RU2230064C1 - 2,4-BIS-(MORPHOLYL)-6-β--OXYCARBONYLMETHYLOXY-SYMMETRICAL-TRIAZINE AS ANTIDOTE - Google Patents

Abstract

FIELD: organic chemistry, agriculture. SUBSTANCE: invention relates, in particular, to derivative of sym.-triazine used as a compound protecting culturing sunflower plants against phytotoxic effect of herbicides. Invention describes 2,4-bis-(morpholyl)-6-β-oxycarbonylmethyloxy-sym.-triazine of the formula: β that is an antidote against phytotoxic effect of herbicide 2,4-dichlorophenoxyacetic acid on sunflower germinating seeds and seedlings. Invention provides preparing a new compound eliciting valuable biological properties. EFFECT: valuable properties of compound. 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 trimethylammonium salts of derivatives of sim-triazine structure:

containing alkylamine substituents at the positions of the 4,6-triazine ring, such as —N (CH ₃ ) ₂ and —N (C ₂ H ₅ ) ₂ , which are used as intermediates in cyclization reactions to produce bicyclic annelated derivatives of sim triazine [ cm. V.V.Dovlatyan, K.A. Eliazyan, A.V. Dovlatyan. Rearrangements in the series of haloalkoxy (amino) -sim-triazines. - CHC. 1977, No. 7, p. 989-992]. The use of such salts as compounds having antidote activity is not known.

It is also known to use 1,2-dioximethylcarborane (DMC) of the formula:

as a soil antidote that protects sunflower plants from the phytotoxic effect of 2,4-dichlorophenoxyacetic acid and its butyl ether (2,4-D herbicide and 2,4-D BE) [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.

The technical solution to the problem is to effectively increase the length of the roots and yield of sunflower on the background of the phytotoxic effect of herbicides, expanding the range of known antidotes.

The objective is achieved by obtaining a new compound 2,4-bis (morpholyl) -6-β-hydroxycarbonylmethyloxy-triazine of the formula:

which can be used as an effective, water-soluble 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 fact that a new compound of the 1,3,5-triazine series is proposed as an antidote to vegetative sunflower plants, which allows to increase the length of the roots and hypocotyl of sunflower seedlings.

Moreover, the claimed compound is obtained by a known method — acid hydrolysis of the corresponding cyanomethyloxy derivative in solution, in water, at a temperature of 20 ° C [see V.V. Dovlatyan, K.A. Eliazyan. Synthesis of pesticides. 2-cyanomethyloxy-4,6-bis-alkyl (dialkyl) amino-sim-triazines and some of their transformations. - Arm.chem.zh., 1971, t.24, No. 4, p. 354-361]. The starting chloride (4,6-dimorpholyl-1,3,5-triazin-2-yl) trimethylammonium for the synthesis of the cyanomethyloxy derivative is obtained by a known method [see A.A. Chesnyuk, S.N. Mykhaylichenko, V.S. Zavodnov, V.N. Zaplichny. Synthesis and transformations of the quaternary trimethylammonium salts of 2-chloro-4,6-disubstituted 1,3,5-triazine in some reactions S _N -CHC, 2002, No. 2, p.197-203]].

Used organic solvents are cleaned before use by known methods [see A. Gordon, R. Ford. Companion chemist. M.: Mir, 1976, 541 pp.].

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

Example 1. 2-Cyanomethyloxy-4,6-bis (morpholyl) -1,3,5-triazine (CTOMT) and 2,4-bis (morpholyl) -6-hydroxycarbonylmethyloxy-triazine (OKMT). A cyanmethylating mixture of 2 ml of water, 0.56 g (8.7 mmol) of potassium cyanide and 0.65 g (8.7 mmol) of a 40% aqueous formalin solution is prepared in a flask. With stirring and at a temperature not exceeding + 5 ° C, a solution of 2 g (5.8 mmol) of (4,6-dimorpholyl-1,3,5-triazin-2-yl) trimethylammonium chloride in 5 ml of water is added dropwise. The reaction mixture was stirred for 2 hours at 20 ° C and diluted with 20 ml of cold water. The resulting white flakes are filtered off, washed thoroughly with water until there is no chlorine ion in the washings, and dried at 50-60 ° C. 1.19 g (75%) of CTOMT are obtained in the form of a white powder with mp. 155-156 ° C, insoluble in water and soluble in alcohol, acetone, methylene chloride and other polar organic solvents.

Found,%: C 51.13; H 6.09; N, 27.60. C ₁₃ H ₁₈ N ₆ O. Calculated,%: C 50.97; H 5.92; N, 27.44.

IR, ν, cm ^-1 (group): 2340 cf. (C≡N); 1580, 1540 s. (C = C, C = N - cont. And cyanurate cycle); 1210, 1170 s. (SOS).

PMR, δ, ppm (group): 5.02 (2H s, OCH ₂ CN); 3.60-3.80 (16H m, NCH ₂ + OCH ₂ ).

Like ion (mass spectroscopically) 274.

To 1 g (3.3 mmol) obtained in Example 1 above and finely divided 2-cyanomethyloxy-4,6-dimorpholyl-sim-triazine (COMT), 3.5 ml of concentrated hydrochloric acid was added and the mixture was kept for 0.5 h at a temperature of 20 ° C. Then, with stirring and at the same temperature, the reaction mixture was made alkaline with a 40% aqueous solution of sodium hydroxide to pH 7. The resulting heavy precipitate was filtered off, washed thoroughly with water and dried at 50-60 ° C. Obtain 0.46 g (70%) of the target OKMT in the form of a white powder with so pl. 186-187 ° C, insoluble in water and soluble in alcohol, acetone, methylene chloride and other polar organic solvents.

Found,%: C 48.15; H, 6.06; N, 21.68. C ₁₃ H ₁₉ N ₅ O ₅ . Calculated,%: C 47.99; H 5.89; N 21.53.

IR, ν, cm ^-1 (group): 3400-3260 broad (OH _acids. ); 1715s (CO);

1600.1580.1540 s (C = C, C = N - res. And cyanurate cycle);

PMR, δ, ppm (group): 12.70-12.80 (1H br s, -COOH); 4.62 (2H s, OCH ₂ COOH); 3.60-3.75 (16H m, NCH ₂ + OCH _{2 morpholyl} ).

Like ion (mass spectroscopic) 325.

Example 2. 2,4-Bis (morpholyl) -6-β-hydroxycarbonylmethyloxy-triazine (OKMT). Under conditions analogous to example 2, from the same quantities of the initial TSOMT and concentrated Hcl, with the only difference being that the order of addition of the initial ones is inverse and the mixing process is increased to 1 h, 0.42 g (64%) of OKMT are obtained in the form of a white color powder with so pl. 186-187 ° C, all the constants of which correspond to those for OKMT in example 1.

The obtained OKMT is used as an antidote to reduce the phytotoxic effect of 2,4-D herbicide on germinated seeds (seedlings) of sunflower in a laboratory experiment. At the same time, its working aqueous solutions of a concentration of 0.01-0.00001 wt.% Are prepared and the germinated sunflower seeds of the VNIIMK 8883 cultivar are sprayed, previously sprayed with 2,4-D dispersion as described below in Example 3. For comparison, an aqueous DMK solution is used ( prototype). Due to the poor solubility in water, the initial OKMT and DMK are preliminarily “diluted” 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 claimed OKMT or known DMK 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 = (KO / K · 100,

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

Examples 4-9 are carried out in exactly the same way as in experiment 3. For comparison, under analogous conditions, experiment 7 was carried out using a 2,4-D herbicide, and 1,2-dioximethylcarborane (prototype) as an antidote, and experiment 8, using only herbicide (standard) and control experiment 9 - treatment with water without the use of a herbicide and 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 2,4-bis (morpholyl) -6-β-hydroxy-carbonylmethyloxy-sim-triazine (OKMT) against the background of the action of the herbicide 2,4-D provides an antidote in comparison with the standard an increase in the length of the roots of sunflower seedlings by 19.2-31% (31-34 mm instead of 26 mm), while the use of the well-known 1,2-dioximethylcarborane means provides an increase of this indicator only by 16.4%. It is also seen that if, due to the phytotoxic effect of the standard (Example 8), the length of the roots of seedlings decreases by 71.43% compared with the control, then the use of the claimed OKMT reduces the phytotoxic effect of the herbicide and the length of the roots decreases only by 80.8-69.0%, while the use of the known compound prototype DMK-reduces this figure by 67.1%.

As can be seen from the data in Table 2, the use of the proposed 2,4-bis (morpholyl) -6-β-hydroxycarbonylmethyloxy-sim-triazine (OKMT) against the background of the action of the herbicide provides an increase in length compared to the reference sunflower hypocotyl by 810-23% (38.5-43.0 mm instead of 35 mm), while the use of the well-known 1,2-dioximethylcarborane means provides an increase of this indicator only by 5.7%. It is also seen that if, due to the phytotoxic effect of the standard (Example 8), the length of the hypocotyl decreases by 52.7% compared with the control, then the use of the claimed OKMT reduces the phytotoxic effect of the herbicide and the root length decreases only by 41.9-47.98%, while the use of the known compound - the prototype DMK - reduces this figure by 50.0%.

The claimed compound OKMT exhibits an antidote effect at concentrations of the working solution of 0.01-0.00001 wt.%, At which the known prototype compound is generally inoperative, which confirms the greater efficiency and much lower costs of the claimed compound for DV.

Thus, the use of the claimed compound 2,4-bis (morpholyl) -6-β-hydroxycarbonylmethyloxy-simriazine as an antidote allows to increase the length of the roots and hypocotyl of sunflower seedlings against the background of the action of the herbicide, as well as expand the range of known antidotes.

Claims (1)

2,4-Bis (morpholyl) -6-β-hydroxycarbonylmethyloxy-triazine of the formula:

which is an antidote to the phytotoxic effect of the 2,4-dichlorophenoxyacetic acid herbicide on germinated seeds and sunflower seedlings.

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