RU2404978C2 - Potassium or hydrazinium salts of 4-dinitromethyl-1,2,3-triazoles, having herbicidal activity - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention describes novel potassium or hydrazinium salts of 4-dinitromethyl-1,2,3-triazoles of general formulae V-VIII:

V, VI

VII, VIII, where Kat⁺ =K⁺ (V,VII), NH₂NH₃ ⁺ (VI;VIII).

EFFECT: higher herbicidal activity.

1 cl, 2 tbl, 4 ex

Description

The invention relates to the field of production of organic substances and can be used in the production of herbicides and other biologically active substances.

Known herbicides [application RU 2004110236/04, A01N 47/38, application RU 2005104088/04, C07D 249/14, application RU 2007103518/04, C07D 487/04] containing in their structure a 1,2,4-triazole ring, associated with arylsulfonylimine or sulfonylimine moieties. Patented compounds in combination with other components improve the tolerance of herbicides by cultivated plants.

Closest to the claimed herbicides are herbicides [application RU 2004127655/04, C07D 403/04, application RU 2004127663/04, C07D 403/04], which are antidotes to the phytotoxic effect of the herbicide 2,4-dichlorophenoxyacetic acid on germinated sunflower seeds. These herbicides are 1,2,3-triazoles linked to the 1,3,5-triazine ring. The disadvantage of these herbicides is the multistage nature of the technological operations when they are received, and with their individual application lower biological activity is achieved.

The objective of this study is to develop a method for producing new herbicides from cheap and affordable starting components without the use of complex technological operations. For this, the use of potassium or hydrazinium salts of 4-acydinitromethyl-1,2,3-triazoles of the general formula V-VIII is proposed:

where Kat ⁺ = K ⁺ (V, VII), NH ₂ NH ₃ ⁺ (VI, VIII).

The method for producing potassium V, VII or hydrazinium VI, VIII salts is based on the nucleophilic substitution reaction of a nitro or ethoxycarbonyl group in N-methylated substituted 4-dinitromethyl-1,2,3-triazoles I-IV with a potassium or hydrazinium group in the presence of alcohol solutions of potassium hydroxide or hydrazine hydrate with a yield of up to 87%.

I, III R = NO ₂ , II, IV R = CO ₂ Et

The initial N-methylated 4-trinitromethyl-1,2,3-triazoles I, III or N-methylated ethyl-1,2,3-triazol-4-yl dinitroacetates II, IV were obtained by treatment with an excess of diazomethane, respectively, of trinitroacetonitrile or ethyldinitroacetonitrile according to the procedure [ D.V. Manuel Structure and chemistry of 4-trinitromethyl-1,2,3-triazoles. Diss ... cand. Chem. sciences. St. Petersburg, 1991, 100 pp.]. The output, decomposition temperature, data of electronic spectra of the obtained salts V-VIII are shown in table 1.

Table 1.
Formulas, yields, decomposition temperatures and electronic spectra of potassium V, VII, hydrazinium VI, VIII salts of 4-acydinitromethyl-1,2,3-triazoles Connection No Compound formula Exit, % T. decomp. ° C (solvent for crystallization) Electronic spectrum ethanol, λ _max. , nm, (Ig ε) V

78 198 (ethanol) 232 (3.76) 365 (3.93) VI

80 142 (methanol) 232 (3.77) 365 (3.94) VII

80 182 (ethanol) 232 (3.73) 365 (3.97) VIII

87 152 (methanol) 232 (3.87) 365 (4.04)

The technical result obtained allows us to synthesize with high yield potassium or hydrazinium salts of 4-acydinitromethyl-1,2,3-triazoles, and thereby substances with herbicidal activity. Thus, the set of essential features set forth in the claims, allows to achieve the desired result.

Examples of the proposed method for producing potassium or hydrazinium salts of 4-acydinitromethyl-1,2,3-triazoles V-VIII

Example 1

Potassium salt of 2-methyl-4-acydinitromethyl-1,2,3-triazole (compound V). To a solution of 0.9 g (0.004 mol) of 2-methyl-4-trinitromethyl-1,2,3-triazole (I) in 10 ml of ethanol is added dropwise at 20 ° C. with stirring a saturated alcoholic solution of potassium hydroxide until the formation of yellow the precipitate of salt V. The precipitate is filtered off and recrystallized from ethanol to obtain 0.66 g (78%) of the target compound. Potassium salt (V) was obtained by counter synthesis from 0.7 g (0.003 mol) of ethyl 2-methyl-1,2,3-triazol-4-yl dinitroacetate (II) and potassium hydroxide alcohol solution, yield 0.44 g (73 %).

Found,%: N 30.48. C ₄ H ₄ KN ₅ O ₄ .

Calculated,%: N 31.11.

Example 2

2-methyl-4-acydinitromethyl-1,2,3-triazole hydrazinium salt (compound VI). To a solution of 0.9 g (0.004 mol) of 2-methyl-4-trinitromethyl-1,2,3-triazole (I) in 10 ml of ethanol was added dropwise at 20 ° C. with stirring a 50% alcohol solution of hydrazine hydrate to halting the formation of a yellow precipitate of salt VI. The precipitate was filtered off and recrystallized from methanol to obtain 0.7 g (80%) of the target compound. Hydrazinium salt (VI) was obtained by counter synthesis from 0.7 g (0.003 mol) of ethyl 2-methyl-1,2,3-triazol-4-yl dinitroacetate (II) and a 50% alcohol solution of hydrazine hydrate, yield 0, 45 g (75%).

Found,%: N 45.09. C ₄ H ₉ N ₇ O ₄ .

Calculated,%: N 44.74.

Example 3

Potassium salt of 1-methyl-4-acydinitromethyl-1,2,3-triazole (compound VII). Prepared analogously to compound (V) from 0.9 g (0.004 mol) of 1-methyl-4-trinitromethyl-1,2,3-triazole (III) and an alcoholic solution of potassium hydroxide.

The recrystallization solvent was ethanol, yield 0.7 g (80%). Potassium salt (VII) was obtained by counter synthesis from 0.7 g (0.003 mol) of ethyl 1-methyl-1,2,3-triazol-4-yl dinitroacetate (IV) and potassium hydroxide alcohol solution, yield 0.46 g (77 %).

Found,%: N 30.59. C ₄ H ₄ KN ₅ O ₄ .

Calculated,%: N 31.11.

Example 4

Hydrazinium salt of 1-methyl-4-acydinitromethyl-1,2,3-triazole (compound VIII). Prepared analogously to compound (VI) from 0.9 g (0.004 mol) of 1-methyl-4-trinitromethyl-1,2,3-triazole (III) and a 50% alcohol solution of hydrazine hydrate. The recrystallization solvent was methanol, yield 0.76 g (87%). The hydrazinium salt (VIII) was obtained by counter synthesis from 0.7 g (0.003 mol) of ethyl 1-methyl-1,2,3-triazol-4-yl dinitroacetate (IV) and a 50% alcohol solution of hydrazine hydrate, yield 0, 48 g (80%).

Found,%: N 44.18. C ₄ H ₉ N ₇ O ₄ .

Calculated,%: N 44.74.

The herbicidal activity of the claimed compounds is ensured by the presence of the 1,2,3-triazole ring, which is an antagonist of the imidazole ring in the triazole analogues of adenine and guanine [Boyer J. Heterocyclic compounds. Ed. R. Elderfield. M., Mir, 1965, v. 7, 295 pp.]. It was revealed that the presence of a common conjugation system of a 1,2,3-triazole ring with a double bond, nitro, carbonyl or carboxyl groups provides a higher herbicidal activity [Vereshchagin LI, Tikhonova LG, Maksikova AV, Gavrilov L.D., Gireyev G.A. Synthesis of acyl and vinyl substituted 1,2,3-triazoles. Zhurn. organ, chemistry. 1979, vol. 15, issue 3, pp. 612-618].

A test of the biological effect of the claimed substances was carried out in the laboratory of mass chemical analyzes of the State National Research Institution “All-Russian Scientific Research Institute of Irrigated Vegetable and Melon Growing” (Astrakhan) using a serial dilution method. As a result of the study, it was found that salts of the general formula V-VIII exhibit different herbicidal activity against weeds of barley, peas, and radish. The obtained biological research data are shown in table 2. As a comparison, the herbicidal composition “Pyrazolate” was used.

Table 2.
The results of the study of the herbicidal activity of potassium V, VII, hydrazinium VI, VIII salts of 4-acydinitromethyl-1,2,3-triazoles Connection No Compound Formula Herbicidal activity, mg / ml peas radish barley V

20,0 20,0 20,0 VI

20,0 20,0 20,0 VII

40,0 40,0 40,0 VIII

40,0 40,0 40,0 The herbicidal composition "Pyrazolate" 20,0 20,0 20,0

From the data of table 2 it is seen that the highest herbicidal activity against weeds of peas, radishes and barley is possessed by the potassium salt of 2-methyl-4-acydinitromethyl-1,2,3-triazole (V) and the hydrazinium salt of 2-methyl-4 -aci-dinitromethyl-1,2,3-triazole (VI).

Thus, the technical result is the synthesis of new potassium or hydrazinium salts of 4-acydinitromethyl-1,2,3-triazole, which are proposed to be used as herbicides, since useful plants exhibit good tolerance when treated with these agents.

Claims (1)

Potassium or hydrazinium salts of 4-dinitromethyl-1,2,3-triazole of the general formulas V-VIII:

where Kat ⁺ = K ⁺ (V, VII), NH ₂ NH ₃ ⁺ (VI, VIII).