EA016222B1 - Composition for treating seeds having grow-regulating action - Google Patents

Abstract

The invention relates to agriculture. A composition comprises as an active component alkyl ether 2-hydroxy-2-(4-methylaminophenyl)-3,3,3-trifluoropropionic acid or salts thereof, ethyl ether 2-hydroxy-2-(4-methylaminophenyl)-3,3,3-trifluoropropionic acid or hydrochloride thereof, or phosphate in the amount of (0.1-0.0001 wt%) and water are used therefor. The composition can further comprise a cellulose derivative selected from the group: sodium salt of carbomethylcellulose, methoxycellulose, oxyethylcellulose; and also fungicide selected from the group: tetramethylthiuramdisulphide and tebuconazole. The invention provides to realize said application.

Description

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

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

The use of gibberellin, an analogue of the claimed compound, by its properties as an activator of wheat seed germination is known (Muromtsev GS, Chkanikov DI, et al. Fundamentals of chemical regulation of plant growth and productivity, Chapter 2, Gibberellin. - Moscow: VO Agropromizdat, 1987, p. 3380).

However, gibberellin, being a product of microbiological synthesis, is not readily available. The plants to which gibberellins are applied, and the period of time during which they are applied, are limited; their action 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 trifluoropropyvate with dimethylaniline (Dipe-bshd / Kao, I a I li, Na 1-Bo / Kapu, Wap- Aka Ai, Oppa arac, LeGerz, 47 (2006) 2511-2514). However, data on its growth-regulating activity is not available.

Known plant growth regulator (AS 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 it uses 2,6-dichlorobenzoic esters as a benzoic acid derivative acids of general formula

S.N.SI'ISNS.S S-K

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 of components, wt.%:

Fir needles75-85

Cellulose product10-15 sodium salts of triterpene acids4-5

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

Known composition (AO No. 9325078), used for coating seeds, containing a polysaccharide hydrolyzate, for example, carboxymethylcellulose hydroxyl or carbomethyl starch. Aqueous solutions of these compounds can also be sprayed on the surface of the seeds in a relatively concentrated (30%) form.

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

Known composition as a growth regulator (RF patent No. 2194389), consisting of an aqueous solution of dimethylethynylcarbinol with a concentration of 0.0001-0.1%, chosen by us as a prototype.

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

The task is achieved by developing a growth regulating composition, including as an active component alkyl ester of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3 trifluoropropionic acid or its salt and water with the following content of components, wt.%: Alkyl ester 2- hydroxy-2- (4-methylaminophenyl) -3,3,3 trifluoropropionic acid and / or its salt 0.1 -0,0001 water the rest, where as the alkyl ester of 2-hydroxy-2- (4-methylaminophenyl) -3, 3,3-trifluoropropionic acid is used or 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropio ethyl ester New acid (I), or 2-hydroxy-2- (4-methylaminophenyl) -3,3,3,3 ethyl ester hydrochloride

- 1 016222 trifluoropropionic acid (II), or 2-hydroxy-2- (4-methylaminophenyl) 3,3,3-trifluoropropionic acid ethyl ester phosphate (III).

The inventive composition having growth-regulating activity for treating seeds of agricultural crops as a film-forming agent additionally contains a cellulose derivative selected from the group: sodium salt of carbomethylcellulose, methoxycellulose, hydroxyethylcellulose with the following content of components, wt.%:

2-hydroxy-2- (4-methylaminophenyl) -3,3,3- ethyl ester

trifluoropropionic acid Cellulose derivative Water 0.1 0.0001 1-3 rest

The growth control composition further comprises a fungicide selected from the group: tetramethylthiuram disulfide and tebuconazole in the following ratio, 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 the rest

The composition is prepared by mixing the active component, for example ethyl ester of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid (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 13% solution of 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 . one).

When preparing compositions containing the fungicide, the latter is added as an aqueous suspension to a solution of the active ingredient, prepared as described above, followed by stirring the mixture at room temperature (Examples 21-27 in Table 1).

As alkyl ester of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid, 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester is used, which is obtained according to a procedure similar to the synthesis of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid methyl ester (Zipe-тtd ΖΗαο, Ы Ьш, На1-Во 7йп§, Uap-Siao Shi, Oopi Shapd App Wid 1ip Sip. 06) 2511-2514), by reacting Ν-methylaniline (GOST 5855-78) with trifluoropyruvic acid ethyl ester in a solvent, for which 1,1,2-trifluoro-1,2,2trichloroethane is used, at a temperature of 0-5 ° C with stirring, followed by separation of the obtained product by known methods. The compound is a white crystalline substance with so pl. 4850 ° C. K = 0.53 (CC1 ₄ - methyl ethyl ketone, 3: 1). PMR (E ₂ O) spectrum: 7.63 d (2H, aromatic), 7.45 d (2H, aromatic), 4.22 kV (2H, CH ₂ ), 2.75 s (3H,-SND 1 , 19 t (3H, C-CH ₃ ). NMR ¹⁹ F (E ₂ O): -2.4 ppm C ₁₂ H ₁₄ P ^ O _3. Found: C = 51.66; H = 5, 18; N = 5.07; P = 20.41. Calculated: C = 51.99; H = 5.09; N = 5.05; P = 20.56.

The compound is stable when stored under normal conditions, 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 3,3,3- trifluoropropionic acid.

Hydrochloride is prepared by known procedures 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. Hydrochloride is a white crystalline substance with so pl. 188-190 ° C. PMR (E ₂ O) spectrum: 7.60 d (2H, aromatic), 7.33 d (2H, aromatic), 4.18 kV (2H, CH ₂ ), 2.81 s (3H,-SND) , 1.09 t (3H, C-CH ₃ ). NMR ¹⁹ F (E ₂ O): -2.2 ppm C C 1U1R _: \ O _; Found: C 45.91; H 4.83; N 4.65. Calculated: C 45.93; H 4.78; N 4.46.

Phosphate of 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester is obtained by reacting 2-hydroxy-2- (4-methylaminophenyl) -3,3,3trifluoropropionic acid ethyl ester with phosphoric acid at room temperature. Phosphate is a white crystalline substance, readily soluble in water and stable when stored under normal conditions. Spectrum ¹ H NMR (E ₂ O): 7.60 d (2H, aromatic), 7.33 d (2H, aromatic), 4.18 kV

- 2,016,222 (2H, CH2), 2.81 s (3H,-CH3), 1.09 t (3H, C-CH3). ¹⁹ P NMR ^ O): -2.2 ppm ΟηΗ ^ ΝΟγΡ. 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 as tetramethylthiuram disulfide (TMTD) or tebuconazole.

In tab. 1 shows examples of specific performance of the compositions.

Example number of composition __________________________ Table 1

The amount of the component composition, mass%

I

0.1

0.01

0.001

0.0001

0.001

0.001

II

III

Cellulose derivative

Fungicide

Water

0.1

0.01

0.001

0.0001

0.1

0.001

0.0001

0.1

0.001

0.0001

0.001

0.0001

0.001

0.001

0.1

0.1

0.1

0.1

0.1

0.01

0.001

0.1 _____

0.0001

0.1 _____

0.001

0.0001

1% haCMC

1% OC

1% (LaCMC) 1% (NaCMC) 1% (LaCMC)

1% OC

1% OC 1% OC 2% OC 2% ааКМЦ 3% ШКМЦ 1% МЦ 1% I-KMTS 1% I-KMTS

1% MC

1% OC

1% OC

1% ЫаКМЦ

1% ЫаКМЦ

15% TMTD 20% Tebuconazole _____

20% TMTD 17% Tebuconazole _____

20% TMTD 20% TMTD 20% TMTD

The Rest The Rest The Rest The Rest The Rest The Rest The Rest The Rest

The Rest The Rest The Rest The Rest The Rest

Rest

Rest

1% (LaCMC) 1% (LaCMC) 1% (OC)

The Rest The Rest The Rest The Rest The Rest The Rest

The prepared compositions are used for pre-sowing treatment of seeds of agricultural crops, such as cotton, corn, sunflower, rape, using known methods. Method for determining growth-regulating activity on the germination of cotton seeds. Delintered non-pickled cotton seeds of the variety AH-Bayaut 2 are germinated in cuvettes with sand in a thermostat at 28 ° C for 18 hours. Selected nested seeds that are treated by soaking in the claimed composition for 30 minutes. The amount of the composition is calculated on the basis of a given dose of 50 g / t. Seeds of the control variant are soaked in water. Sowing of seeds is carried out in vegetation vessels with a soil capacity of 0.5 kg. In each vessel, 20 seeds are sown, repeated five times. The vessels are kept in artificial climate chambers at an average daily air temperature of 12.2 ° C for two weeks, followed by keeping the seeds at an average daily air temperature of 19.6 ° C for 10 days.

Accounting seed germination spend 9, 14 and 24 days after sowing.

The effect of the claimed composition on the germination of cotton seeds is presented in table. 2

- 3 016222

table 2

Sample number The concentration of the active component,% Activity on cotton seeds,% After 9 days After 14 days After 24 DAYS 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 * five 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 eight 0.01 0 9.5 64.5 9 0.001 9.8 * 23.3 * 84.6 * ten 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 14 0.1 2.2 * 5.1 * 65.9 * 15 0.001 7.2 * 29.1 * 81.5 * sixteen 0.0001 2.0 7.2 82.4 17 0.001 4.3 12.9 65.7 18 0.0001 0 25.2 83.7 nineteen 0.001 5.2 22.6 83.7 20 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 29 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 the increase in germination compared with the control are reliable at the level of probability P = 0.05.

The method 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 maize.

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

After one day, the seeds treated with the compositions are grown according to the standard vegetation test method 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 crops of corn, rapeseed and sunflower in VCI, a controlled mode is maintained: illumination of 20 thousand lx. for 16 hours (day), without lighting - 8 hours (night) per day. Air temperature - 20 ° С at night and 25 ° С in the afternoon; relative air humidity - 70%; daily watering of the soil substrate in vegetation vessels is carried out at the level of 60% of the PS. The repetition of the experience is fivefold.

The effectiveness of the compositions is assessed 30 days after sowing of the treated seeds with the claimed compositions as compared to the control, in which the raw seeds are used, according to the difference in the wet weight of the aboveground plant organs.

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

- 4 016222

Table 3

Example Composition Number The concentration of the active component,% Germination of oilseeds treated with compositions, compared with control,% * corn sunflower rape Control - one 0.1 108 110 123 2 0.01 113 116 131 3 0.001 109 OF 124 four 0.0001 88 95 87 five 0.001 110 120 122 6 0.001 119 125 157 7 0.1 117 119 141 eight 0.01 107 109 132 9 0.001 116 116 117 ten 0.0001 106 117 121 eleven 0.1 105 103 119 12 0.001 98 90 101 13 0.0001 98 102 103 14 0.1 109 120 129 15 0.001 105 107 115 sixteen 0.0001 90 93 95 17 0.001 106 109 116 18 0.0001 120 126 161 nineteen 0.001 119 120 149 20 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 OF 28 0.1 104 106 114 29 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

* HCPo5 = 11% * consumption of the composition in 50 g per 1 ton of seeds

The inventive compositions have a significant stimulating effect on the germination of cotton seeds in conditions of low air temperature, exceeding in activity the growth-regulating drug, such as tetranyl (see table. 1). Compositions based on 2-hydroxy-2- (4-methylaminophenyl) -3,3,3trifluoropropionic acid ethyl ester, taken in an amount of 0.001-0,0001, containing 1% Να CMC, have the greatest activity in stimulating seed germination. As evidenced by the data presented in table. 2 and 3, all the studied drugs show growth-stimulating activity on the test cultures studied, they are superior in their activity to such well-known drugs as tetranyl and mival.

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

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

The technical result of this work is to create a composition with high activity as a growth regulator, with a wide range of applications and not having harmful effects on the environment and humans.

As shown by the results of the primary toxicological tests, the compounds included in the inventive compositions as active ingredients belong to low-toxic substances (for example, the acute toxicity of BI ₅₀ 2100-2200 mg / kg when administered orally in experiments on white mice).

Claims (6)

1. Plant growth-regulating composition, including C _1-5 2-hydroxy-2- (4 methylaminophenyl) -3,3,3-trifluoropropionic acid alkyl ester or its salt as an active component and water in the following components, wt.% : 2-hydroxy-2- (4-methylaminophenyl) -3,3,3 trifluoropropionic acid alkyl ester and / or its salt 0.1 - 0.0001 water 2. A composition according to claim 1, characterized in that as C _1-5 alkyl ester of 2-hydroxy-2- (4metilaminofenil) -3,3,3-trifluoropropionic acid using ethyl 2-hydroxy-2- (4 - 5 016222 methylaminophenyl) -3,3,3-trifluoropropionic acid. 3. The composition according to claim 1, characterized in that the active ingredient is 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid ethyl ester hydrochloride. 4. The composition according to claim 1, characterized in that the active ingredient is phosphate of ethyl 2-hydroxy-2- (4-methylaminophenyl) -3,3,3-trifluoropropionic acid. 5. The 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.%: C ^ alkyl ^E F ^I P 2-hydroxy-2- (4-methylaminophenyl) -3,3,3triftorpropionovoy acid 0.1 - 0.0001 Cellulose Derivative 1-3 Water rest 6. The composition according to claim 1, characterized in that it further comprises a fungicide selected from the group: tetramethylthiuramdisulfide and tebuconazole in the following ratio, wt.%: FROM]. _5-2 -hydroxy-2- (4-methylaminophenyl) -3,3,3 trifluoropropionic acid alkyl ester 0.1 - 0.0001 Cellulose Derivative 1-3 Fungicide 15-20 Water rest Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2