DE1058044B - Process for the preparation of O, O-dialkylphosphoric acid esters of substituted halobutenols, particularly suitable for pest control - Google Patents

Description

Process for the production of, in particular for pest control suitable 0,0-dialkylphosphoric acid esters of substituted halobutenols It is known that triesters of phosphoric acids are obtained when dialkoxyphosphoric acid monohalides or dialkoxythiophosphoric acid monohalides with alcohols or phenols. In the process known from US Pat. No. 2,536,647, for example, one leaves the alkali salt of p-nitrophenol on the reaction of sulfur with chloro-bis (ß-chloroethyl) phosphite available bis (ß-chloroethyl) thiophosphoryl chloride act, whereby the bis (ß-chloroethyl) p-nitrophenyl thiophosphate forms. The alcohols used for the reaction with phosphoric acid ester halides both saturated, unsaturated, straight-chain or branched-chain alcohols or Thio alcohols used. For example, one obtains by reacting methallyl alcohol or its alkali salts with phosphoric acid ester halides, e.g. B. with 0-mono or 0,0-dialkyl phosphoric acid halides, the corresponding methallyl phosphates (cf. U.S. Patent 2,176,416).

Many of the phosphoric acid triesters already produced in large numbers have considerable technical importance and are used as a means of killing insects or rodents or can be used as corrosion inhibitors, flame retardants, Use flotation agents, plasticizers or as additives for high pressure lubricants.

It has been found that new 0,0-dialkylphosphoric acid esters of substituted halobutenols of the general formula can be obtained, especially those suitable for combating pests where R and R 'are alkyl groups, X is an oxygen or sulfur atom and Hal is a halogen atom, Z is hydrogen or an optionally substituted alkyl, alkenyl, cycloalkyl or aryl radical and Y is an oxygen or sulfur atom or a sulfone -, sulfoxy or imino group, which can also be alkyl, alkenyl or cycloalkyl-substituted or whose hydrogen atom is replaced by such radicals, eg. B. alkylene radicals, which form a nitrogen-containing ring with Z, obtained when 0,0-dialkylphosphoric acid monohalides of the general formula in which X is an oxygen or sulfur atom and Hal is a halogen atom, with a 3-halobutene- (3) -ol- (2) of the general formula which is substituted in the 1-position converts, where Hal, Y and Z have the meaning given.

Suitable 1-substituted 3-halobutene- (3) -ole- (2) are for example 1-methoxy-3-chlorobutene- (3) -ol- (2); 1-methoxy-3-bromobutene- (3) -ol- (2), 1-metboxy-3-iodine buten- (3) -ol- (2), also the corresponding 1-ethoxy, 1-propoxy, 1-butoxy, 1-pentoxy, 1-heptoxy-, 1-allyloxy-, 1-chlorallyloxy-, 1-phenoxy-, 1-chlorophenoxy, 1-dichlorophenoxy, 1-nitrophenoxy, 1-chloronitrophenoxy, 1-alloxyphenoxy derivatives of 3-chloro, bromine or iodobutene (3) ols (2). The derivatives such as 1-methylamino, 1-ethylamino, 1-propylamino, 1-butylamino, 1-pentylamino, 1-hexylamino, 1-allylamino, 1-cyclohexylamino, 1-cyclooctylamino, 1-dimethylamino, 1-diethylamino, 1-dipropylamino, 1-dibutylamino, 1-diallylamino, 1-methylethylamino, 1-ethyleneimino-, 1-pyrrolidyl-3-chlorobutene- (3) -ol-2,1-anilino-, 1-chloroanilino-, 1-nitroanilino-, 1- (chloro) -methylanilino-, 1- (chloro-dimethylanilino) -3-chloro-, bromo- or iodobutene- (3) -ol- (2). Of the 3-halobutene- (3) -olen- (2) which are in the 1-position are substituted by an alkylthiol or cycloalkylthiol radical, the sulfur atom can also be oxidized to a sulfoxy or sulfone group are representatives called: 1-ethylmercapto-, 1-phenylmercapto-, 1-ethylsulfoxy-, 1-phenylsulfoxy-, 1-ethylsulfonyl-, 1-phenylsulfonyl-3-chlorobutene- (3) -ol-2.

Of the 0,0-dialkylphosphoric acid monohalides which can be used as the second reaction component are especially the chlorides, bromides and iodides of O, 0-dialkylphosphoric acids and 0,0-dialkylthiophosphoric acids are suitable. The 0,0-dialkyl phosphoric acid monohalides are easily accessible connections. For example, they can be implemented by repositioning of phosphorus oxychloride or phosphorothiotrichloride with the calculated: amount of aliphatic monohydric alcohols are obtained. As a representative of this reaction component are especially dimethyloxyphosphoric acid monochloride, dimethoxyphosphoric acid monobromide and iodide, also the corresponding halides of O, 0-diethyl, O, 0-dipropyl and 0,0-dibutylphosphoric acid as well as chlorides, bromides and iodides of 0,0-dimethylthiophosphoric acid, 0,0-diethylthiophosphoric acid, 0,0-dipropylthiophosphoric acid and 0,0-dibutylthiophosphoric acid called.

The reaction takes place by combining the two reaction components, it is generally unimportant which component is presented. Appropriate the dialkoxyphosphoric acid monohalide is added to the substituted halobutenol to. The starting materials are used in approximately equivalent amounts. Sometimes However, it can also be advantageous to use one or the other starting material in a small amount Use excess. Working in the presence of inert diluents can may be appropriate. As a diluent, for. B. hydrocarbons, such as benzene, toluene, xylene, benzines and cyclohexane or chlorinated hydrocarbons, z. B. methylene chloride, chloroform, and ethylene chloride and carbon tetrachloride to serve. The implementation is already noticeably taking place in the cold, but is working one expediently at higher temperatures, for. B. about 15 to 120 'C, advantageous at about 40 to 50 'C.

When carrying out the process, it is advisable to use hydrogen halide binding agents Means, e.g. B. pyridine, or other tertiary amines, whose boiling point is expediently above the reaction temperature, e.g. B. triethylamine or tributylamine, add, to bind the hydrogen halide released during the reaction. Also alkali carbonates or alkali bicarbonates can be used for this purpose.

The obtained new 0,0-dialkylphosphoric acid esters of the substituted Halobutenols are strongly insecticidal and ovicidal and are also distinguished characterized in that they are less toxic to warm-blooded animals than other known insecticides effective phosphoric acid esters.

If one compares, for example, the insecticidal effect of the O, O-dialkylphosphoric acid esters of substituted halobutenols obtainable according to the invention, e.g. B. the compound of the formula prepared according to Example 3 and the compound of the formula obtainable according to Example s with that of known phosphoric acid esters derived from unsaturated alcohols, e.g. B. from US Pat. No. 2,394,829 (Examples 1 and 2) known esters of allyl alcohol of the formula using the usual test methods, the results given in the table are obtained: Tabel Drosophilatest application test cockroach test LDba after housefly LDsa permanent contact Effective 6 hours 48 hours Fabric y240 cm 'after 4 hours o / active substance in Wall area @@ n active ingredient in 500 mg dust (Mean value) 1 acetone per 75 cm area I 1.61 y 0.04. / 0 0.5010 1I 3.03 y 0.0760 /, 0.250 /, III 500y still 10/0 even more than 10/0 ineffective ineffective In detail, the test methods listed in the table were carried out as follows: Drosophila test: beakers with a capacity of 250 cm3 are evenly lined with 1 cm- 'of the acetone solution of the active ingredient to be tested. After the solvent has evaporated, the glass is placed with the opening facing down on a clean surface after 20 to 30 specimens of Drosophila melanogaster (4 days old a 'and, Q) have been introduced. Each attempt at a particular concentration range was made with five glasses. carried out. The effect was determined by the probit method (Fi nney, 1952, Cambridge University Press) as LDSO after 6 hours.

Application test: 4 day old houseflies (Musca domestica) obtained in C02 anesthesia each 1 mm3 of the acetone solution of the active ingredient on the ventral Abdomen. Then 20 animals each with the same treatment are placed in a clean observation glass brought. Mortality is determined after 4 hours.

Cockroach test: adult specimens of Blatta orientalis are produced to 500 mg of a dust containing a certain amount of active ingredient in glass vessels 9 cm in diameter and 1 1 volume set. The effect will be after 48 hours Permanent contact determined.

The parts given in the examples are parts by weight. EXAMPLE 1 56.4 parts of diethoxythiophosphoric acid monochloride are added to a mixture of 40th, 8 parts of 1-methoxy-3-chlorobutene- (3) -ol- (2) and 23.7 parts of anhydrous pyridine with vigorous stirring at about 40.degree run in slowly and, after the addition is complete, stir for about 5 hours at 40 to 45 ° C. to complete the reaction. The reaction mixture is cooled to room temperature, 30 to 40 parts of water and 50 parts of benzene are added, the mixture is stirred thoroughly and the mixture is separated in a separating funnel non-aqueous layer. It is extracted with a little dilute hydrochloric acid and then with water, then dried over sodium sulfate and distilled. 75 parts of a compound with a boiling point of oo .. 96 ° C. are obtained as a colorless oil. Yield: 880 /, the theory. The compound has the formula Example 2 564 parts of diethoxythiophosphoric acid monochloride are allowed to run into the mixture of 594 parts of 1-phenoxy-3-chlorobutene- (3) -ol- (2) and 237 parts of pyridine at 30 ° to 40 ° C. with stirring. After the addition has ended, the mixture is stirred for a further 4 hours at 40.degree. C. and worked up as described in Example 1. After the solvent has been distilled off, 910 parts of diethoxy- (1-phenoxy-3-chlorobutene- (3) -oxy) -2-thiophosphate remain as a pale yellowish oil. The product can only be distilled with partial decomposition. Yield: 87% of theory. EXAMPLE 3 188 parts of O, O-diethoxythiophosphoric acid monochloride are slowly added to 163 parts of 1-n-propylamino-3-chlorobutene- (3) -ol- (2) and 79 parts of pyridine with thorough stirring, and the reaction temperature is kept below by good cooling 42 ° C. After the addition has ended and the reaction has subsided, the mixture is stirred for a further 3 hours at 45 ° C. The reaction mixture is cooled to room temperature, 50 parts of water and 100 parts of benzene are added, the mixture is stirred thoroughly and the layers are separated. The aqueous layer is extracted again with 60 parts of benzene each time and the extracts are combined with the non-aqueous layer. The benzene solution obtained is washed with 50 parts of water, dried over sodium sulfate and distilled from the solvent in vacuo. The residue left behind is 241 parts of a reddish, non-distillable oil with the following formula: Yield: 77% of theory. EXAMPLE 4 As stated in Example 3, 53.1 parts of 1-diethylamino-3-chlorobutene- (3) -ol- (2) are reacted with 56.4 parts of diethoxythiophosphoric acid monochloride in the presence of 23.7 parts of pyridine and obtained after the work-up 63 parts of O, O-diethyl- (4-diethylamino-3-chlorobutene- (3) -oxy) -2-thiophosphate as a reddish, non-distillable oil. Yield: 64 "/, of theory.

Example 5 56.4 parts of diethoxythiophosphoric acid chloride are slowly run into a mixture of 49.8 parts of 1-ethylmercapto-3-chlorobutene- (3) -ol- (2) and 23.7 parts of anhydrous pyridine, with thorough stirring. The temperature is not allowed to rise above about 40 ° C. by cooling. The mixture is stirred for a further 4 hours at 40 to 50.degree. C. and worked up as indicated in Example 1. After distilling off the solvent, 91 parts of the new thiophosphoric acid ester are obtained as a pale yellowish oil of the formula Yield: 95% of theory. Example 6 594 parts of 1-phenoxy-3-chlorobutene- (3) -ol- (2) and 237 parts of anhydrous pyridine are mixed and 516 parts of diethoxyphosphoric acid chloride are run in at 30 ° to 40 ° C. with thorough stirring. The mixture is subsequently stirred for 3 hours at 40 to 50 ° C., worked up as indicated in Example 1, and 900 parts of the new phosphoric acid ester are obtained as a non-distillable oil of the formula Yield: 90% of theory. Example 7 In a mixture of 33.3 parts of 1-Äthyhnercapto-3-chlorobutene- (3) -ol- (2) and 15.8 parts of pyridine are allowed to 32.1 parts of O, O with stirring at 30.degree. To 40.degree - dimethylthionophosphoric acid monochloride. The mixture is stirred at 40 to 50 ° C. for a further 4 hours. Ulan cools the reaction mixture and adds 80 parts of methylene chloride. The solution obtained is extracted twice with 30 parts of water each time and the organic layer separated from the water is dried with sodium sulfate. The solvent is distilled off in vacuo and 40 parts of the compound of the formula are obtained as a light brown oil, which can only be distilled with partial decomposition at bp 95 to 100 ° C. The yield is 700 /, of theory.

If you work as stated above, but instead of 32.1 parts of O, O-dimethylthionophosphoric acid monochloride, 41 parts of O, O-dimethylthionophosphoric acid monobromide are used, 43 parts corresponding to 75% of theory of the compound obtainable according to paragraph 1 are obtained. EXAMPLE 8 A mixture of 163 parts of 1-n-propylamino-3-chlorobutene- (3) -ol- (2) and 79 parts of pyridine is charged with 0.0-dibutylthionophosphoric acid monochloride with vigorous stirring at a temperature of 35 to 45.degree slowly in an amount of 244 parts and then stirred for a further 6 hours at 50.degree. It is cooled and the reaction mixture is worked up as described in Example 3. 342 parts of the compound of the formula are obtained as a yellowish oil that can only be distilled with strong decomposition. The yield is 920 / "of theory. Example 9 216 I parts of 0, 0-Dipropylthionophosphoric acid chloride are added with vigorous stirring to a mixture of 166 parts of 1-ethylmercapto-3-chlorobutene- (3) -ol- (2) and 79 parts of pyridine 40 to 45 ° C. After the addition, stirring is continued for 5 hours at 45 ° C. and the reaction mixture is worked up as indicated in Example 7. 295 parts of the compound of the formula are obtained as a yellowish oil. The yield is 84.5% of theory. Example 10 163 parts of 1-n-propylamino-3-chlorobutene- (3) -ol- (2) and 79 parts of pyridine are mixed and 172 parts of 0,0-diethylphosphoric acid monochloride are allowed to flow into the mixture at 30 ° to 40 ° C. with stirring . The mixture is then stirred for a further 4 hours at 50 ° C. and worked up as described in Example 3. 275 parts of the compound of the following formula are obtained as a light oil. The yield is 92% of theory. EXAMPLE 11 37.6 parts of 0,0-diethylthionophosphoric acid chloride are slowly introduced into a mixture of 46 parts of phenyl- (2-oxy-3-chlorobutenyl- (3)) sulfone and 15.8 parts of pyridine, with stirring, so that the Temperature does not exceed 50 ° C. After the introduction, the mixture is stirred at 50 ° C. for a further 4 hours. It is allowed to cool, 10 parts of water are added to the reaction mixture and it is acidified with dilute hydrochloric acid to a pH of 5. After shaking with water, the solution is extracted with benzene, the benzene extract is washed with water and dried with anhydrous sodium sulfate. After the sodium sulfate has been filtered off, the solvent is distilled off. The remaining residue is distilled on a boiling water bath under vacuum. There remain 52 parts of a non-distillable oil of the formula Yield: 82.5% of theory. Example 12 59.1 parts of 1-anilido-3-chlorobutene- (3) -ol- (2) and 23.7 parts of pyridine are mixed thoroughly and 56.4 parts of 0 are mixed in the mixture at 45 to 50 ° C. with vigorous stirring , 0-diethylthionophosphoric acid chloride entered. Stirring is continued for a further 6 hours at 50 ° C., the reaction mixture is cooled and worked up as described in Example 3. 86 parts of a compound of the formula are obtained The yield is 83% of theory.

If instead of the 59.1 parts of 1-anilido-3-chlorobutene- (3) -ol- (2), 36.3 parts of 1-amino-3-chlorobutene- (3) -ol- (2) are obtained with otherwise the same procedure and the same reaction conditions, 65 parts, corresponding to 80% of theory, of the compound EXAMPLE 13 To a mixture of 52.5 parts of 1-pyrrolidino-3-chlorobutene- (3) -ol- (2) and 23.7 parts of pyridine are added 56.4 parts of 0.0- Diethylthionophosphoric acid chloride. The mixture is stirred for a further 5 hours at 50 ° C., the mixture is cooled and worked up as described in Beispie13. 56 parts of a reddish oil of the formula are obtained Yield: 57% of theory. EXAMPLE 14 56.4 parts of 0 are added to a mixture of 48.3 parts of 1-allylamino-3-chlorobutene- (3) -ol- (2) and 23.7 parts of pyridine with thorough stirring at 35 to 40.degree , 0-diethylthionophosphoric acid chloride run in. The mixture is then stirred for a further 5 hours at 50 ° C., the reaction mixture is cooled to room temperature and it is worked up as described in Example 3. 67 parts of a yellowish oil are obtained, which has the following formula: Yield: 71.5 % of theory.

Claims (2)

PATENT CLAIMS: 1. Process for the preparation of 0,0-dialkyl-phosphoric acid esters of substituted halobutenols of the general formula which are particularly suitable for pest control where R and R 'are alkyl groups, X is an oxygen or sulfur atom and Hal is a halogen atom, Z is hydrogen or an optionally substituted alkyl, alkenyl, cycloalkyl or aryl radical and Y is an oxygen or sulfur atom or a sulfone -, sulfoxy or imino group, which is also optionally alkyl, alkenyl or cycloalkyl-substituted or whose hydrogen atom is replaced by such radicals, eg. B. alkylene radicals which form a nitrogen-containing ring with Z, characterized in that O, O-dialkylphosphoric acid monohalides of the general formula in which R and R 'are alkyl groups, X is an oxygen or sulfur atom and Hal is a halogen atom, with a 3-halobutene- (3) -ol- (2) of the general formula which is substituted in the 1-position converts, where Hal, Y and Z have the meaning given. 2. The method according to claim 1, characterized in that the reaction is carried out in the presence of hydrogen halide binding agents Agent carries out. References Considered: U.S. Patent No. 2 394 829.