CN112341360A

CN112341360A - Butylbenzone-ethyl derivative and synthetic method thereof

Info

Publication number: CN112341360A
Application number: CN202011300787.5A
Authority: CN
Inventors: 张红夺; 金峰; 金涛
Original assignee: Nanjing Astor Pharmaceutical Technology Co ltd
Current assignee: Nanjing Astor Pharmaceutical Technology Co ltd
Priority date: 2020-11-19
Filing date: 2020-11-19
Publication date: 2021-02-09

Abstract

The invention discloses a butylbenzone-ethyl derivative and a synthesis method thereof. The method comprises the following steps: step 1, taking a compound I as a reaction initiator, taking aluminum trichloride as a catalyst, and reacting with butyryl chloride to obtain an intermediate II, and step 2, taking trichloromethane as a reaction solvent, and reacting with hydrogen chloride gas to obtain a corresponding derivative III. Or the intermediate II reacts with dimethyl sulfate in dichloromethane or trichloromethane under the alkaline condition to obtain the corresponding derivative IV. The butylbenzone-ethyl derivative has the advantage of ryegrass inhibition for generating resistance to butylbenzone-ethyl. The synthesis method has the advantages of safety, environmental protection, high yield, easy operation and the like.

Description

Butylbenzone-ethyl derivative and synthetic method thereof

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a butylbenzone-ethyl derivative and a synthesis method thereof.

Background

The chemical name of the butafenacet is 5- (3-butyryl-2, 4, 6-trimethylphenyl) -2- [1- (ethoxyimino) propyl ] -3-hydroxy-cyclohex-2-en-1-one, the pure product is pink crystal, and the melting point is 80.8 ℃. The structural formula is as follows:

butylbenzone belongs to cyclohexenone herbicides. It is an ACCase inhibitor, belongs to a systemic conduction type stem and leaf treatment herbicide, has excellent selectivity, has strong killing effect on gramineous weeds, and is safe to dicotyledonous crops. The stem and leaf treated can be quickly absorbed by leaf surface and transferred into meristem, and can inhibit biosynthesis of branched chain fatty acid and flavonoid in sensitive plant, so that cell division is destroyed, activity of plant meristem is inhibited, and plant growth is delayed. Plants were chlorosis and subsequently died by leaf drying within 1-3 weeks after application. Is mainly used for preventing and controlling grassy weeds in broad-leaved crop fields.

However, tralkoxydim has developed resistance to some plants, such as ryegrass, wild oats, sorghum halepense, and the like. Therefore, the finding of the substitute of the clethodim has practical significance. Meanwhile, the weeding performance of the clethodim is improved by adding functional groups to the clethodim, and the clethodim is a subject worthy of research.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a butylbenzone-ethyl derivative and a synthesis method thereof.

The technical scheme is as follows: the butylbenzone derivative has a structural formula shown in formulas (III and IV).

Further, the derivatives of the benzofenap provided by the invention are synthesized according to the following synthesis route.

Specifically, the derivatives of butylbenzone provided by the invention comprise the following steps:

step 1, taking a compound I as a reaction initiator, and taking aluminum trichloride as a catalyst to react with butyryl chloride to obtain an intermediate II, namely 5- (3-butyryl-2, 4, 6-trimethylphenyl) -2- [1- (ethoxyimino) propyl ] -3-hydroxycyclohex-2-en-1-one;

and 2, reacting the intermediate II with hydrogen chloride gas by using trichloromethane as a reaction solvent to obtain a corresponding derivative III.

and 2, reacting the intermediate II with dimethyl sulfate in dichloromethane or trichloromethane under an alkaline condition to obtain a corresponding derivative IV.

and 2, simultaneously obtaining the corresponding derivative III and the derivative IV from the intermediate II at high temperature and high pressure by using methane chloride as a reaction solvent and a 4A molecular sieve as a reaction catalyst.

Further, the reaction temperature of the step 1 is 20-30 ℃, and the reaction time is 3-5 hours.

Further, in the process of preparing the compound III, the reaction temperature of the step 2 is 65-70 ℃, and the reaction time is 6-12 hours.

Further, in the process of preparing the compound IV, in the step 2 of the present invention, the base includes one or more of potassium carbonate, sodium carbonate, and triethylamine; the reaction time is 4-8 hours, and the reaction temperature is 20-35 ℃.

Further, in the process of simultaneously preparing the compound III and the compound IV, in the step 2, the reaction temperature is 180-.

Has the advantages that: the butylbenzocotrione derivative has the advantage of ryegrass inhibition of butylbenzocotrione resistance.

The synthesis method has the advantages of safety, environmental protection, high yield, easy operation and the like.

Further, the present invention develops a synthetic route to obtain both derivative III and derivative IV.

Drawings

FIG. 1 shows hydrogen spectrum of butafenazate (compound I)

FIG. 2 shows the hydrogen spectrum of Compound III

FIG. 3 shows the hydrogen spectrum of Compound IV

Detailed Description

The following examples illustrate the invention in more detail, but the scope of the invention is not limited to the examples.

In the case of the example 1, the following examples are given,

preparation of Compound II, 5- (3-butyryl-2, 4, 6-trimethylphenyl) -2- [1- (ethoxyimino) propyl ] -3-hydroxycyclohex-2-en-1-one:

adding 30 g of compound I and 200 ml of dichloromethane into a 500 ml round-bottom flask, reducing the temperature to 0 ℃, adding 54 g of aluminum trichloride, stirring for 30 minutes, adding 60 g of butyryl chloride, heating to room temperature, reacting for 3 hours, adding 100 g of ice after the reaction is finished, obviously releasing heat of the reaction system, continuing stirring for 30 minutes, and separating an organic layer. The organic layer was simultaneously concentrated to give a crude brown oil. Adding 50 g of methanol and 50 g of water into the crude product for recrystallization to obtain an intermediate II, namely 31 g of 5- (3-butyryl-2, 4, 6-trimethylphenyl) -2- [1- (ethoxyimino) propyl ] -3-hydroxycyclohex-2-en-1-one, wherein the yield is 89%;

in the case of the example 2, the following examples are given,

preparation of compound III:

adding 10 g of intermediate II and 100 ml of trichloromethane into a 250 ml round-bottom flask, heating to 70 ℃, introducing hydrogen chloride gas, refluxing and reacting for 12 hours, stopping introducing the hydrogen chloride gas, concentrating under reduced pressure, recrystallizing by using 100 ml of petroleum ether to obtain 9.5 g of compound III, wherein the yield is 94%, in example 3,

preparation of compound IV:

in a 250 ml round bottom flask, 10 g of intermediate II and 100 ml of dichloromethane were added, while 6 g of sodium carbonate and 4 g of dimethyl sulfate were added to react at room temperature for 6 hours, 50 ml of water was added, the organic layer was separated, and then dried over 10 g of anhydrous sodium sulfate and filtered, and the organic layer was concentrated. Finally, 100 ml of petroleum ether is used for recrystallization to obtain 8.3 g of the corresponding compound IV with the yield of 82 percent.

In the case of the example 4, the following examples are given,

preparation of compound IV:

a250 ml round bottom flask was charged with 10 g of intermediate II and 100 ml of dichloromethane, and simultaneously 5 g of triethylamine and 4 g of dimethyl sulfate were added to react at room temperature for 4 hours, 50 ml of water was added, the organic layer was separated, and then dried over 10 g of anhydrous sodium sulfate and filtered, and the organic layer was concentrated. Finally, 100 ml of petroleum ether was used for recrystallization to obtain 8.9 g of the corresponding compound IV with a yield of 86%.

In the case of the example 5, the following examples were conducted,

preparation of compound IV:

a250 ml round bottom flask was charged with 10 g of intermediate II and 100 ml of chloroform, while adding 6 g of sodium carbonate and 4 g of dimethyl sulfate to react at room temperature for 8 hours, 50 ml of water was added, the organic layer was separated, and then dried over 10 g of anhydrous sodium sulfate and filtered, and the organic layer was concentrated. Finally, 100 ml of petroleum ether was used for recrystallization to obtain 9.1 g of the corresponding compound IV with a yield of 89%.

In the case of the example 6, it is shown,

preparation of compound IV:

a250 ml round bottom flask was charged with 10 g of intermediate II and 100 ml of chloroform, and simultaneously with 5 g of triethylamine and 4 g of dimethyl sulfate, reacted at room temperature for 6 hours, 50 ml of water was added, the organic layer was separated, and then dried over 10 g of anhydrous sodium sulfate and filtered, and the organic layer was concentrated. Finally, 100 ml of petroleum ether was used for recrystallization to obtain 8.7 g of the corresponding compound IV with a yield of 84%.

Example 7

adding 30 g of compound I and 200 ml of dichloromethane into a 500 ml round-bottom flask, reducing the temperature to 0 ℃, adding 64 g of zinc chloride, stirring for 30 minutes, adding 60 g of butyryl chloride, heating to room temperature, reacting for 6 hours, adding 100 g of ice after the reaction is finished, obviously releasing heat of the reaction system, continuing stirring for 30 minutes, and separating an organic layer. The organic layer was simultaneously concentrated to give a crude brown oil. Adding 50 g of methanol and 50 g of water into the crude product for recrystallization to obtain an intermediate II, namely 32 g of 5- (3-butyryl-2, 4, 6-trimethylphenyl) -2- [1- (ethoxyimino) propyl ] -3-hydroxycyclohex-2-en-1-one, with the yield of 92%;

example 8

Simultaneous preparation of Compounds III and IV,

Adding 10 g of the intermediate II and 100 ml of methane chloride into a 250 ml round-bottom flask, simultaneously adding 0.5 g of 4A molecular sieve, heating to 185 ℃ under the pressure of 10-12 MPa, reacting for 16-18 hours, stopping heating after the reaction is finished, and concentrating an organic layer. And isolated on silica gel to give compound III 2.3 g in 25% yield and compound IV 6.7 g in 64% yield.

Example 11

Herbicidal activity test of 5- (3-butyryl-2, 4, 6-trimethylphenyl) -2- [1- (ethoxyimino) propyl ] -3-hydroxycyclohex-2-en-1-one and derivatives thereof

(1) Test materials:

tralkoxydim, compound III, compound iv. ryegrass seeds with tralkoxydim resistance.

(2) Preparation of test standard solution

0.1 g of 3 compounds to be detected are weighed in three 250 ml flasks, 0.01 g of sodium polycarboxylate, 0.03 g of ethylene glycol, 0.05 g of organic bentonite, 0.03 g of polymeric aluminum trichloride and 50 g of water are added into each flask, and then the mixture is stirred at high speed for 30 minutes by an emulsifying instrument for later use.

(3) Design of experiments

Preparing four artificial soil culture boxes with the soil temperature of 15 ℃ and the humidity of 20%, planting 200 ryegrass with butylbenzone-ethyl resistance, after four leaves grow out, respectively spraying 50 ml of three standard solutions and purified water on the leaf surfaces through a knapsack sprayer, and measuring and calculating the number of plants 15 days after spraying.

Preliminary herbicidal activity research shows that the inhibition rate of ryegrass of the compounds III and IV to the butylbenzone-resistance is higher than that of a reference substance (compound II), so that the herbicidal activity of the compounds III and IV has better selectivity, and the compounds III and IV can be used as lead structures to develop novel selective herbicides.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application.

Claims

1. The butylbenzone-ethyl derivative is characterized by having a structural formula shown as formula (III, IV)

2. The process for the synthesis of a derivative of tralkoxydim according to claim 1, wherein the synthesis is carried out according to the following synthesis scheme

3. The derivative of tralkoxydim according to claim 1, comprising the steps of:

4. The derivative of tralkoxydim according to claim 1, comprising the steps of:

5. The derivative of tralkoxydim according to claim 1, comprising the steps of:

step 1, taking a compound I as a reaction initiator, and taking zinc chloride as a catalyst to react with butyryl chloride to obtain an intermediate II, namely 5- (3-butyryl-2, 4, 6-trimethylphenyl) -2- [1- (ethoxyimino) propyl ] -3-hydroxycyclohex-2-en-1-one;

6. The derivative of butafenac according to claims 3, 4 and 5, wherein the reaction temperature in step 1 is 20-30 ℃ and the reaction time is 3-5 hours.

7. The derivative of butylbenzocotrione according to claim 3, wherein in the preparation of compound III, the reaction temperature of step 2 is 65-70 ℃ and the reaction time is 6-12 hours.

8. The derivative of butafenac according to claim 4, wherein in the preparation of compound IV, in step 2, the reaction temperature is 20-35 ℃ and the reaction time is 4-8 hours, and the base comprises one or more of potassium carbonate, sodium carbonate and triethylamine.

9. The derivative of tralkoxydim according to claim 5, wherein in the step 2, the reaction temperature is 180-.