CS199226B2 - Process for preparing new esteramides of thiophosphoric acid - Google Patents

Description

The present invention relates to a process for the preparation of novel thiophosphoric acid amidesters of the general formula I

R10 S

P X / \ /

Rz NH 0 — C = C (I),

I \

CH3 COOR3 in which

R1 and R2 are the same or different alkyl groups having from 1 to 4 carbon atoms,

R 3 is C 1 -C 5 alkyl and

X represents a hydrogen, chlorine or bromine atom having insecticidal, acaricidal and nematicidal properties.

The compounds of the formula I can be prepared according to the invention by: the compound of formula II

Y S

CH3 COOR3 in which

R 1, R 3 and X are as defined above and

Y is a halogen atom, such as chlorine or bromine, reacted with an amine of formula III

R 2 NH 2 (III), wherein R 2 is as defined above, in the presence of an acid acceptor.

In the process according to the invention, to the compound of the formula II in a reaction-inert solvent, for example in an aromatic hydrocarbon such as toluene, xylene and the like, in a halogenated hydrocarbon such as chlorobenzene or chloroform, or in an ether such as of dioxane, added within 0.5 to 2 hours at a temperature of from -20 ° C to + 50 ° C, preferably at a temperature of from -10 ° C to 0 ° C, preferably an equivalent amount (required to replace the halogen atom of Y) of the compound of formula III, preferably with an equivalent amount of an acid acceptor, such as triethylamine, trimethylamine, dimethylaniline, diethylaniline or sodium carbonate. The reaction mixture is stirred at room temperature for about 10 to 20 hours and then worked up in the usual manner.

Compounds of formula (II), used as starting materials in the

By the process of the invention, it is possible to prepare the compounds of formula IV Y s \ Z P X Z \ Z Y 0 — c = c 1 \ CH3 COOR3 (IV),

in which K3, X and Y are as defined above, in an inert solvent under reaction conditions, for example an aromatic hydrocarbon such as chlorobenzene, chloroform, dioxane and the like, are reacted with an excess amount at a temperature of from -20 to +50 ° C. relative to the amount required to exchange one halogen atom) of a compound of formula V * RtOH (V), wherein R 1 is as defined above. Compounds of formula (IV) required as starting materials for the preparation of compounds of formula (II) can be prepared according to Swiss Patent Specification No. 507,990 and DOS No. 1,935,630 by reaction of a phosphorus thiohalide such as PSCI3 with an acetic acid ester of formula VI.

T and b for 1k and 1 of the compound

CH 3 COCHX-COOR 3 (VI), wherein R 3 and X are as defined above, in the presence of 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 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 according to the invention exhibit at the same time only a slight warm-blood toxicity.

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

Toxicity LD50 mg / kg (male white rat) of oral dermal of Formula I of the invention

Ri R2 R3 1) CH3 C2H5 I-C3H7 122 2000 2) CH3 I-C3H7 I-C3H7 90 1290 3) CH3 I-C3H7 C2H5 69 800 4) ’CH3 Known ** 11-C3H7 I-C3H7 108 1250 ' 5) Mevinphos 0 (CH 3 O) 2 POO-C (CH 3) = CHC-OCH 3 3—7 3—90 6) Azodrin O (CH3O) 2POOC (CH3) = CHCNHCH3 21 354 (rabbit) 7) ENT 27625. O OCH3 íll = CHCNCH3 (CH3O) 2POOC (CH3) 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, peanut, hops, lettuce, rim Indian culture plant], pear, peas, paprika, sugar beet, tomato, tobacco, young stone fruit plants, potatoes, rice, pumpkin] has been shown to be fully compatible with the compounds of the invention without any signs of plant damage due to phytotoxicity.

The novel compounds can therefore be used as a pest control agent in living quarters, cellars and paved rooms, 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 such as 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 alkylene 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.

Spraying or dusting compositions may contain conventional inert carriers such as talc, diatomaceous earth, bentonite, pumice or other additives such as cellulose derivatives and the like, as well as conventional wetting agents and adhesives 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) Mixing 25 parts by weight of the compound of the formula I with 25 parts by weight of isooctylphenyl-decylglycol ether and 50 parts by weight of xylene gives a clear solution which is easily emulsifiable in water. The concentrate obtained is diluted with water to the desired concentration;

b) 25 pbw of a compound of formula I are mixed with 30 pbw of isooctylphenyloctaglycol ether and 45 pbw 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.

He did

O- (1-isopropoxycarbonyl-1-propyn-2-yl) -O-ethyl-N-n-propylphosphorothioamidate

C2H5O S \ II

P = OC = CHCOOCH (CH3) 2 / I-C3H7NH CH3

A solution of 286.7 g (1 mol) of cis-O-ethyl-O- (1-isoproxycarbonyl-1-propen-2-yl) thionophosphorochloridate of the formula

C1 (C2H5O) P (S) OC (CH3) = CHCOOCH (CH3) 2 in 1 liter toluene was added to a mixture of 59.1 g (1 mol) propylamine and 101.2 g [1] at 20 ° C over 2 hours. mol) of triethylamine. The reaction mixture was stirred at 20 ° C for 36 hours, then filtered to remove triethylamine hydrochloride, the filtrate was washed with water, dried, the solvent was evaporated and the product distilled in vacuo.

O- [l-isopropoxycarbonyl-l-propen-2-yl) -O-ethyl-Nn-propylfosforothioamidát boils at a pressure of 5.10 ^'3 torr at 87-89 ° C and consists almost exclusively of the cis-form (as in the rest of crotonic acid) ;

η ₀ 2θ = 1.489

For C12H24NO4PS (309.4) calculated:

H, 7.8; N, 4.5; P, 10.0%

10.4% S;

found:

H, 7.8; N, 4.8; P, 9.9%.

10.6% S.

The starting O-ethyl-O- (1-isopropoxycarbonyl-1-propen-2-yl) thiophosphorochloridate can be prepared as follows:

To 276 g of ethanol is added 277.1 g of cis-O- (1-isopropoxycarbonyl-1199226 at -5 ° C).

-propen-2-yl) thiophosphorodichloridate, the temperature is allowed to rise to 10-12 ° C, the reaction mixture is maintained at this temperature for 0.5 hours, then diluted with 500 ml of toluene and stirred vigorously at -10 to 10 ° C. - 5 ° C neutralized with 200 ml of 20% aqueous sodium hydroxide solution. The resulting mixture is then poured into 200 ml of ice-water, the organic phase is separated, washed thoroughly with sodium bicarbonate solution and then with water, dried over magnesium sulphate, filtered and evaporated at 40 ° C in vacuo. The product obtained can be purified by distillation; However, the crude product may also be used to further prepare the compound of formula (I).

O- (1-isopropoxycarbonyl-1-propen-2-yl) thiophosphorodichloridate was obtained as follows.

To a mixture of 169.4 g (1 mol) of thiophosphoryl chloride and 144.2 g (1 mol) of isopropyl acetate is added, with stirring at 10 ° C, for 0.5 hour 105 g (1.03 mol) of triethylamine, triethylamine hydrochloride precipitates. .

The reaction mixture was stirred at between -10 and +10 ° C for 0.5 hour, then at 30 ° C for 0.15 hour, 500 ml of chloroform were added thereto, the mixture was washed, and after drying the solvent was distilled off under water pump vacuum. at a bath temperature of 50 ° C. The obtained compound can be further processed either as a crude product or after distillation.

The compounds of general formula (I) are summarized in the following tables in an analogous manner to that described in Example 1, the cis-trans isomer ratio in the crotonic acid residue being the same as in the starting materials:

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Claims (1)

A process for the preparation of the novel thiophosphoric acid esteramides of the formula I R10 S \ Z P X Z \ Z R 2 NH-C = C (1), I \ CH3 COOR3 in which. 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 YNÁLEZU Y s \ z P X Z \ Z R 10 O — C = C (II), I \ CHs COOR3 in which R1 and R3 are as defined above and Y is a halogen atom, such as chlorine or bromine, reacted with an amine of formula III R 2 NH 2 (III), wherein R 2 is as defined above in the presence of an acid acceptor.