CS234890B1 - SpOsc / on the production of OiO-Oimethyl-O-S-aietyl-β-nitro-phenylthiophosphate - Google Patents

Abstract

The invention relates to chemistry. The invention provides for the production of 0,0-dimethyl-0-(3-methyl-4-nitrophenyl)thiophosphate by condensation of 0,0-dimethylchlorothiophosphate with sodium 3-methyl-4-nitrophenolate. The condensation takes place in the presence of a hydrogen chloride binding agent, an aromatic hydrocarbon or an aromatic hydrocarbon and water. Part of the sodium salt of 3-methyl-4-nitrophenol is added in the form of an aqueous solution with a concentration of 0.5 to 40% by weight and contains sodium hydroxide and/or mineral salts and is contaminated with organic compounds of phosphorus, sulfur and/or chlorine. Water is distilled from the reaction mixture with an aromatic solvent, from which it is separated after condensation.

Description

234890

The present invention relates to the preparation of O, O-dimethyl-O- (3-methyl-4-nitrophenylthio phosphate with Ο, Ο-dimethylchlorothiophosphate with 3-methyl-4-nitrophenolate sodium in the presence of a chloride-binding agent. O-dimethyl-O- (3-methyl-4-nitrophenyl) thio-phosphate is used as an effective insecticide predominantly in agriculture, it is omnohomenous for humans and for warm-blooded animals such as O, O-dimethyl-O- (4 Most commonly, O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate is prepared by reacting O, O-dimethylchlorothiophosphate with 3-methyl-4-nitrophenol. in the presence of a binding agent acid or in the presence of a powdered medium is described, for example, in British Patent No. 670,030 and NSR Pat., No. 814,297. French Patent No. 1,266,417 describes the preparation of O, O-dimethyl-O - (3-methyl-4-nitrophenyl) tallow phosphate in the presence of potassium carbonate and powder medium in toluene medium with 3-O-dimethylchlorothiophosphate with 3 sodium or potassium 4-nitrophenolate. U.S. Patent No. 1,272,685 uses chlorobenzene as the reaction medium. The condensation of O, O-dimetilchlorothiophosphate with 3-methyl-4-nitrophenolate in anhydrous acetone in the presence of sodium carbonate at reflux temperature is described in U.S. Pat. No. 2 520 393, brit. pat. No. 644,610, French. pat. No. 957,803, the preparation of O, O-dialkyl-O- (4-nitrophenylthiophosphate by reaction of O, O-di-alkyl chlorothiophosphate with 4-nitrophenol sodium in chlorobenzene, ethanol or aqueous media) is described by Fletcherv J. Am. Soc., 70, 3943 (1948). Preparation of 0,0-Dimethyl 10- (3-methyl-4-n -trophenyl) thiophosphate by the reaction of Ο, Ο-dimethylchlorothiophosphate with 3-methyl-4-nitrophenol riches der deutschen chem. Gesellschaft, 404322. Production of 0,0-dimethyl-O- (3-methyl-4-nitro-phenyl) thiophosphate by reaction of O, O-dimethylchlorophosphate with 3-methyl-4-nitrophenolate of an alkali metal, or 3-methyl-4-nitrophenol in the presence of acid-binding agents is described in U.S. Pat. No. 89,124. An insecticidal preparation of Ο-dimethyl-O- (3-methyl-4-nitrophenyl) thiosulfate and the process for its preparation by reaction. O, O-diol or an alkaline salt thereof is described in Japanese Patents Nos. 28 075 and 30 541 (1959), hereinafter referred to in German Patent No. 1,116,790, U.S. Pat. No. 3,091,565. organophosphoruspes of the general formula

Where R 1 and R 2 are alkyl of 1 to 4 C atoms, O or S and R 3 is aryl, optionally aryl substituted by alkyl with halogen and / or nitro group, wherein the impurities are distilled off with water. , describes MS. pat. No. 129,591. Preparation of O, O-dimethyl-O- (3-methyl-4-nitro-phenyl) -thiophosphate according to U.S. Pat. pat. Nos. 89,124 and 129,591, wherein water is azeotropically distilled during the reaction to describe MS. AO # 211,804. Preparation of O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thio-phosphate by reaction of 3-methyl-4-nitrophenol with 0,0-dimethylchlorothiophosphate in the presence of K 2 CO 3 in methyl ethyl ketone, the reaction mixture is cooled and the sol1 is precipitated as described in G. Schrader, Die Entwicklung neuer insektizi-der Phosphorsadre Ester, Verlag ChemieGMBH Weinheim p. 293 (1963). In the aforementioned references, attention is drawn to the use of solutions of 3-methyl-4-nitrophenolate sodium, which are lost in the process of its manufacture or further processing.

The aforementioned drawbacks are eliminated by the production of O, O-dimethyl-O- (3-methyl-4-nitrophenylthiophosphate, which is characterized in that O, O-dimethyl-O- (3-methyl-4-nitro- trophenyl thiophosphate is prepared by condensing 0,0-dimethylchlorothiophosphate with 3-methyl-4-nitrophenolate sodium in an aromatic hydrocarbon or aromatic hydrocarbon / water medium in the presence of hydrogen chloride. % methyl-4-nitrophenol-sodium concentrations of 0.5 to 40% by weight containing sodium hydroxide and / or mineral salts and contaminated with organic sulfur, phosphorus and / or chlorine compounds.

The sodium 3-methyl-4-nitrophenolate solution is added during condensation. The water is distilled off from the reaction mixture along with the aromatic hydrocarbon from which the aromatic hydrocarbon is distilled off after condensation, and it is added again to the reaction mixture.

According to the process of the present invention, the use of 3-methyl-4-thiophenolate sodium is better achieved by adding it in crystalline form and thus also yielding a higher yield. In the reaction, the solution of 3-methyl-4-nitrophenol sodium used in its production or processing is used directly. Treatment of 3-methyl-4-nitrophenolate sodium solutions from the production of 0,0-dimethyl-O- (3-methyl-4-nitrophenol) thiophosphate at present low concentrations and characterized by unpleasant odors, limiting use. However, these properties do not hinder the production of O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate. By utilizing the sodium 3-methyl-4-nitrophenolate solution, the wastewater content and the content of 3-methylphenol derivatives in them are reduced, thereby improving the living environment. The embodiment of the invention is simple and requires only a minimal cost and can be converted to the current manufacturing equipment. Example 1

To a three-necked flask equipped with a stirred-bed condenser, a thermometer and a separator, was added 500 ml of toluene, 77 g of technical 3-methyl-4-nitrophenolate sodium containing 76.2 wt. Sodium 3-methyl-4-nitrophenolate and 10 g of technical K 2 CO 3. Delia-

Claims (3)

1. A process for producing O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate by condensation of Ο, Ο-dimethylchlorothiophosphate with sodium 3-methyl-4-nitrophenolate in the presence of a hydrogen chloride binding agent, in an aromatic hydrocarbon or hydrocarbon / water environment; characterized in that the condensation is carried out in the presence of a solution of sodium 3-methyl-4-nitrophenolate at a concentration of 0.5 to 40% by weight containing sodium hydroxide and / or mineral INVENTION salts and contaminated with organic compounds of sulfur, phosphorus and / or chlorine. 2. The process of claim 1 wherein the sodium 3-methyl-4-nitrophenolate solution is added during condensation. 3. The process according to claim 1, wherein the water is distilled off from the reaction mixture with an aromatic solvent from which it is separated after condensation.