CN103130663A - Cinnamylate ester compound and application thereof - Google Patents

Abstract

The invention provides a cinnamylate ester compound and application and purposes of the cinnamylate ester compound, and the structure of the cinnamylate ester compound is shown by a formula I. The compound and salt of the compound have good plant growth regulation activity and has obvious root taking promotion and production increasing functions by soaking seeds, dressing the seeds or spraying foliage. As a plant growth adjustment agent, the cinnamylate easter can be widely applied to agriculture or forestry production and has the advantages of being low in cost, good in medicine effect, safe to use and the like.

Description

A kind of cinnamate compound and its application

Technical field The invention belongs to the field of agricultural plant growth regulators, in particular to a cinnamate compound and its application.

Background Art With the increase of population and the reduction of arable land, producing more food on limited land is an important means to solve the problem of food security. Plant growth regulators have been widely used as plant chemical control methods in crop yield increase, early maturity, quality improvement and stress resistance. At present, the types of plant growth agents commonly used in China mainly include sodium nitrophenolate, amine fresh fat, sodium naphthalene acetate, and ethephon, etc., which have shortcomings such as single function, use safety, and insufficient efficacy. Therefore, the development of comprehensive performance is good, The use of safe green plant growth regulator varieties is necessary for the development of agriculture in our country. CN1091123 reports the preparation of the following compound (formula II) and its plant growth regulating activity, which is used to increase the yield of crops such as wheat and rapeseed by more than 17%.

In the prior art, there is no disclosure of cinnamate compounds and their plant growth regulating activity as described in the present invention

SUMMARY OF THE INVENTION The object of the present invention is to provide a plant growth regulator that promotes rooting, has a good yield-increasing effect, is low in cost, and is safe to use, and specifically provides a cinnamic acid ester compound, which can be used to greatly increase yield in agriculture and forestry or increase the survival rate.

Technical scheme of the present invention is as follows:

A cinnamate compound, the structure is as shown in formula I:

The preparation reaction formula of formula I compound and salt thereof is as follows:

Among them, RCOOH: citric acid, oxalic acid, fumaric acid, succinic acid dichlorocinnamic acid react with thionyl chloride in a suitable solvent at 10°C to reflux temperature for 2-4h, and distill off the solvent and excess chlorinated sulfoxide to obtain 2,4-dichlorocinnamoyl chloride; add the obtained acid chloride to a suitable solvent to form a solution, and add it dropwise to the solution prepared by diethylaminoethanol and a suitable solvent under stirring at -10°C-10°C In the resulting solution, the hydrochloride of the compound of formula I is obtained; the compound hydrochloride is dissolved in water, and neutralized with a saturated sodium carbonate solution to obtain the compound of formula I; the compound of formula I is reacted with an organic acid in equimolar The organic acid salt of the compound of formula I is obtained. Suitable solvents for the reaction process can be selected from dichloromethane, benzene, toluene, ethyl acetate. Diethylaminoethanol is both a reaction raw material and an acid-binding agent, so the generation of the compound hydrochloride of formula I does not need additional acid-binding agent. In the process of preparing its organic acid salt, the organic acid is selected from citric acid, oxalic acid, fumaric acid, succinic acid, preferably citric acid to prepare the citrate of the compound of formula I. Since the compound of formula I is a water-insoluble flowing liquid, it is easy to oxidize and change color when exposed to air, so it usually appears in the form of inorganic salt or organic acid salt when used as a plant growth regulator. Compared with similar compounds known on the market, the cinnamic acid ester compound of the present invention has higher plant growth regulating activity, and its rooting-promoting performance and production-increasing effect are not only significantly better than similar products DA-6 (amine fresh fat), It is also significantly better than widely used plant growth regulators such as "sodium nitrophenolate" and "sodium naphthalene acetate". The cinnamate ester compound and the salt thereof of the present invention have the advantages of simple synthesis method, environmental protection, low synthesis cost, less effective dosage and the like. Therefore, the purpose of greatly increasing the yield of crops or increasing the survival rate of forestry can be achieved with lower use cost and outstanding plant growth regulating activity.

The present invention also includes the compound of formula I or its salt as the plant growth regulator composition of the active component, and the weight percentage of the active component in the composition is between 0.5% and 95%, and in the plant growth regulator composition Also included are agriculturally or forestry acceptable carriers.

The composition of the present invention can be administered in the form of preparations, and the compound of formula I or its salt is dissolved or dispersed in the carrier as an active component to be formulated into an aqueous agent, a microemulsion, an emulsion in water, an emulsifiable concentrate or a soluble powder, in order to improve the utilization rate of the effective component , usually add an appropriate amount of surfactant when preparing the preparation.

The technical scheme of the present invention also includes a method for regulating plant growth: applying the composition of the present invention to the medium requiring growth regulation at a concentration of 0.1-500 ppm of the active component, and preferably using a concentration of 20-200 ppm.

For some applications, one or more other fungicides, insecticides, plant growth regulators or fertilizers, etc. can be added to the plant growth regulator composition of the present invention as required, which can produce additional advantages and effects.

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

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 preparation of formula I compound

(1) Synthesis of 2,4-dichlorocinnamoyl chloride

Add 43.2g (0.2mol) 2,4-dichlorocinnamic acid, 200mL toluene and 35.4g thionyl chloride (0.3mol) successively in the 500mL reaction flask, slowly heat up under stirring (release HCl and SO ₂ gas, use 20 % NaOH solution absorption), react at 40-60°C, 60-80°C, and 80-100°C for 1 hour, then reflux for 1 hour; cool down to room temperature, rotary distill off toluene and excess thionyl chloride to obtain 45.0 g of light yellow oily liquid , yield 95.5%.

(2) Synthesis of 2,4-dichlorocinnamic acid diethylaminoethanol ester hydrochloride

Add 23.4g (0.2mol) diethylaminoethanol and 150mL toluene to a 500mL reaction flask in sequence, cool down to -5-0°C in an ice-salt bath, and add dropwise 47.1g (0.2mol) of 2,4- A solution composed of dichlorocinnamoyl chloride and 50mL toluene was controlled at a temperature of 0-5°C. After the dropwise addition was completed, the reaction was stirred at room temperature for 2 hours; filtered with suction, the filter cake was washed with an appropriate amount of toluene, the filtrate was re-distilled and used mechanically, and dried to obtain 67.0 g of a white solid. Yield 96.0%. The melting point is 207-212°C.

(3) 2, the preparation of 4-dichlorocinnamic acid diethylaminoethanol ester (formula I compound)

Add 53.0g (0.15mol) of the compound hydrochloride of formula I prepared above, 150mL water in the 500mL reaction flask, stir and dissolve. Add 100mL dichloromethane, add dropwise under stirring at room temperature 16g (0.15mol) sodium carbonate and 80mL The solution made 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 dichloromethane Methane, to obtain 43.5g of light yellow oily liquid, yield 92%, ¹ H NMR (500MHz, DMSO-d6) δ (ppm) of the compound of formula I: 0.978～1.007 (t, -CH ₃ , 6H), 2.528～2.571 (q, -CH ₂ , 4H), 2.708～2.732(t, -CH ₂ , 2H), 4.210～4.234(t, -CH ₂ , 2H), 6.339～6.371(d, J=16, -CH, 1H ), 7.163~7.473 (m, Ar-H, 3H), 7.908~7.940 (d, J=16, -CH, 1H).

Example 2, 2, the preparation of 4-dichlorocinnamic acid diethylaminoethanol ester organic acid salt

(1) Preparation of 2,4-dichlorocinnamic acid diethylaminoethanol citrate

Add 0.05mol citric acid and 80mL ethanol successively to the 250mL reaction flask, stir to dissolve, slowly add dropwise the mixed solution of 0.05mol2,4-dichlorocinnamic acid diethylaminoethanol ester (formula I compound) and 20mL ethanol under stirring, drop After completion, the stirring was continued for 0.5 h, the solvent was evaporated by rotary evaporation, and 25.4 g of white solid was obtained by drying, with a yield of about 100%.

(2) Preparation of 2,4-dichlorocinnamic acid diethylaminoethanol oxalate

Add 0.05 mol of oxalic acid, 100 mL of ethyl acetate and 0.05 mol of 2,4-dichlorocinnamic acid diethylaminoethanol (compound of formula I) to a 250 mL reaction flask successively, heat up and reflux for 1 h, cool down, suction filter, and dry to obtain White solid 19.9, yield 98%.

According to method (1) or (2), the succinate and fumarate of the compound of formula I can be prepared respectively.

Composition Formulation Example

Example 3, (1) 5% 2,4-dichlorocinnamic acid diethylaminoethanol ester hydrochloride aqueous solution

Add 5g of formula I compound hydrochloride and 90g of water to a 250mL reaction flask, stir to dissolve, add 5g of Tween-80, and stir for 0.5h to obtain 5% diethylaminoethanol 2,4-dichlorocinnamate hydrochloride agent.

(2) 50% 2,4-dichlorocinnamic diethylaminoethanol citrate wettable powder

Weigh 50g of 2,4-dichlorocinnamic acid diethylaminoethanol citrate, 45g of potassium chloride and 5g of tea saponin, mix them evenly and grind them to 80-100 meshes to obtain 50% 2,4-dichlorocinnamic acid Diethylaminoethanol Citrate Wettable Powder.

Biological activity test

Example 4, measurement of cucumber cotyledon rooting

Select cucumber seeds Jinyan No. 4, sow the seeds on 0.7% agar after soaking for 2 hours, culture in a dark room at 25°C for 72 hours, remove cotyledons for later use, take 10 cotyledons and put them in a 6cm-diameter petri dish, which contains a piece of filter paper and 30mL The solution to be tested was cultured in a dark room at 25°C for 5 days, and the rooting of petioles and stems was measured, and the root length and root fresh weight were measured on the 6th day.

The compound (formula I) hydrochloride synthesized by the present invention is tested, and commercially available sodium binitrophenolate, DA-6, and sodium naphthalene acetate are used as contrast agents, and the experimental results are shown in Table 1

Table 1 The results of bioactivity assays of different plant growth regulators

As can be seen from the measurement results in Table 1, the compound of the present invention (formula I) has a very significant promoting effect on the rooting of cucumber cotyledons, and the promoting effect is enhanced with the increase of the concentration. It shows that the compound of the present invention not only has a strong rooting-promoting effect, but also is safe to use, while the inhibitory effect or phytotoxicity occurs in the comparison growth regulator.

Dilute 500 times (100ppm) of 5% 2,4-dichlorocinnamic acid diethylaminoethanol ester hydrochloride aqueous solution prepared in composition preparation embodiment 3 (1) and spray 2 times in the crop growth period, and the interval between two sprays After 15 days, the yield-increasing rates of peanut, ginger and corn reached 21%, 16.7% and 22.4% respectively, significantly better than the 11.5%, 8.3% and 14.0% yield-increasing efficiencies of DA-6 at the same concentration.

Claims (3)

1. A cinnamate compound, the structure is as shown in formula I:

2. according to the cinnamic acid ester compound described in claim 1, be prepared into better inorganic acid salt or organic acid salt of chemical stability, as hydrochloride, phosphate or citrate, oxalate, fumarate , Succinate. 3. according to the inorganic acid salt or the organic acid salt of the cinnamic acid ester compound described in claim 1 and the cinnamic acid ester compound described in claim 2, can be used as plant growth regulator active component and agriculture or forestry Accepted carrier.