PL150438B1

PL150438B1 - Method of obtaining novel non-substituted trialkyl- and triaryltin aminocarbodithiates

Info

Publication number: PL150438B1
Application number: PL26641087A
Authority: PL
Priority date: 1987-06-24
Filing date: 1987-06-24
Publication date: 1990-05-31
Also published as: PL266410A1

Description

The invention relates to a process for the preparation of new N-substituted organotin aminocarbodithates of the general formula shown in the figure, in which Y is an alkyl, cycloalkyl, alkylaryl or aryl group, N _R is a raetylamino, 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl group, N, N * -ethylenediamine or acylhydrazide, and n has a value of 1 or 2

N-substituted aminocarbodithiates of alkali metals, zinc, iron and manganese have a strong fungicidal effect, some of them are widely used in practice fungicides.These preparations are also ethosic in mixtures with trialkyltin chloridesl / Fennite A / in potato crops N-substituted aminocarbodithiates The organotin compounds are new and have not yet been described in the literature. The process according to the invention consists in reacting a trialkyl or triaryltin, cycloalkyl or alkylaryltin hydroxide or hexaalkyl or alkylaryltin oxide in an aqueous suspension, optionally with addition of methylene chloride, with an amine of by the general formula R, R *, R * N, in which R is a methyl group, R * and R are hydrogen or R * and R together form a piperidine, pyrrolidine or morpholino group or with ethylenediamine or with acylhydrazide and carbon disulfide at a temperature 5-40 ° C, preferably 15-30 ° C, under normal pressure. The amine is preferably used methylamine, ethylenediamine, pyrrolidine, piperidine, morpholine or acylhydrazide. The separated product is sufficiently pure and can be used for the preparation of a formulation without additional purification. The method according to the invention allows to obtain N-substituted organotin aminocarbodithates of high purity above 90% with high yield 64 - 85%, and the technological process is simple and uncomplicated The method according to the invention is explained in more detail in the working examples.

150 438

Example 1 To a suspension of 7.8 g of finely divided hexa (2-phenyl-2-methylpropyl) tin oxide in 50 ml of water, 1.14 g of carbon disulfide and 0.45 g of ethylenediamine were added in portions with vigorous stirring at room temperature. until yellowish and stirring was continued for another 4 hours. Then the yellowish precipitate was filtered off, washed with water and dried. 7.9 g of N, N'-ethylenebisdithiocarbamate-tri- /

2-phenyl-2-methylpropyl / tin, mp 80-85 ° C, 84.4% of theory. The pure product, after crystallization from acetone, melted at 85-87 ° C. The structure of the product was confirmed by elemental analysis and spectroscopic examinations. Elemental analysis:

calculated for the formula ^c g4 ^H Q4 ^S 4 ^N 2 ^Sn : C 61.7, H 6.7, N 2.3% Found: C 62.0, H 7.0, N 1.9%

Example II. The process was carried out in the same manner as described in Example 1, using 5 g of hexa (2-phenyl-2-methylpropyl) tin oxide in 50 ml of water, 0.7 g of carbon disulfide and 0.85 g of piperidine. The reaction was carried out at 20-25 ° C. The crude product was obtained with a melting point of 70-74 ° C in a theoretical yield of 79.7%. Pure tri (2-phenyl-2-methylpropyl) tin-1-piperidinecarboditate had a melting point of 74-76 ° C. The product structure was confirmed by elemental analysis and spectroscopic studies, Elemental analysis:

calculated for the formula ^C 36 ^H 4 g ^S 2 ^{NSnj C} 63.8, H 7.2, N 2.1% Found: C 63.9, H 7.3, N 2.0%

Example III. The process was carried out in the same manner as described in Example 1 using 7.3 g of triphenyltin hydroxide in 50 ml of water, 1.52 g of carbon disulfide and 0.6 g of ethylenediamine. The crude product was obtained, mp 112-117 ° C, with a yield of 64%. After crystallization from acetone, pure triphenyltin N, N * -ethylenebisdithiocarbamate was obtained, mp 117-119 ° C.

Elemental analysis:

calculated for the formula C Η NS Sn: C 52.8, H 3.9, N 3.1%

36 2 4 Found: C 53.1, H 3.9, N 3.1%

Example IV. 5 g of hexa (2-phenyl-2-methylpropyl) tin oxide was dissolved in 20 ml of methylene chloride by adding 20 ml of water and 0.35 g of pyrrolidine at 20 ° C. Then 0.76 g of carbon disulfide was added with vigorous stirring. After 4 hours, the organic layer was separated, washed with water, and methylene chloride was distilled off under reduced pressure, regenerating it almost quantitatively. 5.5 g of crude product are obtained with a melting point of 88-90 ° C, which is 82.9% of theory. After crystallization from acetone, pure tri (2-phenyl-2-methylpropyltin 1-pyrrolidinecarboditate) was obtained, mp 91-98 ° C.

Elemental analysis:

calculated for the formula C3 ₅ H ₄₇ S ₂ NSn: C 63.3, H 7.1, N 2.1% Found: C 63.5, H 7.2, N 2.0%

EXAMPLE 5 The process was carried out in the same manner as described in Example IV using 5.2 g of hexa (2-phenyl-2-methylpropyl) tin oxide in 20 ml of methylene chloride, 20 ml of water, 0.76 g of carbon disulfide and 1 , 6 g of phenoxyacetylhydrazide. · A crude product was obtained with a melting point of 105-110 ° C, yield 72.5%. After crystallization from methanol, pure N * - (phenoxyacetylhydrazine) tri (2-phenyl-2-methylpropyl) tin dithian was obtained, mp 110-112 ° C.

Elemental analysis:

calculated for the formula θ39 ^Η 48θ2 ^Ν 2 ^δ 2 ^δπ : C 61.7, H 6.3, N 3.7% found: C 61.7, H 6.8, N 3.5%

Example VI. To a mixture of 7.3 g of trifenylocynowego hydroxide, 3.3 g fenoksyacetylohydrazydu and 40 ml of water was added with vigorous stirring at ²⁵ C 1.5 g

150 438 carbon disulfide The mixture was stirred for 4 hours, during which a yellow precipitate formed, which was filtered off, washed with water and dried. 8 g of crude product were obtained with a melting point of 130-138 ° C (decomposition), which is 67.7% of theoretical · After recrystallization from methanol pure N * - (phenoxyacetylhydrazine / triphenyltin dithate) was obtained, mp 136-138 ° C.

Elemental analysis:

calculated for the formula CH ON S Sn:

Claims

The method for the preparation of new N-substituted organotin aminocarbodithates of the general formula shown in the figure, where Y is an alkyl, cycloalkyl, alkylaryl or aryl group, Np is a methylamino group, 1-pyrrolidinyl, 1-piparidinyl, 4-morpholinyl, N, N * -ethylenediamine or acylhydrazide, n is 1 or 2, characterized in that a trialkyl- or triaryltin, cycloalkyl- or alkylaryltin hydroxide or hexaalkyl- or alkylaryltin oxide in an aqueous suspension, optionally with addition of methylene chloride, is reacted with an amine of general formula R, R *, RN, where R is a methyl group, R * and R are hydrogen atoms or R * and R together form a pyrrolidine, piperidine or morpholino group or with ethylenediamine or with acyl hydrazide and carbon disulfide, at a temperature of 5 - 40 C, under normal pressure