DE1035153B - Process for the preparation of insecticidally active thiophosphoric acid esters - Google Patents

Description

GERMAN

kl. 12 ^ mm

INTEBNAT. KL. C 07 f

PATENT OFFICE

F20758IVb / 12q

REGISTRATION DATE: JULY 10, 1956

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL JULY 31, 1958

It is known that phenylthioalkyl ethers which are substituted in the p-position can be mixed with formaldehyde and hydrochloric acid easily into the corresponding 2-chloromethyl-phenylthioalkyl ethers can be transferred (see German patent specification 569 569).

It is also known that these thioethers react with hydrogen peroxide to form the corresponding sulfoxides or let it oxidize to the corresponding sulfons.

It has now been found that the 2-chloromethylphenylthioalkyl ethers with the salts of dialkyldithiophosphoric acids and with the salts of dialkylthiolphosphoric acids, in a manner known per se, in smooth reaction to form insecticidally active thiophosphoric acid esters implement the following general formula:

(O) ₁ -SR

SO)

CH ₉ -S ρ:

.OR ₁
"OR,

procedure

for the production of insecticidal thiophosphoric acid esters

in which R, R ₁ and R ₂ stand for alkyl radicals and X stands for an optionally substituted alkyl radical and ζ can have the values 0, 1 or 2.

The reaction can expediently be carried out at a somewhat elevated temperature in the presence of a diluent make. The reaction products can be worked up in a manner known per se.

The phosphoric acid esters obtained according to the invention are characterized by low toxicity against warm-blooded animals due to very good contact insecticidal and acaricidal effect Applicant:

Paint factories Bayer Aktiengesellschaft / Leverkusen-Bayerwerk ■:

Dr. August Dörken, Wuppertal-Sonnborn,

and Dr. Gerhard Schrader, Wuppertal-Cronenberg,

have been named as inventors

the end. Some of the compounds are also effective against the eggs of the red spider (ovicidal effect). '

The thiophosphoric acid esters of the formula I, II and III obtained according to the invention were compared with the thiophosphoric acid esters of the formulas IV, V and VI known from German patent specification 885 176. the better insecticidal effectiveness of the compounds according to the invention, as well as the reduced toxicity against Warm-blooded animals can be clearly seen from the following comparison:

According to the invention German patent 885 176 O SCH ₃ S.
Il (C ₂ H ₅ O) ₂ PS-CH ₂ - ^ - (C ₂ H ₅ O) ₂ P- S -ζ y IV / \ ι OCH ₃ V Oral toxicity rat
Aphids CH ₃ DL ₅₀ 10 mg / kg
0.01% 40%
without effect
without effect Spider mites DL ₅₀ 50 mg / kg
0.01% 100%
0.01% 100%
0.1% 100 V ₀ Ovicide effective at
Spider mites

809 579/489

3 According to the invention SCH ₃
I. - \ -f 4th S. Patent 885 176 10 mg / kg S.
Il A π A ₁ in German Ii
(C ₂ H ₅ O) ₂ P- 40% (C ₂ H ₆ O) ₂ PS-CH ₂ Y \ / S.
Il ς / f \ - ν
\ / / U
100%
without effect CH ₃ CH ₃ Il
(C ₂ H ₆ O) ₂ P- OC ₂ H ₆ 50 mg / kg 1000 mg / kg DL ₉₅ DL ₉₅ 100% 100% 0.01% 50 mg / kg Oral toxicity rat 0.01% 100% / U
100% DL ₉₆ 0.00001%
0.000001% 40%
100% Aphids 0.01% SO ₂ CH ₃
I. 0.01%
0.05% 100 o / _o
without effect S.
I! 0.1%
0.01% Spider mites Il
(C ₂ H ₆ O) ₂ PS-CH ₂ S- / ~ V-OC ₂ H ₈ VI DL ₉₆ 0.01% *** IU
0.000001% Oral toxicity rat Aphids Mosquito larvae

example 1

58 g of diethylthiolphosphoric acid ammonium are dissolved in 200 ecm of methyl ethyl ketone. Is added dropwise with stirring at 40 ⁰ C a solution of 58 g of 4-methyl-2-chloromethyl-thioanisole in 50 cc of methyl ethyl ketone. The reaction product is kept at 75 ° C. for 75 minutes with stirring. It is then cooled and the ammonium chloride formed is filtered off with suction. The solvent is removed by vacuum distillation. The residue is taken up in a little ether, washed with water and the ethereal solution is dried with sodium sulfate. 87 g of the new ester of the formula are obtained

O S-CH ₃

C ₂ H ₆ O _x left

medium by distillation. The residue obtained is taken up in 100 ecm of ether and washed with it little water through. After the ethereal solution has dried, the ether is evaporated in vacuo. It this leaves 85 g of the new ester of the formula

NS,

C ₂ H ₅ O.
C ₂ H ₅ O

-S-CH ₂ -, ^

CH _a

^ P-S-CH,

0.H ₁₁ O '

At a pressure of 0.01 mm, the ester changes over at a constant 144 ° C. Yield 91% of theory, based on the diethylthiolphosphoric acid ammonium used.

The ester showed a mean toxicity of 100 mg / kg in the rat per os. Spider mites are still in a Concentration of 0.01% 100% killed.

Example 2

42 g of dried and sieved potassium carbonate are suspended in 180 ecm of methyl ethyl ketone. Is added to this slurry at 50 ⁰ C 47 g Diäthyldithiophosphorsäure. Is then added dropwise with stirring at 60 ⁰ C. 48 g of 4-methyl-2-chloromethyl-thioanisole (dissolved in 70 cc of methyl ethyl ketone) thereto. After a reaction time of about 4 hours at 65 to 7O ⁰ C is cooled to room temperature and filtered off with suction the precipitated potassium chloride. The solution is removed from the filtrate. The ester is distilled at 0.01 mm pressure at 127 to 13O ⁰ C. There are obtained 76 g, corresponding to 90.5% of theory, based on the Diäthyldithiophosphorsäure. 0.01% solutions kill spider mites 100%.

Example 3

42 g of dried and sieved potassium carbonate are suspended in 140 ecm of methyl ethyl ketone. 54 g of diisopropyldithiophosphoric acid are added at 50 ^{° C. to this.} A solution of 48 g of 4-methyl-2-chloromethylthioanisole in 70 ecm of methyl ethyl ketone is then added dropwise in about 20 minutes. The reaction product is kept at 65 ° C. for a further 3 hours and then worked up as described in Example 2. 87.5 g of the new ester of the formula are obtained
S S-CH ₃

(CH ₃ ) ₂ -CHO _X κ

; p-s-cn

(CHg) ₂ -CHO '

CHj

• corresponding to a yield of 96% of theory, based on the diisopropyldithiophosphoric acid used. Even in a high vacuum, the new ester is not without it Decomposition can be distilled.

The ester shows an average toxicity of 500 to 1000 mg / kg in the rat per os. 0.01% solutions kill aphids 100%.

Example 4

40 g of diethylthiolphosphoric ammonium are dissolved in 150 ecm of methyl ethyl ketone. To this solution there one dissolves 44 g of the sulfone of the following constitution at 30 ° C:

SO ₂ • CH ₃
^, -CH ₂ -Cl

CH ₃

(prepared by oxidation of 4-methyl-2-chlormethylthioanisols in glacial acetic acid with hydrogen peroxide, mp. 84-85 ⁰ C) in 100 cc of methyl ethyl ketone. The reaction product is heated to 60 ° C. for about 3 hours with stirring and then worked up in the usual way. 57 g of the new ester of the formula are obtained

/ PS-CH ₂ -

C ₂ H ₅ O

CH ₃

■ corresponding to a yield of 81%, based on the used ammonium salt of diethylthiol phosphoric acid. After a short time the crude product crystallizes. Mp. 63 ° C.

The new ester showed a mean toxicity of 100 mg / kg in the rat per os. Spider mites are affected by the Ester in 0.1% concentration killed to 100%.

Example 5

34g dried and sieved potassium carbonate are suspended in 120 ecm methyl ethyl ketone. At 20 ⁰ C. 37.6 g Diäthyldithiophosphorsäure instilled. Is then added with continued stirring at 50 ⁰ C a solution of 44 g of the following sulphonic:

CH ₂ -Cl

usual way. 73 g of the new ester are obtained formula

CH ₃

dissolved in 70 ecm methyl ethyl ketone, too. One holds the Re _ä H ₅ O

CH,

The ester crystallized in colorless needles, which show, after recrystallization from acetone have a melting point of 18O ⁰ C. Yield 76% of theory, based on the diethyldithiophosphoric acid used.

Average oral toxicity in rats: 1000 mg / kg. Mosquito larvae are still in a concentration of 0.0001% killed to 100%.

Example 6

SOCH ₃

C ₂ H ₅ O.

P-S-CH,

CHO
^{2 5}

₃₅

44 g of diethylthionothiolphosphoric acid ammonium are dissolved in 175 ecm of methyl ethyl ketone. To this solution is added dropwise in 10 minutes at 30 to 35 ⁰ C, a resolution of 41 g of SuIfoxydes the following constitution:

SOCH ₃

-CH ₂ Cl

CH ₃

(produced by the oxidation of 2-chloromethyl-4-methyl-thioanisole in glacial acetic acid with hydrogen peroxide; Mp. 98 ° C) in 125 ecm of methyl ethyl ketone. The reaction mixture is kept at a temperature of 50 to 55 ° C for 4 hours. After cooling, the ammonium chloride formed is suctioned off and the solvent is removed by distillation. The residue crystallizes on cooling and can be obtained from a little benzene-petroleum ether mixture be recrystallized. 70 g of the new ester are obtained in the form of white crystals with a melting point of 76 ° to 77 ° C. The new compound is insoluble in water.

55

Example 7

C ₂ H ₅ O

SOCH

60 CH ₃

To a solution of 45 g ammonium diäthylthiolphosphorsaurem in 175 cc of methyl ethyl ketone is added dropwise with stirring and cooling at 30 ⁰ C, a solution of 45 g of Sulfoxydes described in Example 6 in 125 cc

d kiih h

p action mixture 5 hours at 6O ⁰ C and then works in 70 methyl ethyl ketone. The reaction mixture is still stirred

4 hours at 60 ° C. After suctioning off ammonium salt the filtrate is freed from the solvent by distillation. The remaining viscous oil crystallizes after standing for several days. From a benzene-petroleum ether mixture recrystallized, 64 g of the new ester with a melting point of 56 ° C. are obtained. The new ester is light in water soluble.

Claims (1)

PATENT CLAIM: Process for the preparation of insecticidally active thiophosphoric acid esters of the general formula (O), - S - R s (O) Λ "/ ' Y-CH ₈ . S. PC " Il ^ OR ₁ OR, in which R, R ₁ and R ₂ stand for alkyl radicals, X stands for an optionally substituted alkyl radical and ζ can have the values 0.1 or 2, characterized in that compounds of the formula (O) ₁₅ -SR ^{/ X} -CH ₀ Cl in which R, X and ζ have the meaning given above, is reacted in a manner known per se with the salts of dialkyldithiophosphoric acids or with the salts of dialkylthiolphosphoric acids. Considered publications:
German patent specifications No. 830 509, 885 176. I 809 579/489 7.58