RU2629232C1 - Method for protecting vegetating sunflower plants from damaging effect of 2,4-dichlorophenoxyuxic acid - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: to protect the sunflower vegetating plants from the damaging action of 2,4-D, they are treated with 3-[(4-methylphenyl)carboxamid]-1,4,6-trimethyl-5-R-pyrazolo-[3,4-b]pyridine in the amount of 30 g/ha in 1 day after the use of herbicide.

EFFECT: method for protecting sunflower vegetating plants allows to increase the amount of preserved crop.

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Description

The invention relates to a technology for the protection of cultivated plants from the damaging effects of herbicides.

The use of chemical means of weed control is an integral element of modern agricultural production technologies. Among other classes of chemical plant protection products, herbicides occupy a leading position in terms of production and use. However, they are toxic not only to weeds, but also to cultivated plants. Careful adherence to chemical treatment regulations eliminates the negative consequences of the use of herbicides. However, in the practice of crop production, there are frequent cases of unintentional damage to large areas of crops by herbicides.

A known method of protecting vegetative crops from the damaging effects of herbicides, providing for their treatment with an antidote after using the herbicide [Pitina M.R. and others. The current level and promising areas of protection of crops from undesirable consequences of the use of herbicides // Agrochemistry, 1986, No. 4, p. 107-136].

Sunflower is a very sensitive crop to the effects of 2,4-D type herbicides, therefore, crop protection products should include means to reduce the phytotoxic effect of these herbicides - antidotes.

The objective of the invention is to expand the arsenal of antidotes for sunflower from the damaging effects of 2,4-D.

The technical result of the invention is the protection of vegetative sunflower plants from the damaging effects of 2,4-D, which is expressed in an increase in yield compared to a herbicide-treated control.

This result is achieved by the fact that in the method of protecting vegetative plants from the damaging effects of 2,4-D, comprising treating them with an antidote after using the herbicide, 3 - [(4-methylphenyl) carboxamido] -1,4,6 is used as an antidote -trimethyl-5-R-pyrazolo- [3,4-b] pyridines of the formula 1-2

1 - R = CH ₃ ;

2 - R = Cl;

in an amount of 30 g / ha 1 day after using the herbicide.

The synthesis of antidotes was carried out by the authors according to the scheme:

Synthesis Techniques

Synthesis of 3 [(4-methylphenyl) carboxamido] -1,4,5,6-tetramethyl-pyrazolo [3,4-b] pyridine (compound 1).

To a suspension of 0.70 g (3.7 mol) of 3-amino-1,4,5,6-tetramethylpyrazolo [3,4-b] pyridine and 0.38 g (3.7 mol) of triethylamine in 20 ml anhydrous benzene, a solution of 0.69 g (4.4 mol) of 4-methylbenzoyl chloride in 10 ml of anhydrous benzene is added dropwise over 40-50 minutes, maintaining the temperature of the reaction mixture in the range of 10-12 ° C. Upon completion of the addition, stirring is continued at the same temperature for another 10-20 minutes, then at room temperature for 3 hours. From the reaction mass, the precipitate was separated by filtration, washed with warm water (3 × 20 ml), and dried. The mother liquor is evaporated to dryness, the residue is taken up in 15 ml of diethyl ether and dried. Both precipitates are combined, recrystallized from ethanol, to obtain 1.2 g (72%) of target product 1 in the form of white crystals with so pl. 218-220 ° C.

Found,%: C 70.46; H, 6.62; N, 18.04. C ₁₈ H ₂₀ N ₄ O.

Calculated,%: C 70.11; H 6.54; N, 18.17.

PMR, δ, ppm (group): 2.28 (3H, s, CH ₃ Ph); 2.29 (3H, s, 5-CH ₃ Ru); 2.36 (3H, s, 4-CH ₃ Ru); 2.43 (3H, s, 6-CH ₃ Ru); 3.87 (3H, s, N-CH ₃ ); 7.20 ... 7.59 (4H, m, Ar); 12.23 (1H, br s, NH).

Synthesis of 3 [(4-methylphenyl) carboxamido] -1,4,6-trimethyl-5-chloro-pyrazolo [3,4-b] pyridine (compound 2).

To a suspension of 0.78 g (3.7 mol) of 3-amino-1,4,6-trimethyl-pyrazolo [3,4-b] pyridine and 0.38 g (3.7 mol) of triethylamine in 20 ml anhydrous benzene, a solution of 0.69 g (4.4 mol) of 4-methylbenzoyl chloride in 10 ml of anhydrous benzene is added dropwise over 40-50 minutes, maintaining the temperature of the reaction mixture in the range of 10-12 ° C. Upon completion of the addition, stirring is continued at the same temperature for another 10-20 minutes, then at room temperature for 3 hours. From the reaction mass, the precipitate was separated by filtration, washed with warm water (3 × 20 ml), and dried. The mother liquor is evaporated to dryness, the residue is taken up in 15 ml of diethyl ether and dried. Both precipitates are combined, recrystallized from ethanol, to obtain 1.1 g (71%) of target product 2 in the form of white crystals with so pl. 168-170 ° C.

Found,%: C 62.41; H 5.32; N, 17.30. C ₁₇ H ₁₇ CIN ₄ O.

Calculated,%: C 62.10; H, 5.21; N, 17.04.

PMR, δ, ppm (group): 2.24 (3H, s, CH ₃ Ph); 2.35 (3H, s, 4-CH ₃ Ru); 2.59 (3H, s, 6-CH ₃ Ru); 3.89 (3H, s, N-CH ₃ ); 7.23 ... 7.63 (4H, m, Ar); 12.04 (1H, br s, NH).

In this case, 3-amino-1,4,6-trimethyl-5-R-pyrazolo [3,4-b] pyridines 3 were obtained by the reaction of 4,6-dimethyl-2-chloronicotinonitriles 4 with methylhydrazine (Dmitrieva I.G., Dyadyuchenko L.V., Kaygorodova E.A., Interaction of some 2-chloronicotinonitriles with hydrazine and alkylhydrazines // Izv. Vuzov. Chemistry and Chemical Engineering, 2005, V. 48, No. 12, pp. 29-31).

The antidote activity of the obtained compound on sunflower plants was evaluated on the experimental field of the All-Russian Scientific Research Institute of Plant Biological Protection. As a prototype, a structural analogue was used - 3- [3,5-dinitrophenyl) carboxamido] -1,4,6-trimethyl-5-chloropyrazolo [3,4-b] pyridine - compound 5 ("3- [3,5 -dinitrophenyl) carboxamido] -1,4,6-trimethyl-5-chloropyrazolo [3,4-b] pyridine as a 2,4-D antidote on sunflower. " Strelkov V.D., Dyadyuchenko L.V., Isakova L.I., Nazarenko D.U., Dmitrieva I.G., Pat. RF №2358973 dated 06/20/2009, application No. 2008105177):

The prototype was used at a dose of 30 g / ha with a flow rate of 300 l / ha, as well as the claimed compound.

Evaluation of the antidote activity of the claimed compounds 1-2 and the prototype (compound 5) was carried out according to the following method.

In the field, flagman sunflower plants in the 10-16 leaf phase were treated with 2,4-dichlorophenoxyacetic acid butyl ether at a dose of 18 g / ha and after 1 day an antidote solution was applied at a dose of 30 g / ha with a working fluid flow rate of 300 l / ha .

In the experiment, the following options are provided:

- control - untreated plants;

- “herbicide” (standard) - plants treated with a herbicide;

- “herbicide + antidote” - plants treated with herbicide and antidote.

The experiments were carried out on plots with an area of 2.8 m ² , a fivefold repetition. Harvesting of sunflower seeds was carried out at the time of complete ripening of seeds.

The antidote effect was determined by the absolute value of the yield increase to the herbicidal standard and in percentage by the formula:

,

,

And _x is the antidote effect,%;

A - crop in the variant antidote + herbicide;

E - crop in the standard version (herbicide).

The data obtained are statistically processed using t-student test.

The test results are presented in the table.

Thus, the present invention allows to provide an antidote effect at the level of 31% and 46%, respectively, against 21% of the prototype, which increases the yield of sunflower by 4.6-7.0 kg / ha.

Claims (5)

A method for protecting vegetative sunflower plants from the damaging effects of 2,4-D, comprising treating them with an antidote after using a herbicide, characterized in that 3 - [(4-methylphenyl) carboxamido] -1,4,6-trimethyl-5 is used as an antidote -R-pyrazolo- [3,4-b] pyridines of the formula 1-2

1 R = CH ₃ ; 2 R = Cl; in an amount of 30 g / ha 1 day after using the herbicide.