RU2582354C1 - Growth retardant for vegetative organs of cucumbers and preparation method thereof - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: composition is intended for germination and growth of cucumbers. Retardant growth has molecular formula C₉H₁₈Cu₂N₁₄O₁₀ and consists of active substance, 4H-1,2,4-triazol-4-yl([4H-1,2,4-triazol-4-yl [(4H-1,2,4-triazol-4-yl-amino)methyl]amino]methyl] amino)methanol coordinated with ions of copper(II). To obtain retardants reacting copper(II) nitrate with 4H-1,2,4-triazol-4-yl([4H-1,2,4-triazol-4-yl[(4H-1,2,4-triazol-4-yl-amino)methyl]amino]methyl] amino)methanol (L):

2Cu(NO₃)₂+3H₂O+L→(CuOH)₂L(NO₃)₂·H₂O↓+2HNO₃, obtained by reaction of condensation of 4-amino-1,2,4-triazole with formaldehyde in aqueous medium at temperature 60 °C for 45 minutes

.

EFFECT: higher efficiency of growth of cucumbers.

2 cl, 2 dwg, 1 tbl

Description

The invention relates to the field of agriculture, in particular to the production of new complex compounds of the class 4-amino-1,2,4-triazole.

It is a procedure for the synthesis of a complex compound of copper (II) nitrate with a nitrogen-containing compound of the composition C ₉ H ₁₄ Ni ₂ O - 4H-1,2,4-triazol-4-yl ([4H-1,2,4-triazol-4 -yl [(4H-1,2,4-triazol-4-yl-amino) methyl] amino] methyl] amino) methanol.

Plant Growth Regulators (PPPs) are typically any substances or mixtures of substances intended to accelerate or slow down the rate of growth or ripening, or otherwise alter plant development. PPPs are known in the field of plant protection products and are described in The Pesticide Manual, 12th ed., Ed. C.D.S. Tomlin Retardants are substances that slow down the growth of plants in height, thicken the stem and give a darker color to the leaves.

To an analogue in the structure of the nitrogen-containing compound 4H-1,2,4-triazol-4-yl ([4H-1,2,4-triazol-4-yl [(4H-1,2,4-triazol-4-yl- amino) methyl] amino] methyl] amino) methanol can be assigned poly (hexahydrotriazine) [Jeannette M. Garcia, Gavin O. Jones, Kumar Virwani, Science, Recyclable, strong thermosets and organogels via paraformaldehyde condensation with diamines, 2014, V. 344, P. 732-735]. As the closest analogue in structure, a technical solution is proposed according to EP 1952691 A2 (BASF SE) 08/06/2008, which discloses a method for improving plant health using triazolopyrimidine derivatives. An analogue of the copper complex is a complex of copper chloride with 5-acylmethyl-3- (2-pyridyl) -1,2,4-triazine [A.M. Prokhorov, D.N. Kozhevnikov, V.L. Rusinov, A.I. Matern, 5-acylmethyl-3- (2-pyridyl) -1,2,4-triazines: synthesis and complexes with Cu (II), Russ. J. of Org. Chem., 2005, V. 41, No. 11, P. 1702-1705].

Nitrogen-containing heterocyclic compounds of the 1,2,4-triazole class are known as properties analogues. So, for example, paclobutrazole (4,4, -dimethyl-2- (1,2,4-triazol-1-yl) -1- (4-chlorophenyl) -pentanol-3) is used in agriculture as plant growth retardants , while it exhibits fungicidal properties. Derivatives of 1,2,4-triazole exhibit a similar binary activity: uniquezole, diniconazole and baronet-1,2 [A.T. Soldatenkov, N.M. Kolyadina, A. Le Tuan, Pesticides and Growth Regulators, Binom, Moscow, 2013, 220 pp.]. It has been established that by slowing down some triazole fungicides provide more compactly arranged plants with earlier flowering and fruiting, which have a higher tolerance to extreme temperatures and drought.

The active substances can be used by treating the plants themselves and plant growth media (e.g., soil). Also, the treatment can be carried out before the plants germinate, by applying chemical active substances so that they affect the seeds, seed germination and growth of the sprouted plants, either by introducing the substances into the growth medium near the seeds, or more preferably by applying the substances directly to themselves seeds.

The patent RU 2257059 C1 (NNPP "NEST M") 07/27/200512 describes methods for producing a growth-regulating complex and a preparation based on it, and their use in agricultural practice. Patent RU 2444896 C2 (SINGENTA PARTIES AG) 03/20/2012 describes methods and a composition intended for influencing plant germination and growth and controlling plant diseases, comprising a combination of at least one plant growth regulator selected from paclobutrazole, ciproconazole, uniconazole.

As the closest analogue in properties, a technical solution is proposed in accordance with RU 2124838 C1 (Irkutsk State Agricultural Academy) 01/20/1999, revealing the effect of inhibitors of germination of spring wheat seeds.

The proposed pre-emergence processing methods have certain disadvantages. So, when the active substance is introduced into the growth medium or directly on the seeds before planting, the active substance often tends to bind to certain soil components (with metal ions) with the formation of sufficiently strong complex compounds. The processes of complexation of metal ions with the active substance can lead to a change in its biological activity.

The objective of the present invention is to develop methods for the synthesis of a new complex compound of copper (II) nitrate with a nitrogen-containing heterocyclic compound of the series 4-amino-1,2,4-triazole having the properties of plant growth retardant.

The present invention is a coordination compound of copper (II) nitrate with a nitrogen-containing ligand of the class 4-amino-1,2,4-triazole. This compound contains a complexed metal ion, which leads to a constant biological properties when the active substance enters the soil. Plant treatment includes immersing the roots, soaking, spraying, soaking, dressing the seeds. Preferably, the treatment includes seed treatment.

The technical result consists in expanding the arsenal of biologically active substances obtained synthetically for use in agriculture as plant growth regulators. In this case, the interaction of the organic ligand with a copper ion leads to a constant biological activity.

The invention is illustrated in FIG. 1, 2. In FIG. 1 describes the growth characteristics of plants, in FIG. 2 - the beginning of flowering retardant form.

The invention is as follows:

4H-1,2,4-triazol-4-yl ([4H-1,2,4-triazol-4-yl [(4H-1,2,4-triazol-4-yl-amino) methyl] amino] methyl] amino) methanol (molecular formula C ₉ H ₁₄ N ₁₂ O).

A portion of 4-amino-1,2,4-triazole (0.2522 g; 0.003 mol) was dissolved in 7 ml of distilled water, and 0.46 ml (0.003 mol) of a 17% formaldehyde solution was added to the resulting solution. The mixture was heated with constant stirring at a temperature of 60 ° C for 45 minutes. After the end of the process, water was removed from the resulting solution in a rotary evaporator. The resulting colorless product was dried in air and then in a desiccator above the anhydrone until the water was completely removed.

Found (%): C, 36.0; H, 4.9; N, 55.9. C ₉ H _l4 Ni ₂ O. Calculated (%): C, 35.2; H, 4.6; N, 54.9. IR spectrum, ν / cm ^-1 : 3380, 1650 (OH, NH ₂ ); 3108 (C-H); 1504, 650 (NH ₂ trz); 1198, 1205 (N-NH ₂ ).

4H-1,2,4-triazol-4-yl ([4H-1,2,4-triazol-4-yl [(4H-1,2,4-triazol-4-yl-amino) methyl] amino] methyl] amino) methanol with Cu (NO ₃ ) ₂ (C ₉ H ₁₈ Cu ₂ N ₁₄ O ₁₀ ) (complex)

4H-1,2,4-triazol-4-yl ([4H-1,2,4-triazol-4-yl [(4H-1,2,4-triazol-4-yl-amino) methyl] amino] methyl] amino) methanol (0.001 mol) was dissolved in 20 ml of ethanol, the resulting oily film was removed using a blue ribbon filter. An ethanol (15 ml) solution of Cu (NO ₃ ) ₂ · 3H ₂ O (0.3622 g; 0.0015 mol) was added to the obtained ligand solution (L). Immediately after mixing, a blue precipitate formed:

The precipitate was filtered off and washed several times with ethanol, and dried in air.

The copper content was determined trilonometrically after decomposition of the samples in a mixture of conc. H ₂ SO ₄ and HClO ₄ (1: 1).

Found (%): C, 16.2; H, 3.6; N, 34.4; Cu, 21.1. C ₉ H ₁₈ Cu ₂ N ₁₄ O ₁₀ . Calculated (%): C, 17.7; H, 3.0; N, 32.2; Cu, 20.9. IR spectrum: ν / cm ^-1 : 3394, 1650 (OH, NH ₂ ); 3266 (C-H); 1557, 630 (NH ₂ trz); 1212 (N-NH ₂ ).

Evaluation of the activity of the compounds was carried out on the seeds of cucumbers of the variety "Mazay".

Cucumber seeds were germinated in 0.025% solutions of the obtained ligand 4H-1,2,4-triazol-4-yl ([4H-1,2,4-triazol-4-yl [(4H-1,2,4-triazole -4-yl-amino) methyl] amino] methyl] amino) methanol, its complex, as well as in a solution of the well-known plant growth activator Energen (ZAO TPK Technoexport, Russia). As a control, cucumber seeds soaked in distilled water were used. On the 4th and 8th day, the number of germinated seeds was counted and the root length of each seedling was measured. On the 15th day, the stem length, root, and leaf surface area of an adult plant were measured.

The increase in the root length of seedlings in solution L relative to the control experiment was 21%, and that of an adult plant was 20%. For Energene, these are indicators of 8% and 38%, respectively. The solution of the complex exhibits opposite properties - the root length of the seedlings relative to the control is lower by 72%, of an adult plant by 89%. The leaf surface area in experiments with L is 17% more relative to the control and the stem length is 36% lower. The surface area of the leaf in experiments with the complex practically does not differ from the control, and the stem length of an adult plant is 72% lower, the same indicators are observed in the experiment with Energen. The number of germinated seeds in the solution of the complex was 100%.

As follows from the table and FIG. 1, 4H-1,2,4-triazol-4-yl ([4H-1,2,4-triazol-4-yl [(4H-1,2,4-triazol-4-yl-amino) methyl] amino] methyl] amino) methanol exhibits the properties of a plant growth activator, and the complex of the same compound with copper (II) nitrate has the opposite properties of a retardant.

The impact of the invention on plant seeds did not lead to a decrease in the yield of Mazay cucumbers, with a high rate of at least 1.5 kg per week from the bush. A marked acceleration of the onset of flowering of the retardant form was noted (Fig. 2, b) - two weeks earlier than the rest of the samples (Fig. 2, a).

The complex compound demonstrates the excellent properties of the growth retardant of the vegetative organs of an annual herb Plant common cucumber (Cucumis sativus) of the Pumpkin family (Cucurbitaceae) and has a wide range of applications, including agricultural use (to reduce lodging and increase yield) and various applications, including the use of a retardant for regulation growth and breeding of dwarf forms of ornamental crops and / or lawn grasses.

Claims (2)

1. The growth retardant of the vegetative organs of cucumbers, having the molecular formula C ₉ H ₁₈ Cu ₂ N ₁₄ O ₁₀ , consisting of the active substance 4H-1,2,4-triazol-4-yl ([4H-1,2,4-triazole -4-yl [(4H-1,2,4-triazol-4-yl-amino) methyl] amino] methyl] amino) methanol coordinated by copper (II) ions. 2. The method of obtaining the growth retardant of the vegetative organs of cucumbers by the interaction of copper (II) nitrate with 4H-1,2,4-triazol-4-yl ([4H-1,2,4-triazol-4-yl [(4H-1, 2,4-triazol-4-yl-amino) methyl] amino] methyl] amino) methanol (L)

obtained by the condensation reaction of 4-amino-1,2,4-triazole with formaldehyde in an aqueous medium at a temperature of 60 ° C for 45 minutes

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