DE2263816C3 - 01/08/72 Japan 4853-72 O.S.S.-Allyldithiophosphorsäuretriester, process for their preparation and their use - Google Patents

Description

(R ₁ O) ₂ PSR + MSH

R-S O

P {■ M + R ₁ SH

/ \\
R ₁ -OS

R ₂ -SO

/ \
R ₁ -OS

(IV)

with a halide of the general formula V

R - shark

(V)

45

converts, where M is an alkali metal cation and Hai is a halogen atom.

3. Use of the compounds according to claim 1 as nematocides.

(R ₁ O) ₂ PSR ₂ + MSH

R.2 ο

R ₁ -O

M + R ₁ SH

(IV

Known nematocides are z. B. D - D, d. H. a mixture of dichloropropene and dichloropropane, EDB, d. i.e., ethylene dibromide, DBCP; H. 1,2-dibromo-3-chloropropane, and chloropicrine. These nematocides diffuse through the soil as a gas that kills the nematodes. To complete the nematocidal However, the soil usually has to be covered with water or sealed in effect. the The expression "cover with water or seal" means that the soil containing the gas z. B. with covered with a plastic film and the space between the floor and the plastic film with Water is filled. A transplanting or an off-Specific examples of these compounds are that Potassium salt of O-ethyl-S-n-propylthionothiophosphoric acid diester, the sodium salt of O-ethyl-S-n-propylthionothiophosphoric acid diester, the potassium salt of O-methyl-S-n-propylthionothiophosphoric acid diester, the sodium salt of O-methyl-S-n-propylthionothiophosphoric acid diester, the potassium salt of O-ethyl-S-n-butylthionothiophosphoric acid diester and the sodium salt of O-Ethy! - S-n-butylthionothiophosphoric acid diester.

The process according to the invention is generally carried out in the presence of an inert solvent, usually at temperatures from room temperature to about 100 ° C or the boiling point of the one used Solvent carried out.

The solvents used are preferably polar solvents, such as water, alcohols, e.g. B. Methanol or ethanol, or ketones such as acetone and methyl ethyl ketone. The response time depends on

the other reaction conditions. Usually it is about 1 to 4 hours. In some cases amines or iodides can be added to the reaction mixture can be added to speed up the reaction to ~ accelerate and increase the yield. This Separation of the O ^ S-Allyldithiophosphorsüuretri-

Esters of the general formula I from the reaction mixture can be prepared by methods known per se be performed.

Examples of the OiLS-Aiiyidithiophosphorsäuretriester of the general formula I are summarized in the table below.

Connect
application no. Structural formula C ₂ H ₅ O CH ₃ O CH ₃ O O
P - S. -CH ₂ Br
C = CH ₂ Refraction'odcv 1.546S 1 nC ₃ HS
\ n-C, H-S nC, HS
\ nC ₄ H, S C ₂ H ₅ O CH., 0 \ O nC \ HS
\ n-CH-S
\ C ₂ H ₅ O P - S. -CH ₂ CH = CHCI 1.5299 ■> \ el 1 η Γ C ₂ H ₅ O O Cl nC, HS
\
\ Ii
P - S. -CH ₂ -C = CH, 1.5215 \ η '/ 0
P - S. —Cu _: Cl
-C = CH; 1.5227 4th η γ O P - S. -CH ₂ -CH = CHCl 1.5325 5 nf O Br η S. -CH, -C = CH ₂ 1.5482 6th η γ ' O
Ij P - S. -CH ₂ -CH = CH ₂ 1.5120 7th e i s d i e B e i s ρ i B.

A solution of 25.1 g of the potassium salt of O-ethyl According to Example 1, 25.1 g of the potassium salt of

S-n-propylthionothiophosphoric acid diester in 100ml O-ethyl-S-n-propylthionothiophosphoric acid diester

Ethanol is mixed with 20.0 g of 1,2-dibromo-2-propene with 11.1g of 1,3-dichloro-2-propene in 100 ml of ethanol

sets, and the mixture is reacted for 2 hours with reverse. 22.1 g of O-ethyl-S-n-propylfluss are Hs cooked and stirred. The ethanol is then 6o S- (3-chloro-2-propenyl) -dithiophosphoric acid triester

distilled off under reduced pressure and the (compound no. 2) obtained as a yellow oil, n £

250 ml of benzene are added to the residue. The obtained = 1.5299. Solution is with 5% aqueous sodium carbonate

solution and then wipe with water. Then example 3
the benzene is distilled off under reduced pressure

lates. There remain 28.8 g of O-ethyl-S-n-propyl According to Example 1, 25.1 g of the potassium salt of

S- (2-bromo-2-propenyl) -dithiophosphoric acid triester O-ethyl-S-n-propylthionothiophosphoric acid diester

(Compound No. 1) as a light yellow oil. n? = 1.5409. with 11.1g 1.2-dichloro-2-propene in 100 ml ethanol

implemented. 22.4 g of O-ethyl-Sn-propyl-S- (2-chloro-2-propenyl) -dithiophosphoric acid triester (compound no. 3) are obtained as a yellow oil, ηψ = 1.5287.

Examples 4 to 7

In the manner outlined above, the following. " Connections made:

Q-Methyl-S-n-propyl-S- (2-chloro-2-propenyI) -dithioophosphoric acid triester (Compound No. 4);

η? - = '1.5227,

O-methyl-Sn-propyl-S-ß-chloro-1-propcnyl) -dithiophosphoric acid triester (compound no. 5); n'i = 1.5325,

O-methyl-S-n-propyl-S- (2-bromo-2-propenyl) -dithiophosphoric acid triester (Compound No. 6); «;" = 1.5482, O-ethyl-S-n-butyl-S- (2-propenyl) -dithiophosphoric acid triester (Connection no. 7): / i | ' = 1.5120.

Most O ^ S-allyl dithiophosphoric acid triesters of the general formula I are liquids and can therefore be used as such or together with customary liquid or solid carriers or in some cases also used in gaseous form will. The compounds can also be used as emulsifiable concentrates, wettable powders, oil sprays, Dust. Anoint. Granules. Aerosols or fumigants can be used. The production these preparations are made according to methods known per se, if necessary with the addition of auxiliaries. The compounds can also be used together with other nematocides, insecticides, herbicides. Fungicides, seed disinfectants. Mix fertilizers or soil disinfectants! and can be used.

Claims (2)

Patent claims: 1. O.S.S - Allykiithiophosphorsäuretriester der general formula I. R-S 0 ! l P —S —R, (D IO R ₁ -O in which R _{1 is} methyl or ethyl, R η-butyl and R _{2 is} allyl or R is n-propyl and R _{2 is} an allyl substituted in the 2- or 3-position by chlorine or bromine. 2. Process for the preparation of the compounds according to claim 1, characterized in that an alkali metal salt of an O, S-thionothiophosphoric acid diester is used in a manner known per se of the general formula II R —S R ₁ -O (H) with a halide of the general formula III R ₂ -HaI (III) or an alkali metal salt of an O, S-thionothiophosphoric acid diester of the general formula IV sasi during the time during which the gas remains in the soil is not possible because the plants or the Seeds are damaged. It is therefore often necessary to let the soil rest for a long time after this soil treatment or a so-called Carry out gas removal treatment in which the gas is expelled from the ground. This MaIJ took are uneconomical. The use of chloropicrin also has the disadvantage that it is essential its high toxicity causes environmental problems. The other nematocides mentioned above have the Disadvantage that the cost per unit area is relatively high. The object of the invention is to provide new O, S, S-dithiophosphoric acid triesters to create a high nematocidal effect, but not phytotoxic ^ Have an effect and are practically non-toxic to warm-blooded animals. This object is achieved by the invention solved. The invention thus relates to the subject matter characterized in the claims. The alkali metal salts of the O.S-Thionothiophosphorsäurediester of the alicemeinen used according to the process Formulas II and IV can be prepared according to the following reaction scheme: