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United States Patent 0 C6 3,076,009 Patented Jan. 29, 1963 1 2 phosphoric acid esters. This reaction is preferably carried 3,076,009 out at‘. temperatures of. between 40 and 100° C. but lower or higher temperatures may also be applied. It is ex THIOPHOSPHORIC ACID ESTERS AND PRODUCTION pedient to work in a suitable solvent such as benzene or Gerhard Schrader, Opladen, and August Diirken, Wupper tal-Sonnborn, Germany, assignors t0 Farbenfabriken toluene. However, ketones such as for example acetone or methyl-ethyl ketone are also suitable for carrying out Bayer Aktiengesellschaft, Leverkusen, Germany, a cor poration of Germany No Drawing. Filed Feb. 8, 1956, Ser. No. 564,108 Claims priority, application’ Germany Feb. 10, 1955 5 Claims. (Cl. 260—461) the reaction. It is further possible to use an excess of the corresponding a-halogen-carboxylic acid ester as solvent. The reaction leading to this class‘ of compounds may be 10 This invention relates to thiophosphoric acid esters of the general formula 15 R and R’ stand for aliphatic or aromatic radicals, R" 20 in which R, R’, R” and X have the meaning set forth in stands for hydrogen, aliphatic or aromatic radicals, X column 1. stands for oxygen or sulfur whereby one X must be sulfur. The invention is further illustrated by the following examples without‘ being, restricted thereto. Example I An object of this invention is to provide new thiophos phoric acid esters having good insecticidal properties. Another object of this invention is to provide processes ’ for making these new thiophosphoric acid esters. Further objects will become apparent as the following S description proceeds. 00139 The thiophosphoric acid esters according to the inven correspond to the formula 30 OCH3 80 grams of the ammonium salt of dimethyl-thiol-phos phoric acid are suspended in 200 grams of u-bromo-phenyl acetic acid ethyl ester. The mixture is heated to 60° C. 35 and maintained at 60~70° C. for a half hour. The reac tion is completedwith slight heat' evolution. The mix ture is cooled to room temperature, diluted with 500 milli wherein R, R’, R" and X have the abovesaid meaning. For instance, R and R’ may be methyl, ethyl, propyl, butyl, hexyl, phenyl, nitrophenyl chlorophenyl, tolyl, benzyl etc.; 40 R" may stand for the same radicals or may be hydrogen. The new thiophosphoric acid esters wherein the chalco genic X attached to CH and P is oxygen, can be regarded litres of ether, the salts’ are ?ltered off by suction and the ethereal layer is washed twice with 100 millilitre portions of water. After drying over sodium sulphate the ether is distilled oif. At a pressure of 0.01 mm. Hg there are obtained 100 grams of ?rst runnings which come over at 50-60" C., chie?y consisting of unchanged a-bromo phenyl-acetic acid ethyl-ester. By further distillation there as phosphoric acid derivatives of a-hydroxy carboxylic are obtained about 100 grams of the new ester coming over at 122-125“ C./0.01 mm. Hg as a colourless sparingly acid esters. These esters can be prepared by reaction of u-hydroxy carboxylic acid esters with 0,0-dialkyl-thiono water-soluble oil. phosphoric acid monohalides in the presence of acid bind ing agents such as tertiary amines, alkali alcoholates, alkali hydroxides and alkali carbonates‘. The reaction leading to this class of compounds may be 50 represented by the following equation: Example 2 0113-03-0 o 0 (H55 (H) 0011, S——P/ 0011. 160 grams of the’ ammonium salt of dimethyl-thiol 55 phosphoric acid are suspended with 320 grams of a-bromo propionic acid ethyl ester; The mixture is heated with stirring to about 60° C. and maintained at this temperature for an hour. It is then cooled down, 600 millilitres of ether are added thereto, the salts thus formed are ?ltered in which R, R' and R" have the meaning set‘ forth in column 1. The reaction is preferably carried out in suitable sol vents such as lower aliphatic alcohols, lower aliphatic 60 off by suction and the ethereal solution is washed three ketones, lower aliphatic nitriles, hydrocarbons such’ as benzene and toluene. It is advantageous to conduct the reaction at a temperature of between 40 and 80° C. but lower or higher temperatures may also be applied. The new thio- or dithiophosphoric acid esters, wherein the chalcogenic X attached to CH and P is sulfur, may be prepared by reaction of u-halogen-carboxylic acid esters 70 with the salts of dialkyl-thiol or dialkyl-thiol-thiono times with 100 millilitre portions of water. The ethereal solution is dried and then fractionated. 100 grams of the new ester, B.P. 76-7 8° C./ 0.01 mm. Hg, are thus obtained. The excess u-bromo-propionic acid ethyl ester used is recovered as ?rst runnings. Example 3 CH3-CH-O 0-0 0.3, s--P 002B) 3,076,009 4 3 Example 8 38 grams of diethyl-thiol-phosphoric acid ammonium salt are dissolved in 125 millilitres of 99 percent ethyl GH-C 0-0 02H; alcohol. 38 grams of e-bromo-propionic acid ethyl-ester H/OCzHg are added with stirring at 75° C. and the temperature is 3 maintained for an hour. The salts are then ?ltered o? by 5 0-P suction, the ?ltrate is diluted with water, the water-insolu 002115 ble residue is taken up with chloroform, dried over sodium 54 grams of mandelic acid ethyl ester are dissolved in sulphate and distilled. 40 grams of the new ester, B.P. 25 grams of pyridine. 57 grams of diethyl-thiono-phos~ 78-79° C./0.01 mm. Hg, are thus obtained. 10 phoric acid monochloride are added thereto with stirring Example 4 at 40° C. and the mixture is heated to 60° C. for 2 hours. The viscous reaction mixture is introduced into a mixture of 300 millilitres of water and 30 millilitres of concen trated hydrochloric acid. 46 grams of diethyl-thiol-phosphoric acid ammonium salt are suspended in 100 millilitres of methyl-ethyl-ketone. is distilled oif. 70 grams of the new ester are obtained as viscous water-insoluble oil. The new ester can be distilled 61 grams of a-bromo-phenyl-acetic.acid ethyl ester are , in high vacuum only with decomposition. The new ester kills red spiders at 0.01% concentration. added with stirring at 60° C., and the mixture is heated to 60-65° C. for an hour. The salts are then ?ltered off by suction, the bulk of the solvent is distilled off, the product Example 9 taken up with ether, washed with water and the ethereal solution is dried. By fractionating there are obtained 50 grams of the new ester, B.P. 127° C./0.01 mm. Hg. The new ester is a colourless oil which is able to kill plant lice at a concentration of 0.005 percent and red spiders at 0.01 CHg-OH-C 0-0 02115 S H/ 0 02115 0-1? percent concentration. Example 5 The water-insoluble part is taken up in chloroform and the chloroform solution is shaken with 100 millilitres of a 5% sodium bicarbonate solution. After drying with sodium sulphate the solvent 30 002B; 24 grams of lactic acid ethyl ester are added to a (Heron-o0 0 0,115 sodium ethylate solution (4.6 g. of sodium in 200 milli litres of alcohol) at 20° C. 39 grams of diethyl-thiono 5 phosphoric acid monochloride are added drop by drop 00 H u/ 2 ‘ to the solution at 40° C. and the temperature is kept at 001B; 40° C. for 30 minutes. The reaction product is placed in a large quantity of water, the water-insoluble por tion taken up in chloroform, dried and fractionated. 35 8-? 83 grams of powdered and screened potassium carbonate grams of the new ester, B.P. 69° C./0.01 mm. Hg, are are suspended in 150 millilitres of methyl-ethyl-ketone. obtained. The new ester has a toxicity of about 1000 98 grams of diethyl-dithio-phosphoric acid are slowly added with stirring at 40° C. 90 grams of w-brOmO 40 mg./kg. when applied to rats per os. The ester kills red spiders at 0.05% concentration. propionic acid ethyl ester are then added drop by drop We claim: at 65° C. and the temperature is maintained at 60° C. for 1. A thiophosphoric acid ester of the formula four hours. By usual working up, 110 grams of the new ester, B.P. 134° C./2 mm. Hg, are obtained. Example 6 CH-CO 0 C231! 45 S O OOH: ' OCH; ll/ s-r 0033 OCH: 84V CHg-CH——G 0 0 CeHil 50 2. A thiophosphoric acid ester of the formula 40 grams of dimethyl-thiol-phosphoric acid ammonium salt are suspended in 100 millilitres of methyl-ethyl-ketone. 47 grams of u-bromo-propionic acid-n-hexyl ester (B.P. 65—67° C./1 mm. Hg) are added thereto with stirring at 55 65° C. The temperature is maintained for about an hour and the product then worked up in usual manner. 35 grams of the new ester, B.P. 98-100° C./0._01 mm. Hg, are _ thus obtained. 3. A compound of the formula The new ester shows with rats per 0s a ' R0 toxicity of LD 50:500 mg./kg. It kills plant-lice at a 60 concentration of 0.05 percent. s \ll P-X-CHCOOR R0 Example 7 ' wherein each R is lower alkyl, R’ is phenyl and X is a 0112-00-0 02B! 65 member selected from the group consisting of oxygen and sulfur.‘ 4. A compound of claim 3 wherein X is oxygen. 5. A compound of claim 3 wherein X is sulfur. 0 02115 50 grams of diethyl-dithio-phosphoric acid ammonium salt are dissolved in 150 millilitres of methyl-ethyl-ketone. 70 25 grams of mono-chlor-acetic acid ethyl ester are added with stirring thereto at 70° C. The temperature is main tained at 65 ° C. for'two hours and the product is then worked up in usual manner. 33 grams of the new ester, B.P. 137° C./ 1.5 mm. Hg, are thus obtained. 75 References Cited in the ?le of this patent UNITED STATES PATENTS 2,266,514 2,494,126 Romieux et a1 _________ __ Dec. 16, 1941 Hoegberg ____________ __ Jan. 10, 1950 (Other references on following page) 3,076,009 5 6 UNITED STATES PATENTS 2,494,283 2,645,657 2,802,856 d t 1. _______ __ J . 10, 1950 142001) (1953) £331? eatyai _a_________ __ 1:11; 14,1953 _________ __ A Norman et a1 OTHER REFERENCES ‘ Melnikov et al.: “J. Gen. Chem. U.S.S.R.,” 23, 1417 Hg . 1 , 1957 3 Bacon et 'aL: “J. Am. Chem. Soc.,” 76, 670.675 5 (1954). Kosolapo?: “Chemical Abstracts,” v01. 48, pp. 6639.. 6640, 9902—3 (1954). Whitemore: “Organic Chemistry,” D. Van Nostrand Mastryukova et al.: “Bull. Acad. Sci. U.S.S.R., Div. Co., Inc., NY. (1937), pp. 37-39. Chem. Sci,” p. 433 (1956). Melnikov et a1.: “Doklady Akad. Nauk S.S.S.R.” 86, Germany, application Ser. No. F 13502, IV b/ 12-0. 543-6 (1952). 10 Printed Jan. 26, 1956.