairs Du Yinhua added 50 grams (1 * 37 mols) of hydrochloric acid gas to 2 benzene 1 within 1 hour to mixed bases 2} Mo to your ears, part 5 but Mo Hou I} Part 2 cold 5 but adjacent to the ear II. Back., Of Mo Di ο ran)) 5 into ·,, {But part 2 Gak Shishi cold 1 · Hou 4 miniaturization has been οran. 4 Chlorine {Into; 9 2 Hydrogen plus 4 grams of amines floating, 4 small {synthetic base suspended P. 2 amine mixed into 5 9 mixed with mixed base 5 4 stirred acid撹 甲 素 I ί vinegar P I ο amine P hydroxy ο oxygen fermentation 5 醯 5 2 6 grams of valeric acid 5 groups I 8 is to vinegar I benzene ο. Gram heat hydroxyl ο group 5 1 〇 plus 2 5 45 based on chlorine. The size of this paper applies to China National Standards (CNS) A4 (210 X 297 mm) printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (/) t, Ml 75 ml of water diluted to M. 159.7 grams of a 30% aqueous sodium hydroxide solution were added to keep the temperature at 20-30 = 0. The organic phase was separated, dried and concentrated. The production director was 133.1 grams (79%). The E / Z isomer ratio of the oxy-methyloxime side chain was 92 · 6: 7 · 4. Replacing n-pentanol in the above method with formazan results in an unpleasant 83:17 E / Z isomer ratio. W — 3 Preparation of 2 — [α — {[[Imethyl-1,3-trifluoromethylbenzyl) imine] oxy) -o-methylbenzyl] pentanoylmonooxymethyloxime

Within 20 minutes, 87 grams of a 30% sodium methylate solution (in methanol) was added dropwise to 98.2 grams of 3-trifluoromethylacetophenone (0.48 mol) at 200 to pull up dimethyl A solution formed in acetylacetamide. Distilled off 1 96 ml of solvent at 5 5-7 ° under a slight vacuum. After 1 g of potassium iodide was added, 150 g of o-nitromethylpentyl monooxy-methoxyimine diglycolate acetate having a purity of 95 * 9% of 150 g was added within 1 hour at 55-65C. After 2 hours, the reaction mixture was added to a mixture of 400 ml of water and 250 ml of toluene at room temperature over 30 minutes, and its pH was adjusted to 5 by concentrated citric acid. With 150 mm-1 2- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) I—IJ Pack—III Order—III —. —K (Please read the notes on the back before filling (This page) A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (γ) The aqueous phase was extracted twice with liters of toluene. The mixed organic phase was washed with 150 ml of water, and the solvent was distilled off under vacuum and 60P. , To obtain 227 grams of crude oil with a content of 83%. -1 3- This paper size applies to China National Standard (CNS) Α4 size (210X297 mm) ^^ 1 mu 1 ^ 1 I. «N nn 1 ^ 1. Mn ^ — Please read the note on the back first (Fill in this page again)

Claims (1)

Patent application scope 1-Method for preparing o-monomethylphenylphenyl of formula I Amine dihydroxyarsonate CH, Wherein R is (C3-C8) alkyl, in this method, o-monomethylphenyldihydroxyammonium amine of formula I ί I III Order (Please read the notes on the back before filling this page) Printed by 2QD Zhidu Fanyuan in the presence of or without diluent, the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, (a) and Oxymonomethylhydroxylamine is oximized, and (b) is esterified with (C3-C8) alkanes under acidic conditions. The oximation may be carried out before or after the esterification, preferably at the same time. 2 · For example, the method of the first item of the Shenfan Patent · It includes simultaneous oximation and tritiation. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 1-Method for preparing o-monomethylphenylphenyl of formula I Amine dihydroxyarsonate CH, Wherein R is (C3-C8) alkyl, in this method, o-monomethylphenyldihydroxyammonium amine of formula I ί I III Order (Please read the notes on the back before filling this page) Printed by 2QD Zhidu Fanyuan in the presence of or without diluent, the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, (a) and Oxymonomethylhydroxylamine is oximized, and (b) is esterified with (C3-C8) alkanes under acidic conditions. The oximation may be carried out before or after the esterification, preferably at the same time. 2 · For example, the method of the first item of the Shenfan Patent · It includes simultaneous oximation and tritiation. This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) S8329? Μ D8 6. Application for patent scope 3. If the method of applying for the first item of the patent scope, including the reaction at 40 μM 7 〇 Ό . 4. If the method of the patent application _ item 1, which includes the use of-C8) alkalase reaction as a dilution 5. As the method of the patent application phr. 4 method, which includes the use of n-pentanase ° 6 ·-Preparation The method of o-monomethyl phenyl diazide_acidamide of formula II, IIIIII, I binding 'I (please read the precautions on the back before filling this page) by 1 ot in the presence or absence of solvent : Temperature range painting to 50 < 0, M0. 8 to 1.5 moles of water / partial acid hydrolysis of cyanide I per ophthalmic chloride of formula I, o-chloromethylbenzidine cyanide, employee of Central Fengfeng Bureau Consumer Cooperatives 7. The method according to item 6 of the patent application, which comprises This paper size is applicable to Chinese national standard (CNS> A4 size (2 丨 〇 > < 297mm) • 〇 A8 Β8 C8 D8 6. Scope of Patent Application Adding acid gas and / or aqueous acid solution to carry out retort. 8 · A method for preparing a tritium methylphenylmethoxyimide diester of formula I * CH, wherein R is (C3_C8) alkyl, and the method includes (a) an o-aminomethyl group of formula II Partial acid saponification of benzamidine cyanide O-Aminomethylphenylglyoxylic acid sulfonamide of formula I I I The reaction conditions are as defined in the patent application _ item 1, and (b) M-oxymonomethylhydroxylamine and (C3_C8) alkane fermentation, conversion of o-chloromethylphenyldihydroxyacetamide | Where the reaction conditions are as defined in the patent application _ item 1. This paper size applies to China National Standards (CNS) A4 specifications (210X297 mm) --II — I--this ______ Τ ______ / Λ, (Please read the note on the back before filling this page) Central Standards of the Ministry of Economy Printed and applied for patent scope A8, B8, C8, D8 9 by the Office of the Consumers' Cooperative. • If the method of the eighth scope of the patent application, the method includes the use of (C5-C 6) alkalase. 1 0 · The method according to item 9 of the patent application * which includes the use of n-pentanase 0 1 1 · A compound of formula I I I III. (Please read the precautions on the back before filling out this page) 2 · —Type I compounds Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs where R is (Cs -C8) alkyl. 13. The compound of formula I as claimed in claim # 12, wherein R is (C s -C 6) alkyl. 14. The compound of formula I according to item 13 of the patent application, wherein R is n-pentyl. 1 5 * —Type I V compound This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 383297 Patent application scope A8 B8 C8 D8 〇.A IV. Where R is (Cs_C8) alkyl, and A is -N = CR2R3, and Rz is (Ct-C4) alkyl, and R3 is (C! _C4) haloalkyl-substituted phenyl. 16. The compound of formula IV as claimed in claim 15 in which R is (Cs-C6) alkyl. 17 · The compound of the formula IV according to item 15 of the scope of the patent application * where R is n-pentyl * and R2 is methyl, and R3 is 3-trifluoromethylphenyl. I tn I nn II ^ I nn I _ n T n III l · — IA · (Please read the notes on the back before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shelley Consumer Cooperatives This paper is printed in accordance with Chinese national standards (CNS) A4 specification (210X297 mm)