DE1693197C - 0.0 Dialkyl S (or 0) (N alkox ymethyl) carbamoylmethyl thionophosphoric acid ester and process for their preparation - Google Patents

Description

R ¹ OS

VY-CH ₂ -CO-NH-CH ₂ • OH

R ¹ O.

etherified.

The compounds of the invention generally have better contact insecticidal properties than their counterparts unsubstituted N-methylol compounds. In addition, many of the new compounds are oils, making them easy to use as insecticides Agents can be processed, and a large number of them have good water solubility, which supports their systemic activity in the plants. Another benefit of the connections of the invention resides in that it is generally easy and in good yield from readily available starting materials can be produced.

For those compounds of the invention in which Y is an oxygen atom, during the Production or isomerization during storage.

The connections

O, O dimethyl-S- (N-methoxymethyl) -carbamoylmethyl-thionothiol-phosphoric acid ester and
CO-Dimethyl-S-fN-ethoxymethyO-carbamoylmethyl-thionothiol-phosphoric acid ester

aren't all good contact insecticides. but also have very systemic properties.

The connections

OO-diethyl-S-iN-methoxymethyO-carbamoylmethyl-thionothiol-phosphoric acid ester,
O, O-diethyI-S- (N-ethoxymethyl> carbamoylmethyl-thionothiol-phosphoric acid ester,
O, O-diethyl-O- (N-methoxymethyl) -carbamoylmethyl-thionophosphoric acid ester and
O, O-diethyI-O- (N-ethoxymethyl) -carbamoylmethyl-thionophosphoric acid ester

also have good contact insecticidal and systemic properties as well as lasting Effect. However, their toxicity is greater than that of the first two compounds.

The Ο, Ο-dimethyl-thionothiol-phosphoric acid ester according to the invention are not very stable and lose their biological activity when standing or when exposed to elevated temperatures.

Their stability can be improved by adding acid-binding agents to them.

The acid binding agent can be an inorganic compound, for example ammonia, or a organic compound, for example an epoxy

compound, or an organic base such as pyridine.

For example, while the agent itself is active in a few months ^{when stored in 15 ° C}

can lose, the activity remains if Ia one Alkanol is dissolved, all other things being equal received several months.

example 1

0,0-diethyl-S- (N-methoxymethyl) -carbamoylmethyl-thionothiolphosphoric acid ester,

(C ₂ H ₅ O) ₂ P (S) SCh ₂ CONHCH ₂ OCH ₃

a) A mixture of 22.4 g of Ο, Ο-diethyl potassium thionothiol phosphoric acid ester and 12.35 g of N-methylol-a-chloroacetamide in 150 ecm of methanol was refluxed for 2 hours. After cooling, the precipitated potassium chloride was filtered off. The solution obtained of the 0,0-diethyl-S- (N-oxymethyl) -carbamoyhnethyl-thionothiol-phosphoric acid ester was treated with 2 ecm of concentrated hydrochloric acid (36%), and the solution was set aside for 16 hours at room temperature. Then the mixture was neutralized with sodium bicarbonate and the solvent was removed under reduced pressure. Chloroform was added to the residue, the solid salts were filtered off, and the solvent was separated from the filtrate. A chlorine-free oil was obtained in an amount of 27.9 g. (The theory requires 28.7 g.) Ni? 1.5269. The acetone was then removed, leaving a yellow, chlorine-free oil measuring 13.9 g (theory requires 14.35 g). η S 1.5267.

Example 2

O, O - dimethyl - S - (N - raethoxymethyl) - carbamoylmethyl-thionothiol-phosphoric acid ester,

(CH ₃ O) ₂ P (S) SCH ₂ CONHCH ₂ OCh ₃

1560 g of O, O - dimethyl - hydrogen - thionothiolphosphoric acid ester and 738 g of N-methylol-α-chloroacetamide were dissolved in 1500 ecm of methanol. 318 g anhydrous sodium carbonate was added and the mixture was heated to 50 ° C for 3 hours The precipitated solid material was filtered off, and the filtrate was treated with 132 ecm of concentrated hydrochloric acid added, after which it was left to stand for 16 hours at room temperature. The mixture was made with sodium carbonate neutralized, freed from the solid material by filtration, and the filtrate was the solvent separated at 50 "C under reduced pressure, where 155Og Ο, Ο-dimethyl-S-N - methoxymethyl) - carbamoylmethyl - thionothiolphosphoric acid ester in the form of a yellow oil were obtained. (The theory requires 1550 g.) / 1? 1.5397.

C ₈ H ₁₈ NO ₄ PS ₂ :

Calculated ... N 4.88, P 10.80; found ... N 4.38. P 10.47.

b) 6.17 g of N-methylol-a-chloroacetamide were dissolved in 40 ecm of methanol and 2.5 ecm of concentrated hydrochloric acid were added to the solution. The solution was set aside for 16 hours at room temperature and then neutralized with sodium bicarbonate. Then the solvents were separated from the mixture. Acetone was added to the residue and the solid material was filtered off. 11.2 g of O, O-diethyl potassium thionothiol phosphoric acid ester were added to the filtrate. The mixture was left to stand at room temperature and the precipitated potassium chloride was filtered off. C ₆ H ₁₄ NO ₄ PS ₂ :

Calculated ... N 5.41, P 12.0; found ... N 5.26, P 12.30.

The following were produced in a corresponding manner:

OO-Dimethyl-S-iN-ethoxymethylJ-carbamoylmethyl-thionothiolphosphoric acid ester, (CH ₃ O) ₂ P (S) SCH ₂ CONHCH ₂ Oc ₂ H ₅

as yellow oil, n? 1.5353,
0.0 - Diethyl - O - (N - ethoxymethyl) - carbamoylmethyl-thionophosphoric acid ester * (C ₂ H ₅ O) ₂ P (S) OCH ₂ CONHCH ₂ Oc ₂ H ₅

as a pale yellow oil, nf 1.4858.

Claims (2)

I 693 claims: 1. O, O-dialkyl-S- [or. -O-XN-alkoxymethyl} -carbamoylmethyl-thiiono-phosphoric acid ester the general formula R ¹ OS P • Y • CH ₂ • CO • NH - CH ₂ • OR ² R ¹ O in der_ Y a sulfur or oxygen atom and R ¹ and R ^{2 represent} the methyl or ethyl group. 2. Process for the preparation of the compounds according to claim 1, characterized in that a thionophosphoric ester salt of the general formula is used in a manner known per se 20th R ¹ OS ll P-Y-M R ¹ O in which M is a hydrogen or alkali atom or the ammonium group, with a compound the general form! A · CH ₂ · CO · NH · CH ₂ · OR ² in which A is a chlorine, bromine or iodine atom, or a compound of the general formula R ¹ OS R ¹ O etherified. PY-CH ₂ • CO • NH • CH ₂ • OH 35 40 45 The present invention relates to O, O-dialkyl-S- [or. -O -] - (N-alkoxymethyl) -carbamoylmethylthionophosphoric acid ester of the general formula R ¹ OS P · Y · CH ₂ CO · NH · CH ₂ · OR ² /
R ¹ O in which Y represents a sulfur or oxygen atom and R ¹ and R ^{2 represent} the methyl or ethyl group, and a process for the preparation of these compounds which consists in using a thionophosphoric acid ester salt of the general formula in a manner known per se R ¹ OS PYM R ¹ O in which M is a hydrogen or alkali atom or the ammonium group, with a compound of general formula. A-CH ₂ -CO-NH-CH ₂ -OR ² in which A is a chlorine, bromine or iodine atom or a compound of the general formula