CN106831494B - A kind of mebenil base hexichol carbamide compounds and application thereof - Google Patents

Abstract

The invention discloses a kind of a kind of mebenil base hexichol carbamide compounds of structure shown in formula I, as plant growth regulator.Compound of formula I has the double action for promoting cell division and cell elongation, have it is excellent inspire bud, take root and increasing yield and improving quality effect, can be widely used for agricultural or the volume increase of forestry or survival rate improve.

Description

A kind of o-amidodiphenylurea compound and its application

Technical field The present invention belongs to the field of plant growth regulators in pesticides, and specifically relates to an o-amidodiphenylurea compound and its application.

BACKGROUND OF THE INVENTION Plant growth regulators play an important role in increasing agricultural production, income, and quality. Auxin promotes cell elongation and growth, but has no effect on cell division. Patents ZL 201310729318.9, ZL201310730571.6, ZL 201310730613.6, ZL 201310732463.2 and ZL 201310732348.5 disclose that amides containing N-alkylamino substitutions and their salts are used as plant growth regulators, which have the functions of promoting seed germination, promoting rooting, increasing production, and stress resistance , Precocious, improve the quality of the role. Aryl urea compounds such as commercial diphenylurea (4-PU), fenfenuron, and thiadizuron are used as cytokinins. The physiological effects of cytokinins are to cause cell division, induce bud formation and promote bud growth. grow. In the prior art, the o-amidodiphenylurea compound and its activity as described in the present invention have not been disclosed at home and abroad.

SUMMARY OF THE INVENTION The object of the present invention is to provide an o-amidodiphenylurea compound having both auxin activity and cytokinin activity, which can be used as a plant growth regulator for promoting cell division and cell elongation to increase yield of crops. quality.

Technical scheme of the present invention is as follows:

A kind of o-amidodiphenylurea compound, the structure is as shown in formula I:

The compound of formula I can be prepared by the following reaction formula:

The preparation method of the compound of formula I is shown in the synthesis example of the present invention.

The present invention also includes the plant growth regulator composition of the compound of formula I as the active component, and the active component refers to the compound of formula I or the compound of formula I and other active components such as sodium naphthalene acetate, sodium binitrophenolate, indole A composition composed of one, two or more plant growth regulators such as sodium oxybutyrate and trifenfenuron, the plant growth regulator composition also includes an agriculturally or forestry acceptable carrier.

Advantage and positive effect of the present invention:

Indoor and field tests show that the compound of the formula I of the present invention has dual effects of auxin and cytokinin, and the synergistic effect of cell growth and cell division can significantly promote seed germination, rooting, cell differentiation, increase production and improve quality. The cucumber cotyledon expansion test showed that the cytokinin activity of the compound of formula I was superior to that of the known diphenylurea cytokinin (see Example 3, Table 1). Can significantly improve the germination rate of wheat, its germination promotion rate reaches 32.6%, is much higher than DA-6 (seeing example 4, table 2); It is obviously better than DA-6 (seeing example 5, table 3) aspect promoting rooting. The field test shows that the plant growth regulator can make the wheat stalks strong, the leaves dark green, improve the ability to resist drought and waterlogging, and increase the yield by 17% (see example 6). Accelerate apple coloring, improve soluble sugar and VC content in apple, make mouthfeel sweeter, make apple fruit expand, improve first-grade fruit rate, and prevent fruit drop, increase yield nearly 25% (see example 7, table 4). After the compound of formula I is sprayed on the tomato leaves, the number of fruit set per plant and tomato yield can be improved, the fruit shape is correct, thick, and the taste is good, and the yield is increased by nearly 25% (see Example 8, Table 5). The compound of formula I has wide sources of raw materials, simple synthesis, no by-products, low production cost and no pollution. The compound has low toxicity, good biodegradability, safe and convenient use, and has high application value and commercialization potential.

It should be understood that various changes and modifications can be made within the scope of the present invention defined by the claims.

Detailed ways

The following synthesis examples, preparation examples and bioassay results can be used to further illustrate the present invention, but are not meant to limit the present invention.

synthetic example

Example 1, the synthesis of formula I compound:

(1) Preparation of formula II compound:

Take 0.1mol (16.31g) of isatoic anhydride in a 250mL three-necked flask, and add 100mL of ethyl acetate as a solvent. 0.12 mol (7.41 g) of propylenediamine was added dropwise under stirring at room temperature for about 1 hour, traced by TLC, isatoic anhydride disappeared, and the reaction was completed. The reaction solution was washed with water, and liquid-separated. After drying, the solvent was removed by rotary evaporation to obtain about 20.9 g of product II with a yield of 96%.

(2) Preparation of formula I compound:

Add the compound of formula II prepared above into a 250 mL three-necked flask filled with 100 mL of toluene, heat to dissolve, and reflux for dehydration. When no water comes out, the temperature is lowered and cooled, and excess (0.13mol) phenyl isocyanate is added dropwise. After reacting for about 20 minutes, a large amount of solids appeared. After reacting for about 1 hour, the reaction was completed by TLC tracking. The solid was obtained by suction filtration and dried to obtain about 31.2 g of product I with a total yield of 92.9%. Melting point of compound of formula II: 138.9-142.6°C.

1H NMR (500MHz, DMSO), δ/ppm: 1.653-1.709(m, 2H, CH2), 2.135(s, 6H, CH3), 2.261-2.296(m, 2H, CH2), 3.282-3.308(t, 2H ,CH2),6.938-6.967(t,1H,ArH),7.020-7.050(t,1H,ArH),7.243-7.275(t,2H,ArH),7.410-7.441(t,1H,ArH),7.498- 7.514(d,1H,ArH),7.608-7.624(d,1H,ArH),8.202-8.219(d,1H,ArH),8.716-8.737(t,1H,NH),9.679(s,1H,NH) ,10.285(s,1H,NH).

Formulation example

The preparation of example 2,10% formula I compound suspending agent:

Take by weighing 10g formula I compound, 2g sodium lignosulfonate, 3g polycarboxylate dispersant Sokalan CP 5 (maleic acid-acrylic acid sodium salt), 1g organosilicon milk defoamer (THIX-108 water-based silicon emulsification defoamer foaming agent), 2g of magnesium aluminum silicate and 5g of ethylene glycol in a 250mL beaker, add 77g of water, stir evenly, grind with a sand mill for 2 hours, the speed is 3000 rpm, and the particle size is 3-5μm, and white fluidity is obtained. suspending agent.

Bioassay example

1. Plant regulatory activity test

Example 3, cucumber cotyledon expansion test

The cucumber variety to be tested was Jinyan No. 4. After soaking the seeds, they were sown in an enamel dish with a cover filled with 0.7% agar, and cultured in a dark environment at 26°C for 72 hours. The cotyledons with uniform size were selected for use. For the filter paper method in the determination of hormone active substances, the sample test concentration is 100, 10 μg/mL, and the solvent is DMF.

The specific method is: prepare the compound of formula I and diphenylurea (4-PU) as 1000, 100 μg/mL mother liquor, and then take 0.3mL of each mother liquor and evenly drop it on a Φ6cm filter paper sheet. After the solvent is air-dried, cultivate In each dish, put 1 piece of filter paper containing the sample, add 3 mL of distilled water, and 10 cotyledons, that is, 100, 10 μg/mL treatment. Distilled water was used as a control. Place them at 26°C and cultivate under a light intensity of 3000 Lux, and measure the fresh weight of every 10 cotyledons after 72 hours. Each treatment was repeated twice, and the results were averaged, and the test results are shown in Table 1.

Table 1 Comparison test of cucumber cotyledon expansion

The test results in Table 1 show that the compound of formula I of the present invention has better cytokinin activity than the known diphenylurea cytokinin.

Example 4, wheat seed germination experiment

The compound of formula I was prepared as a suspending agent by the method of Example 2, and then compared with DA-6 (produced by Henan Zhengshi Chemical Co., Ltd.) aqueous solution and clear water. Dilute with distilled water to form plant growth regulator solutions with concentrations of 12.5 μg/mL, 25 μg/mL, 50 μg/mL and 125 μg/mL, respectively. Cultivate the wheat seeds with the above dilution for 8 hours, treat 100 seeds, divide the seeds into 3 parts (30-40 grains per part) and place them in a petri dish with double-layer filter paper, keep warm at 25°C to accelerate germination, and keep the filter paper moist. During germination, observe the germination situation of each treatment. The length of the germ is about 1/2 of the length of the seed as a standard. After 24 hours, the germination rate of wheat in each dish is counted. Calculate the germination promotion rate of each dilution, and the results are shown in Table 2 below.

As can be seen from the results in Table 2, when the formula I compound of the present invention is at 12.5 μg/mL, 25 μg/mL, and 50 μg/mL concentrations, its germination rate is better than that of the DA-6 contrast agent, and as the concentration increases, there is an inhibitory effect, low Concentration is better to use. Its overall germination rate is significantly better than that of clear water treatment (Ck), indicating that it has the effect of promoting germination.

Table 2 wheat germination test data

Example 5, seed soaking to promote rooting experiment

The 5% suspension concentrate and DA-6 aqueous solution of the compound of formula I were respectively diluted with distilled water to form plant growth regulator solutions with concentrations of 12.5 μg/mL, 25 μg/mL, 50 μg/mL and 125 μg/mL. Select wheat seeds with uniform grain size and plumpness, sterilize the seeds with hypochlorous acid solution, put them into gauze, soak them in the above dilution solution in a beaker for 8 hours, and then evenly discharge the wheat seeds on a moist paper bed, When placing the bed, the embryo is up and facing the same side of the germination box. There must be a certain distance between the seeds to ensure that the seeds can fully absorb water. Put 20 grains of wheat in each treatment. After placing the seeds, put them into the full smart climate plant Germinate in the box for 24 hours, during which distilled water should be added regularly to keep the paper bed moist. When the main root of wheat is about 2mm exposed, it is planted in solidified medium, and each treatment is repeated 3 times, and then put into a full-smart climate plant box for cultivation. After 40 hours, measure the main root and stem height with a caliper, and make detailed records. At the same time, the same concentration of DA-6 and clear water (Ck) were used as controls, and the results are listed in Table 3 below.

Table 3 seed soaking and rooting test data

As can be seen from the data in Table 3, the compound of formula I can promote the growth of roots, and the main root and lateral root are longer than the contrast agent DA-6, and are better than clear water, indicating that it can act on the developed root system, which is beneficial to the growth of wheat. In terms of stem height, it will not be too high, and it will not resist lodging. The comprehensive effect is better than that of the control agent DA-6.

Example 6, wheat field experiment

Test location: Zhangjiafang Village, Cuijiaji Town, Pingdu, Qingdao City, Shandong Province. Time: March-June 2016. Object: spring wheat. Test method: Divide the same plot into three areas, each area has 1 mu, and the compound of formula I and the blank control each have 1 mu. At the tillering and earing stages of wheat, it was artificially sprayed once with a backpack sprayer, the concentration was 100 μg/mL, and the dosage was 15 kg of water per acre. It was compared with the blank group without application. Results: The appearance of the application group showed thick stems, dark green leaves and plump granules. The blank yield is 550 kilograms per mu, and the application formula I compound yields 645 kilograms per mu, an increase of 17.3%.

Example 7, field experiment: 3 treatments are established in the apple experiment, and each treatment selects 3 large branches with equal growth potential on the Xingala apple tree to carry out. Fuji apples were sprayed once at the young fruit stage and the fruit swelling stage (concentration is 100 μg/mL), and water was sprayed on the leaves as a control. After harvesting, the quality indicators of the apples were measured respectively. The phenol-indophenol method was used for determination, and the soluble sugar content was determined by the anthrone colorimetric method. The results are shown in Table 4 below.

Table 4 Test data of apple quality index

As can be seen from the data in Table 4, after the compound of formula I is sprayed on the leaves of apples, while increasing the yield of apples, the appearance and internal quality of apples are also significantly improved. It can be seen that the compound of the present invention is a comprehensive performance Excellent plant growth regulator.

Example 8, field experiment: 30 tomato plants with uniform growth were selected in the test, sprayed once at the seedling stage and flower bud stage, and the concentrations of the three treatments were 20 μg/mL, 50 μg/mL, and 100 μg/mL. The time was 10 days, and 10 plants were selected to be sprayed with clear water on their leaves as a control. The number of fruit set per plant, total fruit yield and yield increase rate were investigated, and the results were averaged. The test results are listed in Table 5.

Table 5 Tomato test data

As can be seen from the data in Table 5, after the compound of formula I is sprayed on the tomato leaves, the number of fruit set per plant and tomato yield can be significantly improved.

Claims (3)

1. a kind of mebenil base hexichol carbamide compounds, structure is shown in formula I：

2. the purposes of a kind of mebenil base hexichol carbamide compounds described in claim 1, it is characterised in that compound of formula I is used as Plant growth regulator.

3. a kind of plant growth regulator composition, contains the compound of formula I described in claim 1 as active component and agricultural Acceptable carrier in upper or forestry.