DE1136334B - Process for the production of thionothiol or thiolphosphonic and -phosphinic acid esters - Google Patents

Description

GERMAN

PATENT OFFICE

F 30719 IVb / 12 ο

REGISTRATION DATE: MARCH 9, 1960

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: SEPTEMBER 13, 1962

It has been found that thionothiol b2w. Thiolphosphonic and phosphinic acid esters of the general formula

R-P

SR "

be obtained if one thionophosphonic or phosphonic acid ester monochloride or phosphinic acid monochloride the general formula

P (S)

R '

R-P

with trithiocarbons
formula

Cl

Salts S

the general

Me-S —C-SR "

implements.
In the above formulas, R denotes an alkyl, process for preparation

of thionothiol or thiolphosphonic

and phosphinic acid esters

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen

Dr. Dr. H. c. Gerhard Schrader,

Wuppertal-Cronenberg has been named as the inventor

denote radical, while R ″ represents an alkyl, aralkyl or aryl radical and Me represents a metal atom stands.

Surprisingly, the process according to the invention does not result in the internal anhydrides Thionothiol or thiolphosphonic or -phosphinic acids and trithiocarbonic acid esters, but the Thionothiol or thiolphosphonic or thionophosphinic acid esters of the general formula given above. Let the following reaction equation

Alkenyl or aryl radical, R 'has the same meaning in the course of the process according to the invention R and can also be an alkoxy lauter:

O (S)
Il R '

R -P

Cl

MeS- C-SR "

O (S)
^{R /}
II / s — c—
H SR " R -P
\ Il
_ S _

O (S)

1 R '

II /

- »R - P + CS ₂

SR "

In the aforementioned formulas, the radicals R, R 'and R *' and Me have the meanings given above.

In the German patent 835 302, among other things, the implementation of phosphonic resp. Thiophosphonic acid ester chlorides with the alkali salts of monoalkyl esters of trithiocarbonic acid described to the corresponding (thio) -phosphonic acid ester-S-trithiocarbonates leads. Furthermore are from Magyar core. Folyöirat 1955, pp. 80 to 84, reported in Chemical Abstracts, Vol. 49, 1955, column 16 309 e, already phosphorus-containing organic compounds based on mixed anhydrides of diethylthiophosphoric acid and organic acids, e.g. B. trithiocarboxylic acids are known. the compounds mentioned are made by reacting 0,0-diethylthiophosphoric acid chloride with the Alkali salts of the corresponding sulfur-containing

209 640/343

Acids or from said phosphoric acid chloride and the free organic acid in the presence made from pyridine.

In contrast, in the case of the invention Process, as already stated above, does not select the internal anhydrides concerned Thionothiol or thiol-phosphonic or -phosphinic acids and trithiocarbonic acid esters, but it the esters of the above general formula are split off with carbon disulfide educated.

The compounds of the present invention, some of which are known, are pesticides, which can be used primarily in the field of plant protection.

example 1

CH ₃ S

\ ll

CH ₃

SC ₂ H ₅

Example 3

P SC ₂ H ₅

C ₂ H ₅ O

To a solution of 44 g (0.25 mol) of trithiocarbonic acid ethyl ester potassium salt 40 g of methyl thionophosphonic acid O-ethyl ester chloride are added to 100 ml of methyl ethyl ketone with stirring at 40 ° C to. The mixture is stirred for a further 1 hour at 40 ° C. and the reaction mixture is then worked as in the example 1 on. In this way 39 g of the new ester are obtained as a colorless, water-insoluble oil. Yield 60% of theory.

Calculated for moles 184 ... S 34.8%, P 16.80 / ₀ ; _έ0 found S 35.0 <> / ₀ , Ρ 16.0 <> / ₀ .

To a solution of 44 g (0.25 mol) of trithiocarbonic acid ethyl ester potassium salt: .

Il

C ₂ H ₅ S -C-SK

33 g of dimethyl thionophosphinic acid chloride are added to 100 ml of methyl ethyl ketone at 30 to 40 ° C. with stirring to. The mixture is allowed to stir for 1 hour at 40 ° C. and then poured into 300 ml Water. The separated oil is taken up in 200 ml of benzene and mixed with a 4% sodium carbonate solution washed neutral. The benzene solution is dried with sodium sulfate and evaporated then the solvent in vacuo. The residue obtained solidifies in crystalline form. When recrystallizing 14 g of the new ester are obtained from ligroin in the form of colorless crystals with a melting point of 86 bis 87 ° C. Yield 24% of theory.

Calculated for mole 154 ... S 41.5%, P 20.2%; found S 40.6%, P 20.7%.

Example 2
(CHj) ₂ C = CH O

P-SC ₂ H ₅

C ₂ H ₅ O

To a solution of 45 g (0.25 mol) of trithiocarbonic acid ethyl ester potassium salt 46g are added to 100 ml of methyl ethyl ketone at 40 ° C. with stirring Isobutylene phosphonic acid O-ethyl ester chloride too. The temperature is kept at 40 ° C. for a further hour and then works up the reaction mixture as in Example 1. In this way, 47 g of the obtained new ester as a colorless, water-insoluble oil. Yield 66% of theory.

Calculated for moles 208 ... S 15.4%, P 14.9%; found S 16.0 <y ₀ , P 14.00 / ₀ . .

45

■ SS

Claims (1)

PATENT CLAIM: Process for the preparation of thionothiol or thiolphosphonic and thionophosphinic acid esters, characterized in that thionophosphonic or phosphonic acid ester monochlorides and phosphinic acid monochlorides of the general formula 9®, R-P Cl in which R denotes an alkyl, alkenyl or aryl radical, R 'has the same meaning as R. and can also designate an alkoxy radical, with tri-thiocarbonic acid salts the general formula Me-S —C —SR " wherein Me represents a metal atom and R ″ represents an alkyl, aralkyl and aryl radical, to compounds the general formula R-P SR " converts, where R, R 'and R "have the same meaning as stated above. Considered publications: German Patent Specifications No. 835 302, 953 795; Magyar core. Folyoirat, 1955, pp. 80 to 84, reported in Chemical Abstracts, 49, 1955, column 309 e. © 209 640/343 9.62