CS199740B2 - Process for preparing new organic esters of phosphoric acid - Google Patents

Description

The present invention relates to a process for the production of novel organic phosphoric esters having excellent insecticidal, acaricidal and nematicidal activity.

The compounds produced by the process according to the invention correspond to the general formula I

R 10 O X Y I II p — o — ch — c — Y / I

SY R ² (I) in which represents

R ¹ is alkyl having 1 to 3 carbon atoms,

R ( ^{2) is} alkyl of 3 or 4 carbon atoms or alkoxyalkyl of 3 to 6 carbon atoms,

X is hydrogen, trihalomethyl or C 1 -C 4 alkoxy; and

Y is fluorine or chlorine.

In accordance with the invention, the compounds of formula (I) are prepared by phosphite of formula (II)

R10 X Y \ I I

P — O — CH — C — Y

Z I

HO Y (II), in which

R, X and Y have the above meanings, is reacted with a sulfenyl halide of the general formula III ¹

R ² S-Hal (III) in which

R ² has the abovementioned meaning and

Hal represents a halogen atom.

Examples of phosphites of the formula II which are suitable as starting materials in the process according to the invention are mentioned

O-methyl-O-2,2,2-trifluoroethyl phosphite,

O-methyl-0-2,2,2-trichloroethyl phosphite,

O-ethyl 1-0-1,1,1,3,3,3-hexafluoro-2-propylphosphite,

O-ethyl 1-0-1,1,1,3,3,3-hexachloro-2-propylphosphite,

O-ethyl-O-1-ethoxy-2,2,2, -trifluoroethyl phosphite,

O-n-propyl-0-2,2,2-trifluoroethyl phosphite,

O-ethyl-0-2,2,2-trifluoroethyl phosphite and O-ethyl-0-2,2,2-trichloroethyl phosphite.

Examples of sulfenyl halides of the formula III which are suitable as starting materials in the process according to the invention are:

1-Propanesulfenyl chloride

1-butanesulfenyl chloride, isobutanesulfenyl chloride,

2-butanesulfenyl chloride, methoxy ethanesulfenyl chloride, ethoxyethanesulfenyl chloride, n-propoxyethanesulfenyl chloride, isopropoxyethanesulfenyl chloride and n-butoxyethanesulfenyl chloride, as well as the corresponding bromides.

All sulfenyl chlorides or bromides can be readily prepared in a conventional manner by reacting the corresponding disulfide with chlorine, bromine, sulfuryl chloride or sulfuryl bromide.

If O-ethyl-O-2,2,2-trlchloroethyl phosphite and 1-butanesulphenyl chloride are used as starting materials in the process according to the invention, the reaction scheme can be described as follows:

C2H5O \

P = OH + CH 3 CH 2 CH 2 CH 2 Cl 2 -> Z

CCl3CH2O

C2H5O

------ P — O — CH2Cl3 + HCl z

CH3CH2CH2CH2S

The reaction according to the invention can be carried out in the presence of an acid binding agent. Examples of suitable acid binding agents are alkali metal hydroxides, carbonates, bicarbonates and alkoxides, as well as tertiary amines, for example triethylamine, diethylaniline or pyridine.

The reaction according to the invention is preferably carried out using a solvent or diluent. Examples of suitable solvents or diluents include water and inert organic solvents such as aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, trichlorethylene and the like. chlorobenzene, ethers such as diethyl ether, methylethyl ether, diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketane, methylisopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile, propionitrile and acrylonitrile, acrylonitrile ethanol, isopropanol, butanols and ethylene glycol, esters such as ethyl acetate and amyl acetate, acid amides such as dimethylformamide and dimethylacetamide, sulfones and sulfoxides such as dimethylsulfoxide and dimethylsulfone, and organic bases such as pyridine.

The reaction according to the invention can be carried out over a wide temperature range. In general, the reaction is carried out at a temperature of from -20 ° C to the boiling point of the reaction mixture, preferably at 0 to 100 ° C. The reaction is conveniently carried out at atmospheric pressure, but can also be carried out at elevated or reduced pressure.

As mentioned above, the compounds of the invention exhibit excellent insecticidal, acaricidal and nematicidal activity. These substances can therefore be used to combat plant pests and pests occurring in the field of hygiene and to protect stocks or materials. Said substances exhibit a combination of low phytotoxicity with good action against stinging, biting insects and mites.

Tests for the efficacy of the compounds produced by the process of the invention, as well as a description of the composition and preparation of suitable compositions containing the compounds of formula I as active ingredient, are given in U.S. Pat. No. 199,738.

The invention is illustrated by the following non-limiting examples.

Example 1

C2H5O

P — O-CH2Cl3 /

CH3CH2CH2CH2S

1.78 g of n-butyldisulfide are dissolved in 10 ml of toluene, and 1.35 g of sulfuryl chloride is added dropwise at -5 ° C. After the addition was complete, the mixture was stirred at room temperature for 30 minutes, then cooled to -5 ° C, and 4.83 g of O-ethyl-O- (2,2,2-trichloroethyl) phosphite was added dropwise. The reaction mixture was washed with ice-water, 5% aqueous potassium hydroxide solution and water, dried over anhydrous sodium sulfate, evaporated and the residue distilled under reduced pressure to give 5.6 g of O-ethyl-Sn. butyl-0-2,2,2-trichloroethylphosphorothioate having a boiling point of 134-136 ° C / 80 Pa and a refractive index n _D ²⁰ = 1.4885.

The following compounds summarized in the table below can also be prepared in an analogous manner:

R> 0 0 X Y \ il I I

P — O — CH — C — Y (I), / I

R ² SY

Example number Rl R ² X Y Physical channels 2 CH3- n-C3H7- H Cl bp 125-128 ^c C / 67 Pa; n _D ²⁰ = 1.4997 3 C2H5- n-C3H7- CFs F n _D ²⁰ = 1.3898 4 C2H5- n-C3H7- CCI3- Cl n _D ²⁰ = 1.5194 5 C2H5- n-C3H7- -OC2H5 F boiling point 90-92 ° C / 107 Pa 6 n-C3H7- n-C3H7- H F boiling point 80-83 ° C / 67 Pa; n _D ²⁰ = 1.4155 7 C2H5- n-C4Hg- H F boiling point 77-80 ^c C / 27 Pa; n _D ²⁰ = 1.4242 8 C2H5- n-C 6 H 9 - CF3- F boiling point 80-82 ° C / 27 Pa; n _D ²⁰ = 1.4040 9 C2H5- ÍSO-C4H9- H Cl ¹ n _D ²⁰ = 1.4852 10 C2H5- ÍSO-C4H9- H F n _D ²⁰ = 1.4165 11 C2H5- sek.C4H9- H Cl boiling point 81-83 ° C / 27 Pa; n _D ²⁰ = 1.4200 12 C2H5- sek.Cdřft- H Cl b.p. 122-124 ^C C / 27 mbar; n _D ²⁰ = 1.4895 13 C2H5- sek.C4H9- CF ₃ F boiling point 74-76 ° C / 80 Pa; n _D ²⁰ = 1.3965 14 C2H5- CH3OCH2CH2- H F bp 86-91 ° C / 53 Pa; n _D ²⁰ = 1.4227 15 Dec C2H5- C2H5OCH2CH2- H F b.p. 90-91 ^C C / 27 mbar; n _D ²⁰ = 1.4203 16 C2H5- C2H5OCH2CH2- H Cl bp 143-145 ° C / / 1 mbar; η _π ² θ = 1.4901 17 C2H5- C2HSOCH2CH2- CF3- F boiling point 79-81 ° C / 53 Pa; n _D ²⁰ = 1.3975 18 C2H5- . n-C3H7OCH2CH2- H F b.p. 98-102 ^C C / 40 mbar; n _D ²⁰ = 1.4260 19 Dec C2H5- 1SO-C3H7OCH2CH2- ; H F boiling point 94-98 ° C / 27 Pa; n _D ²⁰ = 1.4269 20 May C2H5- ÍSO-C3H7OCH2CH2- Ή Cl boiling point 127-132 ° C / 27 Pa; n _D ²⁰ = 1.4843 21 C2H5- n-C 4 H 8 OCH 2 CH 2 H F boiling point 109-112 ^c C / 53 Pa;

n * _D ²⁰ = 1.4261

Claims (1)

Process for the preparation of the novel organic phosphoric esters of the general formula I R 10 O X Y 1 I p — o — ch — c — Y / I SY R ² (I) in which represents R ¹ is alkyl having 1 to 3 carbon atoms, R ( ^{2) is} alkyl of 3 or 4 carbon atoms or alkoxy of 3 to 6 carbon atoms, X is hydrogen, trihalomethyl or C1 -C4 alkoxy; and Y is a fluorine or chlorine atom, characterized in that the phosphite of the general formula II R 10 X Y \ I I P — O — CH — C — Y / I HO Y (Π) in which R1, X and Y are as defined above, reacted with a sulfenyl halide of formula III R ² S-Hal (III) in which R ² has the abovementioned meaning and Hal represents a halogen atom.