CS215463B1 - New phosphoryl+l tiophosphoryl+p hydrazano+l substituted malein+p acid and method of preparation thereof - Google Patents

Description

The present invention provides novel phosphoryl (thiophosphoryl) hydrazono (substituted maleic) acids as well as a process for their preparation. Said compounds may be used as fungicides.

Reactions of thiophosphorylhydrazines are known from the literature. new with aldehydes and ketones to form tiofosforylhydrazónov Any of the formula I, / ^ a / ₂ L

NH - N

'0?

R ³ and R ⁴ are halogen, in particular chlorine, ethylthio, or form together with a melainimido group

wherein R ^{1 is} alkyl, R ² alkyl, R ³ alkyl, cycloalkyl (USP 2,965,667).

We have now found new phosphoryl (thiophosphoryl) hydrazono (substituted maleic) acids of formula II,

X is oxygen or sulfur.

At the same time, a process for the preparation of compounds of formula II by reacting phosphoryl, thiophosphorylhydrazines of formula V,

C0 "

NH in which R ¹ , R ² and X are as defined above, with substituted maleic anhydride of formula VI,

In which R ¹ and R ² represent the same or different C 1 -C 4 alkyl, or together with the oxygen and phosphorus form a heterocyclic ring of formula III

CH-, 'X

CH,

CH

CH 3, wherein R ³ and R ⁴ are as previously defined, in an organic diluent such as benzene, toluene, xylene, heptane, cyclohexane, ethyl alcohol and the like at 80 to 120 ° C.

The following examples illustrate but do not limit the scope of the invention.

Example 1

O, O-Diethylthiophosphorylhydrazono-3,4-dichloromaleic acid

To 0.1 mole of dichloromaleic anhydride in 120 ml of benzene was added 0.1 mole of O, O-diethylthiophosphoryl hydrazine with stirring. The reaction mixture was heated to reflux and azeotroped with benzene

1.8 ml reaction water. After cooling, the precipitated product was collected by filtration to give 30.6 g of a white crystalline solid, m.p. M.p. = 82-83 ° C.

Analysis for

C ₈ H _n Cl ₂ N ₂ O ₄ PS Off: 9.31% P 9.62% S 21.31% Cl, (mh = 333.10) Find: 9.13% P 10.01% S 21.07% Cl.

The structure of the compound was confirmed by IR spectroscopy.

IR in chloroform:

(NN): 3395 cm ^-1 (C = O): 1804 cm ^-1 (C = O): 1760 cm ^-1 (P = S): 665 cm ^-1 (PN): 1026 cm ^-1

The following compounds were prepared according to the procedure of Example 1:

O-ethyl-O-isopropylthiophosphorylhydrazono-3,4-dichloromaleic acid

mp = 40-42 ° C Analysis for

C ₉ H ₁₃ Cl ₂ N ₂ O ₄ PS Off: 8.07% N 8.93% P 20.45% Cl

9.23% S (mh = 347.13) Found: 8.22% N 9.03% P 20.79% l Cl ¹

9.38% N

O, O-diethylphosphorylhydrazono-3,4-dichloromaleic acid

tt = 130-132 ° C Analysis for ΰ ₈ Η _η α ₂ Ν ₂ Ο ₅ Ρ Off: 8.89% N 9.84%

P 22.56% Cl (MW = 315.04) Found: 8.84% N 9.80%

P 22.37% Cl

5,5-Dimethyl-2-thiono 1,3,2-dioxaphosphorinanhydrazono-3,4-dichlormelaic acid

mp = 129-131 ° C;

I

Analysis for

C 8 H 10 Cl 2 N 3 O 2 S Calc .: 8.92% P 9.27%

S 20.54% Cl (MW = 345.57) Found: 8.90% P 9.36%

S 20.41% Cl

O, O-diethylthiophosphorylhydrazono-3,6-dithio-3,4,5,6-tetrahydrophthalic acid

mp = 154-156 ° C Analysis for

C ₁₀ H ₁₅ N ₂ O ₄ PS ₃ Off: 8.75% P 7.91%

N 27.12% S (MW = 354.38) Found: 9.03% P 7.92%

N, 27.24%

Tabuíka 1 *

A compound of the invention Dose in g / 100 kg % efficiency O, O-diethylthiophosphorylhydrazono-3,4-dichloromaleic acid 10 100 O-ethyl-O-isopropylthiophosphorylhydrazono-3,4-dichloromaleic acid 10 100 O, O-diethylphosphorylhydrazono-3,4-dichloromaleic acid 10 90 5,5-Dimethyl-2-thiono-1,3,2-dioxaphosphorinanhydrazono-3,4-dichloro-maleic acid 10 52 O, O-diethylthiophosphorylhydrazono-3,6-dithia-3,4,5,6-tetrahydrophthalic acid 10 67 methylenrodanide - standard 10 100

SUBJECT

Claims (2)

The following examples illustrate but do not limit the invention. EXAMPLE 1 0,0-Diethylthiophosphorylhydrazono-3,4-dichloroaminoic acid 0.1 mol of O, O-diethylthiophosphoryl hydrazine was added to 0.1 mol of dichloromaleic anhydride in 120 ml of benzene with stirring. The reaction mixture was heated to reflux and azeotroped with benzene by 1.8 mL of reaction water. After cooling, the precipitated product was collected by filtration to give 30.6 g of a white crystalline solid, m.p. = 82-83 ° C. Analysis for C 8 H 11 Cl 2 N 2 O 4 PS Off: 9.31% P 9.62% S 21.31% Cl, (MW = 333.10) Found: 9.13% P 10.01% S 21.07% Cl. The structure of the compound was confirmed by IR spectroscopy. IR in chloroform: (NN): 3395 cm < -1 >: (C = O): 1804 cm < -1 > (C = O): 1760 cm < -1 > (P = S): 665 cm < -1 > (PN): 1026 cm < -1 > in Example 1, the following compounds were prepared: O-ethyl-O-isopropylthiophosphoryl hydrazono-3,4-dichloromethaleic acid tt = 40-42 ° CAnalysis for C9H13C12N2O4PS Off: 8.07% N 8.93% P 20.45% Cl 9.23% S (mh = 347.13) Observe: 8.22% N 9.03% P20.79% ClCl 9.38% S, O, O-Diethylphosphorylhydrazono-3,4-dichloromethylic acid tt = 130-132 ° CAnalysis for 215463 ΰ8Ηηα2Ν2Ο5Ρ Off: 8.89% N 9.84% P 22.56% Cl (mh = 315.04) Find: 8.84% N 9.80% P 22.37 % CI 5,5-dimethyl-2-thiono 1,3,2-dioxaphosphorinanhydrazono-3,4-dichloromethylanic acid tt = 129-131 ° C Analysis for C 8 H 11 Cl 2 N 2 O 2 S: Calc .: 8.92% P 9.27% S 20.54% Cl (mh = 345.57) Found: 8.90% P 9, 36% S 20.41% Cl O, O-diethylthiophosphorylhydrazono-3,6-dithio-3,4,5,6-tetrahydrophthalic acid tt = 154-156 ° CAnalysis for C10H15N2O4PS3 Off: 8.75% P 7.91% N 27.12% S (mh = 354.38) Find: 9.03% P 7.92% N 27.24% TABLE 1 * Compound of the Invention Dosage g / 100 kg% efficacy 0,0-diethylthiophosphorylhydrazo-3,4-dichloromaleic acid 10 100 O-ethyl-O-isopropylthiophosphorylhydrazono-3,4-dichloroamycinic acid 10 100 0,0-diethylphosphorylhydrazono - 3,4-dichloromaleic acid 10 90 5,5 -dimethyl-2-thiono-1,3,2-dioxaphosphorinanhydrazono - 3,4-dichloromaleic acid 10 52 0,0-Diethylthiophosphorylhydrazo -no-3,6-dithia-3,4,5,6-tetrahydro-drophthalic acid 10 67 methylenrodanid - standard 10 100 OBJECT OF THE INVENTION 1. New phosphoryl (thiophosphoryl / hydrazono / substituted maleic) acids of the general formula II, CH CH CH - CH-- R 3 and R 4 are halogen, especially chloro, ethylthio, or together with a maleimido group they form a ring of formula IV. wherein R 1 and R 2 are the same or different alkyl of 1 to 4 carbon atoms, or together with the oxygen and phosphorus form a heterocyclic ring of Formula III, CO 3 X is oxygen or sulfur. 2. A method of preparing a yellowing according to claim 1, characterized in that it reacts with phosphoryl, thiophosphoryl hydrazines of formula V, wherein R 1, R 2, and X are as defined above, with substituted maleic anhydride of formula VI, 215463 wherein R 3 and R 4 are as defined above, in an organic diluent environment such as benzene, toluene, xylene, heptane, cyclohexane, ethanol, 80 to 120 ° C.