CS199227B2 - Process for preparing new esteramides of thiophosphoric acid - Google Patents

Description

R 6, R 18 and X 18 are as defined above and

Y represents a halogen atom such as chlorine or bromine, and reacts with a compound of formula III

RlOM (III) wherein

R1 is as defined above and

M represents a hydrogen atom or an alkali metal, - provided that when M is a hydrogen atom in formula III, the reaction is carried out in the presence of an acid acceptor.

In the process according to the invention, to the compound of the formula II in a solvent inert under the reaction conditions, for example in an aromatic hydrocarbon such as toluene, xylene and the like, in a halogenated carbon. hydrogen, such as chlorobenzene or chloroform, or an ether, such as dioxane, is added over a period of 0.5 to 2 hours at a temperature of from -20 to + 50 ° C, preferably at a temperature of from 0 ° C to +20 ° C, preferably an equivalent amount (necessary to exchange a halogen atom of Y) of a compound of formula III wherein M is hydrogen, preferably with an equivalent amount of an acid acceptor such as triethylamine, trimethylamine, dimethylaniline or diethylaniline. The reaction mixture is then stirred at 20 ° C for about 20 to 100 hours.

Instead of reacting with a compound of formula III wherein M is a hydrogen atom and an acid acceptor, one halogen atom of Y may be substituted for an alkoxy group of formula R10 by reaction with an equivalent amount of a compound of formula III wherein M is an alkali metal preferably sodium.

The compounds of formula (II) required as starting materials in the process of the present invention can be prepared as described in DOS 2021728, for example by reaction of a compound of formula (IV)

Y S

CH3 COOR3 in which

R3, X and Y are as defined above, with a mixture of an equivalent amount (needed to exchange one halogen atom of Y) of the amine of formula V

Table I of the compound of formula I according to the invention

R2NH2 (V) wherein

R 2 is as defined above, and an acid acceptor.

The phosphoric acid esters of the formula I according to the invention are oils which can be distilled under high vacuum without decomposition and which can be characterized in the usual manner by their physical constants. These products, prepared by the above processes, contain the same ratio of cis-trans isomers (in the crotonic acid residue) as the starting materials, are soluble in organic solvents and readily emulsifiable in water.

The compounds of formula I exhibit potent insecticidal, acaricidal and nematicidal properties. Said substances have both an excellent action against voracious as well as absorbent insects and an excellent action against spider mites. The compounds of the present invention are superior in pest control activity to known compounds with similar chemical structures and thus represent a true enrichment of the prior art.

In addition to the above-mentioned excellent action against insects, mites and nematodes, the compounds of the invention exhibit at the same time only low toxicity to warm-blooded animals.

Significantly more favorable toxicity values for the warm-blooded compounds of the present invention, as compared to prior art substances, are shown in Table I below:

toxicity LD50 mg / kg (male white rat) oral dermal

Ri R2 r ₃ 1) CH3 C2H5 I-C3H7 122 2000 2) CH3 I-C3H7 I-C3H7 90 1290 3) CH3 I-C3H7 C2H5 69 800 4) CH3 n-C3H7 «) I-C3H7 108 1250 5) Mevimphos known O II (CH 3 O) 2 POO-C (CH 3) = CHC-OCH 3 3—7 3—90 6) Azodrin 0 II (CH3O) 2POOC (CH3) = CHCNHCH3 21 354 (rabbit) 7) ENT 27625 00CH3 III (CH3O) 2POOC (CH3) = CHCNCH3 2 107 (rabbit)

* ’Data taken from Commercial and Experimental Organic Insecticides, page 107

The compounds of the invention are also practically not phytotoxic at all. In the laboratory tests, no phytotoxicity of the compounds of the invention to cucumbers, watercress and oats was shown at all. In extensive experiments with more than 20 plant species [apple, apricot, bean, kale, Brussels sprouts, maize, cotton, cucumber, fodder beet, grapevine, peanuts, hops, lettuce, okra (Indian culture plant), pear, peas , pepper, sugar beet, tomato, tobacco, young stone fruit plants, potatoes, rice, pumpkin] have been shown to be fully compatible with the compounds of the invention without any signs of plant damage due to phytotoxicity. The new compounds can therefore be used as a pest control agent in living areas, cellars and paved areas, stables, etc., and can protect living organisms from the plant and animal kingdoms at various stages of development against pests, such as harmful insects, mites and nematodes.

The control of the pests is carried out in a conventional manner, for example by treating the respective site to be protected with active substances. For use as plant protection or pest control agents, the compounds of the invention may be formulated as dusts or sprays, for example solutions or dispersions, together with water or suitable organic solvents such as alcohol, kerosene , tar distillates and the like, as well as emulsifiers such as liquid polyglycol ethers formed from higher molecular weight alcohols, mercaptans or alkylphenols by addition of glylene oxide. Suitable organic solvents, such as ketones, aromatic or halogenated hydrocarbons, mineral oils and the like, can also be added to the mixtures as solubilizers.

The compositions applied by spraying or dusting may contain conventional inert excipients, such as talc, diatomaceous Melina ^1, bentonite, pumice, or other additives such as cellulose derivatives and the like., And further usual wetting and adhesive to improve wettability and adhesion.

The active compounds according to the invention can be present in the compositions and spray suspensions in admixture with other known active compounds. The compositions generally contain between 2 and 90% by weight of active ingredient, preferably between 5 and 50%. Useful suspensions generally contain between 0.02 and 90% by weight of active ingredient, preferably between 0.1 and 20%.

The active agents may be prepared in a manner known per se, for example as follows:

a) Combining 25 parts by weight of a compound of formula I with 25 parts by weight of isooctylphenyldecylglycol ether and 50 parts by weight of xylene gives a clear, water-emulsifiable, clear solution. Concentrate obtained with water to the desired concentration.

bj 25 parts by weight of the compound of the formula I are mixed with 30 parts by weight of isooctylphenyloctaglycol ether and 45 parts by weight of the kerosene fraction boiling in the range of 210 to 280 ° C (d = 0.92). The concentrate obtained is diluted with water to the desired concentration.

c) 50 parts by weight of a compound of the formula I are mixed with 50 parts by weight of isooctylphenyloctaglycol ether. A clear concentrate, readily emulsifiable in water, is obtained which is diluted with water to the desired concentration.

The preparation of the compounds of the invention is illustrated by the following non-limiting examples. Temperatures are given in degrees Celsius in the examples.

Example 1

O [1-chloro-1-ethoxycarbonyl-1-propen-2-yl) •• O-methyl-N-n-propylphosphorothioamidate

CH3 O3

P = OC = CClCOOC2H5 / n-C3H7NH CH3

320 g of O- (1-chloro-1-ethoxycarbonyl-1-propen-2-yl) -N-n-propylphosphoramidochloridothionate of the formula

Cl (n-C3H7NH3P (S) OC (CH3) = CClCOOC2Hs (cis: trans = 9: 1)) is dissolved in a mixture of 500 ml of toluene and 500 ml of chloroform, and the resulting solution is added over 2 hours at 0 ° C. 32.1 g (1 mol) of methanol and 101.2 g (1 mol) of triethylamine The reaction mixture is stirred for 5 hours at 0 ° C and then for 100 hours at 20 ° C, the precipitated triethylamine hydrochloride is filtered off, the filtrate is washed, dried The O- (1-chloro-1-ethoxycarbonyl-1-propen-2-yl) -O-methyl-N-propylphosphorothioamidate obtained is boiled under a pressure of 1.33 Pa at 107 DEG C. The ratio of cis: trans isomerism in the residue Crotonic acid is 9: 1; n _D ²⁰ = 1.510.

For C10H19ClNO4PS (315.8) calculated:

38.0% C, 6.1% H, 11.2% Cl, 4.4% N,

9.8% P, 10.2% S;

nalszsxio *

38.4% N, 6.3% h, 11.5% Cl, 4.4% N,

9.7% P, 10.8% S.

The starting O- (1-chloroethoxycarbonyl-1-propen-2-yl) -N-n-propylphosphoramidochlorodothionate can be prepared as follows:

To a solution of 297.5 g (1 mol) of O- (1-chloro-1-ethoxycarbonyl-1-propen-2-yl) thiophosphorophosphorus dichloridate in 1 liter of toluene at 0 ° C is added a mixture of 59.1 g ( 1 mole of n-propylamine and 102 g (1 mole) of triethylamine were stirred at 0 ° C for 0.5 hour and then at 20 ° C for 1 hour, the precipitated triethylamine hydrochloride was filtered off, washed with water, dried over sodium sulfate. and distills.

O- (1-chloro-1-ethoxycarbonyl-1-propen-2-yl) thiophosphorodichloridate can be prepared as follows:

To a mixture of 169.4 g (1 mol) of thiophosphoryl chloride and 164.5 g (1 mol) of ethyl 2-chloroacetate were stirred at 10 ° C for 105 hours (105 g, 1.03 mol) of triethylamine, precipitating triethylamine hydrochloride. The reaction mixture is stirred for a further 0.5 hours at a temperature between -10 ° C and + 10 ° C and then for a further 0.25 hours at 30 ° C, 500 ml of chloroform are added thereto, the mixture is washed and dried. under a water pump vacuum at a bath temperature of 50 ° C. Furthermore, the compound obtained can be used either in the raw state or after distillation.

The compounds summarized in the following table are also prepared in an analogous manner to Example 1. These compounds correspond to the general formula I in which X represents a hydrogen atom. The ratio of cis-trans isomerism in the crotonic acid residue is the same as in the starting materials.

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139227

A process for the preparation of the novel thiophosphoric acid esters of the general formula I

SUBJECT OF THE INVENTION

Claims (3)

SUBJECT OF THE INVENTION in which R2NH R2, R3 and X are as defined above and Y is a halogen atom, such as chlorine or bromine, reacted with a compound of formula III wherein: O — C — C I v CH3 COOR3 (I) RiOM in which (III), R1 and R2 are the same or different alkyl groups having 1 to 4 carbon atoms, R 3 is C 1 -C 5 alkyl and X represents a hydrogen, chlorine or bromine atom, characterized in that the compound of formula (II) is present Y S \ Z P R 2 NH O-C = C I Z CH3 COOR3 (II) R1 is as defined above and M represents a hydrogen atom or an alkali metal, provided that when M in formula III is hydrogen, the reaction is carried out in the presence of an acid acceptor. 2. A process according to claim 1, wherein the reaction is carried out with an equivalent amount of a compound of formula (III) required to replace the halogen atom of Y. 3. A process according to claim 1 or 2, wherein the starting material of formula III, wherein M is hydrogen, is used in the presence of an equivalent amount of an acid acceptor. i / \ Severography, n. P., Plant 7, Most