CN101805288A - Novel method for synthesizing cloquintocet-mexyl - Google Patents
Novel method for synthesizing cloquintocet-mexyl Download PDFInfo
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- CN101805288A CN101805288A CN 201010151603 CN201010151603A CN101805288A CN 101805288 A CN101805288 A CN 101805288A CN 201010151603 CN201010151603 CN 201010151603 CN 201010151603 A CN201010151603 A CN 201010151603A CN 101805288 A CN101805288 A CN 101805288A
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Abstract
The invention relates to a novel method for synthesizing cloquintocet-mexyl. The method is characterized by comprising the following steps: 1, adopoting 5-chlorine-8-oxyquinoline as the initial raw material to react with methyl chloroacetate in the presence of sodium carbonate and sodium hydroxide to obtain the intermediate 5-chlorine-8-quinolyloxido methyl acetate; and 2, and carrying out transesterification to synthetize the cloquintocet-mexyl. The invention has the advantages of simple reaction, easy realization and mild conditions, and the generated phenylmethane waste liquor containing methanol can be recycled after treatment, thereby reducing the production cost.
Description
Technical field
The present invention relates to a kind of chemistry security agent and organic synthesis, medicine intermediate field, specifically relate to a kind of production technique of novel cloquintocetmexyl.
Use: the safener of alkynes grass ester
Packing: 25kgs fiber can
The safener of alkynes grass ester.Organic synthesis, medicine intermediate.
Background technology
The chemical name of cloquintocetmexyl is 1-methyl hexyl (5-chloro-8-quinoline oxy) acetic ester.Molecular formula is C
18H
22ClNO
3, relative molecular mass is 335.83.Its chemical structural formula is:
The cloquintocetmexyl English name is Cloquintocet-mexyl, and the CAS accession number is 99607-70-2.The industrial goods outward appearance is the light yellow solid powder, and fusing point is 69.4 ℃.
Cloquintocetmexyl industrial mainly as organic synthesis and medicine intermediate.Application on agricultural chemicals mainly is the safener as weedicide alkynes grass ester.Be made into preparation with alkynes grass ester with 1: 4 proportioning and use, can effectively improve the resistance of granule cereal, prevent of the poisoning of alkynes grass ester, enlarged the scope of application of alkynes grass ester granule cereal.
The traditional synthesis of cloquintocetmexyl is to adopt Mono Chloro Acetic Acid and 2-enanthol to carry out esterification to generate intermediate (1), and (1) synthesizes cloquintocetmexyl with 5-chloro-oxine again; This route is in reaction process, because the esterification of Mono Chloro Acetic Acid and 2-enanthol is not easy to carry out fully, the reaction times is longer, and yield is on the low side, is not easy to carry out large-scale industrial production; Intermediate (1) purification difficult, and higher to the conditional request of reaction, when being synthesized cloquintocetmexyl, second step very easily generates impurity, influence product quality; The total yield of this method is low, unreasonable economically.
Because cloquintocetmexyl is of many uses, simultaneously because the quality of the different resultant products of the operational path that adopts is also uneven.By consulting of Chinese and foreign documents also do not found to use the report that ester exchange synthetic method is produced cloquintocetmexyl at present.
Summary of the invention
The novel method that the objective of the invention is to overcome the deficiencies in the prior art and a kind of synthetic cloquintocetmexyl is provided.
The novel method of synthetic cloquintocetmexyl of the present invention is to adopt 5-chloro-oxine and methyl chloroacetate reaction synthetic intermediate 5-chloro-8-quinoline oxy methyl acetate, and mode and the 2-enanthol with transesterify synthesizes cloquintocetmexyl again.
Ester exchange synthetic method of the present invention, raw material is easy to get, the reaction conditions gentleness, process is controlled easily, and the high impurity of the purity of product is few, is fit to large-scale industrial production.
Ester exchange synthetic method technology of the present invention comprises the steps:
1, intermediate 5-chlorine 8-quinoline oxy methyl acetate is synthetic:
Add 5-chloro-oxine in the solvent dimethyl sulfoxide (DMSO), sodium hydroxide solution carries out adding yellow soda ash, toluene after the normal-temperature reaction; In about 1 hour temperature of reaction is elevated to 80-155 ℃, azeotropic dehydration is till the toluene of deviating from is limpid; Cool to 40-80 ℃ then, drip methyl chloroacetate, temperature of reaction is controlled at 30-90 ℃ and obtains 5-chloro-oxine ethoxyacetic acid methyl esters.
Reaction process is as follows:
Wherein in dripping the methyl chloroacetate production process, temperature of reaction is preferably 30-90 ℃
2, cloquintocetmexyl is synthetic:
Add 2-enanthol and intermediate 5-chloro-8-quinoline oxy methyl acetate in solvent, keep vacuum to 0.025-0.07Mpa, heat temperature raising steams and removes about partial solvent; Keep 60-120 ℃ of temperature, add appropriate amount of catalysts and keep temperature of reaction at 60-120 ℃, steam partial solvent, final temp drops to 60 ℃, and the adding solvent cools to 1-20 ℃ and obtains crystalline product.
Reaction process is as follows:
Wherein in ester-exchange reaction, temperature of reaction is preferably 60-120 ℃, and catalyzer is preferably the mixture of organic bases, mineral alkali or organic bases and mineral alkali, and solvent is methyl alcohol, ethanol, toluene, dimethylbenzene, diacetone alcohol, ether, sherwood oil etc.
Specific embodiment
Following examples describe the present invention in detail, and embodiment mainly is for the present invention is described but not is used for limiting the present invention.
1, intermediate 5-chloro-8-quinoline oxy methyl acetate is synthetic:
Get 5-chloro-oxine 300g dimethyl sulfoxide (DMSO) 1000mL and add in the 3L reaction flask, start stirring, under the room temperature, drip the 200g sodium hydroxide solution, drip off back insulation reaction 1 hour; Add 500g yellow soda ash and 100mL toluene then, temperature of reaction is elevated to 80-155 ℃, azeotropic dehydration is till the toluene of deviating from is limpid; Cool to 40 ℃, drip methyl chloroacetate 250g, temperature of reaction is controlled at 30-90 ℃; Insulation reaction reaction in 3 hours finishes, and is cooled to 20 ℃, adds 1200mL water, and suction filtration, solid materials water are given a baby a bath on the third day after its birth inferior, and fully drain, and obtain intermediate 5-chloro-8-quinoline oxy methyl acetate.
2, cloquintocetmexyl is synthetic:
Get intermediate 5-chloro-8 quinoline oxy methyl acetate 400g, toluene 500mL, the 1000g2-enanthol adds in the 3L reaction flask, starts stirring, keeps vacuum to 0.025-0.07Mpa, and heat temperature raising steams and removes about 50mL toluene; Keep 60-120 ℃ of temperature, drip several catalyzer in reaction flask; And keep temperature of reaction at 60-120 ℃, and steaming methyl alcohol, reaction finishes the back temperature and drops to 60 ℃, and solubilizing agent 2000mL cools to 1-20 ℃ and keep suction filtration after 1 hour, obtains the cloquintocetmexyl filter cake, and oven dry promptly obtains drying products.
Claims (3)
1. the novel method of a synthetic cloquintocetmexyl.It is characterized in that this technology comprises the steps: 1, intermediate 5-chloro-8-quinoline oxy methyl acetate synthetic: add 5-chloro-oxine in the solvent dimethyl sulfoxide (DMSO), sodium hydroxide solution carries out adding yellow soda ash, toluene after the normal-temperature reaction; In about 1 hour temperature of reaction is elevated to 80-155 ℃, azeotropic dehydration is till the toluene of deviating from is limpid; Cool to 40-80 ℃ then, drip methyl chloroacetate, temperature of reaction is controlled at 30-90 ℃ and obtains 5-chloro-oxine ethoxyacetic acid methyl esters.2, cloquintocetmexyl is synthetic: add 2-enanthol and intermediate 5-chloro-8-quinoline oxy methyl acetate in solvent, keep vacuum to 0.025-0.07Mpa, heat temperature raising steams and removes about partial solvent; Keep 60-120 ℃ of temperature, add appropriate amount of catalysts and keep temperature of reaction at 60-120 ℃, steam partial solvent, final temp drops to 60 ℃, and the adding solvent cools to 1-20 ℃ and obtains crystalline product.
2. the novel method of synthetic cloquintocetmexyl according to claim 1 is characterized in that catalyzer is preferably the mixture of organic bases, mineral alkali or organic bases and mineral alkali.
3. the novel method of synthetic cloquintocetmexyl according to claim 1 is characterized in that solvent is preferably methyl alcohol, ethanol, toluene, dimethylbenzene, diacetone alcohol, ether, sherwood oil etc.
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| CN 201010151603 CN101805288A (en) | 2010-04-21 | 2010-04-21 | Novel method for synthesizing cloquintocet-mexyl |
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| CN 201010151603 CN101805288A (en) | 2010-04-21 | 2010-04-21 | Novel method for synthesizing cloquintocet-mexyl |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106719707A (en) * | 2017-02-22 | 2017-05-31 | 佛山市普尔玛农化有限公司 | A kind of Herbicidal combinations comprising topramezone Yu clodinafop-propargyl |
| CN113121431A (en) * | 2021-04-18 | 2021-07-16 | 新沂市永诚化工有限公司 | Method for chemically synthesizing cloquintocet-mexyl |
| CN113135851A (en) * | 2021-04-26 | 2021-07-20 | 甘肃联凯生物科技有限公司 | Synthesis method of cloquintocet-mexyl |
| CN113461610A (en) * | 2021-05-10 | 2021-10-01 | 新沂市永诚化工有限公司 | Preparation process and preparation system of cloquintocet-mexyl |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1568314A (en) * | 2000-06-28 | 2005-01-19 | 辛根塔参与股份公司 | Process for the preparation of quinoline derivatives |
| CN101293870A (en) * | 2008-05-29 | 2008-10-29 | 健雄职业技术学院 | Cloquintocet-mexyl synthesizing method |
-
2010
- 2010-04-21 CN CN 201010151603 patent/CN101805288A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1568314A (en) * | 2000-06-28 | 2005-01-19 | 辛根塔参与股份公司 | Process for the preparation of quinoline derivatives |
| CN101293870A (en) * | 2008-05-29 | 2008-10-29 | 健雄职业技术学院 | Cloquintocet-mexyl synthesizing method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106719707A (en) * | 2017-02-22 | 2017-05-31 | 佛山市普尔玛农化有限公司 | A kind of Herbicidal combinations comprising topramezone Yu clodinafop-propargyl |
| CN113121431A (en) * | 2021-04-18 | 2021-07-16 | 新沂市永诚化工有限公司 | Method for chemically synthesizing cloquintocet-mexyl |
| CN113135851A (en) * | 2021-04-26 | 2021-07-20 | 甘肃联凯生物科技有限公司 | Synthesis method of cloquintocet-mexyl |
| CN113461610A (en) * | 2021-05-10 | 2021-10-01 | 新沂市永诚化工有限公司 | Preparation process and preparation system of cloquintocet-mexyl |
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Open date: 20100818 |