DE1942013C3 - Thiazolo (thiono) phosphor (phosphonic) acid esters, process for their preparation and compositions containing them - Google Patents

Description

in which R and R 'is C ₁ - to C ^ alkyl, R' is also Cr to C ₄ -alkoxy, R "is methyl, ethyl or phenyl and X is oxygen or sulfur.

2. Process for the preparation of the compounds according to claim 1, characterized in that (Thiono) phosphorus (phosphonic) acid ester halides are used in a manner known per se of the formula (H)

RO X

¹ - Ha!

with 2-Hydroxy-4-methyl-5-alkylmercapto- or 5-phenyl-mercaptothiazoles of the formula (III)

N - r - C Hi
HO--. _r . "—SR"

in the presence of acid acceptors or in the form of the corresponding salts of the thiazole derivatives converts, where Hai stands for a halogen atom.

3. Insecticidal, acaricidal and fungicidal agents, characterized by a content of thiazolo (thiono) phosphorus (phosphonic) acid esters according to claim 1 and customary carriers and diluents.

If O.O-diethylthionophosphoric acid ester chloride is used and 2- ^ 0 ^^ - 4-016 ^ 1-5-3 ^^ 6 ^ 10-thiazole as starting components, the reaction can be carried out by the following equation be reproduced:

HO

Siiurcacceptin "
HCI

^: cn,

SC, Il

CH ₁
SC ₂ Il,

In the formula of claim 1, R and R 'stand for straight-chain or branched alkyl radicals with 1 to 4 carbon atoms, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sea- or tert-butyl, also denotes R 'is a Ci- to Gralkoxy radical, e.g. B. methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sea- or tert-butoxy, while Hai preferably represents a chlorine atom

As examples of (THono) phosphorus (phosphonic) acid ester halides that can be used are mentioned in detail:

O, O-dimethyl-, 0,0-diethyl-, 0,0-diisopropyl-, 0,0-di-n-butyl, O, O-di-tert-butyl-, C-methyl-O-ethyl, O-methyl-O-isopropyl-, O-methyl-O-n-butyl- and

O-methyl-O-tert-butyl-phosphoric acid ester chloride
or bromide and the corresponding thiono analogs, also O-methyl-methane, O-ethyl-methane, O-iso-propyl-methane, O-ethyl-ethane, O-iso-propyl-ethane, 0 -Butyl-Ethane-. O-methyl-propane, O-ethyl-propane, O-ethyl-isopropane phosphonic acid ester chloride or bromide and the corresponding thiono compounds.

The acid ester halides (II) required as starting materials have already been described in the literature. the Thiazole derivatives (III), some of which are also known, can be prepared, for example, by adding 1-alkyl or phenylmercapto-i-chloroacetone form! (IV)

-15 O Cl
CHj-C-CH SR "

(IV)

in DT-AS 11 93 953 already methylthiadiazo (thiono) phosphoric acid derivatives, z. B. O ₁ O-Di-

ethyl-0- {3-methyl-1,2,4-thiadiazol (5) -yl] thionophosphorus and O-ethyl-O- [3-methyl-1,2,4-thiadiazol- (5) -yl] -ethanthionophosphonic acid ester described, which have a pesticidal, in particular insecticidal activity.

In contrast, the invention relates to the subject matter characterized in the claims.

Surprisingly, the thiazolo (thiono) phosphorus (phosphonic) acid esters according to the invention are distinguished by a considerably higher pesticidal, in particular insecticidal and acaricidal effect than the known methylthiadiazole (thiono) phosphoric acid / ester of analogous constitution and the same direction of action. They are particularly effective against sucking and biting insects and mites. You own at the same time fungicidal and bactericidal properties with only low phytotoxicity. The pesticidal effect continues fast and lasts longer.

with O-alkylthiocarbamylic acid esters of the structure iV)

RO - C --- NH ₁

implements.

The process for the preparation of the new thiazolo (thiono) phosphorus (phosphonic) acid esters of the formula (I) is generally carried out with the use of suitable solvents or diluents. When practically all inert organic solvents can be used. This includes especially aliphatic and aromatic, optionally chlorinated hydrocarbons, e.g. B. benzene, chlorobenzene, toluene, Xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, Ethers, such as diethyl and dibutyl ethers, dioxane, and ketones, e.g. B. acetone, methyl ethyl, Methyl isopropyl and methyl isobutyl ketone, as well as nitriles such as acetonitrile.

Furthermore, the bmsei / ung is left in the presence of Acid acceptors run off, but practically all common acid binders can be used. When Alkali carbonates and alcoholates, such as sodium and potassium carbonate, have proven particularly suitable, methylate or ethylate, also aliphatic, aromatic or heterocyclic amines, for example 1 >. I-amine, dimethylamine, dimethykiniline, dimethyl! ., / ylamin and pyridine.

Instead of working in the presence of acid accepients, it is just as possible to use salts first, preferably the Alkali or ammonium salts of 2-hydroxy-4-methyl-5-alkylmercapto- or -5-phenylmercaptotriiazole (III) in substance and this with the (thiono) phosphorus (phosphonic) acid ester halides (II) to implement.

The reaction temperature can be varied within a relatively wide range. In general, between 30 and 100, preferably at 60 to 70 ^° C., are used.

The reaction is generally carried out under normal pressure.

To carry out the process, one uses equimolar Ratios of the starting components in one of the abovementioned solvents for those specified Temperatures in the presence of an acid acceptor around. After stirring for several hours in the heat, it becomes the reaction mixture poured into water, added with a hydrocarbon, preferably benzene and worked up in a known manner.

Depending on their intended use, the new active ingredients can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These are in produced in a known manner.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient.

K Dl) NlIt UlIlUl

C ₂ H ₅ OS
P.

C, ll _s
i (, HO S

SC ₂ H ₅

N, CH,

S

Ul,

SC

(C-Ji ₅ O) ₂ P - ο-i ¹ . _s ! I

SCH,

⁽⁾ N- _r CH,

(C ₂ Ii ₅ O) ₂ I '-o-4 _s .l ^

SCH,

- \ ι, Ν — ι — CH,

P-O

C ₂ H ₅ O

SC ₂ H ₅

C ₂ H ₅ S

P-O-II

C ₂ H ₅ O SCH,

Physical ligcnsLhafU'ii llircchunüsinüex)

) i = 1.54X2

ii "= 1.5507

ην = 1.5379

irV = 1.5105

tv,: = 1.5903

nf = 1.5541

(C ₁ H ₅ OIjP-O

17.5 g (0.1 mol) of 2-hydroxy-4-methyl-5-ethylmercaptothiazole and 14 g of potassium carbonate are _stirred in 100 ml of SO acetonitrile together with 19 g of Ο, Ο-diethylthionophosphoric acid ester chloride for 3 hours at 60 to 70 ° C. Then the reaction mixture is poured into water, taken up with benzene, the benzene extract dried, the solvent removed under reduced pressure _5S removed and the residue distilled.

The yield is 26 g (80% of theory). The OO-diethyl-O - ^ - methyl-S-ethylmercapto-thiazol- (2) yl-] thionophosphoric acid ester has the refractive index η γ = 1.5308.

Calculated for C ₁₀ HI ₈ O ₃ NS ₃ P (molecular weight 327):

N 4.3%, S 29.4%, P 9.5%;
found:

N 4.3%, S 28.4%, P 10.06%.

The following connections are made in the same way:

nV = 1.5739

C ₂ H ₅ O

^ClHsO N ? N-TT-CH,

P-O-4

iv'o - 1.5522

C ₂ H ₅ O

The 2-hydroxy-4-methyl-5-alkylmercapto- or -5-phenylmercaptothiazoles can, for. B. can be produced as follows:

C ₂ H ₅ S

OH

153 g (1 mol) l-Äthylmercapto-i-chloroacetone and 92 g (lmole) O-Äthylthiocarbamyl-säureester hour are reacted at 90 to 100 ⁰ C. The mixture is then dissolved in sodium hydroxide solution, the product is precipitated with hydrochloric acid, filtered off and dried.

The yield is 60% of theory. The 2-hydroxy-4-methyl-5-ethylmercaptothiazole melts at 60 ° C. "

5

Calculated for GH ^ ONS ^ molar weights 175): CH ₁ ; ₍ N,

N 8.0%, S 36.6%; } _s ^IJ ''

found: _{(]) S} ' _{() 1} ,

N 7.82%, S 36.38%. ⁽

^(H - 'ji' f lp. 145 to 147 C

The following output / S

materials received: (<JUS OH

Claims (1)

Patent claims: 1. Thiazolon-Ohionojphosphoriphosphonji.äurcester of formula (I) R (J X 1 »(J SR "