RU2803728C1 - 3,3'-(1,4-PHENYLENE)BIS(7-[2-{3,4-DIMETHOXYPHENYL}-1-CYANOVINYL]-1,2,3,4-TETRAHYDROPYRAZOLO[1,5-a][1,3,5]TRIAZINE-8-CARBONITRILE) AS ANTIDOTE TO 2,4-D ON SUNFLOWER - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to new synthetic, chemical biologically active substances from a number of heterocyclic compounds used to protect sunflower plants from the phytotoxic effect of the herbicide 2,4-dichlorophenoxyacetic acid.

EFFECT: to expand the arsenal of biologically active substances obtained synthetically and used in agriculture as an antidote on sunflower, it is proposed to use 3.3'-(1,4-phenylene)bis(7-[2-{3,4-dimethoxyphenyl}-1-cyanovinyl]-1,2,3,4-tetrahydropyrazolo[1,5-a][1,3,5 ]triazine-8-carbonitrile).

1 cl, 1 tbl, 1 ex

Description

The invention relates to new synthetic, biologically active substances from a series of heterocyclic compounds used to protect sunflower plants from the phytotoxic effect of the herbicide 2,4-dichlorophenoxyacetic acid (antidotes).

As is known, sunflower is an extremely sensitive crop to hormonal herbicides of the 2,4-D group, and in cases of unintentional exposure of the herbicide to its crops, losses can be up to 100%, depending on the dose [Chkanikov D.I., Sokolov M. S. Herbicidal effect of 2,4-D and other halophenoxy acids, M.: Nauka, 1973, 95 pp.].

Despite intensive research to find new antidotes, the protection of vegetative sunflower plants from the damaging effects of 2,4-D remains relevant and unresolved [Strelkov V.D., Dyadyuchenko L.V., Dmitriev I.G. Synthesis of new herbicide antidotes for sunflower. Krasnodar: Education-South, 2014. P. 79].

The closest analogue in structure and properties to the claimed compound is 3-amino-2-[N-(4-fluorophenyl)urea]-4,6-dimethylthieno[2,3-b]pyridine of formula 1 [US Pat. No. 2277333 RF, IPC A01N 25/32 ( 2006.01 ) A01P 15/00 ( 2006.01 )]

Compound 1 (prototype) under field conditions at a dose of 200 g/ha on vegetative sunflower plants exhibits an antidote effect against 2,4-D at a level of 22-24% and can be used as a sunflower protection agent. However, its antidote activity is not high enough, while a dose of 200 g/ha is quite high and can cause negative environmental problems.

The technical result of the claimed invention is the expansion of the arsenal of biologically active substances obtained synthetically for their use in agriculture as antidotes.

This is achieved by using 3,3'-(1,4-phenylene)bis(7-[2-{3,4-dimethoxyphenyl}-1-cyanovinyl]-1,2,3,4-tetrahydropyrazolo[1,5-a ][1,3,5]triazine-8-carbonitrile) 2:

exhibiting antidote activity against 2,4-dichlorophenoxyacetic acid on sunflower seedlings in laboratory conditions.

Preparation of 3,3'-(1,4-phenylene)bis(7-[2-{3,4-dimethoxyphenyl}-1-cyanovinyl]-1,2,3,4-tetrahydropyrazolo[1,5-a][ 1,3,5]triazine-8-carbonitrile) 2.

1. In a 100 ml round-bottom flask equipped with a reflux condenser, mix 1.00 g (0.007 mol) of 5-amino-3-cyanomethyl-1H-pyrazole-4-carbonitrile 3, 1.10 g (0.007 mol) 3.4 -dimethoxybenzaldehyde, 20 ml of ethanol and add morpholine in a catalytic amount (0.3 ml). The reaction mixture is boiled for 4 hours, cooled, kept at 25°C for 24 hours, the precipitate is filtered off, washed with ethanol (25 ml), dried at room temperature, 5-amino-3-(2-[3,4- dimethoxyphenyl]-1-cyanovinyl)-1H-pyrazole-4-carbonitrile 4 in the form of a yellow fine-crystalline powder.

2. Place 0.80 g (0.0028 mol) of 5-amino-3-(2-[3,4-dimethoxyphenyl]-1-cyanovinyl)-1H-pyrazol obtained in the first stage into a heat-resistant beaker with a volume of 50 ml. 4-carbonitrile 4, 0.80 ml (0.022 mol) 37% aqueous formalin, 0.16 g (0.0015 mol) para-phenylenediamine and 11 ml DMF. The solution is kept at 160°C for 33 minutes with constant stirring (control according to the results of thin layer chromatography (TLC) on Sorbfil-A plates, eluent - ethyl acetate-hexane 1:1), cooled at 25°C, after 24 hours the precipitate is filtered off, dried at room temperature. Compound 2 is obtained in the form of a light green powder, yield 47%.

IR spectrum, ν, cm ^-1 : 3325 ml (NH), 2937 ml, 2839 ml (CH), 2214 ml (2 C≡N).

^1H NMR spectrum (400 MHz, DMSO-d ₆ ), δ, ppm: 3.80 (s, 6H, 2 OCH ₃ ), 3.84 (s, 6H, 2 OCH ₃ ), 4.92 (br.s, 4H , 2 NCH ₂ NH), 5.69 (br.s, 4H, 2 NCH ₂ N), 7.11-7.18 (m, 3H, H Ar), 7.45-7.52 (m, 2H, H Ar), 7.60-7.63 (m , 3H, H Ar), 7.79-7.88 (m, 2H, H Ar), 8.31 (br.s, 2H, 2 NH).

¹³ C NMR DEPTQ spectrum (101 MHz, DMSO-d ₆ ), δ, ppm: 55.5* (2 OCH ₃ ), 55.8* (2 OCH ₃ ), 57.6 (2 NC ² H ₂ N), 63.2 ( 2 NC ⁴ H ₂ N), 69.3 (2 = C -CN), 99.6 (2 C ⁸ ), 111.4* (2 C ² H 3,4-(MeO) ₂ C ₆ H ₃ ), 111.8* (2 C ⁵ H 3,4-(MeO) ₂ C ₆ H ₃ ), 111.9* (CH NC ₆ H ₄ N), 114.0 (2 C≡N), 116.6 (2 C≡N), 124.4* (2 C ⁶ H 3,4-(MeO) _2C6H3 ) _{, 125.3} ( ^2C1 3,4-(MeO) _2C6H3 ), 144.0* ( 2ArCH =), _144.9 ( ^2C7 ₎ , 148.7 (2 C ³ -OMe 3,4-(MeO) ₂ C ₆ H ₃ ), 148.8 (C ¹ NC ₆ H ₄ N), 149.7 (2 C ⁴ -OMe 3,4-(MeO) ₂ C ₆ H ₃ ), 151.6 (C ^8a ). *Signal is out of phase.

Example 1. Evaluation of compound 2 for antidote activity on sunflower seedlings

Sprouted sunflower seeds of the Master variety with a germinal root length of 2-4 mm were placed for 1 hour in a solution of 2,4-dichlorophenoxyacetic acid (2,4-D) at a concentration of ^10-3 % in order to obtain 40-60% inhibition of hypocotyl growth. After herbicide treatment, the seedlings were washed with water and placed in solutions of substances tested for antidote activity in concentrations of 10 ^-2 , 10 ^-3 , 10 ^-4 , 10 ^-5 % (herbicide + antidote option). After 1 hour, the seeds were washed with water and laid out on strips of filter paper (size 10x75 cm), 20 pieces each, which were rolled up and placed in glasses with 50 ml of water. Further seed germination was carried out in a thermostat for 3 days at a temperature of 28°C. The temperature of solutions and wash water is 28°C. Seeds of the “herbicide” variant (comparison standard) were kept for 1 hour in a solution of 2,4-D at a concentration of ^10-3 % and for 1 hour in water. The control seeds were kept in water for 2 hours. The experiment was repeated three times. In each replication, 20 seeds were used.

The protective (antidote) effect was determined by the increase in the length of the hypocotyl and root in the herbicide + antidote option relative to the named values in the “herbicide” (standard) option, as a percentage.

Statistical processing of experimental data was carried out using Student's t-test at P = 0.95.

The research results are shown in Table 1.

Table 1
Antidote activity of compounds 1 and 2 to the herbicide 2,4-D on sunflower seedlings of the Master variety A drug Concentration,
% Hypocotyl length Root length mm K 2,4-D,% mm K 2,4-D,% Control 0 75 - 161 - 2,4-D 10 ^-3 52 - 61 - 2,4-D+
connection 2 10 ^-2
10 ^-3
10 ^-4
10 ^-5 68
79.5
79.5
74 131*
153*
153*
142* 89.5
91
93
92 147*
149*
152*
151* 2,4-D+
connection 1 (prototype) 10 ^-2
10 ^-3
10 ^-4
10 ^-5 58
67
61
58 112*
129*
117*
112* 73
73
75
75 120*
120*
123*
123*

*Differences between options are significant at P=0.95.

As can be seen from the data in Table 1, the use of the herbicide proposed as an antidote, 3,3'-(1,4-phenylene)bis(7-[2-{3,4-dimethoxyphenyl}-1-cyanovinyl]-1, against the background of exposure to 2,3,4-tetrahydropyrazolo[1,5-a][1,3,5]triazine-8-carbonitrile) 2 significantly weakens the toxic effect of the herbicide. Compound 2 reduced the negative effect of 2,4-D on hypocotyls of sunflower seedlings by 31-53% when used mainly in three or more concentrations, while compound 1 (similar in structure) showed an antidote effect of 12-29%.

Compound 2 reduced the inhibitory effect of 2,4-D on the roots of seedlings by 47-52%, also when used in three or more concentrations, compound 1 (prototype) exhibited an antidote effect at the level of 20-23%.

Claims (3)

3,3'-(1,4-phenylene)bis(7-[2-{3,4-dimethoxyphenyl}-1-cyanovinyl]-1,2,3,4-tetrahydropyrazolo[1,5-a][1 ,3,5]triazine-8-carbonitrile) exhibiting an antidote effect to 2,4-dichlorophenoxyacetic acid on sunflower.