RU2277334C2 - Antidote against phytotoxic action of 2,4-dichlorophenoxyacetic acid herbicide onto germinated sunflower seeds - Google Patents

Abstract

FIELD: herbicides.

SUBSTANCE: invention relates to application of 2-diethylamino-6-methoxy-4-[(4'-ethoxycarnonyl-5'-methyl-1',2',3'-triazole)-1'yl]1,3,5,-triazine of formula

as antidote against phytotoxic action of 2,4-dichlorophenoxyacetic acid herbicide onto germinated sunflower seeds.

EFFECT: more effective sunflower germ root length and hypocotyl elongation on background of phytotoxic 2,4-D herbicide action.

2 tbl, 3 ex

Description

The invention relates to the field of chemistry and agriculture, specifically to a derivative of a number of 1,3,5-triazine as a compound that protects against the phytotoxic effect of herbicides during the cultivation of sunflower (antidote).

Known 2-methoxy-4-morpholyl-6 - [(4'-phenylcarbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine (MPTT ) formulas:

which is an antidote to the phytotoxic effect of the 2,4-D herbicide on germinated seeds and sunflower seedlings [see RF Patent No. 2230066; (June 10, 2004) IPC ⁷ C 07 D 403/04, A 01 N 43/68; S.N.Mikhailichenko, A.A. Chesnyuk, I.G. Dmitrieva, A.V.Suslov, N.S. Kotlyarov, V.N. phenylcarbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine as an antidote. Bull. Fig. 2004, No. 16]. The disadvantage of its use is the relatively low activity in reducing the phytotoxic effect of the 2,4-D herbicide on seeds and sunflower seedlings.

The technical solution to the problem is to more effectively increase the length of the roots and hypocotyl of sunflower seedlings against the background of the phytotoxic effect of 2,4-D group herbicides, as well as expanding the range of known antidotes.

The objective is achieved by the use of 2-diethylamino-6-methoxy-4 - [(4'-ethoxycarbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine formulas:

which can be used as an effective antidote, from the phytotoxic effect of the herbicide of 2,4-dichlorophenoxyacetic acid on sunflower.

The novelty of the proposed proposal is seen in the application of the previously known (TimTec Stock Library, CAS 06/01/2004, No. 663936-89-8) compound 2-diethylamino-6-methoxy-4 - [(4'-ethoxycarbonyl-5'-methyl- 1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine (DMET) (there is no evidence of an antidote in the literature) as an antidote for seedlings and vegetative sunflower plants, which allows to increase the length of the roots and hypocotyl of sunflower seedlings and reduce the phytotoxic effect of the herbicide.

In this case, the compound used (DMET) is obtained by a known method — by reacting the corresponding 2-azido-4,6-disubstituted 1,3,5-triazines with an equimolar amount of a methylene dicarbonyl compound in solution, in dimethylformamide, in the presence of triethylamine at a temperature of 30-40 ° C [see General Organic Chemistry / Edited by D. Barton and W.D. Uolyais. - M .: Chemistry. 1981, v.1, s.268]. The starting 2-azido-4,6-disubstituted 1,3,5-triazines are also obtained by a known method [see Weigand Hilgetag. Experimental methods in organic chemistry. - M.: Chemistry, 1969. p.443].

Used acetoacetic ester, dimethylformamide and triethylamine immediately before use are cleaned and dried by known methods [see A. Gordon, R. Ford. Companion chemist. M .: World. 1976. - 541 p.].

Examples of the execution of the proposed proposal are presented below.

Example 1. 2-Diethylamino-6-methoxy-4 - [(4'-ethoxycarbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine (DMET). To a solution of 3.35 g (0.01 mol) of 2-azido-4-methoxy-6-diethylamino-1,3,5-triazine in 20 ml of dry and purified dimethylfomamide with stirring at a temperature of 20 ± 1 ° C, add dropwise a mixture of 3.0 g (0.02 mol) of acetoacetate and 2.03 g (0.02 mol) of dry and freshly distilled triethylamine. The reaction mixture is stirred for 40 hours at 35-40 ° C and, with stirring, poured into a 100 ml of water cooled to 10 ° C with a thin stream. The resulting white precipitate is filtered off, washed thoroughly with water from residual solvent and triethylamine and dried at 50-60 ° C. 1.95 g (87.0%) of DMET are obtained in the form of a white powder with mp. 100-101 ° C, insoluble in water, but soluble in polar organic solvents.

Found,%: C 50.01; H, 6.49; N, 29.03. C ₁₄ H ₂₁ N ₇ O ₃ . Calculated,%: C 50.13; H, 6.31; N, 29.24.

IR, ν, cm ^-1 (group): 1720 cf. (C = O); 1530, 1580 s. (C = C, C = N, N = N - cont. And cyanurate cycle.); 1050, 1110 cf. SOS.

PMR, δ, ppm (group): 3.2-4.40 (2H q, OCH ₂ CH ₃ J-4.5); 3.56-3.85 (12H, m, NCH ₂ + OCH ₃ ); 2.83 (3H s. C = CCH ₃ ); 1.53-1.73 (6H m, CH _{2 piperidyl} )); 1.32-1.40 (3H t, OCH ₂ CH ₂ ) J = 4.5.

Like ion (mass spectroscopically) 335.

Example 2. 2-Diethylamino-6-methoxy-4 - [(4'-ethoxycarbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine (DMET). Under conditions analogous to Example 1, from 3.35 g (0.01 mol) of 2-azido-4-methoxy-6-diethylamino-1,3,5-triazine, 2.6 g (0.02 mol) of acetoacetic ester and 2.02 g (0.02 mol) of dry and freshly distilled triethylamine, with the only difference being that the addition of acetone ester and triethylamine is carried out at 23 ± 1 ° C, and the mixture is stirred for 38 hours at 40-43 ° C, get 1, 95 g (87.0%) of DMET in the form of a white powder with so pl. 100-101 ° C, insoluble in water, but soluble in polar organic solvents.

Found,%: C 50.01; H, 6.49; N, 29.03. C ₁₄ H ₂₁ N ₇ O ₃ . Calculated,%: C 50.13; H, 6.31; N, 29.24.

IR, ν, cm- ¹ (group): 1720 cf. (C = O); 1530, 1580 s. (C = C, C = N, N = N - cont. And cyanurate cycle.); 1050, 1110 cf. SOS.

PMR, δ, ppm (group): 3.2-4.40 (2H q, OCH ₂ CH ₃ J = 4.5); 3.56-3.85 (12H, m, NCH ₂ + OCH ₂ ); 2.83 (3H s. C = CCH ₃ ); 1.53-1.73 (6H m, CH _{2 piperidyl)} ); 1.32-1.40 (3H t, OCH ₂ CH ₃ ) J = 4.5.

Like ion (mass spectroscopically) 335.

DMET is used to reduce the phytotoxic effect of the 2,4-D herbicide on germinated seeds (seedlings) of sunflower in a laboratory experiment. At the same time, working aqueous solutions of a concentration of 0.01-0.00001 wt.% Are prepared and the germinated sunflower seeds of the VNIIMK 8883 variety are treated, previously sprayed with a 2.4-D aqueous dispersion (standard) as described below in Example 3. For comparison, use MPTT aqueous solution (prototype). Due to the poor solubility in water, the MPTT, DMET, and 2,4-D used are previously “diluted” in a small amount of alcohol. As a control, use the option with water treatment.

Example 3. In a laboratory experiment, sprouted on constantly wet filter paper in a Petri dish, sunflower seeds (25 seeds per cup in five repetitions) 4 days after the start of germination at 23 ° C are subjected to sequential exposure to an aqueous dispersion of 2,4-D herbicide, and after 1 h - an aqueous solution of the declared DMET of a given concentration. Germination is continued under the same conditions for another 3 days and the length of the root of the seedling is determined (data are entered in the table). The decrease in the length of the roots and hypocotyl in the experimental variants in comparison with the control (A _mind ) in% is determined by the formula:

And the _mind. = (K-O / K) · 100,

where K and O are the length of seedlings in the control and experimental variants, respectively.

Examples 4-9 perform strictly in the same way as experiment 3. For control, experiment 4 is carried out using only water (control) and also an experiment using only 2,4-D herbicide in the indicated concentration (reference). For comparison, under similar conditions, experiments are carried out using the known MPPT compound as an antidote. All experimental data are subjected to statistical processing using t-student test at a probability level of 0.95.

As can be seen from the data table. 1, the use of the proposed compound DMET against the background of the action of the herbicide 2,4-D as an antidote provides an increase in the length of the roots of sunflower seedlings by 45.16-70.96% (45-53 mm instead of 31 mm in the case of the standard), in comparison with the standard, while the use of the known MTFT means provides an increase in this indicator only by 23.1-46.0% (32-38 mm instead of 26 mm in the case of the standard). It is also seen that if, due to the phytotoxic effect of the standard, the length of the hypocotyl seedlings is reduced in comparison with the control by 64.5% (30 mm instead of 66), then the use of the claimed DMET reduces the phytotoxic effect of the herbicide and the length of the hypocotyl increases compared to the standard to 38.3- 58.3% (41.5-47.5 mm), while the use of the known compound prototype MPTT reduces this figure by only 8.9-14.3%.

Thus, the use of 2-diethylamino-6-methoxy-4 - [(4'-ethoxycarbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3 as an antidote , 5-triazine allows against the background of the phytotoxic effect of the 2,4-D herbicide, to increase the length of the roots and hypocotyl of seedlings, as well as expand the range of known antidotes.

Claims (1)

The use of 2-diethylamino-6-methoxy-4 - [(4'-ethoxycarbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine (DMET ) formulas

as an antidote to the phytotoxic effect of 2,4-dichlorophenoxyacetic acid herbicide on germinated sunflower seeds.