CN105481762A - Cinnamic acid pyridine ethyl ester compound and application - Google Patents

Abstract

The invention discloses a cinnamic acid pyridine ethyl ester compound with the structure shown in the formula I and salt thereof. X is H, and Y is H; X is Cl, and Y is Cl. The salt is inorganic acid salt or organic acid salt. The compound shown in the formula A and the salt thereof have the excellent plant growth regulation activity, and can be independently used or used in cooperation with other active components for crop production increasing and quality improvement.

Description

A kind of pyridine ethyl cinnamate compound and application

Technical field The present invention belongs to the field of plant growth regulators in pesticides, and specifically relates to a pyridine ethyl cinnamate 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. CN103130663A discloses the application of a cinnamic acid diethylaminoethanol ester compound as a plant growth regulator. CN103719082B discloses the application of a cinnamic amide compound as a plant growth regulator, which can be widely used in plants to promote seed germination, root promotion, yield increase, stress resistance and quality improvement.

In the prior art, there is no disclosure of the pyridyl ethyl cinnamate compound and its plant growth regulating activity as described in the present invention.

Contents of the invention

The object 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 a pyridyl ethyl cinnamate compound, which 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 cinnamate compound and its salt with the structure shown in formula I:

In the formula: X is H, Y is H; X is Cl, Y is Cl; the salt is an inorganic acid salt or an organic acid salt.

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

In the formula, the definitions of X and Y are the same as before; AH is citric acid, lactic acid, oxalic acid or p-aminobenzenesulfonic acid. Cinnamic acid represented by formula II is reacted with thionyl chloride in a suitable solvent at 10°C to reflux temperature for 2-4 hours, and the solvent and excess thionyl chloride are distilled off under reduced pressure to obtain cinnamoyl chloride represented by formula III; Add the prepared acid chloride to a suitable solvent to form a solution, add it dropwise to the solution prepared by dissolving dipyridine ethanol in a suitable solvent under temperature control -10°C-10°C with stirring, to obtain the hydrochloride of the compound of formula I Dissolve the compound hydrochloride in water and neutralize with saturated sodium carbonate solution to obtain the compound of formula I; react the compound of formula I with the inorganic acid or organic acid in equimolar reaction to obtain the inorganic acid or organic acid salt of the compound of formula I .

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

Since some compounds of formula I are water-insoluble liquids at room temperature, they are easily oxidized and discolored when exposed to air, and are inconvenient to use, so they usually appear in the form of inorganic acid salts or organic acid salts when used as plant growth regulators. Inorganic acid refers to hydrochloric acid, phosphoric acid or nitric acid, and organic acid refers to citric acid, lactic acid, oxalic acid or p-aminobenzenesulfonic acid.

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 amount of active ingredients, safe and convenient use, and are obviously better than DA-6 (see table 1) in terms of wheat seed germination and rooting. After spraying on the apple tree leaves, While increasing the output, the appearance and internal quality have also been significantly improved. 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.

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.

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

detailed description

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 Ia compound (X=H, Y=H)

(1) Synthesis of Cinnamoyl Chloride

Add 14.8g (0.1mol) of cinnamic acid, 150mL of toluene, and 14.3g (0.12mol) of thionyl chloride to a 250mL three-neck flask in sequence, add 0.2mL of N,N-dimethylformamide dropwise under stirring at room temperature, and heat up to reflux for 2h. The completion of the reaction was monitored by TLC, and the solvent and excess thionyl chloride were evaporated to obtain 16.1 g of light yellow oily liquid with a yield of 96.4%.

(2) Synthesis of pyridyl ethyl cinnamate hydrochloride

Add 12.3g (0.1mol) of 2-pyridineethanol and 150mL of ethyl acetate to a 250mL three-necked flask in sequence, add 20.0g (0.12mol) of cinnamoyl chloride and 50mL of ethyl acetate dropwise under ice-salt bath conditions to form After the dropwise addition was completed, the reaction was stirred at room temperature for 2 h; suction filtered, the filter cake was washed with an appropriate amount of ethyl acetate, and dried to obtain 26.7 g of a white solid, with a yield of 92.1%.

(3) Synthesis of pyridyl ethyl cinnamate

In the 250mL reaction flask, add 29.0g (0.1mol) of formula Ia compound hydrochloride and 150mL water prepared above, 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 23.5 g of light yellow oily liquid with a yield of 92.9%.

¹ HNMR (500MHz, DMSO-d6) of the compound of formula Ia, δ (ppm): 3.115-3.140 (t, 2H, CH ₂ ), 4.525-4.550 (t, 2H, CH ₂ ), 6.369-6.401 (d, 1H , CH), 7.130-7.152(t, 1H, Ar-H), 7.233-7.248(d, 2H, Ar-H), 7.353-7.369(d, 2H, Ar-H), 7.713(s, 2H, Pyridyl -H), 7.582-7.614 (d, 1H, CH), 7.855-7.872 (d, 1H, Pyridyl-H), 8.497-8.503 (d, 1H, Pyridyl-H).

Example 2, the preparation of formula Ia compound (X=H, Y=H) citrate

Add 9.6g (0.05mol) citric acid and 80mL methanol successively to the 250mL reaction flask, stir to dissolve, slowly add dropwise the mixed solution of 12.7g (0.05mol) pyridyl ethyl cinnamate (compound of formula Ia) and 20mL methanol under stirring , After dropping, continue to stir for 0.5h, and dry to obtain 22.1g of white solid, with a yield of about 99.1%.

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

Example 3, the synthesis of formula Ib compound (X=Cl, Y=Cl)

According to the method of Example 1, changing cinnamic acid into 2,4-dichlorocinnamic acid can obtain compound Ib2,4-dichlorocinnamic acid pyridyl ethyl ester and 2,4-dichloro cinnamic acid pyridyl ethyl ester lemon salt.

The compound of formula Ib has a melting point of 69.5°C to 71.2°C. ¹ HNMR (500MHz, DMSO-d6), δ (ppm): 3.113-3.137 (t, 2H, CH ₂ ), 4.526-4.551 (t, 2H, CH ₂ ), 6.668-6.700 (d, 1H, CH ), 7.230-7.252(t, 1H, Ar-H), 7.331-7.348(d, 1H, Ar-H), 7.452-7.4969(d, 1H, Ar-H), 7.723(s, 2H, Pyridyl-H), 7.772-7.804 (d, 1H, CH), 7.955-7.972 (d, 1H, Pyridyl-H), 8.499-8.506 (d, 1H, Pyridyl-H).

Preparation example

The preparation of example 4,5% dipyridyl ethyl cinnamate citrate aqueous solution

Add 5 g of pyridyl ethyl cinnamate 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 cinnamate citrate.

Example 5, Preparation of 5% 2,4-dichlorocinnamic acid pyridyl ethyl ester citrate aqueous solution

Add 5g of 2,4-dichlorocinnamate pyridyl ethyl citrate and 88g of water to a 250mL beaker, stir to dissolve, add 3g of Tween 80, 4g of alkyl glycosides, stir well for 0.5h to obtain 5% 2,4 - Pyridinyl ethyl cinnamate citrate aqueous solution.

Example 6, the preparation of 5% 2,4-dichloro-cinnamic acid pyridyl ethyl ester microemulsion

Add 5g of pyridyl ethyl 2,4-dichlorocinnamate, 10g of ethyl acetate, 5g of AEO-7 and 20g of Nongru 500# into a 250mL beaker, stir evenly, add 60g of water, and stir thoroughly for 0.5h to obtain 5% 2 , 4-Pyridine ethyl cinnamate microemulsion.

Example 7, Preparation of 10% 2,4-dichlorocinnamic acid pyridyl ethyl citrate · DA-6 aqueous solution

Add 5g of 2,4-dichlorocinnamic acid pyridyl ethyl citrate, 5g of DA-6 and 70g of water respectively into a 250mL beaker, stir to dissolve, add 10g of alkyl glucoside, 10g of Nongru 1601#, and stir thoroughly for 0.5h to obtain 10% 2,4-dichlorocinnamic acid pyridyl ethyl citrate · DA-6 aqueous solution.

Bioactivity assay

Example 8, seed germination experiment

The paper bed germination method was adopted. Formula Ia compound citrate, Ib compound citrate and DA-6 (Henan Zheng's) were prepared into 5% aqueous solution respectively, and were diluted with distilled water to concentration of 10 μg/mL, 20 μg/mL, 30 μg/mL, respectively. 60 μg/mL and 120 μg/mL plant growth regulator solutions. 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 9, seed soaking to promote rooting experiment

Formula Ia compound citrate, Ib compound citrate and DA-6 (Henan Zheng's) were prepared into 5% aqueous solution respectively, and were diluted with distilled water to concentration of 10 μg/mL, 20 μg/mL, 30 μg/mL, respectively. 60 μg/mL and 120 μg/mL plant growth regulator solutions. 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 clean 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 10, 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. structure is such as formula the styracin pyridine ethyl ester compound shown in I,

In formula: X is H, Y is H; X is Cl, Y is Cl.

2. the salt of styracin pyridine ethyl ester compound according to claim 1, it is characterized in that described inorganic acid salt refers to hydrochloride, phosphoric acid salt or nitrate, organic acid salt refers to Citrate trianion, lactic acid salt, oxalate or sulfanilate.

3. the purposes of styracin pyridine ethyl ester compound according to claim 1 and salt thereof, is characterized in that being used as plant-growth regulator.

4. a plant growth regulator composition, containing formula I according to claim 1 or its salt as acceptable carrier in active ingredient and agricultural or forestry.