RU2369094C1 - Seed treating composition with growth regulation effect - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: as an active component the composition contains alkyl either of 2-hydroxy-2-(4-methylaminephenyl)-3,3,3-trifluoropropionic acid or its salts with ethyl either of 2-hydroxy-2-(4-methylaminephenyl)-3,3,3-trifluoropropionic acid or its hydrochloride or phosphate in the amount of (0.1-0.0001 wt %) being used as the above salts, and water. The composition can additionally contain a cellulose derivative chosen from the group: sodium salt of carbomethylcellulose, methoxycellulose, oxyethylcellulose, as well as a fungicide chosen from the group: tetramethylthiuram disulfide and tebuconazole.

EFFECT: invention allows for the implementation of the said purpose.

6 cl, 3 tbl

Description

The invention relates to the field of agriculture, in particular to means that regulate plant growth, and in particular to compositions based on fluorine-containing organic compounds, specifically to compositions based on alkyl ether 2-hydroxy-2- (4 methylaminophenyl) -3,3,3- trifluoropropionic acid or its salt.

The invention can find the widest use for presowing treatment of seeds of agricultural crops as a means of accelerating seed germination, as well as a means of biological protection from diseases, which thereby contributes to the growth rate of plants such as cotton, corn, sunflower, rape.

It is known to use gibberellin, an analogue of the claimed compound by properties, as an activator of germination of wheat seeds (Muromtsev G.S., Chkanikov D.I. et al. Fundamentals of chemical regulation of plant growth and productivity, Ch. 2, Gibberellin. M.: Agropromizdat ", 1987, p. 3380).

However, gibberellin, being a product of microbiological synthesis, is inaccessible. The plants to which gibberellins are applied and the period of time during which they are applied are limited; their effect is unstable, and their use is toxic to plants.

Known methyl ester of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid obtained by reacting methyl trifluoropyruvate with dimethylaniline (June-Ling Zhao, Li Liu, Hai-Bo Zhang, Yan-Chao Wu, Dong Wang and Yong Jun Chen. Rapid and convenient synthesis of aryl- and heteroaryl-α-hydroxy-α-trifluoromethyl acetate via Friedel-Crafts alkylation under solvent- and catalyst-free conditions. Tetrahedron Letters 47 (2006) 2511-2514). However, data on its growth regulating activity are not available.

Known plant growth regulator (A.S. USSR 582738) based on a benzoic acid derivative and an auxiliary component selected from the group of solvent, emulsifier, carrier and dispersant, characterized in that 2,6-dichlorobenzoic esters are used as a benzoic acid derivative acids of the general formula: C ₆ H ₄ Cl ₂ C (= O) OCH ₂ C≡CR

Known biologically active drug intended for presowing treatment of seeds (RF patent No. 2247498), which is a finely divided composite containing fir needles, cellulose-containing product, water-soluble sodium salts of triterpene acids in the following ratio, wt.%

Fir needles 75-85;

Cellulosic product 10-15;

sodium salts of triterpenic acids 4-5.

A disadvantage of the known drug is its powder form, which complicates the processing and requires additional costs. The use of such a drug leads to an incorrect dosage, which can have a detrimental effect on the seeds.

A known composition, (WO No. 9325078) used for coating seeds, containing a polysaccharide hydrolyzate, for example, carbomethyl cellulose hydroxylate or carbomethyl starch. Aqueous solutions of these compounds can also be sprayed onto the seed surface in a relatively concentrated (30%) form.

However, the use of such a composition requires a significant amount of water, special equipment necessary for coating the seeds.

A known composition as a growth regulator (RF Patent No. 2194389), consisting of an aqueous solution of dimethylethinylcarbinol with a concentration of 0.0001-0.1%, selected by us as a prototype.

The objective of the invention is to obtain new compositions for seed treatment based on alkyl ester of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid or its salts, which have a high growth-regulating activity that increases the germination and productivity of crops, such as cotton, corn, sunflower and rapeseed, as well as a wide range of effects on plants, combined with low toxicity and fungicidal activity, promising in agricultural practice.

The problem is achieved by the development of a growth-regulating composition, including as an active component, 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid alkyl ester or its salt and water with the following content of components (wt.%):

2-Hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid alkyl ester and / or its salt 0.1-0.0001 Water Rest,

where 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid alkyl ester is used or 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester ( I), or 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester hydrochloride (II), or 2-hydroxy-2- (4-methylaminophenyl) -3.3 ethyl ester phosphate , 3-trifluoropropionic acid (III).

The inventive composition having growth-regulating activity for treating seeds of agricultural crops as a film former further comprises a cellulose derivative selected from the group: sodium salt of carbomethyl cellulose, methoxycellulose, hydroxyethyl cellulose in the following components, (wt.%):

2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester 0.1-0.0001 Cellulose derivative 1-3 Water Rest

The growth-regulating composition additionally contains a fungicide selected from the group: tetramethylthiuramdisulfide and tebuconazole, in the following ratio of components (wt.%):

2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester 0.1-0.0001 Cellulose derivative 1-3 Fungicide 15-20 Water Rest

The composition is prepared by mixing the active component, for example 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester (examples 1-4), or its hydrochloride (examples 7-10), or phosphate with water (examples 28-32) (see table 1).

To prepare compositions containing a cellulose derivative, a 1-3% solution of the cellulose derivative in water is preliminarily prepared, which is then mixed with the active component at room temperature until the active component is completely dissolved (examples 5-6, 11-27, 30-32) (see table 1).

In the preparation of compositions containing fungicide, the latter is added in the form of an aqueous suspension to a solution of the active component obtained as described above, followed by stirring the resulting mixture at room temperature (examples 21-27 in table 1).

As 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid alkyl ester, 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester, which is obtained by a method analogous to the synthesis of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid methyl ester (June-Ling Zhao, Li Liu, Hai-Bo Zhang, Yan-Chao Wu, Dong Wang and Yong Jun Chen. Rapid and convenient synthesis of aryl- and heteroaryl-α-hydroxy-α-trifluoromethyl acetate via Friedel-Crafts alkylation under solvent- and catalyst-free conditions. Tetrahedron Letters 47 (2006) 2511-2514), by reaction of N- methylaniline (GOST 5855-78) with trifluoropyro ethyl ether inogradnoy acid in a solvent which is used as 1,1,2-trichloro-1,2,2-trifluoroethane at a temperature of 0-5 ° C with stirring, followed by isolation of the product obtained by known methods. The compound is a white crystalline substance with so pl. 48-50 ° C. R _f = 0.53 (CCl ₄ - methyl ethyl ketone, 3: 1) 1 H-NMR spectrum (D ₂ O): 7.63 d, (2H, aromatic), 7.45 d (2H, aromatic), 4.22 sq. (2H. CH ₂ ), 2.75 s. (3H, N-CH ₃ ), 1.19 t. (3H. C-CH ₃ ). NMR ¹⁹ F (D ₂ O): - 2.4 ppm C ₁₂ H ₁₄ NO ₃ . Found. C = 51.66; H = 5.18; N = 5.07; F = 20.41. Calculated. C = 51.99; H = 5.09; N = 5.05; F = 20.56.

The compound is stable during storage under ordinary conditions, it is sparingly soluble in water, good in alcohols, ketones, highly donor protophilic solvents and moderately in aromatic hydrocarbons (xylenes).

As salts of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid alkyl ester, either hydrochloride or 2-hydroxy-2- (4-methylaminophenyl) ethyl ester phosphate is used trifluoropropionic acid.

The hydrochloride is prepared according to known methods by passing anhydrous hydrogen chloride through a solution of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester in diethyl ether at a rate of 50 ml / min. The hydrochloride is a white crystalline substance with so pl. 188-190 ° C. PMR spectrum (D ₂ O): 7.60 d, (2H, aromatic), 7.33 d (2H, aromatic), 4.18 q. (2H. CH ₂ ), 2.81 s. (3H, N-CH ₃ ), 1.09 t. (3H. C-CH ₃ ). NMR ¹⁹ F (D ₂ O): - 2.2 ppm C ₁₂ H ₁₅ ClF ₃ NO ₃ Found. C 45.91; H 4.83: N 4.65. Calculated. C 45.93. H 4.78. N, 4.46.

2-Hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester phosphate, obtained by reacting 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester with phosphoric acid at room temperature. Phosphate is a white crystalline substance, readily soluble in water and stable when stored under ordinary conditions. Spectrum ¹ H NMR (D ₂ O): 7.60 d, (2H, aromatic), 7.33 d (2H, aromatic), 4.18 q (2H, CH ₂ ), 2.81 s. (3H, N-CH ₃ ), 1.09 t (3H C-CH ₃ ). ¹⁹ F NMR (D ₂ O): - 2.2 ppm C ₁₂ H ₁₇ F ₃ NO ₇ P Found: C 38.45; H 4.54: N 3.38%. Calculated: C 38.41. H 4.57. N, 3.37%.

The inventive composition also contains a fungicide, which is used tetramethylthiuramdisulfide (TMTD) or tebuconazole.

Table 1 shows examples of specific performance of the compositions.

Table 1 Sample Song Number The amount of the component of the composition, wt.% I II III Cellulose derivative Fungicide Water one 0.1 - - - - Rest 2 0.01 - - - - Rest 3 0.001 - - - - Rest four 0.0001 - - - - Rest 5 0.001 - - 1% Na CMC - Rest 6 0.001 - - 1% OC - Rest 7 - 0.1 - - - Rest 8 - 0.01 - - - Rest 9 - 0.001 - - - Rest 10 - 0.0001 - - - Rest eleven - 0.1 - 1% (Na CMC) - Rest 12 - 0.001 - 1% (Na CMC) - Rest 13 - 0.0001 - 1% (Na CMC) - Rest fourteen - 0.1 - 1% OC - Rest fifteen 0.001 - 1% OC - Rest 16 0.0001 - 1% OC - Rest 17 0.001 - 2% OC - Rest eighteen 0.0001 - 2% NaKMTS - Rest 19 0.001 - 3% Na CMC - Rest twenty 0.001 - 1% MC - Rest 21 0.1 - 1% Na CMC 15% TMTD Rest 22 - 0.1 - 1% Na CMC 20% tebuconazole Rest 23 - 0.1 - 1% MC 20% TMTD Rest 24 0.1 - 1% OC 17% tebuconazole Rest 25 - 0.1 - 1% OC 20% TMTD Rest 26 - 0.01 - 1% Na CMC 20% TMTD Rest 27 - 0.001 - 1% Na CMC 20% TMTD Rest 28 - - 0.1 - - Rest 29th - - 0.0001 - - Rest thirty - - 0.1 1% (Na CMC) - Rest 31 - - 0.001 1% (Na CMC) - Rest 32 - - 0.0001 1% (OC) - Rest

The prepared compositions are used for pre-sowing treatment of seeds of agricultural crops, such as cotton, corn, sunflower, rapeseed by known methods.

The methodology for determining the growth-regulating activity by germination of cotton seeds.

The delinted, non-etched cotton seeds of the AN-Bayaut 2 variety are germinated in sand cuvettes at 28 ° C for 18 hours. The sticky seeds are selected, which are treated by soaking in the inventive composition for 30 minutes. The amount of composition is calculated based on a given dose of 50 g / t. The seeds of the control variant are soaked in water. Sowing seeds is carried out in vegetation vessels with soil with a capacity of 0.5 kg. 20 seeds are sown in each vessel, 5-fold repetition. The vessels are kept in artificial climate chambers at an average daily air temperature of 12.2 ° C for two weeks, followed by seed aging at an average daily air temperature of 19.6 ° C for 10 days.

Seed germination of seeds is carried out on 9, 14 and 24 days after sowing. The effect of the claimed composition on the germination of cotton seeds is presented in table 2.

table 2 Example Number The concentration of the active component,% Activity on cotton seeds,% After 9 days After 14 days In 24 days The control - 0 7.6 64.0 one 0.1 0 10.3 64.2 2 0.01 0 17.4 65.5 3 0.001 11.9 * 22.0 85.1 four 0.0001 13.0 * 35.2 * 86.6 * 5 0.001 10.7 25.1 86.8 6 0.001 11,2 36.3 88.7 7 0.1 0 9.2 64.5 8 0.01 0 9.5 64.5 9 0.001 9.8 * 23.3 * 84.6 * 10 0.0001 9.6 * 22.0 * 78.0 * eleven 0.1 2.3 7.7 66.5 12 0.001 0 24.1 86.3 13 0.0001 0 30,2 84.1 fourteen 0.1 2.2 * 5.1 * 65.9 * fifteen 0.001 7.2 * 29.1 * 81.5 * 16 0.0001 2.0 7.2 82.4 17 0.001 4.3 12.9 65.7 eighteen 0.0001 0 25,2 83.7 19 0.001 5.2 22.6 83.7 twenty 0.001 8.6 * 24.9 * 85.2 * 21 0.1 2.0 12.5 64.9 22 0.1 1,2 3.2 64.7 23 0.1 1.2 24.9 65.8 24 0.1 9.0 13.0 63.9 25 0.1 13.3 35.5 86.6 26 0.01 1.2 9.2 64.1 * 27 0.001 1.0 7.3 65.0 28 0.1 0 0 65.1 29th 0.001 4.2 6.4 79.2 thirty 0.1 0 0 65.3 31 0.001 3.6 28,2 86.1 32 0.0001 0 6.5 78.6 tetranyl 0.1 0 0 64.9 0.01 0 0 67.9 0.001 0 3,5 68.6 0.0001 1,2 10,2 70.1 Note. * - differences in increased germination compared to control are significant at a probability level of P = 0.05.

The methodology for determining the growth-regulating activity on the seeds of corn, sunflower and rape.

The effect of the compositions on the growth and development of the following test cultures was studied: sunflower, rapeseed and corn.

The experiments are carried out in a chamber of an artificial climate laboratory (VCI) manufactured by the Federal Republic of Germany, Fetch according to the following procedure: the seeds of these test cultures are treated with the composition on a rotary evaporator. The amount of the claimed composition is calculated based on a given dose of 50 g / t

After a day, the seeds treated with the compositions are grown according to the generally accepted method of growing experiments in waxed paper cups with a diameter of 100 mm and a capacity of 600 cm ³ filled with a mixture of sod-podzolic soil, sand and peat (1: 1: 1).

When growing test cultures of corn, rapeseed and sunflower in VCI, a controlled regime is maintained: illumination of 20 thousand lux for 16 hours (day), without illumination - 8 hours (night) per day. Air temperature - 20 ° С at night and 25 ° С during the day; relative humidity of air - 70%; daily irrigation of the soil substrate in the vegetation vessels at the level of 60% of PV. The repetition of the experiment five times.

The effectiveness of the compositions is evaluated 30 days after sowing the treated seeds with the claimed compositions in comparison with the control, which is used as untreated seeds, by the difference in the fresh weight of the aerial organs of plants.

The effect of the claimed composition on the germination of seeds of corn, sunflower and rapeseed are presented in table 3.

Table 3 Sample Song Number The concentration of the active component,% Germination of oilseeds treated with the compositions, compared with the control,% * corn sunflower rape The control - ? ? ? one 0.1 108 110 123 2 0.01 113 116 131 3 0.001 109 113 124 four 0.0001 88 95 87 5 0.001 110 120 122 6 0.001 119 125 157 7 0.1 117 119 141 8 0.01 107 109 132 9 0.001 116 116 117 10 0.0001 106 117 121 eleven 0.1 105 103 119 12 0.001 98 90 101 13 0.0001 98 102 103 fourteen 0.1 109 120 129 fifteen 0.001 105 107 115 16 0.0001 90 93 95 17 0.001 106 109 116 eighteen 0.0001 120 126 161 19 0.001 119 120 149 twenty 0.001 107 110 140 21 0.1 114 115 115 22 0.1 108 110 128 23 0.1 103 101 104 24 0.1 99 95 95 25 0.1 96 99 97 26 0.01 111 115 119 27 0.001 103 108 113 28 0.1 104 106 114 29th 0.001 111 112 120 thirty 0.1 122 128 159 31 0.001 120 119 145 32 0.0001 109 111 149 Mival 0.001 106 110 112 0.01 101 106 108 * HCP ₀₅ = 11%
* composition consumption of 50 g per ton of seeds

The inventive compositions have a significant stimulating effect on the germination of cotton seeds under conditions of low air temperature, superior in activity to a growth-regulating preparation, such as tetranil (see table 1). Compositions based on ethyl ester of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid, taken in amounts of 0.001-0.0001, containing 1% NaCMC, have the greatest activity in stimulating seed germination. As shown by the data presented in tables 2-3, all studied drugs show growth-stimulating activity in the studied test cultures, they surpass in their activity such well-known drugs as tetranil and mival.

As a result of the studies, it was found that the claimed compounds and compositions based on them have a pronounced growth-regulating activity in various crops in combination with low toxicity. The above properties allow us to consider them as promising for implementation in agriculture.

The inventive composition is soluble in water, has high adhesion to plant material, is active and stable in aqueous solutions at pH = 6-7, does not have phytotoxicity.

The technical result of this work is the creation of a composition with high activity as a growth regulator, with a wide range of applications and without harmful effects on the environment and humans.

As shown by the results of initial toxicological tests, the compounds included in the composition of the claimed compositions as active components are low-toxic substances (for example, acute toxicity LD ₅₀ 2100-2200 mg / kg when administered orally in experiments on white mice).

Claims (6)

1. A composition having a growth-regulating effect, comprising as an active component 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid alkyl ester and / or its salt and water in the following components, wt.% :
2-hydroxy-2- (4-methylaminophenyl) -3,3,3- alkyl ester trifluoropropionic acid or its salt 0.1-0.0001 Water Rest 2. The growth-regulating composition according to claim 1, characterized in that 2-hydroxy-2- (4-methylaminophenyl ethyl ester is used as the 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid alkyl ester ) -3,3,3-trifluoropropionic acid. 3. The growth regulating composition according to claim 1, characterized in that 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester hydrochloride is used as the active component. 4. The growth-regulating composition according to claim 1, characterized in that the active component is 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester phosphate. 5. The growth-regulating composition according to claim 1, characterized in that it further comprises a cellulose derivative selected from the group: sodium salt of carbomethyl cellulose, methoxycellulose, hydroxyethyl cellulose in the following components, wt.%:
2-hydroxy-2- (4-methylaminophenyl) -3,3,3- alkyl ester trifluoropropionic acid or its salt 0.1-0.0001 Cellulose derivative 1-3 Water Rest 6. The growth-regulating composition according to claim 1, characterized in that it further comprises a fungicide selected from the group of tetramethylthiuramdisulfide and tebuconazole, in the following ratio, wt.%:
2-hydroxy-2- (4-methylaminophenyl) -3,3,3- alkyl ester trifluoropropionic acid or its salt 0.1-0.0001 Cellulose derivative 1-3 Fungicide 15-20 Water Rest