[2-trimethylammoniumchloride-4,6 - bis(ethoxycarbonylmethylene)]-1,3,5 - triazine, which is the antidote

 

(57) Abstract:

Describes the new Quaternary salt [2-trimethylammoniumchloride-4,6-bis(ethoxycarbonylmethylene)] -1,3,5-triazine, which is the antidote from fetotoksicheskoe action of the herbicide 2,4-dichlorophenoxyacetic acid and its butyl ester of sunflower. The technical result is an effective increase in root length and yield of sunflower in the background fetotoksicheskoe of herbicides. table 2.

The invention relates to the field of chemistry and agriculture, specifically to the derived SIM-triazine [2-trimethylammoniumchloride-4,6-bis(ethoxycarbonylmethylene)]-1,3,5-triazine (THAT) formula

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as compounds that protect against fetotoksicheskoe actions of herbicides in the cultivation of sunflower (antidote).

Known trimethylammonium salt derivatives SIM-triazine containing alkylamino substituents in positions 4,6-triazino cycle, such as-N(CH3)2and-N(C2H5)2that are used as intermediates in the reactions of cyclization upon receipt bicyclic annelated derivatives SIM-triazine [see centuries Dovlatyan, K. A., Eliasen, A. C. Dovlatyan. Peregriono in the synthesis of compounds with antidote activity is unknown.

It is also known the use of 1,2-dioxymethylene (DMK) formula:

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as a soil antidote protecting sunflower plants from fetotoksicheskoe action of 2,4-dichlorophenoxyacetic acid and its butyl ether (herbicide 2,4-D and EB 2,4-D) [see Chemical encyclopedic dictionary. - M. : Soviet encyclopedia, 1983, S. 550]. The disadvantages of using DMK are poor solubility in water and the necessity of preliminary bodrstvovaniya in alcohol, low efficiency, relatively high costs of its (200 g/ha of the active ingredient), the inability to effectively increase the length of roots of sunflower seedlings and yield on the background of the use of herbicides and the need for soil application.

The technical solution is an effective increase in root length and yield of sunflower in the background fetotoksicheskoe of herbicides.

This object is achieved by obtaining a new Quaternary salt [2-trimethylammoniumchloride-4,6-bis(ethoxycarbonylmethylene)]-1,3,5-triazine (THAT) formula

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which can be used as an effective, water-soluble antidote from fetotoksicheskoe d is as stated suggestions seen in what a new Quaternary salt of ethyl ether triazine-carboxylic acid as an antidote vegetative plants of sunflower that can increase the length of the roots of seedlings and seed yield of sunflower. Salt has a high solubility in water, which simplifies the technology of preparation of working solutions and their application.

At the same time declared Sol receive a known method by the reaction of 2-chloro-4,6-bis(ethoxycarbonylmethylene)-SIM-triazine with an excess of dry trimethylamine with 101o[See centuries Dovlatyan, K. A., Eliasen, A. C. Dovlatyan. Rearrangements in the row halogenoalkane(amino)-s-triazines.- CHC. 1977, 7, S. 989 - 992] . Source cyanuric chloride immediately prior to use purify by crystallization from carbon tetrachloride. Ethyl ester of glycine - get [see E. Fisher. Ber., 190], Bd.34, p. 433]. The triethylamine and benzos cleaned and dried by [see A. Weisberger, E., Proskauer, J. Riddick, E. Tops. Organic solvents. Izd-vo IL, M: 1958, - 517 S.].

Examples of performance stated suggestions are presented below.

Example 1. [2-Trimethylammoniumchloride-4,6-bis(ethoxycarbonylmethylene)] -1,3,5-triazine (THAT). The solution to 4.62 g (24 mmol) of 2,4,6-trichloro-1,3,5-is to see a mixture of 5 g (48 mmol) of ethyl ether aminouksusnoy acid (ethyl ester of glycine) and 4,96 g (49 mmol) of dry, fresh of triethylamine in 5 ml of abs. benzene and continue stirring 1 h at the same temperature, 1 h at 25-30oC and 1 h at 35-40oC. the precipitation is filtered off, the filtrate is evaporated to dryness in a water-jet pump vacuum and the dry residue was washed with water (350ml) and dried. Get 6,1 g (71 %) of 2-chloro-4,6-bis(ethoxycarbonylmethylene)-1,3,5-triazine (HAT) in the form of a white crystalline powder with so pl. 178-179oC.

Found, %: C 41,71; N 5,19; N 22,18; Cl 12,05; C11H16N5lO4.

Calculated, %: C 41,58; N 5,08; N 22,04; Cl Of 11.15.

X , cm-1: 3250, 3180cf.(N-H); 1740c.(C=O); 1575, 1540C.,cf.,(C=C and C=N - comp.); 1240cf.(C-N); 1190, 1130cf.(C-O-C).

PMR-spectrum , M. D.: 8,10ush.with.(2H, -N-H); 4,05...4,20m(4H, -CO2); 3,85...4,0m(4H,-NCH2); 1,20... 1,30m(6N,-CH3).

Mol. ion 317 (mass.by a spectroscope).

Through a solution of 5 g (16 mmol) received the HAT in 30 ml of abs. benzene in a stream of nitrogen, with stirring and a temperature of 101oWith bubbled dry trimethylamine. The saturation of trimethylamine continued for 1 h and the reaction mixture is stored at 20oWith 12 o'clock Formed abundant precipitate is filtered off, primarycare-4,6-bis (ethoxycarbonylmethylene)]-1,3,5-triazine (THAT) in the form of a white crystalline powder with so pl. 180-180,5oC.

Found, %: C 44,73; N For 6.81; N 22,40; Cl At 9.53. WITH14H25N6lO4.

Calculated, %: C 44,59; N 6,69; N 22,30; Cl 9,40.

X , cm-1: 3435, 3225cf.(N-H); 1730c. (C=O); 1590, 1560, 1510C.,cf.C=C and C=N - comp.); 1190, 1150cf.(C-O-C).

PMR-spectrum , M. D. : 8,12ush.with.(2H, N-H); 4,08...4,23m(4H, OCH2); a 3.87. . . 4,01m(4H, NCH2); 3,20m(N, N(CH3)3); 1,22... 1,31m(6N, -CH3).

Example 2. Carried out under conditions analogous to example 1, from 5 g (16 mmol) HAT in 35 ml of abs. benzene, with the only difference that the bubbling dry trimethylamine continue for 1.5 h at 51oC, then incubated the reaction mixture at the 18oWith another 15 hours and get by 5.87 g (99%) [2-trimethylammoniumchloride-4,6-bis(ethoxycarbonylmethylene)]-1,3,5-triazine (THAT) in the form of a white crystalline powder with so pl. 180-180,5oC.

Found, %: C 44,73; N For 6.81; N 22,40; Cl At 9.53. WITH14H25N6lO4.

Calculated, %: C 44,59; N 6,69; N 22,30; Cl 9,40.

X , cm-1: 3435, 3225cf.(N-H); 1730S.(C=O); 1590, 1560, 1510C.,cf.(C=C and C=N - comp.); 1190, 1150cf.(C-O-C).

PMR-spectrum , M. D.: 8,12 ush.with.(2H, N-H); 4,08... 4,23m(4H, och

The obtained Sol THAT used as an antidote to reduce fetotoksicheskoe action of the herbicide 2,4-D and its butyl ether on germinated seeds and vegetative plants of sunflower in laboratory and field experiments.

When preparing aqueous solutions of salts THAT concentrations of 0.01 and 0.0001 wt. % treated germinated seeds or vegetative plants of sunflower varieties VNIIMK 8883, pre-sprayed with a dispersion of 2,4-D or EB 2,4-D, as described below in example 3.

For comparison, using the aqueous dispersion of the DMK - 1,2-dioxymethylene (prototype). As a control, use the option of no-treated plants.

Example 3.

A) laboratory experience germinated on constantly moist filter paper sunflower seeds after 4 days from the beginning of germination at 23oWith subjected to sequential exposure to aqueous dispersions of the herbicide 2,4-D, and after 1 h in an aqueous solution of the stated THAT a given concentration. Continue germination under the same conditions for another 3 days and determine the root length of seedlings (data inserted in table. 1). The reduction in root length of seedlings in the advanced options in comparison with control (Opytnyh options, respectively.

B) In field experiments to achieve vegetative plants of sunflower phase 10-16 leaves (area 3 m2a three-fold repetition) plots with plants treated by spraying the aqueous dispersion EB 2,4 D in the amount of 20 g/ha at the rate of solution flow rate 500 l/ha After 5 days of plots subjected to spraying with an aqueous solution THAT a concentration of 0.1 wt. per cent, at the rate of solution flow rate 500 l/ha to achieve full ripeness of the baskets they are cut, are threshed and the number of harvested seeds by the method of weighing to determine the yield (data inserted in table.2). The decrease in seed yield of sunflower in the advanced options in comparison with control (Umind.in %, determined by the formula

THEmind.= (K/K)100,

where About is the yield in the control and experimental variants, respectively.

Examples 4-10 carry out strictly the same experience 3 way. For comparison, in similar conditions hold for the experience 8 use of the herbicide 2,4-D and its butyl ether, and as an antidote 1,2-dioxymethylene(prototype), experience 9 using to process only herbicide(standard) and control experience 10 - without the use of herbicide and antidote.

All experimental Yes

As can be seen from the data table.1, the application on the background of the impact of the herbicide 2,4-D proposed Quaternary salt: THAT as antidote provides in comparison with the standard increase in root length of seedlings of sunflower as at 31 - 44% (47-52 mm instead of 36 mm), while the use of known means 1,2-dioxymethylene provides an increase of only 19.4%. It is also clear that if as a result of fetotoksicheskoe steps reference (example 9) length of roots of seedlings is reduced in comparison with control by 45.5%, the use of the claimed THAT reduces fetotoksicheskoe herbicide action and length of roots decreased by 21.3-34,1%, while the use of known compounds prototype DMK reduces this rate is 34.9%.

As can be seen from the data table.2, when used on the background of the impact of herbicide EB 2,4-D as an antidote to the claimed salt THAT productivity (yield) of sunflower seeds increased in comparison with the standard of 1.3 to 2.3 t/ha, or by 24.5 - 43,3%, compared to 6.6 and 7.6 t/ha instead of 5.3 t/ha), while the use of the known compounds of the prototype increases this figure only 16.9%. It is also clear that if as a result of fetotoksicheskoe steps reference (example 9) yields cf the IDA and the yield decreases only 54.5-60.5 per cent, while the use of known compounds prototype DMK reduces this figure by 62.9%.

Thus, the use of the claimed compounds as the antidote allows for the impact of herbicide to increase the length of the roots of seedlings and productivity of seeds of sunflower plants (yield), and to simplify the technology of preparation and use working solutions.

The Quaternary salt of 1,3,5-triazine of the formula

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which is the antidote from phyto-toxic action of the herbicide 2,4-dichlorophenoxyacetic acid and its butyl ether on the germinating seeds and vegetative plants of sunflower.

 

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