SU522605A1 - Thiocyanate derivatives possessing fungicidic activity and their preparation method d - Google Patents

Description

The invention relates to new chemical compounds, more specifically to allyl thiocyanates of the formula

. -s Shayson

Olfttl

Oh oh oh

showed kltsim fungicidal activity, and the way they are received.

4-Thiocyanatosulfene-2 (I). and H- (thiocyanatomethyl) sulfenyne-3 (II) possess fungicidal activity. They can also be used as seed disinfectants for wheat against a hard head.

Compounds known are substituted 3-rhodanothiophenes of general formula II

“2

where R and R2 H alkyl, CN, halogen;

R, j - NHCOR,

obtained by treating thiophene derivatives, unsubstituted in Population 3, with the rhodium salt of an alkali metal and bromine in the medium of an organic solvent at 3-5 ° C, followed by isolation of the target product.

; Such compounds possess only pharmacological properties. In particular, 3-rhodanothiophenes of the formula III, where R;, - C C H, R - N 0 and K.-,

O is a drug

Artec with a narrow spectrum of action: it exhibits only antifungal action.

Nova derivatives of allyl thiocyanates of 5 formulas

(H2 & (11

&with

g, g

O 0

I o

in contrast to the known analogues, they exhibit the fungicidal activity of a wide spectrum of action, due to which they can be used as an accelerator for the growth of agricultural crops, and also as seed disinfectants for wheat seeds against a hard head.

According to the invention, novel compounds-allyl thiocyanates, namely 4-thiocyanatosulfol-2 and 3- (thiocyanatomethylene) sulfene-3, are described.

(H2 $ dM

Q

exhibiting fungicide activity, and a method for their preparation, consisting in that the salts of rhodium hydrochloric acid are reacted with sulfolene-2-yl-4-halides, sulphonates or 3- {halogeno (sulphonato) methylene sulpholones-3 in an inert polar gas the solvent at 50-80 ° C, followed by separation of the target product.

In order to obtain in this way the thiocyanates of the sulfene series jg, 3,4-dihaloesulfolanes or 3,4-disulfonate sulfonanes are introduced into the reaction with the salts of rhodium hydrocyanic acid.

Alkali metal rodanides or ammonium rhodium are used as salts of hydrocyanic acid.

When implementing the proposed method, it is advisable to use the following solvents: dimethylformamide, ethyl acetate, tetrahydrofuran, dioxane, acetone, alcohols, or a mixture of these solvents.

Derivatives of allyl thiocyanates of formulas I and II are relatively stable and isomerization reactions and are not converted into isothiocyanates, either under the conditions of preparation or in the presence of isomerization catalysts, such as, for example, sulfonic sulfides — white crystalline substances that are highly soluble in higher alcohols, dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetone, poorly soluble in lower alcohols and water.

The resulting compounds of formulas I and I1 are of interest as accelerators for the growth of agricultural crops and as seed disinfectants for wheat against a hard head.

Compound I has a pronounced fungicidal action, superior in activity to the standards — copper sulfate and figon, but somewhat inferior to Na pentachlorophenol. Compound I I in fungicidal activity approaches the standards and is characterized by selectivity of action. The most sensitive to the toxic effects of the drug 1I are Alternaria radlcina and Hemi nthospor i urn satirrem test organisms. Compound) I is also an effective seed dressing agent, at a dose of 2 kg / ton, not inferior in activity to the standards of TMTD and PCNB. It protects the seedlings from head smut, improves seed germination in field conditions and somewhat shortens the length of the internodes of straw.

Example 1. 4-Thiocyanatosulfene-2.

To 8.2 g (0.03 g mol) sulfole-2-yl-4-benzenesulfonate 60 ml of ethyl acetate was added 3 g (0.03 g-mol) of potassium rhodanide, and then boiled for 4 hours with stirring and the precipitated potassium benzenesulfonate is filtered off. The residue after distillation of ethyl acetate is crystallized from ethanol. 5 g (95%) of 4-thiocyanatosulfene-2 are obtained. 114115 ° C.

Found,%: N 7.89; 8.12; S 36.60; 36.90.

,,

Calculated,%: N 8.0; S 36.60.

In the IR spectra: Si 1130-1147, 1300 (S02), 2150 (NaCI), 2160 (LiCI) (SCH), 1610 (s).

Example 2. From 1.97 g (0.01 p. Mol) of 4-bromosulfolene 2, 1 g (0.01 g-mol) of potassium rhodanide in 25 ml of dimethylformamide (). After heating at 50 ° C for 1 h, as in Example 1, 1.1 g (90%) of 4-thiocyanatosulfene-2 with mp. 114-115 ° C (from ethanol).

Example 8 from 28 g (0.1 g-mol) of 3,4-dibromosulfolane, 20 g (0.2 g-mol) of potassium rhodanide in 200 ml of DMFA at 10 h. (from isopropyl alcohol), 12 g (70%) of 4-thiodianate sulfenene-2 are obtained with a melting point of 200 mg. 114115 ° C.

Example 4. 3- (Thiocyanatomethylene) -sulfene-3.

A mixture of 2.1 g (0.01 gmol) of 3-brommeo: ilensulfolene-3, 1 g (0.01 gmol of potassium rhodanide, 20 ml of dimethylformamide is heated with stirring for 15 minutes at 65-70 ° C. Then the reaction, the mixture is cooled, potassium bromide is filtered off, DMF is evaporated in vacuo, the residue is washed with water and recrystallization from ethanol gives 1.5 g (.0%) of 3- (thiocyanatomethylene) sulfolen-3 with a melting point of 141142 ° C.

Found%

C 37.97;

37.76; H 3.61; 3.70 N, 7.19; 7.41; S 33.70; 34.0.

C H-jN02S2.

Calculated,%: C 38.07; H 3.72; ML, 40; S 33.88.

|. In the IR spectra, cm 2150 (NaCI), 2165 (LiCI) (SCN) 1120, 1330 (SOn), .1640 ().

60 Resistance of the obtained compounds to isomerization.

A mixture of sulfolenil thiocyanate in acetonitrile and zinc chloride is refluxed for 60 hours. The starting sulfolothiocyanocyanate is obtained. The presence of isocyanate by IR spectroscopy and thin layer chromatography was not detected.

Fungicidal activity of sulfenyl thiocyanates.

The fungicidal activity of sulfolylthiocyanates is determined by the method of inhibition of mycelium growth on a solid (potato-dextrose) medium. A portion of the substance, dissolved in acetone, is added to the agar, mixed thoroughly, and the agar is poured into Petri dishes. After hardening, the agar is inoculated with pieces of mycelium (23 years old) of pure cultures of the Fungi and the cup is placed in a thermostat at 25-26 s. The procedure is repeated 4 times. Through

70 h measure the growth rate of GriCl and determine the toxicity of the preparations with respect to controls and standards (copper sulfate, 2,3-dichloro-1,4-naphthoquinone, sodium pentachlorophenol t). The results are presented in Table 1.

Compound II. Is tested as a seed dresser of wheat against a solid head. A portion of the seeds is treated with water-acetone solutions of substances, dried and sown on the bases of the Academy of Sciences of the Ukrainian SSR. New cultures, p. Glevakha. After months of centimeters, germination and length of plants are taken into account, and in the fall, crops are harvested and smut.

The results are presented in table 2.

Table

100

0.1

100

0.05

92

0.02

96

0.1

100

0.1

64

  0.05 0.2

88

OD

81

0.05

69 0.01

100

OD

lorfe100 sodium 0.05

0,0l

100

00

100

100

100 90 83

100 100

43

99,100

6

85

67

35

91

100 100

100

87 56 93

5 33

ABOUT

88

68

60

80

63

50

60

48

37

100

100

100

100

100

100

100

98

98

table 2

Claims (4)

Claim 1. Derivatives of allyl thiocyanates of the formula exhibiting fungicidal activity. 2. The method of producing compounds according to claim 1, characterized in that the corresponding salt of rhodanic acid is subjected to 'Interaction with sulfolen-2-yl-4-halogenide or sulfolen-2-yl-4 -sulfonate, or 3- [halogeno (sulfonato) methylene2-sulfylene-3 in 25 medium of an inert polar solvent. For example ethyl acetate, at 5080 ° C, followed by isolation of the target product. 3. The method according to claim 2, with so on and with the fact that as the salt • of rhodanic acid use alkali metal thiocyanates or ammonium thiocyanate. 4. The method of pop. 2, distinguishing with the fact that 3,4-dihalo sulfonates or 3,4-disulfonate-sulfolanes.