RU2273131C1 - Antidote against phytotoxic effect of herbicide 2,4-dichlorophenoxyaxetic acid - Google Patents

Abstract

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes using 2-pyrrolidine-6-diphenylamino-4-[(4'-ethoxycarbonyl-5'-methyl-1',2',3'-triazol)-1'-yl]-1,3,5-triazine of the formula:

as an antidote against phytotoxic effect of herbicide 2,4-dichlorophenoxyaxetic acid on sunflower germinated seeds. The proposed compound allows significant increasing roots and hypocotyls length of seedlings and to expand assortment of the known antidotes.

EFFECT: valuable properties of antidote.

2 cl, 2 tbl, 3 ex

Description

The invention relates to the field of chemistry and agriculture, specifically to the use of a derivative of a number of 1,3,5-triazine as a compound protecting the herbicide from the phytotoxic effect when growing sunflower (antidote).

A compound is known that is used to protect sunflower plants from the phytotoxic effect of 2,4-dichlorophenoxyacetic acid and its butyl ether (2,4-D and BE 2,4-D herbicide) using 1.2-dioximethylcarborane (DMC) of the formula:

At the same time, DMK is used as a soil antidote [see Chemical Encyclopedic Dictionary. - M .: Soviet Encyclopedia. 1983, p. 550]. The disadvantages of using DMK are its low efficiency, its relatively high costs (200 g / ha in terms of DV), the inability to effectively increase the length of the roots of sunflower seedlings and the yield when using herbicides, and the need for soil application.

Also known is 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 sunflower seeds [see Pat. RF №2230066 (06/10/2004); 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 using 2-pyrrolidin-6-diphenylamino-4 - [(4'-ethoxycarbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine (PDET) formulas:

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

The novelty of the proposed proposal is seen in the application of the previously known (Ambinter Stoks Screening Collections 01.01.2004, No. 695199-21-2) compound 2-pyrrolidin-6-diphenylamino-4 - [(4'-ethoxy-carbonyl-5 ' -methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine (PDET) (there is no evidence of an antidote in the literature) as an antidote for seedlings and vegetative plants sunflower, 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 (PDET) 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 active 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-Pyrrolidin-6-diphenylamino-4 - [(4'-ethoxy-carbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5 triazine (PDET). To a solution of 3.58 g (0.01 mol) of 2-azido-4-pyrrolidin-6-diphenylamino-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 2.6 g (0.02 mol) of acetoacetate and 2.02 g (0.02 mol) of dry and freshly distilled triethylamine. The reaction mixture is stirred for 40 hours at 30-40 ° C and, while stirring with a thin stream, poured into 100 ml of water cooled to 10 ° C. The resulting white precipitate is filtered off, washed thoroughly with water from residual solvent and triethylamine and dried at 50-60 ° C. 3.76 g (80.0%) of PDET are obtained in the form of a white powder with mp. 190-191 ° C, insoluble in water, but soluble in polar organic solvents.

Found,%: C 63.63; H 5.70; N, 23.69. C ₂₅ H ₂₆ N ₈ O ₂ . Calculated,%: C 63.81; H 5.57; N, 23.82.

IR, ν, cm ^-1 (group): 1700 cf. (C = O); 1575, 1520 s. (C = C, C = N, N = N - cont. And cyanurate cycle.); 1105, 1055 cf. SOS.

PMR, δ, ppm (group): 7.20-7.40 (10H m H _Ar ); 4.30-4.39 (2H q, OCH ₂ CH ₃ J = 7.0); 3.35-3.65 (4H, m, CH _{2 pyrrolidine} ); 2.85 (3H s. C = CCH ₃ ); 1.85-2.00 (4H m, CH _{2-pyrrolidine} ); 1.35-1.43 (3H t, OCH ₂ CH ₃ J = 7.0).

Like ion (mass spectroscopic) 470.

Example 2. 2-Pyrrolidin-6-diphenylamino-4 - [(4'-ethoxycarbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine (PDET). Under conditions analogous to Example 1, from 3.58 g (0.01 mol) of 2-azido-4-pyrrolidin-6-diphenylamino-1,3,5-triazine 2.6 g (0.02 mol) of aceto-acetic ether and 2.02 g (0.02 mol) of dry and freshly distilled triethylamine, with the only difference being that the addition of acetone-ester ether and triethylamine is carried out at 25 ± 1 ° C, and the mixture is stirred for 35 hours at 40-45 ° C get 3.76 g (80.0%) of PDET in the form of a white powder with so pl. 190-191 ° C, insoluble in water, but soluble in polar organic solvents.

Found,%: C 63.63; H 5.70; N, 23.69. C ₂₅ H ₂₆ N ₈ O ₂ . Calculated,%: C 63.81; H 5.57; N, 23.82.

IR, ν, cm ^-1 (group): 1700 cf. (C = O); 1575, 1520 s. (C = C, C = N, N = N - cont. And cyanurate cycle.); 1105, 1055 cf. SOS.

PMR, δ, ppm (group): 7.20-7.40 (10H m H _Ar ); 4.30-4.39 (2H q, OCH ₂ CH ₃ J = 7.0); 3.35-3.65 (4H, m, CH _{2 pyrrolidine} ); 2.85 (3H s. C = CCH ₃ ); 1.85-2.00 (4H m, CH _{2-pyrrolidine} ); 1.35-1.43 (3H t, OCH ₂ CH ₃ J = 7.0).

Like ion (mass spectroscopic) 470.

PDET 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 comparisons use an aqueous solution of MPTT (prototype). Due to the poor solubility in water, the MPTT, PDET, and 2,4-D used are pre-dissolved in a small amount of alcohol. As a control, use the option with water treatment.

Example 3. In a laboratory experiment, sunflower seeds sprouted on constantly wet filter paper in a Petri dish (25 seeds per cup in five repetitions) after 4 days from 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 PDET 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 _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 was carried out using only water (control), as well as experiment using only 2,4-D herbicide in the indicated concentration (reference). For comparison, under similar conditions, experiments are carried out using the known MPTT 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 in Table 1, the use of the proposed compound (PDET) against the background of the herbicide, provides, in comparison with the standard, an increase in the length of the roots of sunflower seedlings by 47.3-73.6% (28-33 mm instead of 19 mm in the case of the standard), while the use of the known MPTT 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 61.2% (26 mm instead of 67), then the use of PDET reduces the toxic effect of the herbicide and the length of the hypocotyl increases compared to the standard to 40.4- 57.7% (36.5-41.0 mm), while the use of the known compound prototype MPTT reduces this indicator only by 8.9-14.3%

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

Table 1
Antidote activity of the synthesized compounds in relation to the length of the root Compound Root length mm 2,4-D + antidote in concentration, wt.% * Control (water) 2,4-D (reference) 10 ^-2 10 ^-3 10 ^-4 10 ^-5 Root length
mm % to standard * Root length mm % to standard * Root length mm % to standard * Root length mm % to standard Examples: four 5 6 7 8 9

91 26 37 42 34.5 32,7 38 46 32 23.1

132 19 31.5 65.8 33 73.6 30.5 60.5 28 47.3

table 2
Antidote activity of synthesized compounds in relation to the length of the hypocotyl Compound Hypocotyl length, mm 2,4-D + antidote in concentration, wt.% * Control (water) 2,4-D (reference) 10 ^-2 10 ^-3 10 ^-4 10 ^-5 Root length mm % to standard * Root length mm % to standard * Root length mm % to standard * Root length mm % to standard Examples: four 5 6 7 8 9

74 35 39 11,4 40 14.3 39.5 12.8 38.1 8.9

67 26 36.5 40,4 38.5 48.1 41.0 57.69 38,0 46.15

Claims (1)

The use of 2-pyrrolidin-6-diphenylamino-4 - [(4'-ethoxy-carbonyl-5'-methyl-1 ', 2', 3'-triazole) -1'-yl] -1,3,5-triazine (PDET) formulas

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