RU2175654C1 - Sulfur-containing triazine carboxylic diacid salts eliciting growth-stimulating activity for alfalfa plant - Google Patents

Abstract

FIELD: organic chemistry, agriculture. SUBSTANCE: invention relates to novel salts of sulfur- containing triazine carboxylic diacid of the formula (I)

where X⁺ means NH $\genfrac{}{}{0ex}{}{\text{+}}{\text{4}}$ ,K⁺ or Na⁺. Compounds show the growth-stimulating activity with respect to alfalfa plants and providing increase of alfalfa seeds yield, increase of height growing up of plants after mowing, increase of seeds mass and improvement of seeds germinating capacity. EFFECT: enhanced activity of compounds. 1 tbl, 5 ex

Description

 The invention relates to chemistry and agriculture, specifically to substituted 1,3,5-triazine as a stimulant of alfalfa growth.

где R = OCH₃, N(C₂H₅)₂, NHC₂H₅, NHC₆H₅, N(CH₂)₄O, в качестве отвердителей в составе клеевых композиций конструкционнного назначения [см. а.с. СССР N 836068; БИ, 1981, N 21]. Использование таких дикислот в качестве ростстимуляторов люцерны неизвестно.Known 2-substituted 4,6-bis (4'-carboxyphenoxy) -1,3,5-triazines of the General formula:

where R = OCH ₃ , N (C ₂ H ₅ ) ₂ , NHC ₂ H ₅ , NHC ₆ H ₅ , N (CH ₂ ) ₄ O, as hardeners in the composition of adhesive compositions for structural purposes [see A.S. USSR N 836068; BI, 1981, N 21]. The use of such diacids as growth stimulants of alfalfa is unknown.

 It is known to use indolylacetic acid (heteroauxin) as a growth stimulator of fruit and berry crops, which consists in pre-soaking the planting material in a 0.001% aqueous solution of heteroauxin for 6 hours [see Plant Growth Regulators - Ed. V.S. Shelevuhi. - M.: Agropromizdat, 1911, p. 11 - analogue]. The disadvantages of using this growth stimulator are: poor solubility in water and the difficulty of using a working solution (the need for preliminary dissolution in alcohol), a long (6 h) period of soaking of planting material, and relatively low growth-regulating activity. The ability of heteroauxin to stimulate alfalfa growth is unknown.

 The use of succinic acid 2,2-dimethylhydrazide (daminoside) is also known to increase the yield and compactness of red clover plants by spraying vegetative plants with an aqueous 75 - 85% dispersion of a wettable powder of daminoside [see Regulators of plant growth and development. - M.: Agropromizdat, 1991, p. 13 - analogue of use]. The disadvantages of the use of daminoside are its insolubility in water, the high cost of DV (dispersion of 75 - 85 wt.% Concentration), the need to use special, capable of spraying a 75% aqueous dispersion, spraying aggregates and the environmental danger of its use, as well as low activity as a growth stimulator. The use of daminoside to stimulate alfalfa growth is unknown.

 The technical solution to the problem of increasing the growth height of alfalfa plants after mowing, increasing the mass of 1000 seeds, the mass of seeds from one plant, as well as improving the germination of seeds obtained from the crop, is to use a water-soluble agent with low costs for the active substance (DV), environmentally friendly, not requiring the use of special spraying units and having a higher growth-regulating activity.

где X = Na⁺, K⁺, NH₄ ⁺, которые могут быть использованы в качестве ростстимуляторов, в виде водного раствора, в концентрации 0,0001 - 0,01 мас. %.The task is achieved by obtaining new salts of sulfur-containing diacids: 2-diphenylamino-4,6-bis- [4'-carboxylatomethylthio (X ^- )] - 1,3,5-triazine (thioaxins) of the general formula:

where X = Na ⁺ , K ⁺ , NH ₄ ⁺ , which can be used as growth stimulants, in the form of an aqueous solution, at a concentration of 0.0001 - 0.01 wt. %

 The novelty of the proposed proposal is seen in the fact that the use of salts of sulfur-containing diacid can increase the growth rate of alfalfa plants after mowing, the mass of 1000 seeds and the mass of seeds from one plant, seed productivity and germination of alfalfa seeds obtained from the crop. Salts are characterized by good solubility in water and high growth-regulating activity, eliminate the need for special spraying equipment for highly concentrated dispersions, sharply reduce the consumption of DW salts during processing, which improves the environmental situation.

 In this case, the salt is obtained by a known method - the interaction of the corresponding diacid with the base [see Preparative Organic Chemistry - Under. ed. N.S. Wulfson. - M.- L .: Chemistry, 1964, p. 355]. The starting acid is also obtained by a known method - the interaction of an aqueous-acetone solution of 2,4-dichloro-6-diphenylamino-1,3,5-triazine with an aqueous solution of thioglycolic acid and sodium hydroxide (with a molar ratio of the starting materials equal to 1: 2: 4) followed by acidification with acetic acid [see G.M. Poghosyan, I.A. Asaturian, V.N. Zaplichny. Synthesis of 2-methoxy-4,6-bis (p-carboxyphenoxy-sym-triazine and polymers based on it. - Arm. Chem. Zh., 1976, v. 29, No. 6, p. 505-511].

 For comparison, use industrial drugs brand "hch" - heteroauxin (prototype in structure) and Daminoside (prototype for use).

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

Example 1. 2-Diphenylamino-4,6-bis (carboxymethylthio) -1,3,5-triazine (DCT). A solution of 3.17 g (0.01 mol) of 2,4-dichloro-6-diphenylamino-1,3,5-triazine in 20 ml of acetone is rapidly added to 50 g of finely divided ice with stirring. An aqueous solution of 2.282 g (0.02 mol) of the sodium salt of thioglycolic acid is added dropwise to the resulting dispersion at a temperature of 0 ± 2 ^o C. 1.68 g (0.02 mol) of sodium bicarbonate are slowly added in small portions to the resulting dispersion with stirring at the same temperature. Upon completion of the carbon dioxide evolution and complete homogenization, the reaction mixture was stirred for another 1 h at 10 ^° C and acetone was distilled off in a water-jet vacuum in a boiling water bath. The distillation is continued until the volume of the reaction mixture is reduced by 1/2. The residue is cooled and with stirring and 20 ± 2 ^o C slowly acidified with hydrochloric acid to a pH of 4-5. The resulting white flakes are filtered off, washed with water until there is no chlorion in the washings, and dried at 80 - 90 ^° C. 3.835 g (89.6%) of DCT are obtained in the form of a white powder with mp. 218 - 220 ^o C, insoluble in water and most organic solvents, soluble in dioxane, DMF, DMSO, slightly soluble in acetone and alcohol.

C ₁₅ H ₁₆ N ₄ S ₂ O ₄ . Found,% :, C 53.10; H 3.50; N, 12.89; S 14.76.

Calculated,%: C 53.26; H 3.76; N 13.08; S 14.96
IR, ν, cm ^-1 (group): 3410-3260 usr. (OH acid); 1685 cf. (C = O); 1580, 1500, 1485, 1465 (C = C, C = N - res. And cyanurate cycle.).

PMR, δ, ppm (group): 7.46 - 7.32 m (10H C ₆ H ₅ ); 4.21 s (4H S-CH ₂ ).

Example 2. 2-Diphenylamino-4,6-bis- [carboxylatomethylthio (potassium)] -1,3,5-triazine (CMTC). To a suspension of 2.185 g (0.0051 mol) of finely divided DTC in 8 ml of water, 3 ml of an aqueous solution containing 0.56 g (0.01 mol) of potassium hydroxide was added dropwise with stirring at a temperature of 20 ± 1 ^° C. The mixture was stirred for another 0.5 hours at the same temperature and filtered. The resulting filtrate is added dropwise with stirring in 30 ml of alcohol, the precipitate is filtered off, washed with 2 x 50 ml of dry alcohol and dried in vacuum (12 ml) at 50-60 ^° C to constant weight. 2.288 g are obtained (88.8% with m.p.> 258 ^° C; CMTK as a white powder, soluble in water and insoluble in ordinary organic solvents.

C ₁₉ H ₁₄ N ₄ K ₂ S ₂ O ₄ . Found,%: C 45.05; H 2.62; N, 11.25; S 12.59.

 Calculated,%: C 45.22; H 2.79; N, 11.10; S 12.71.

IR, ν, cm ^-1 (group): 1635 - 1625 br.s. (COO); 1590 - 1565, 1495, 1445 - 1435 cf., p. (C = C, C = N - cont. And cyanur cycle).

Example 3. 2-Diphenylamino-4,6-bis [carboxylatomethylthio (sodium)] -1,3,5-triazine (CMTN). Under conditions analogous to example 2, from 2.185 g (0.0051 mol) of DKT and 0.4 g (0.01 mol) of sodium hydroxide with the only difference that the reaction is carried out at 25 ± 1 ^o C in 15 ml of water, and the target salt is precipitated by addition of an aqueous filtrate in 40 ml of acetone, 2.325 g (96.5%) of CMTN are obtained in the form of a white powder with mp. > 250 ^o C, soluble in water and insoluble in conventional organic solvents.

C ₁₉ H ₁₄ N ₄ Na ₂ S ₂ O ₄ . Found,%: C 48.22; H 2.76; N, 11.72; S 13.41.

 Calculated,%: C 48.30; H 2.98; N, 11.86; S 13.57.

And KK, ν, cm ^-1 (group): 1645-1620 usl (COO ^- ); 1570, 1495, 1450-1440 cf., p. (C = C, C = N - cont. And cyanur cycle).

Example 4. 2-Diphenylamino-4,6-bis [carboxylatomethylthio (ammonium)] - 1,3,5-triazine (CMTA). Under conditions similar to example 3, from 2.185 g (0.0051 mol) of DCT and 1.36 ml of 25% aqueous ammonia containing 0.34 g (0.01 mol) of ammonia, with the only difference being that the reaction was carried out at 30 ± 1 ^o C in 10 ml of water, and the target salt is precipitated by adding the filtrate to 50 ml of methanol, 2.175 g (92.2%) of CMTA are obtained in the form of a white powder with mp. > 230 ^o C, soluble in water and insoluble in ordinary organic solvents.

C ₁₉ H ₂₂ N ₆ S ₂ O ₄ . Found,%: C 49.55; H 4.98; N, 18.03; S 13.95.

 Calculated,%: C 49.33; H 4.79; N, 18.17; S 13.86.

IR, ν, cm ^-1 (group): 1650-1635 words (СОО ^- ); 1590-1575, 1455-1430 r.s. (C = C, C = N - cont. And cyanurate cycle).

 The obtained salts of triazine carboxylic acids (thioauxins) are used as growth stimulants in the composition of the agent for treating vegetative alfalfa plants.

 In this case, prepare aqueous solutions of thioaxin concentration of 0.01 to 0.0001 wt. % and process vegetative plants of alfalfa twice, by the method of ground spraying. For comparison, aqueous solutions of indolylacetic acid (Heteroauxin) and a dispersion of succinic acid diamide (Daminoside) at a concentration of 0.001 and 75 wt.%, Respectively, are used. As a control, a variant with double treatment of alfalfa plants with water is used.

 The use of "Thioauxins" as alfalfa growth stimulants in the composition for presowing treatment of vegetative alfalfa plants is illustrated by the following examples (examples 5-15).

В фазу начала цветения (бутонизация) обработку всех делянок повторяют в аналогичных 1-й обработке количествах и концентрациях прототипа и заявленного Тиоауксина. Массу 1000 семян, массу семян с одного растения и семенную продуктивность (урожайность) определяют для очищенных семян по формуле:

Всхожесть определяют для полученных в урожае семян (25 • 4 на вариант), которые помещают в чашку Петри на постоянно влажную фильтровальную бумагу и проращивают их в закрытой чашке при 25 ± 1^oC. На 7-й день определяют содержание проросших семян в % и в % к контролю.Example 5. On sowing alfalfa of the second year of vegetation, mow plants and weeds at a height of 7 cm from the soil surface and divide into plots of 1 m ² . For each experiment, 3 plots are prepared, which are sprayed with ground sprayers, on the second day after the mowing - with water, an aqueous solution of Heteroauxin (200 l / ha, prototype), or a 75% aqueous emulsion of Daminoside (analogue for use), or - an appropriate concentration option of an aqueous solution of Thioaxin. The consumption of the product or water in all (in all except Damaminoside) variants, including control, is 200 l / ha. In this case, Daminoside is used in the form of a 75% aqueous dispersion, and Hetero-Auxin, due to poor solubility in water, is pre-dissolved in alcohol. After 7 days, selective measurements of the height of regrowth on each plot (l _i ) are carried out, which are compared with the control (l _k ), and the magnitude of the growth in% is determined by the formula:

In the phase of the onset of flowering (budding), the treatment of all plots is repeated in the quantities and concentrations of the prototype and the claimed Thioaxin similar to the 1st treatment. The mass of 1000 seeds, the mass of seeds from one plant and seed productivity (yield) is determined for the purified seeds according to the formula:

Germination is determined for seeds obtained in the crop (25 • 4 per option), which are placed in a Petri dish on constantly wet filter paper and germinated in a closed cup at 25 ± 1 ^o C. On the 7th day, the content of germinated seeds is determined in% and in% of control.

 Examples of using the proposed salts of sulfur-containing triazinecarboxylic diacids to intensify alfalfa growth parameters: to increase the height of plants, the mass of 1000 seeds and the mass of seeds from one plant, as well as yield and germination, are presented in the table (examples 5-15; see the end of the description).

 As can be seen from the table, the application of the proposed method of intensification of the growth parameter of alfalfa (examples 5-15) provides, in comparison with the control, an increase in plant height on the 7th day after mowing by 20.15 - 46.49% (13.0 - 15.85 instead 10.82 cm), at the same time, spraying the plants with an aqueous solution of the known agent Heteroauxin and Daminoside increases this parameter only by 10.35 and 14.78%, respectively (11.94 and 12.42 cm, respectively).

 The mass of 1000 seeds and the mass of seeds from one plant increases in comparison with the control by 3.16-8.42% and 23.08-45%, respectively (1.96 - 2.06 g and 3.20 - 3.77 g instead 1.90 and 2.60 g, respectively); at the same time, treatment with Hetero-Auxin and Daminoside increases these indicators only by 2.63; 16.15% and 3.05; 21.15%, respectively.

 Alfalfa seed productivity increases by 43.19 - 73.24% (3.05 - 3.69 kg / ha instead of 2.13 kg / ha); at the same time, treatment with Hetero-Auxin and Daminoside increases these indicators only by 7.98 and 25.82%, respectively (2.30 and 2.68 kg / ha, respectively).

 The germination rate of seeds obtained in the crop increases in comparison with the control by 8.08 - 16.61%, while treatment with Heteroauxin and Daminoside increases this indicator only by 0.25 and 5.06%, respectively.

 An important advantage in the proposed growth regulator is a decrease in the concentration and consumption of the agent required for processing: from 75 wt.% (Daminoside) to 0.01 - 0.0001 wt.% (Thioaxins), as well as improving the solubility of the agent in water and simplifying the technology for its preparation - the exclusion of the operation of preliminary dissolution in alcohol (Heteroauxin) and the use of direct dissolution in water at ordinary temperature.

 Thus, the use of the claimed Thioauxin salts as growth stimulants allows to increase the alfalfa height after mowing, the weight of 1000 seeds and the weight of seeds from one plant, the seed productivity and germination of alfalfa seeds from the crop, as well as reduce the cost of the product and simplify the technology of its preparation and use.

Claims (1)

Salts of sulfur-containing triazinecarboxylic diacids of the general formula

where X ⁺ = NH ₄ ⁺ , K ⁺ , Na ⁺ ,
with growth-promoting activity against alfalfa plants.

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