DE1302763B - Asymmetrical thiol or thionothiol phosphoric acid ester, process for their preparation and use - Google Patents

Description

OR,

in which R _{1 is} methyl or ethyl, R _{2 is} isopropyl, sea, tert-butyl or cyclohexyl and X is oxygen or sulfur

Z Process for the production of νοηΉπ @ 1- or, IM-onothiolphosphorsäureesteni according to claim 1, characterized in that one. in itself known Way uusyinmetric O.OjDiaJkyl resp. O -alkyl · O-cycloalkyl'thiol- or -thionothiolphosphoric acids the general formula

X OR ₁

II /

H-S -P

OR ₂

in the form of their salts or in the presence of acid binders with N-halomethylbenzazimides.

3. Use of the thiol or thionothiol phosphoric acid ester according to claim 1 as active ingredients for pest control.

The invention relates to asymmetrical thiol or thionothiol phosphoric acid esters of the general formula

and a method for their manufacture and use.

In the above formula, R _{1 represents} methyl or ethyl; R ₂ stands for isopropyl-, sea-, tert-butyl or cyclohexyl; X stands for oxygen or sulfur.

It has been found that compounds of the general formula given above are obtained if unsymmetrical O _s O-dialkyl or O-alkyl-O-cycloalkyl-thiol or thionothiol phosphoric acids of the general formula are used in a manner known per se

X OR ₁

II /

H. .. e ^ _-1 η

OR ₂

in the hair dryer of your sake or in the counterwatt of acidic agents with N-haloeamethyl-benzazimiden um-setat.

The reaction is generally carried out in the presence of inert organic solvents. When

and nitriles, such as acetone, Methyläthyh Iviethyliso ^ opyl- und Methjdisot'Utvlketon, as well as Aceto- and iPföpioBitril, further aromansJie Kohlwf5sefstofTe, ■ for example benzene, toluene »xylene, in question. It is jfedoeh just as well possible «in watery or watery · alcoholic medium, e.g. a mixture of equal parts by volume of methanol and water to work.

Furthermore, it has proven to be expedient to allow the reaction to proceed at a slightly to moderately elevated temperature (30 to 10O ⁰ C, preferably 40 to 70 ⁰ C) and also to allow the reaction mixture to proceed for a longer time after combining the starting components (1 to 3 hours or overnight), possibly with heating to the specified temperatures. In this case, the products are obtained in a particularly pure form and in excellent yields.

The unsymmetrical O, O-dialkyl- or O-alkyl-0-cycloalkylthio-phosphoric acids to be used as starting materials can according to the information from G. Schrader, »The development of new insecticides Phosphorsäureester ", 3rd edition, Verlag Chemie, 1963, p. 112, or the USA patent 2983 644 can be prepared as follows: A mixture consisting of 2 moles of a straight chain is stirred and a branched aliphatic or a cycloaliphatic !! Alcohol at room or slightly elevated temperature with 1 mole of phosphorus pentasulfide. That over the course of 5 to 10 hours resulting mixture of the corresponding asymmetrical thiophosphoric acid and its two symmetrical ones Homologs are then obtained by fractional washing out of the water-soluble components or leaching out the more acidic component with a deficit of alkali separately. The salts of the asymmetrical ones, which are easily accessible in this way even on a large scale 0.0 · Dialkyl or O - alkyl - O - cycloalkylthiof phosphoric acids - preferred are the alkali and Ammonium salts use - are for further use

Implementation pure enough.

The N-halo-methyl-benzazimide to be used as the second starting component, in particular the corresponding N ^ chlorine compounds have already been described in the literature (cf. for example

the German patent office 927 £ 70).

After the reaction mixture has been worked up in the usual way, the products initially mostly fall in the form of colorless ones to light yellow oil; , but the

Cool or solidify in crystalline form after standing for a while. The crystals obtained in this way can be used in Usually by washing with water and then drying in the air or by recrystallization Easily further purified from the common solvents or solvent mixtures will.

The thiol or thionthiol phosphoric acid esters according to the present invention are distinguished by excellent pesticidal, especially insecticidal and acaricidal properties. These show the 0-methyl-O-branched-alkyl compounds and under the-

sen again the O-methyl-O-isopropyl derivatives Maximum effect.

Compared to those known from German Patent 927 270, which are built analogously and are top-quality products commercially available symmetrical Ο, Ο-dialkyl-thiophosphoric acid esters of N-methylbenzazimide the new products have a far superior effectiveness against spider mites and caterpillars. This completely surprising technically valuable superiority of the compounds according to the invention is evident from the comparison test results compiled in the following table:

Ver
binding
No. ■ constitution O
Il // \ C.
V CS OCH ₃
/ \ II /
N-CH ₂ -SP ^
IN OCH ₃
N Γ j N-CH ₂ -SP
N OC ₃ H ₇ ISO
\ // Insecticides and akarici ^ e application
against active substance concentration in% 0.01
0.004 effect
Mortification
the pests A _{f /} 0CH,
N-Cl ₂ -SP
N OC ₃ H ₇ ISO
\ // (known from German patent specification
927 270) "V \ 7
N I. "V \ 7
N O
Il (Invention example 6) Spider mites
(resisteni) 100,
40 (according to the invention example 1) CO OCH ₃ O
Il O
Il 0.01
0.004 Il
GO OC ₃ H ₇ ISO
/ \ II /
Γ N-CH ₂ -SP
IN OC ₃ H ₇ ISo II N ■ Spider mites
(resistant) 0
0 (known from German patent specification
9272701 0.01
0.001
0.00016 III Spider mites
(normally sensitive) 100
100
80 0.01
0.001 ' »■ Spider mites
(normally sensitive) 30th
0

continuation

Net *
binding

No.

constitution

Insecticidal and acaricidal application
against active ingredient concentration in%

effect

Mortification

the pests

in %

Il

VI

O OCH ₃

\ II /

N-CH ₂ -S- P

N 0- ( H.

(according to example 7)
O

O OCH ₃

\ II /

N-CH ₂ -SP

N OCH ₃

(known from German patent specification
927 270)

Caterpillars

Spider mites
Caterpillars

0.01

95

0.001

0.00016

0.01

50

20th

Due to their excellent pesticidal properties, the thiol and thionothiol phosphoric acid esters are found according to the present invention as a pesticide, especially in crop protection Use.

example 1
CO S OCH ₃

\ II /

N-CH ₂ -SP

N OC ₃ H ₇ y

40

45

56 g (0.27 mol) of O-methyl-O-isopropylthionothiolphosphoric acid ammonium (melting point 165 °) are added to a solution of 48.5 g (0.25 mol) of N-chloromethylbenzazimide (melting point 125 ° C.) in 150 ecm of acetone C with decomposition) and the mixture is then stirred for a further 2 hours at 45 to 50 ^° C. or overnight at room temperature. The ammonium chloride which has separated out is then filtered off with suction and the solvent is distilled off from the filtrate in vacuo. The remaining oil is taken up in benzene, the benzene solution is washed first with water and then once with sodium hydrogen carbonate solution. After drying the organic phase over sodium sulfate and distilling off the solvent, the O-methyl-O-isopropyl-S- (3,4-dihydro-4-oxo-l, 2,3-benzotfiazin-3-yl-methyl) - Thionothiölphosphorsääurester obtained as a pale yellow, viscous oil 6s, which slowly crystallizes. The yield is 71 g (82.4% of theory). After recrystallization from an ether-petroleum ether mixture (1: 1), the product precipitates in form of colorless needles, melting at 68 ⁰ C to..

Analysis (molecular weight of 345.4):

Calculated ... N 12.17, S 18.53, P 8.97%;
found .... N 12.26, S 18.59, P 9.07%.

The mean toxicity (DL ₅₀ ) of the compound in rats per os is 5 mg per kg animal.

Example 2

CO S OCH ₃

/ V \ II /

N - CH ₂ - S - P

v \

OC ₃ H ₇ J

A solution of 114.5 g (0.55 mol) of O-methyl-O-isopropylthionothiolphosphoric acid Sodium in 360 ecm of water and 360 ecm of methanol is combined stirred with 97.5 g (0.5 mol) of N-chloromethylbenzazimide for 2 hours at 50 to 60 ° C. After short An oil was created in time. During the implementation, about 5 ecm 2n sodium bicarbonate " alkali in the reaction mixture to maintain a pH of 7 to 7.5. When the mixture cools and rapid stirring the oil solidifies in a spherical shape. The crystal mass is vacuumed off and washed with water and air dry the crystals. The yield is 132 g (76.6% of theory). The one on this O-methyl-O-isopropyl-S- (3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-yl-methyl) -thionothiolphosphoric acid ester obtained in a manner has a melting point of 65 ° C.

Example 3

CO

S OCH ₃

N-CH ₂ -SP

N. OC ₄ H ₉ SeC.

111 g (0.5 mol) of O-methyl-0-sec-butyl-thionothiolphosphoric acid sodium are dissolved in 400 ecm acetonitrile. 94 g (0.5 mol) of N-chloromethylbenzazimide are added to this solution with stirring, the mixture is then stirred for 3 hours at 60 to 70 ^° C. and then cooled to room temperature. The reaction mixture is then poured into 400 ecm of ice water, the precipitated oil is taken up in 400 ecm of benzene, the benzene solution is washed several times with 50 ecm of water each time, the organic phase is dried over sodium sulfate and finally the solvent is evaporated off in vacuo. The remaining residue is heated under a pressure of 0.5 Torr V for ₂ hours to a bath temperature of 70 to 80 ^° C. In this way, 138 g (77% of theory) of the O-methyl-O-sec.-butyl- S- (3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-yl-methyl) -thionothiolphosphoric acid ester was obtained in the form of a viscous, water-insoluble die.

Analysis (molecular weight of 359):

Calculated ... P8.7, S 17.8, N 11.7%;
found .... P 9.1, S 18.2, N 10.8%.

The mean toxicity (DL ₅₀ ) of the compound in rats is 5 mg per os per kg of animal.

Example 4

CO S OCH ₃

/ V \ II /

N - CH ₂ - S - P

\ S

O- <H

124 g (0.5 mol) of sodium O-methyl-O-cyclohexylthionothiolphosphate are dissolved in 400 ecm of acetonitrile, 94 g of N-chloromethylbenzazimide are added to this solution with stirring, the reaction mixture is then stirred for 3 hours at 60 to 70 ° C. and then operated as described in Example 3. There are as residue 108 g (56% of theory) of O-methyl-O-Glyclohe3C3i-S- (3,4-daiydro-4-oxo-1,23-benzotriazin-S-yl-metliyO-tnionotiiiolphosphorsäuresäuresafer = j « Ffsrn sfass Titki> sea. tsasserealdsHü & es Ölcs preserved After a short standing, the compound solidifies in crystalline form and then has a melting point of WC

Analysis (molecular weight of 38S):

Calculated ... P 8,1, S I6Ä N

N 10.4%.

The product has a mean toxicity (DL ₅₀ ) of 5 mg per kg of animal in the rat per os.

Example5
CO O OCH ₃

/ V \ II /

N-CH ₂ -SP

N OC ₃ H ₇ y

54 g (0.25 mol) of N-bromomethylbenzazimide are added to a solution of 53 g (0.25 mol) of O-methyl-0-isopropyl-thiolphosphoric acid potassium in 250 ecm of acetone, while stirring, and the mixture is then heated for a further 1 Hour to 50 ⁰ C, it then cools down to room temperature and the reaction mixture is poured into 500 ecm of ice water. The precipitated oil is taken up in 300 ecm of ether, the ethereal solution is neutralized with a 3% sodium bicarbonate solution, then dried over sodium sulfate and finally the solvent is evaporated in vacuo. The oily residue that remains is heated for a short time under a pressure of 1 torr at a bath temperature of 50 ^° C. and in this way 60 g (73% of theory) of O-methyl-O-isopropyl-S- (3,4- dihydro-4-oxo-1,2,3-benzotriazin-3-yl-methyl) -thiolphosphoric acid ester as a water-insoluble, yellow oil.

Analysis (molecular weight of 329):

Calculated ... N 12.76, S9.74, P9.41%;
found .... N 12.33, S 9.9, P 9.29%.

Example 6

CO O OCH ₃

/ V \ II /.

N - CH ₂ - S - P

I \ / -.

NO - <. H

V \ f

82 g (0.3 mol) of O-methyl-O-cyclohexyl-thiolphosphoric ammonium are dissolved in 200 ecm Aceso ton. To this solution 72 is added g (03 mol) of N-bromomethyl-benzajdmid - dissolved in 200 cc of acetone - the mixture is heated, with stirring, then for 1 hour at 40 to 50 ⁰ C, then cooled to room temperature, and operates it as described in Example 6 described on. 82 g (74% of the ^ Thrie) of the 0-M ^ yi-0-cyciohexyi-s- (3,4> döiydrol ^ brii3lihIJbilhί

säureesters m obtained form a water-insoluble yellow oil.

Analysis (molecular weight of 369):

Calculated ... N 113, S8.68, P8.39%;
geftiaden .... N! ©, 82, S 8.8?, P 8.37%.

Claims (1)

: j ■■ ■: /. Patent claims: L Itosyinmetniiche TMoI- bp. ühionothiolphosphorsäureester the general formula N-CH ₁ -SP X OR ₁ II /