DE1816093A1 - Thionophosphorus and thionophosphonic acid esters - Google Patents

Description

Dr. F. Zumsfein - Dr. E. Assmann

Dr. R. Koenigsberger Case 4/183 Dipl. Phys. R. Holzbauer

Patent attorneys

Dr. Ho / ne Mönchen 2, Bräuhaussira & e 4 / III

CH. BOBHRINGER SON, INGEIHEIM AM RHEIN

Thionophosphorus and thionophosphonic acid esters

The invention relates to thionophosphorus and thionophosphonic acid esters the formula

R ^ O

■ i ^u \ ^ ° (σι)

^Λ 2 - ^ ^ --- D-Ua ₉ Un ₉ -α-λ, ^ j .;

their use in pesticides and processes for their manufacture.

In the formula I and _{below, the substituents R 1} , R ₂ , R, and X have the following meanings:

R ₁ and R denote alkyl radicals with 1 to 3 carbon atoms, R ₂ denotes an alkyl or alkoxy radical with 1 to 3 carbon atoms and

X stands for an oxygen or sulfur atom or the SO group,

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The compounds of the formula I are obtained in accordance with customary methods Methods by reacting a compound of the formula

R ₁ OS

^X P ^ (ID,

R ₂ Q

wherein Q is chlorine or also bromine, with a phenol of the formula

(III)

in the form of a phenolate or in the presence of an acid-binding agent.

The reaction is carried out in a suitable organic solvent such as benzene, dioxane, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, or in water at temperatures of about 30 to 70 ⁰ C. The appropriate phenates can, for example, of alkali bases or from organic bases such as triethylamine, ethylpiperidine , Trimethylamine.

To purify the crude esters, they are taken up in a suitable organic solvent and the Solutions washed with dilute sodium hydroxide solution and water, dried and, if necessary, treated with activated charcoal and narrowed.

The new compounds remain as colorless to light yellow oils of sufficient purity. Some of them are new ester can be distilled in a high vacuum.

To prepare the phenols of the formula III, a compound of the formula is heated

Ü0S826 / 213Ö

- - - '> COPY

Cl - // ^ - S-CH ₂ CH ₂ -XR ₃ (IV)

with sodium hydroxide solution / methanol, preferably to about 170 ^° C., and isolates the phenol from the reaction mixture. Trichlorobenzene derivatives of the formula IT are accessible via the reaction of tetrachlorobenzenes corresponding substitution with the alkali salts of mercaptans of the formula HS-CH ₂ CH ₂ -XR; but they can also be prepared from a corresponding tetrachlorobenzene by first treating it with the sodium salt of Thioglycol to a compound of the formula

(Cl) ₂
Cl _ // "^ C- S-CH ₉ CH ₉ -OH (V)

C.

reacted and then synthesized therefrom by customary methods, the compounds of formula IV. Compounds of the formula III in which X is the group -SO- can be obtained, for example, by oxidation of the corresponding compounds in which X is -S-. The calculated amount of hydrogen peroxide in glacial acetic acid at 20 to 40 ^° C. is used as the oxidizing agent.

The new compounds can be used as active ingredients in pesticides be used. They have a strong insecticidal and acaricidal effect and also have an effect against powdery mildew.

For use, the compounds according to the invention are processed into the customary formulations, e.g. emulsions, suspensions, grit and dust.

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example 1

O.O-Dläthyl-O- (2.5-dic> ilor-4-methoxyethylthlo-phenyl) -thonophosphate

25.3 g of 2,5-dichloro-4-methoxyethylthiophenol are dissolved in 70 ml of tetrahydrofuran and treated with 14.0 g of potassium cartonate. The potassium salt of phenol is formed during this process. While stirring, slowly added dropwise 19 g of 0,0-Diäthylthionophosphorsäurechlorid at 50-6O ⁰ C and then for 3 hours in a water bath heated to reflux. The reaction solution is filtered and concentrated. The residue is taken up in methylene chloride and extracted with dilute sodium hydroxide solution. After the methylene chloride solution has been dried with sodium sulfate, it is filtered and the solvent is completely removed in vacuo.

Yield 40 g - 99% of theory

The substance is uniform according to thin-layer chromatography. Analysis: P calc .: 7.65 i »\ found : 7.60% S calc .: 15.8 $, found: 15.8 % Cl calc .: 17.52%, found : 17, 43 f>

Example 2

0 ₁ 0-Dläthyl-O- (2,5-dichloro-4-ethoxyethylroercaptophenyl) -

thionopho sphat

The compound is prepared according to Example 1 from 2,5-dichloro-4-ethoxyethyl mercaptophenol and 0,0-diethylthionophosphoric acid chloride.
Analysis: P calc .: 7.40%, found: 7.42% 3 calc .: 15.28 #, found: 15.35 $> Cl calc .: 16.95 #, found: 17.02 <$>

Example 3

0.0-diethyl-0- (2 ₁ 5-dichloro-4-methylmercaptoethylmercaptophenyl) ■ thionophosphate

The compound is prepared according to Example 1 from 2,5-dichloro-4-methylmercaptoethyle * U-mercaptophenol and 0,0-diethylthiono-

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phosphoric acid chloride produced:

Analysis: P calc. I 7.36 #, found: 7.40 $> S calc .: 22.8 ji _{f found} : 22.7 # Cl calc.,: 16.89 Ji, found: 17, 10 %

Example 4 Q, O-diethyl-Q- (2 ₁ 5 ~ diohlor-4-ine thylaer captoathylmercapt o-

phenyl) thionopho sphat

The compound is prepared according to Example 1 from 2,3-Dlchlor-4-methylmercaptoethylmercaptophenol and 0,0 ~ diethylthionophosphoric acid chloride manufactured.

Analysis: P "calc .: 7.36 ^ _{8 found} : 7.50 % S calc .: 22.8 Ji _{1 found} : 22.9 $ Cl calc .: 16.89 #, found s 16.71 f °

Example 5

O, OI) imethyl-O- (2 _f '5-dichloro ~ 4 ~ propyl mercaptoäthylmer ca pto- » phenyl) -thionopho3phat

The compound is prepared according to Example 1 from 2,3-dichloro-4-propylraercaptoethyl mercaptophenol and O, 0-dimethylthiono ~ phosphoric acid chloride produced.

Analysis: P calc .: 7 * 36%, found: 7.40 36 S calc .: 22.8 56, found: 22.7 $ Cl calc .: 16.89 96, found: 17.01 $

Example 6

.OyQ - Dipropyl-0- (2,5-dichloro-4-methylmercaptoethylmercapto phenyl) thionophosphate

The compound is prepared according to Example 1 from 2,5-dichloro-4-methylmereaptoäthylmercaptophenol and 0,0-dipropylthionophosphoric acid chloride manufactured.

Analyzes P over _s : 6.90 #., Gef »: 6.85 $> S ber.s 21.41 $, gef ·: 21.3O ^ Cl ber, s 15.82 jS, gef. % 15.85 %

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Example 7 O, Q-dimethyl-O- (2 ₁ S-dichloro ^ -propoxyäthylmercaptophenyl) -

thionophosphate

The compound is prepared according to Example 1 from 2,5-dichloro-4-propoxyethyl mercaptophenol and 0,0-dimethylthionophosphoric acid chloride.

Analysis: P calc .: 7.65 #, found: 7.71 #

S calc .: 15.82 #, found: 15.84 $

Oil cal .: 17.52 #, found: 17.58 #

Example 8

O-ethyl-O- (2, S-diohlor ^ -fflethylmercaptoäthylmerca-ptophenyl) -äthylthionophossphonat

The compound is prepared according to Example 1 from 2,5-dichloro-4-methylmercaptoäthyliaercaptophenol and O-ithyl-ethylthionophosphoric acid chloride manufactured. Analysis: P calc .: 7.65 #, found: 7.80 #

S calc .: 23.72 #, found. ι 23.64 %

Eq calc .: 17.53 %, found : 17.43%

Example 9

O-ethyl «-O- (2,5-dichloro-4-niethylmer-aptoäthylniercaptophenyl) -methylthionophosphonat

The compound is prepared according to Example 1 from 2,5-dichloro-4-methylmercaptoäthylniercaptophenol and O-ethyl-methylthiono- ' phosphoric acid chloride produced.

Analysis: P calc .: $ 8.94, found : 8.88 %

S calc .: 24.62 #, found: 24.60 $

Cl ber .: 18.17 f> _{$ found} : 18.04 ^

σ example 10

0-methyl-0-ethyI-0- (2,5-dlchlor-4-π ^ ethylIDercaptoäthylIDercapto oo phenyl) thionophosphate

^ The compound is prepared according to Example 1 from 2,5-dichloro ^ 4-iDethylnjercaptoäthylniercaptophenol and O-methyl-0-ethyl - »thionophosphoric acid chloride.

to. Analysis: P Der .: 7 _S 62 #, found : 7.73 ^

S ber, % 23 | 62 i, gef _t ? 23.58 96

■ "1 ber. J 17.49? 6 _{f found} : 1.7.45 *

Example 11 Q «O-Dimethyl-O- (.2,5-dichloro-4-methylsulfynylethyl-

sercaptophenyl) thionopho sphat

The compound is prepared according to Example 1 from 2,5-dichloro-4-methylsulfinylethyl mercaptophenol and O, O-dimethylthionophosphoric acid chloride manufactured.

Analysis; P calc .: 7.58 56, found σ 7.60 # S calc .: 23.51 #, found : 23.42 £ Cl ber.i 17.37 j6, found : 17.48 96

Example 12 O.O-diethyl-O ° - (2 «5-dichloro-4-» n3ethyl3Ulf inyläthylmer capto-

phenyl) thionopho sphat

The compound is prepared according to Example 1 from 2,5-dichloro-4-methylsulfinylethyl mercaptophenol and O, O-diethylthionophosphoric acid chloride manufactured.

Analysis: P calc .: 7.12 56, found: 7.03%

S calc .: 20.02%, found: 19.84%

Cl ber .: 17.25%, found: 17.30 %

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Claims (6)

Claims Il compounds of the formula R ₁ OS P.
R ₂ Ρ - </ ^ VS-CH ₂ CH ₂ -XR ₅ (I) in the R ₁ and R, denote alkyl radicals with 1 to 3 carbon atoms, R _{2 is} an alkyl or alkoxy radical having 1 to 3 carbon atoms and X is an oxygen or sulfur atom or an SO-G group designated. 2. 0,0-diethyl-0- (2,5-dichloro-r4-methoxyethyl mercaptophenyl) thionophosphate. 3. Pesticides, characterized by a Content of a compound of the formula I. 4. Process for the preparation of compounds of the formula I, characterized in that a compound of the formula R ₂ Q in which Q is bromine or preferably chlorine, with a phenol of the formula 0098 26/2 138 (Gl) - HO S-CHp CHp "~ Χ ~ · λ · 2 (III) in the form of a phenolate or in the presence of an acid-binding agent Means, preferably at elevated temperature, reacted. 5. Phenols of the formula / Cl) ₂
S-CH ₂ CH ₂ -XR ₅ (III) and their salts. 6. Process for the preparation of phenols of the formula III, characterized in that a compound of the formula _(Q1) Cl C. C. ^V 3 with sodium hydroxide / methanol in dsr heat vorzugisweise at about 17O ⁰ C, and reacting the phenol isolated from desi Reaktionsgeraisch.