DE1643706C - Thinonophosphon (or) acid esters - Google Patents

Description

The invention relates to thionophosphonic acids the general formula

R ₁ O

SO -: CHj

SOCH, + KtZ

IO

in which R, an alkyl radical with 1 to 3 carbon atoms, R ₂ denotes the methyl, ethyl, methoxy, ethoxy or phenyl radical.

The compounds according to the invention are produced by following the reaction scheme

(Z = halogen atom, Kt = monovalent cation or an equivalent of a polyvalent cation) corresponding thiophosphorus or thiophosphonic acid halide is reacted with a suitable phenol salt. The reaction takes place in an organic solvent, for example a ketone, toluene, Dioxar., Or in aqueous solution, optionally at elevated temperature. In the raw materials Z preferably denotes a chlorine atom, while the phenol salts are in particular the alkali metal and ammonium salts come into question.

The compounds prepared by the process of the invention are thin layer chromatography uniformly. A mixture of hexane and acetone 2: 1 was used as the mobile phase and was developed with 3% palladium chloride solution.

The phenols used as starting materials can be prepared by adding the appropriate l.Z ^ -Trichlor- ^ methylmercapto compounds with aqueous methanolic sodium hydroxide in the autoclave at elevated temperature to 2,5-dichloro-4-methylmercaptophenol and then oxidized to sulfoxide with hydrogen peroxide in glacial acetic acid.

The compounds of the invention are highly effective insecticides and acaricides. For the application they are in the usual way with inert auxiliaries and carriers such. B. on emulsions, dusts, Scatter powders, formulated. The use concentrations are about 0.01 to 5%.

The superior effectiveness of the compounds according to the invention compared to that as an insecticide and Acaricide proven commercial product Ο, Ο-Dimethyl-O- (4-methylmercapto-3-methylphenyl) -thionophos- phat (A) is shown in the following comparisons. Therein were the following compounds of the invention examined:

B. 0,0-diethyl-0- (2,5-dichloro-4-methylsulfinylphenyO-thionophosphoric acid ester;

C. O-Ethy! -0- (2,5-dichloro-4-methylsulfinylphenyl) -methyl-thionophosphonic acid ester;

D. O, O-Dimethyl-O- (2,5-dichloro-4-methylsuirinylphenyO-thionophosphoric acid ester;

E. O - methyl - O - (2,5 ■ dichloro - 4 - methylsulfinylphenyl) methylthionophosphonic acid ester;

F. 0-n-Propyl-0- (2,5-dichloro-4-methylsulfinylphenyl) -methylthionophosphonic acid ester;

G. O-Ethyl-O- (2,5-dichloro-4-methylsulfinylphenyl) -phenylthionophosphonic acid ester.

I. Control of aphids on beans,

Field experiment, aqueous emulsion of the active ingredients

Act.slolTc Concentration in% % Kill A.
B.
C. 0.02
0.01
0.01 95
100
100

II. Spider moth caterpillars, field test, aqueous emulsion of the active ingredients

Active ingredients Concentration in% % Kill A.
B.
C. 0.02
0.02
0.02 85
100
100

III. Killing of aphids in the greenhouse experiment, evaluation after 1 hour, aqueous emulsion of the active ingredients

Active ingredient

Killing in% at an active ingredient concentration of 0.0002% 0.0006% 0.001%

10

70

30th
90

80 100

IV. Effect against house flies

Time in minutes to complete 0.1% Active ingredient Killing at an active ingredient concentration of 77 0.01% 44 A. ~ 500 27 E. 143 F. 74

V. Effect against caterpillars (Plutella maculipennis)

Active ingredient Withdrawal concentration (LC ₅₀ ) A.
G 0.003%
0.0003%

The production of the active ingredients according to the invention is explained in more detail below.

B e i s ρ i e I 1

a) O.O-diethyl-O-i ^ S-dichloM-methylsulfinyl-

phenyl) thionophosphoric acid ester

(Molecular weight 377.26)

24.7 g (0.1 mol) of sodium ^ S-dichloM-methylsulfinylphenolat, (melting point of the phenol 210 ⁰ C) in 70 ml of methyl isobutylkeion with 20.8 g (0.11 mol) Ο, Ο-Diäthylthionophosphorsäurechloricf Stirred at 80 ^° C. for hours. The solvent is then distilled off, the residue is dissolved in methylene chloride, extracted with water, then 2N sodium hydroxide solution, then water again and dried over sodium sulfate. The methylene chloride is distilled off and the residue V is heated for ₂ hours on a boiling water bath in an oil pump vacuum.

Yield: 35.7 g (95% of theory), mp 58 to 59 ° C. Analysis:

Calculated ... P 8.22, S 17.03, Cl 18.81%; found .... P 8.14, S 16.94, Cl 19.00%.

The following compounds were produced analogously to Example 1 a:

b) O, O-Dimethyl-O- (2,5-dichloro-4-methylsulfinylphenyl) -thionophosphoric acid ester out

Sodium 2,5-dichloro-4-methylsulfinylphenolate and 0,0-dimethylthionophosphoric acid chloride

Yield 31 g (90% of theory) molecular weight 349.21 Analysis:

Calculated ... P 8.87, S 18.36, Cl 20.26%; found .... P 8.72, S 18.3, Cl 20.10%.

c) O-methyl-O- (2,5-dichloro-4-methylsulfinylphenyl) -methylthionophosphonic acid ester out

Sodium 2,5-dichloro-4-methylsulfinylphenolate and

Methylthionophosphonic acid methyl ester chloride

Yield 30 g (90% of theory; molecular weight 333.21. Analysis:

Calculated ... P 9.30, S 19.28, Cl 21.28%; found .... P 9.40, S 19.20, Cl 21.34%.

d) O-ethyl-O- (2,5-dichloro-4-methylsulfinylphenyl) -methylthionophosphonic acid ester out

Natnum-2,5-dichloro-4-melhyisulfinylphenolate and Methylthionophosphonic acid ethyl ester chloride

Yield 30g

347.24.

Analysis:

Calculated
found .

e) O-ethyl-O- (2,5-dichloro-4-methylsulfinylphenyl) -

üthylthionophosphonsüurecster from

Sodium ^^ - dichloM-methylsulfinylphenolate and Ethylthionophosphonic acid ethyl ester chloride Yield 30 g (83% of theory), molecular weight 361.26.

Analysis:

Calculated ... P 8.56, S 17.78, Cl 19.64%; ίο found .... P 8.50, S 17.92, Cl 19.47%.

O-n-Propyl-O- (2,5-dichloro-4-methylsulfinyI-phenylj-methylthionophosphonic acid ester from sodium 2,5-dichloro-4-methylsulfinylphenolate and methylthionophosphoric acid n-propyl ester chloride

Yield 29 g (82% of theory), molecular weight 361.26.

Analysis:
Calculated
found .

(87% of theory); Molecular weight P 8.56, S 17.78, Cl 19.64%; P 8.47, S 17.86, Cl 19.80% ».

g) O-Isopropyl-O- (2,5-dichloro-4-methylsulfinylphenyl) -methylthionophosphonic acid ester from sodium 2,5-dichloro-4-methylsulfinylphenolate and Isopropyl methylthionophosphoric acid ester chloride

Yield 28 g (80% of theory), molecular weight 361.26.

Analysis:

Calculated
found .

P 8.56, S 17.78, Cl 19.64%; P 8.50, S 17.52, Cl 19.52%.

h) O-EthyI-O- (2,5-dichloro-4-methylsulfinylphenyl) -

phenylthionophosphonic acid ester from

Sodium 2,5-dichloro-4-methylsulfinylphenolate and phenylthionophosphonic acid ethyl ester chloride

Yield 33 g (82% of theory), molecular weight 409.29.

Analysis:
Calculated
found .

P 7.58, S 15.68, Cl 17.35%; P 7.42, S 15.60, C! 17.30%.

Claims (3)

Patent claims: 1. Thionophosphonic (or) acid esters of the general formula P 8.93, S 18.50. Cl 20.42%; P 8.76, S 18.28, Cl 20.20%. in which R _{1 is} an alkyl radical having 1 to 3 carbon atoms. R ₂ denotes a methyl, ethyl, methoxy, ethoxy or phenyl radical. 2. Pesticides, characterized by a content of a compound according to Claim 1 in addition to inert substances. 3. Use of compounds according to Claim 1 for pest control.