CN112209846A - Preparation method of s-metolachlor technical - Google Patents
Preparation method of s-metolachlor technical Download PDFInfo
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- CN112209846A CN112209846A CN202011202975.4A CN202011202975A CN112209846A CN 112209846 A CN112209846 A CN 112209846A CN 202011202975 A CN202011202975 A CN 202011202975A CN 112209846 A CN112209846 A CN 112209846A
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C07—ORGANIC CHEMISTRY
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C07—ORGANIC CHEMISTRY
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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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Abstract
The invention discloses a preparation method of a raw metolachlor drug. Comprises the steps of carrying out catalytic dehydrogenation reaction to synthesize intermediate methoxy acetone, then carrying out reaction on methoxy acetone, 2-methyl-6-ethyl aniline and organic solvent to synthesize intermediate 1-methoxy propyl-2- (2-methyl-6-ethyl phenyl) imine, and introducing H into imine, chiral catalyst and organic solvent2Reacting to obtain intermediate amine ether and Na2CO3Adding chloracetyl chloride into an organic solvent, and after the reaction is finished, carrying out post-treatment and refining to obtain the s-metolachlor. The invention improves the process in the dehydrogenation process, ensures the reaction speed and dehydrogenation conversion rate for industrial production, simultaneously amplifies the requirements of industrial production, reasonably adjusts the related parameters, maintains the reaction yield and the yield in a reasonable balance state, meets the requirements of industrial production, reduces the cost, and is beneficial to the agriculture of ChinaThe popularization of the method is also disclosed.
Description
Technical Field
The invention relates to the technical field of herbicide pesticides, in particular to a preparation method of a metolachlor technical.
Background
S. metolachlor is a novel environment-friendly herbicide with high efficiency and high selectivity, and is a backbone variety of herbicides in developed countries and regions such as European Union, United states and the like. Since the introduction of s-metolachlor, the european union banned the s-metolachlor product in 2002 in order to protect the environment and to limit the use of s-metolachlor in developed countries and regions. The banning of metolachlor in some countries has prompted a dramatic increase in the sales of s.metolachlor, which has reached $ 5.67 billion in 2007, jumping the fourth most herbicide in the world.
The synthetic method of s-metolachlor currently comprises:
1. the chiral source synthesis process method comprises the following steps: the method specifically comprises the steps of using optical raw materials (D) methyl lactate or (D) ethyl lactate as raw materials, firstly reacting with p-toluenesulfonyl chloride to generate (R) -2- (p-toluenesulfonyloxy) propionate, then reacting with 2-methyl-6-ethylaniline to obtain S- (-) -N- (2-methyl-6-ethylaniline) alanine ester, then reacting with a reducing agent C to obtain S- (-) -N- (1, -methyl-2, -hydroxyethyl) -2-methyl-6-ethylaniline, further acylating with chloroacetyl chloride, and finally methylating to obtain (S) -metolachlor. The process has the advantages of complex route, yield lower than 40 percent, high cost, unsuitability for industrial production and serious environmental pollution.
2. The splitting method comprises the following steps: the resolution method is divided into a chemical resolution method and a biological enzyme resolution method, the resolution method has low production efficiency, long process route and low conversion rate, and the synthesized product needs to waste about 50 percent of raw materials, thereby causing high production cost and serious environmental pollution.
3. The asymmetric catalytic synthesis process comprises the following steps: the asymmetric catalytic synthesis process is the most advanced synthesis technology of chiral compounds at present, but the differences of the obtained products and the catalytic efficiency are large due to the different types and large quality differences of chiral catalysts.
The s-metolachlor can be used for various crops such as soybean, corn, peanut, potato, cotton, beet, rape, sunflower, flax, pumpkin, watermelon, sesame, sugarcane, cotton, rape, potato, onion, pepper and the like, has the characteristics of safety, high efficiency, low toxicity, low residue, environmental friendliness and the like, can meet the urgent needs of agricultural production of vast farmers, has great significance for increasing the income of the farmers and improving the agricultural efficiency, and has wide popularization and application prospects in China. The international market at present has a large demand for the product, and has a good export and earning prospect. However, one of the main problems of the product popularized in China at present is that the production cost is too high, the product price is also high, and therefore large-area popularization is difficult at present, and therefore a preparation method which is suitable for large-scale industrial production and has low cost is found, and the preparation method has important significance for popularization of the herbicide in agriculture.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of s-metolachlor.
The complete technical scheme of the invention comprises the following steps:
a preparation method of a metolachlor technical comprises the following steps:
(1) and (3) carrying out catalytic dehydrogenation reaction to synthesize intermediate methoxy acetone: adopting a plurality of fixed bed reactors with the diameter of 10cm and the length of 1.5m, filling inert magnetic rings with different sizes at two ends of each fixed bed reactor in sections, filling a Cu/ZnO catalyst in each fixed bed reactor, adding a liquid raw material 1-methoxyl-2-propanol into the reactor through a plunger pump, and simultaneously heating the reactor by adopting an electric heating device, wherein the reaction formula of the step is as follows:
the relevant parameters in this step conform to the following relationship:
in the formula: t is reaction temperature, and the control range is 220-280 ℃; a is a conversion coefficient and ranges from 6.2 to 10.6; rho is the bulk density of the Cu/ZnO catalyst, and the value range is 700-750 Kg/m3(ii) a L is sent in per unit timeThe amount of the 1-methoxy-2-propanol is 10-30 Kg; s is the specific surface area of the catalyst and has a value range of 120-150 m2/g；
(2) Alkylation dehydration reaction, synthesis of intermediate 1-methoxy propyl-2- (2-methyl-6-ethyl phenyl) imine:
adding 2-methyl-6-ethylaniline, methoxy acetone and benzene into a reaction kettle, wherein the volume ratio of the 2-methyl-6-ethylaniline to the methoxy acetone is as follows: methoxy acetone: benzene 7.5: 15: 12, controlling the reaction temperature to be 75-90 ℃ and the condition time to be 9-10 hours;
after the reaction is finished, separating out benzene by a decompression method, and distilling the residual reaction liquid to obtain a liquid product 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) imine;
the reaction formula of the step is as follows:
(3) hydrogenation reduction reaction, synthesis of intermediate 1-methoxy propyl-2- (2-methyl-6-ethyl phenyl) amine: adding 2-methyl-6-ethyl phenyl-imine, 1-S-diphenyl phosphine-2-R-bis (3, 5-dimethyl phenyl) phosphine cyclopentadienyl ruthenium and iridium bromide into a reaction kettle, wherein the mass ratio of the 2-methyl-6-ethyl phenyl-imine: 1-S-diphenylphosphino-2-R-bis (3, 5-dimethylphenyl) phosphinotrien-ruthenium: iridium bromide 38000:10: 2; controlling the reaction temperature to be 50 +/-5 ℃, the reaction time to be 6 hours and the hydrogen pressure to be 6-8 MPa;
after the reaction is finished, distilling to obtain 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine;
the reaction formula of the step is as follows:
(4) acylation reaction: preparing the s-metolachlor; adding 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine, sodium carbonate and benzene into a reaction kettle, wherein the dosage ratio of the 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine to the sodium carbonate to the benzene is (mass/volume): sodium carbonate: 1.2Kg of benzene: 1 Kg: 7.5L; then adding benzene solution of chloracetyl chloride, continuing to react the reaction solution for lh after the addition is finished, adding water and stirring after the reaction is finished, standing for layering, drying an organic layer, and evaporating the solvent under reduced pressure to obtain a final product (S) -metolachlor;
the reaction formula of the step is as follows:
the main advantages of the invention are:
1. in the step of synthesizing the intermediate methoxy acetone, influence parameters which have obvious effect on the synthesis process are found by researching various influence factors in the dehydrogenation conversion process and utilizing an analytical experiment and fitting method, so that a process determination method suitable for industrial production is obtained, the reaction speed and yield for industrial production are ensured, and the dehydrogenation conversion rate is maintained at a higher level.
2. In other synthesis steps of the s-metolachlor, the requirements of industrial production are amplified according to the research results in a laboratory, and related parameters are reasonably adjusted, so that the reaction yield and the yield are maintained in a reasonable balance state, the requirements of industrial production are met, the cost is reduced, and the product is beneficial to popularization in agriculture in China.
Drawings
FIG. 1 is a process flow of the preparation method of a raw metolachlor drug disclosed by the invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only illustrative and are not intended to limit the present application.
As shown in fig. 1, the basic synthesis process of s-metolachlor is as follows:
1. and (3) carrying out catalytic dehydrogenation reaction to synthesize intermediate methoxy acetone: a plurality of fixed bed reactors with the diameter of 10cm and the length of 1.5m are adopted, and inert magnetic rings with different sizes are filled at two ends of each fixed bed in a sectional mode. Each fixed bed reactor is filled with a Cu/ZnO catalyst, a liquid raw material 1-methoxy-2-propanol is added into the reactor through a plunger pump, and an electric heating device is adopted to heat the reactor. The reaction formula is as follows:
in the actual industrial production of the step, the dehydrogenation conversion rate and the reaction speed need to be comprehensively considered, although the dehydrogenation conversion rate can be improved by prolonging the reaction time, the production beat can be prolonged, the production efficiency can be reduced, and the improper shortening of the reaction time can possibly cause the dehydrogenation conversion rate to be too low, thereby causing waste, improving the cost and being not beneficial to environmental protection.
The reaction speed mainly depends on the amount of the 1-methoxy-2-propanol added and the reaction conditions, and in the invention, the research shows that in the process, under the condition of a certain amount of raw material added, the bulk density, the amount, the reaction temperature and the like of the used catalyst can cause different reaction speeds and dehydrogenation conversion rates, and the conversion rate of the raw material greatly changes under different combination parameters. Therefore, according to the actual industrial requirements, the reaction speed and yield for industrial production are ensured, and the dehydrogenation conversion rate is maintained at a higher level to improve the yield. In the actual production, the influence of various parameter changes in the reaction process on the reaction is respectively researched, parameters with obvious effects are selected, and the following defined relationship is obtained through analysis fitting and actual production verification:
in the formula: t is reaction temperature, and the control range is 220-280 ℃; a is a conversion coefficient which embodies the comprehensive effect of other factors which are not obviously influenced in the actual productionThe value range in the invention is 6.2-10.6; rho is the bulk density of the Cu/ZnO catalyst, and the value range is 700-750 Kg/m3(ii) a L is the amount of 1-methoxy-2-propanol fed in unit time, and the range is 10-30 Kg; s is the specific surface area of the catalyst and has a value range of 120-150 m2(ii) in terms of/g. In the actual reaction process, under the condition that parameters such as the adding amount of 1-methoxy-2-propanol, the bulk density of a catalyst and the like are fixed, a proper reaction temperature is selected to ensure the reaction speed and the dehydrogenation reaction rate, the generated hydrogen is measured by a wet flowmeter, samples are taken 1 time every 2 hours, and the dehydrogenation conversion rate is analyzed by GC to be more than 92%.
2. Alkylation dehydration reaction, synthesis of intermediate 1-methoxy propyl-2- (2-methyl-6-ethyl phenyl) imine: adding the intermediate methoxy acetone, 2-methyl-6-ethyl aniline and an organic solvent into a reaction kettle, reacting at a certain temperature, and rectifying after the reaction to obtain the intermediate imine. The specific parameters of the step are as follows:
adding 2-methyl-6-ethylaniline, methoxy acetone and benzene into a reaction kettle with mechanical stirring, wherein the volume ratio of the 2-methyl-6-ethylaniline: methoxy acetone: benzene 7.5: 15: and 12, controlling the reaction temperature to be 75-100 ℃, controlling the reaction time to be 9-10 hours, separating an organic solvent after the reaction is finished, and rectifying the organic solvent in a rectifying tower to obtain 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) imine, wherein the reaction conversion rate is about 95% by GC analysis.
The reaction formula is as follows:
3. hydrogenation reduction reaction, synthesis of intermediate 1-methoxy propyl-2- (2-methyl-6-ethyl phenyl) amine: adding intermediate imine, chiral catalyst and organic solvent into a high-pressure reaction kettle, and introducing H under certain temperature and pressure conditions2The reaction gives the intermediate amine ether. The specific operation of this step is:
adding 2-methyl-6-ethyl phenyl-imine, 1-S-diphenyl phosphine-2-R-bis (3, 5-dimethyl phenyl) phosphine cyclopentadienyl ruthenium and iridium bromide into a high-pressure reaction kettle, wherein the mass ratio of the 2-methyl-6-ethyl phenyl-imine: 1-S-diphenylphosphino-2-R-bis (3, 5-dimethylphenyl) phosphinotrien-ruthenium: iridium bromide 38000:10: 2. Controlling the reaction temperature to be 50 +/-5 ℃, the reaction time to be 6 hours, and the hydrogen pressure to be 6-8 MPa, after the reaction is finished, distilling to obtain a product, namely a light yellow liquid, namely 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine, wherein the e.e. value is about 95%, and the yield is 90%.
The reaction formula is as follows:
4. acylation reaction: and (3) preparing the s-metolachlor. Mixing amine ether and Na2CO3Adding an organic solvent into a reaction kettle, adding chloroacetyl chloride under certain conditions, and after the reaction is finished, carrying out post-treatment and refining to obtain the fine metolachlor. The specific operation of this step is:
adding 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine, sodium carbonate and benzene into a reaction kettle with a mechanical stirrer, wherein the dosage ratio of the 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine to the sodium carbonate to the benzene is as follows: sodium carbonate: 40.5Kg of benzene: 33.4 Kg: 220L. Then adding benzene solution of chloracetyl chloride to continue reacting for lh, and after the reaction is finished, putting the mixture into a desolventizing kettle to desolventize to obtain the original drug of the metolachlor with the yield of 90 percent and the GC: 96.0 percent.
The reaction formula is as follows:
the above applications are only some embodiments of the present application. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept herein, and it is intended to cover all such modifications and variations as fall within the scope of the invention.
Claims (1)
1. A preparation method of a metolachlor technical is characterized by comprising the following steps:
(1) and (3) carrying out catalytic dehydrogenation reaction to synthesize intermediate methoxy acetone: adopting a plurality of fixed bed reactors with the diameter of 10cm and the length of 1.5m, filling a Cu/ZnO catalyst in each fixed bed reactor, adding a liquid raw material 1-methoxy-2-propanol into the reactor, and simultaneously heating the reactor by adopting a heating device, wherein the reaction formula of the step is as follows:
the relevant parameters in this step conform to the following relationship:
in the formula: t is reaction temperature, and the control range is 220-280 ℃; a is a conversion coefficient and ranges from 6.2 to 10.6; rho is the bulk density of the Cu/ZnO catalyst, and the value range is 700-750 Kg/m3(ii) a L is the amount of 1-methoxy-2-propanol fed in unit time, and the range is 10-30 Kg; s is the specific surface area of the catalyst and has a value range of 120-150 m2/g。
(2) Alkylation dehydration reaction, synthesis of intermediate 1-methoxy propyl-2- (2-methyl-6-ethyl phenyl) imine:
adding 2-methyl-6-ethylaniline, methoxy acetone and benzene into a reaction kettle, wherein the volume ratio of the 2-methyl-6-ethylaniline to the methoxy acetone is as follows: methoxy acetone: benzene 7.5: 15: 12, controlling the reaction temperature to be 75-90 ℃ and the condition time to be 9-10 hours;
after the reaction is finished, benzene is separated out by a decompression method, and the residual reaction liquid is distilled to obtain a liquid product 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) imine.
The reaction formula of the step is as follows:
(3) hydrogenation reduction reaction, synthesis of intermediate 1-methoxy propyl-2- (2-methyl-6-ethyl phenyl) amine: adding 2-methyl-6-ethyl phenyl-imine, 1-S-diphenyl phosphine-2-R-bis (3, 5-dimethyl phenyl) phosphine cyclopentadienyl ruthenium and iridium bromide into a reaction kettle, wherein the mass ratio of the 2-methyl-6-ethyl phenyl-imine: 1-S-diphenylphosphino-2-R-bis (3, 5-dimethylphenyl) phosphinotrien-ruthenium: iridium bromide 38000:10: 2; controlling the reaction temperature to be 50 +/-5 ℃, the reaction time to be 6 hours and the hydrogen pressure to be 6-8 MPa.
After the reaction is finished, distilling to obtain 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine;
the reaction formula of the step is as follows:
(4) acylation reaction: preparing the s-metolachlor; adding 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine, sodium carbonate and benzene into a reaction kettle, wherein the dosage ratio of the 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine to the sodium carbonate to the benzene is (mass/volume): sodium carbonate: 1.2Kg of benzene: 1 Kg: 7.5L; then adding benzene solution of chloracetyl chloride, continuing reaction for lh after the addition is finished, adding water and stirring after the reaction is finished, standing for layering, drying an organic layer, and evaporating the solvent under reduced pressure to obtain the final product (S) -metolachlor.
The reaction formula of the step is as follows:
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS275182B2 (en) * | 1989-01-26 | 1992-02-19 | Univ Slovenska Tech | Method of 1-methoxy-2-propanone preparation |
| CN104803875A (en) * | 2015-03-27 | 2015-07-29 | 江苏长青农化南通有限公司 | Synthetic method for S-metolachlor |
| CN106467473A (en) * | 2016-08-29 | 2017-03-01 | 江苏长青农化股份有限公司 | The synthetic method of S-metolachlor |
| CN109096137A (en) * | 2018-07-30 | 2018-12-28 | 山东万豪肥业有限公司 | A kind of synthetic method of S-metolachlor |
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS275182B2 (en) * | 1989-01-26 | 1992-02-19 | Univ Slovenska Tech | Method of 1-methoxy-2-propanone preparation |
| CN104803875A (en) * | 2015-03-27 | 2015-07-29 | 江苏长青农化南通有限公司 | Synthetic method for S-metolachlor |
| CN106467473A (en) * | 2016-08-29 | 2017-03-01 | 江苏长青农化股份有限公司 | The synthetic method of S-metolachlor |
| CN109096137A (en) * | 2018-07-30 | 2018-12-28 | 山东万豪肥业有限公司 | A kind of synthetic method of S-metolachlor |
Non-Patent Citations (5)
| Title |
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| HANS-ULRICH BLASER: "From a Chiral Switch to a Ligand Portfolio for Asymmetric Catalysis", 《ACC. CHEM. RES.》 * |
| 张海滨: "精异丙甲草胺的合成研究", 《农药科学与管理》 * |
| 景闻华: "除草剂精异丙甲草胺的合成工艺研究", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
| 李倩: "（S）-异丙甲草胺的不对称合成研究", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
| 陈涛 等: "丙二醇甲醚气固相催化合成甲氧基丙酮", 《化学试剂》 * |
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Application publication date: 20210112 |