CN105777618B - A kind of methyl α-naphthyl acetate pyridine ethyl ester type compound and purposes - Google Patents

Abstract

The invention discloses a pyridyl ethyl naphthalene acetate compound and its salt with the structure shown in formula I: Said salts are inorganic acid salts or organic acid salts. The compound of formula I and its salt have excellent plant growth regulating activity, and can be used alone or in combination with other active components to increase yield and quality of crops.

Description

A kind of pyridyl ethyl naphthyl acetate compound and its use

Technical field The present invention belongs to the field of plant growth regulators in pesticides, and specifically relates to a pyridyl ethyl naphthalene acetate compound and its application.

BACKGROUND OF THE INVENTION Plant growth regulators mainly control seed germination and dormancy, promote rooting, regulate plant growth, thin flowers and fruits, enhance stress resistance (disease resistance, drought resistance, salt resistance, cold resistance), and increase production and income in agriculture, improve quality, etc. Plant growth regulators have played an important role in ensuring food security and food safety, and more and more attention has been paid to plant growth regulators.

The commercialized plant growth regulators in my country mainly include: naphthaleneacetic acid, indole acetic acid, gibberellin, ethephon, 6-benzylaminopurine (6-BA), tributyramide, production-stimulating amine, DA-6 (caproic acid di Ethylaminoethanol ester citrate), etc., belong to the few varieties of my country's independent intellectual property rights, and there are shortcomings such as single function and poor safety, so the development of new varieties of efficient and safe plant growth regulators has a positive effect. CN 103636602 B discloses the use of a naphthaleneacetamide compound and its salt as a plant growth regulator, which can be widely used for rooting, strengthening seedlings, increasing production and improving quality of grains, cotton, fruits, vegetables and other crops or plants. Domestic literature reports that triadimenol naphthyl acetate and diniconazole naphthyl acetate have significant activity in inducing soybean seedling rooting (Li Junkai, Tan Tangfeng, Xu Hanhong, et al. Synthesis of naphthaleneacetic acid derivatives and determination of their biological activities. Huazhong Agriculture University Journal, 2008, 27(2):208-212).

In the prior art, there is no disclosure of the pyridylethyl naphthyl acetate compound and its plant growth regulating activity as described in the present invention.

Contents of the invention

The purpose of the present invention is to provide a plant growth regulator that promotes seed germination, rooting, growth and quality, and is safe and convenient to use. Specifically, it is a pyridyl ethyl naphthyl acetate compound that can be used in agriculture to improve crop survival. rate and promote crop yield and quality improvement.

Technical scheme of the present invention is as follows:

The present invention provides a kind of pyridyl ethyl naphthyl acetate compound and salt thereof as shown in the formula I:

Said salts are inorganic acid salts or organic acid salts.

Formula I compound and salt thereof can be prepared by following reaction:

AH is citric acid, lactic acid, oxalic acid or p-aminobenzenesulfonic acid. Naphthaleneacetic acid reacts with thionyl chloride in a suitable solvent at 10°C to reflux temperature for 2-4h, distills off the solvent and excess thionyl chloride under reduced pressure to obtain naphthaleneacetyl chloride; The solvent is made into a solution, which is added dropwise to the solution made by dissolving 2-pyridine ethanol in an appropriate solvent under stirring at -10°C-10°C under temperature control, to obtain the hydrochloride of the compound of formula I; the hydrochloride Dissolve in water and neutralize with saturated sodium carbonate solution to obtain the compound of formula I; react the compound of formula I with inorganic acid or organic acid in equimolar reaction to obtain the inorganic acid salt or organic acid salt of the compound.

The solvent is selected from dichloromethane, benzene, toluene, ethyl acetate.

Inorganic acid refers to hydrochloric acid, phosphoric acid or nitric acid, and organic acid salt refers to citric acid, lactic acid, oxalic acid or p-aminobenzenesulfonic acid. In order to improve the solubility of the compound and facilitate plant absorption, when the compound is formed into a salt, the inorganic acid or organic acid and the compound are in an equimolar proportion.

When the compound of the present invention and its salt are used as a plant growth regulator, it can be used alone or in combination with other active substances to improve the overall performance of the product.

The present invention also includes the compound of formula I and its salt as the plant growth regulator composition, which comprises the compound of formula I and its salt as the active component and an agriculturally acceptable carrier.

The compounds of the present invention can be used in the form of preparations: the compounds of formula I and their salts are dissolved or dispersed in carriers or solvents as active components, and an appropriate amount of surfactant is added to make aqueous agents, emulsifiable concentrates, microemulsions, water emulsions, Suspending agent, etc.

Advantage and positive effect of the present invention:

The compound of formula I and its salt have the advantages of simple synthesis method, low cost, small dosage of active ingredients, safe and convenient use, and the like. A large number of experiments prove that: it is obviously better than DA-6 (see table 1) in wheat seed germination and rooting aspects, spraying in the wheat growth period, the yield increase rate can reach more than 15%; %), the appearance and internal quality are also significantly improved; similar effects are also available for cucumber and ginger. The compound of the present invention can realize the purpose of greatly increasing crop yield with lower use cost and outstanding plant growth regulating activity, and has good market development prospect and commodity development value.

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) Synthesis of Naphthalene Acetyl Chloride

Add 20.8g (0.1mol) sodium naphthalene acetate to a 250mL three-necked flask, add an appropriate amount of water, heat to dissolve, acidify with concentrated hydrochloric acid (36%) while it is hot, adjust the pH to 2-3, cool, and filter with suction to obtain naphthalene The white solid of acetic acid was dried to obtain 18.2 g of white solid, with a yield of 97.8%.

Add 18.6g (0.1mol) of naphthaleneacetic acid, 150mL of toluene, 14.3g (0.12mol) of thionyl chloride to a 50mL three-necked flask in sequence, add 0.2mL of N,N-dimethylformamide dropwise under stirring at room temperature, and heat up to reflux 2h. The completion of the reaction was monitored by TLC, and the solvent and excess thionyl chloride were rotary evaporated to obtain 19.6 g of light yellow oily liquid with a yield of 95.6%.

(2) Synthesis of pyridinyl ethyl naphthalene acetate hydrochloride

Add 12.3g (0.1mol) of 2-pyridineethanol and 150mL of ethyl acetate to a 250mL three-necked flask in sequence, and add 24.6g (0.12mol) of the above-prepared naphthaleneacetyl chloride and 50mL of ethyl acetate dropwise with stirring under ice-salt bath conditions. The solution composed of toluene was added dropwise and stirred at room temperature for 2 hours; suction filtered, the filter cake was washed with an appropriate amount of ethyl acetate, and dried to obtain 30.3 g of a white solid with a yield of 92.4%.

(3) Synthesis of pyridyl ethyl naphthyl acetate

In the 250mL reaction flask, add 32.8g (0.1mol) of compound hydrochloride of formula I prepared above, 150mL water, stir and dissolve, add 100mL dichloromethane, add dropwise by 15.9g (0.15mol) sodium carbonate and A solution made of 80mL of water, after dripping, continued to stir for 0.5h, allowed to stand for stratification, separated the lower organic phase, washed twice with water (30mL×2), dried the organic phase with anhydrous sodium sulfate, and rotary evaporated the solvent Chloromethane to obtain 27.4 g of light yellow oily liquid with a yield of 94.2%.

¹ H NMR (500MHz, DMSO-d6) of the compound of formula I, δ (ppm): 3.015-3.041 (t, 2H, CH ₂ ), 4.088 (s, 2H, CH ₂ ), 4.433-4.460 (t, 2H, CH ₂ ), 7.103-7.1199 (d, 1H, Pyridyl-H), 7.178-7.202 (t, 1H, Pyridyl-H), 7.344-7.448 (m, 2H, Ar-H), 7.501-7.558 (m, 2H , Ar-H), 7.587-7.618 (t, 1H, Pyridyl-H), 7.835-7.877 (t, 2H, Ar-H), 7.920-7.936 (d, 1H, Pyridyl-H), 8.489-8.498 (d , 1H, Ar-H).

The preparation of example 2, formula I compound citrate

Add 9.6g (0.05mol) of citric acid and 80mL of ethanol successively to the 250mL reaction flask, stir to dissolve, and slowly add dropwise a mixture of 14.6g (0.05mol) of pyridyl ethyl naphthaleneacetate (compound of formula I) and 20mL of ethanol under stirring , After dropping, continue to stir for 0.5 h, spin off the solvent, and dry to obtain 24.0 g of white solid with a yield of 99.2%.

In the same way, lactate, oxalate or p-aminobenzenesulfonate of pyridyl ethyl naphthalene acetate can be obtained.

Preparation example

The preparation of example 3,5% pyridyl ethyl naphthalene acetate citrate aqueous solution

Add 5 g of pyridyl ethyl naphthalene acetate and 90 g of water into a 250 mL beaker, stir to dissolve, add 5 g of alkyl glucoside, and stir thoroughly for 0.5 h to obtain a 5% aqueous solution of pyridyl ethyl naphthalene acetate citrate.

The preparation of example 4,10% pyridyl ethyl naphthalene acetate citrate aqueous solution

Add 10 g of pyridyl ethyl naphthalene acetate and 80 g of water to a 250 mL beaker, stir to dissolve, add 3 g of 1601# and 7 g of Tween 80, and stir thoroughly for 0.5 h to obtain 10% pyridyl ethyl naphthalene acetate citrate aqueous solution.

The preparation of example 5,5% pyridine ethyl naphthalene acetate microemulsion

Add 5g of pyridyl ethyl naphthaleneacetate and 10g of ethyl acetate into a 250mL beaker, stir to dissolve, add 5g of AEO-9 and 20g of Nongru 700#, stir well, add 60g of water, and stir thoroughly for 0.5h to obtain 5% naphthaleneacetic acid Pyridyl Ethyl Ester Microemulsion.

Example 6, Preparation of 10% pyridyl ethyl naphthalene acetate citrate DA-6 aqueous solution

Add 5g of pyridinyl ethyl naphthalene acetate citrate, 5g of DA-6 and 70g of water into a 250mL beaker, stir to dissolve, add 10g of alkyl glucoside, 10g of EL-40, and stir thoroughly for 0.5h to obtain 10% pyridinyl naphthaleneacetate Base ester citrate · DA-6 water agent.

Bioactivity assay

Example 7, seed germination experiment

The paper bed germination method was adopted. Formula I compound citrate and DA-6 (Henan Zheng's) were formulated into 5% aqueous solution respectively, and were diluted with distilled water to a concentration of 10 μg/mL, 20 μg/mL, 30 μg/mL, 60 μg/mL and 120 μg/mL respectively. mL of plant growth regulator solution. Select wheat seeds with uniform grain size and plumpness, sterilize the seeds with hypochlorous acid solution, soak the seeds in the beaker with the above dilution solution for 8 hours, and repeat 3 times for each treatment of 100 seeds. In the petri dish with double-layer filter paper, keep a certain distance between the seeds. After placing the seeds, put them in a fully intelligent climate box at 25°C for heat preservation and germination treatment. During the period, distilled water should be added regularly to keep the filter paper moist. For the germination situation of the treatment, the length of the germ is about 1/2 of the seed length as the standard. After 24 hours, the germination rate of the wheat seeds in each petri dish is counted, and the same concentration of DA-6 and clear water (CK) are used as a control, and the dilutions are calculated at the same time. The results are shown in Table 1 below.

Table 1 Experimental data of wheat seed germination

As can be seen from the test data in Table 1, the germination rate of each treatment of the compound of formula I of the present invention is better than that of the contrast agent DA-6, and more significantly better than that of the clear water treatment (CK).

Example 8, Seed Soaking Promoting Rooting Experiment

Formula I compound citrate and DA-6 (Henan Zheng's) were formulated into 5% aqueous solution respectively, and were diluted with distilled water to a concentration of 10 μg/mL, 20 μg/mL, 30 μg/mL, 60 μg/mL and 120 μg/mL respectively. mL of plant growth regulator solution. Select wheat seeds with uniform grain size and plumpness, sterilize the seeds with hypochlorous acid solution, soak the seeds in the beaker with the above dilution solution for 8 hours, and repeat 3 times for each treatment of 20 wheat grains. After treatment, place the seeds evenly in a wet On the paper bed, keep a certain distance between the seeds to ensure that the seeds can fully absorb water. When placing the bed, the embryo is up and facing the same side. After placing the seeds, put them into a fully intelligent climate box for germination treatment for 24 hours. Periodically add distilled water to keep the paper bed moist. When the main root of wheat is about 2mm exposed, it is planted in solidified medium, and then put into a fully intelligent climate box for cultivation. After 40 hours, measure the main root and stem height with a caliper, and make detailed records. The same concentration of DA-6 and clear water treatment (CK) were used as controls, and the results are shown in Table 2 below.

Table 2 Seed soaking to promote rooting experiment data

As can be seen from the results in Table 2, the compound of the present invention has the best rooting-promoting effect on soaking wheat seeds at a concentration of 30 μg/mL, which is significantly better than DA-6.

Embodiment 9, field efficacy test

Three treatments were set up for the apple experiment. For each treatment, three large branches with the same growth potential were selected from the Xingala apple tree. The plants were randomly selected for the test, and the individual plant plots were repeated three times. Spray once during the fruit expansion period, and spray water on the leaves as a control. After harvest, the quality indicators of apples were measured respectively. Among them, the V _C content was determined by the conventional 2,6-dichlorophenol-indophenol method, and the soluble sugar content was determined by the conventional method. Anthrone colorimetric assay, the results are listed in Table 3.

Table 3 Apple quality test data

In summary, it can be seen that the formula I compound of the present invention has a significant effect on seed germination and rooting, and is better than the contrast agent (DA-6); The internal quality is also significantly improved, and it can be drawn that the compound of the present invention is a plant growth regulator with excellent comprehensive performance.

Claims (4)

1. a structure such as pyridyl ethyl naphthyl acetate compounds and salts thereof shown in formula I, 2. the salt of formula I compound according to claim 1 is characterized in that described salt is inorganic acid salt or organic acid salt, and inorganic acid salt refers to hydrochloride, phosphate or nitrate, and organic acid salt refers to lemon salt, lactate, oxalate or sulfanilate. 3. Use of compounds of formula I and salts thereof according to claim 1, characterized in that they are used as plant growth regulators. 4. A plant growth regulator composition, containing the compound of formula I or its salt according to claim 1 as an active component and an agriculturally or forestry acceptable carrier.