CN101941947A - Synthesis method of 2-chloro-6-chloroquinoxaline - Google Patents
Synthesis method of 2-chloro-6-chloroquinoxaline Download PDFInfo
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- CN101941947A CN101941947A CN 201010264471 CN201010264471A CN101941947A CN 101941947 A CN101941947 A CN 101941947A CN 201010264471 CN201010264471 CN 201010264471 CN 201010264471 A CN201010264471 A CN 201010264471A CN 101941947 A CN101941947 A CN 101941947A
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Abstract
The invention belongs to the field of organic synthesis, providing a synthesis method in which an organic solvent is used as a synthesis environment of 2-chlorine-6-chloroquinoxaline. The method adopts p-chloro-m-nitroacetoacetanilide as a starting raw material, and a metal salt is obtained through closed loop, reduction and crystallization in the organic solvent under the alkaline condition. The technology is adopted to improve the stability of the whole synthesis reaction. Compared with the traditional technology, the method has the advantages of simple and practicable operation, high yield and content, wherein the use and the recycle of the organic solvent can greatly reduce the generation of waste water, relieve the pollution of environment and reduce production cost.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate to the synthetic method of agricultural chemicals quizalofopPethyl intermediate 2-chloro-6-hydroxy quinoxaline.
Background technology
QuizalofopPethyl is a kind of novel dry land cauline leaf treatment agent of high selectivity, chemical name is (R)-2-[4-(6-chloro-quinoxaline-2-base oxygen) phenoxy group] ethyl propionate, and 2-chloro-6-hydroxy quinoxaline is the important intermediate of synthetic quizalofopPethyl, its pure product are that white is with pink tabular crystal, industrial goods are light yellow to pink powder, under alkaline condition, generate salt, unstable under acidic condition.
The method of present domestic Synthetic 2-chloro-6-hydroxy quinoxaline, mainly be being starting raw material to the chlorine o-Nitroacetanilide, process closed loop under alkaline environment, reduction, three steps of crystallization are synthetic, ripe in the production at home of this technology, but still the part that comes with some shortcomings is mainly reflected in 2-chloro-6-hydroxy quinoxaline content and yield is generally lower, need a large amount of water as solvent in the production, and meeting produces a large amount of alkaline sewages in the production process, increase the difficulty of water treatment, improved production cost simultaneously.
Owing to the existence of above-mentioned shortcoming, be unfavorable for the scale suitability for industrialized production of quizalofopPethyl, also can't obtain good society and economic benefit.
Summary of the invention
The present invention is directed to the deficiency that existing synthetic method exists, adopt the synthetic environment of organic solvent as 2-chloro-6-hydroxy quinoxaline, adopt this scheme being starting raw material to the adjacent nitro alpha.-acetylacetanilide of chlorine, under the organic solvent alkaline condition, carry out closed loop, reduction, crystallization obtains metal-salt, carries out acidification then, obtain 2-chloro-6-hydroxyl quinoline woods, adopt this technology to improve the stability of whole building-up reactions, compare, have that operation is simple with traditional technology, yield is higher, the advantage that content is higher, wherein the using and reclaiming of organic solvent significantly reduces the generation of waste water, alleviate environmental pollution, reduced production cost.
Reaction mechanism of the present invention is as follows:
Wherein, the contriver has changed in the conventional art that to adopt with water be the technology of reaction solvent, then select to be added with the solvent of the organic solvent of alkaline matter as reaction, and the reaction environment that organic solvent provides, can make entire reaction more stable, can reduce the generation of side reaction, thereby improve product content.With an organic solvent simultaneously, can reduce the sewage quantum of output.
Whole preparation process of the present invention comprises that its concrete technology is as follows to the closed loop and the reduction reaction of the adjacent nitro alpha.-acetylacetanilide of chlorine:
The first step: ring-closure reaction
In reactor, add the organic solvent that contains alkaline matter, add then the adjacent nitro alpha.-acetylacetanilide of chlorine, under 20-30 ℃, initiation reaction 2.5-3.5 hour, be warmed up to 50 ℃-solvent boiling point temperature then and carry out ring-closure reaction, the general reaction times is about 3 hours, sampling, follow the tracks of the adjacent nitro alpha.-acetylacetanilide of chlorine content with liquid chromatography, calculate with the chromatogram area normalization method, if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＜0.1%, then can descend the step to handle, if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＞0.1%, then need to prolong the reaction times, follow the tracks of again, behind adjacent nitro alpha.-acetylacetanilide＜0.1%, can descend step process to chlorine up to reactant;
Second step: reduction reaction
In above-mentioned reactor, add reductive agent, be warming up to about 50-150 ℃, insulation reaction 5-15 hour, whether react completely with the liquid-phase chromatographic analysis oxynitride, if tracking results is amount of nitrogen oxides＜0.1%, then can handle, if tracking results is amount of nitrogen oxides＞0.1%, then need to prolong the reaction times, carry out repetition measurement again, till the reactant amount of nitrogen oxides reaches requirement, after reaction finishes, logical water coolant is reduced to room temperature, feed cold salt then and reduce to 5 ℃ again, be incubated 2 hours, making the whole crystallizations of whole generation material is metal-salt, the frame that re-packs then obtains the crystallisate metal-salt;
The 3rd step: crystallization acidifying
The metal-salt of above-mentioned reactant crystallisation by cooling gained is used the hot water dissolving, add activated carbon decolorizing, get filtrate and carry out acidifying, drip acid solution in filtrate, regulating the pH value is 4-6, the washing desalination, and the filter cake oven dry had both got 2-chloro-6-hydroxy quinoxaline.
By above-mentioned preparation technology, owing to adopt organic solvent, saved a large amount of water and also reduced the generation of alkaline waste water, improved the stability of reaction, and the W-response time decreases, thereby improved the efficient of producing, while reclaims easily owing to the present invention's employing is the solvent immiscible with water, and raw material is dissolved in wherein, obtain better environmental benefit, improved the yield of reaction simultaneously again.
Among the above-mentioned preparation method, the solvent that is adopted is generally polar solvent, can use alcohols such as methyl alcohol, ethanol, propyl alcohol etc.; Ethers such as ether, methyl tertiary butyl ether etc.; A kind of or mixed system in ketone such as the acetone etc.; Why select like this, the first above-mentioned selected organic solvent should be able to dissolve various reactants and generate material, the second selected organic solvent does not react with reactive material, various side reactions do not take place, can avoid organic solvent and raw material reaction to generate impurity as far as possible, reduce product content; The alkaline matter that is adopted is selected from one or more in potassium hydroxide, sodium hydroxide, the salt of wormwood; The reductive agent that is adopted is one or more in an alkali metal salt of reductibilities such as sodium sulphite, sodium polysulphide, S-WAT, sodium bisulfite, POTASSIUM BOROHYDRIDE, potassium sulphide; Above-mentioned reductive agent is to select according to the characteristic of organic solvent, why select like this be since above-mentioned reductive agent except can be organic solvent dissolution, also need be in organic solvent dispersion effect good; Wherein cool off the cold salt of usefulness, be routine techniques, just with CaCl
2Or the aqueous solution of NaCl, carry out the freezing condition that reaches subzero tens degree by freezing unit, use for industrial refrigeration.
In order to make entire reaction can obtain best effect, general control is 1 to the mol ratio of the adjacent nitro alpha.-acetylacetanilide of chlorine, alkali and reductive agent: 3-6: 1-2, here the mol ratio of raw material and alkali and reductive agent is meant the hydrogen-oxygen radical that the monoatomic base metal is provided, the mol ratio of reductive agent is meant can provide the reductive agent that shifts 1 mole of electronics, that is to say that wherein mole number with alkali is according to referring to that the hydrogen-oxygen radical that the monoatomic base metal is provided converts, be meant according to providing the reductive agent that shifts 1 mole of electronics to convert with the mol ratio of reductive agent.
In follow-up crystallization and acidification technique, the crystallization processes that is adopted is crystallization method commonly used, do not repeat them here, and in the acidization, adopt general acidation treatment method in the industry, in order to reach the used acid of better effect can be the concentrated hydrochloric acid or the vitriol oil, adopts dense mineral acid can reduce discharged waste water like this, obtains better environmental benefit.
After finishing above-mentioned technology, can obtain highly purified 2-chloro-6-hydroxy quinoxaline, and in preparation process, having a large amount of organic solvents after the crystallization produces, this part organic solution is called mother liquor, and mother liquid obtained whole covers are used in the production of next batch and gone, and concrete working method is with noted earlier identical, saved production cost so greatly, can make the solvent cycle utilization.In the waste water of follow-up acidification, dissolve method that partial solvent can be by simple distillation with solvent recuperation, reduced the loss amount of solvent like this, farthest rationally utilized solvent.
In sum, its purity of 2-chloro-6-hydroxy quinoxaline by above-mentioned prepared is up to more than 96%, and the yield of entire reaction has also reached more than 90%, compares with traditional technology, has that operation is simple, yield is higher, the advantage that content is higher, wherein the using and reclaiming of organic solvent significantly reduces the generation of prior art neutral and alkali waste water, alleviate environmental pollution, reduced production cost; Also no longer need after the reaction special alkaline waste water treatment unit is set, thereby saved investment and production cost, and this technology is also more stable in production application.
Embodiment
The embodiment of form is described in further detail foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
The ring-closure reaction stage:
In the 5000L reactor, drop into the 300kg sodium hydrate solid, the 1000kg methanol solution is opened stirring, be mixed with basic solvent, logical cooling water temperature to 25 ± 5 ℃, drop into 400kg then to the adjacent nitro alpha.-acetylacetanilide of chlorine, reacted 3 hours down at 25 ± 5 ℃, slowly be warming up to 60-65 ℃ then, reacted 2 hours, get the tracking sample, with liquid-phase chromatographic analysis whether the adjacent nitro alpha.-acetylacetanilide of chlorine is reacted completely,, then can handle if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＜0.1%, if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＞0.1%, then need to prolong reaction times 2h, follow the tracks of again, can descend the step to handle chlorine behind adjacent nitro alpha.-acetylacetanilide＜0.1% up to reactant;
The reduction reaction stage:
In reactor, drop into 200kg Sodium sulfhydrate and 500kg methyl alcohol, slowly be warming up to 70 ℃, reach reflux state, about reaction 15h, get the tracking sample, whether react completely with the liquid-phase chromatographic analysis oxynitride, if tracking results is amount of nitrogen oxides＜0.1%, then can handle, if tracking results is amount of nitrogen oxides＞0.1%, then need to prolong the reaction times, carry out repetition measurement again.Till the reactant amount of nitrogen oxides reaches requirement.After reaction finished, logical water coolant was reduced to room temperature, feeds cold salt then and reduces to 5 ℃ again, is incubated 2 hours, and making the whole crystallizations of whole generation material is sodium salt, and the frame that re-packs then obtains the crystallisate sodium salt;
The acidification reaction stage:
Gained sodium salt 2000L, hot water dissolving about 60 ℃ changes still, adding the 50kg gac decoloured 1 hour under 60 ℃ of temperature, frame re-packs, get filtrate, drip concentrated hydrochloric acid in reactor, temperature is being controlled at about 40 ℃, and rate of addition was controlled at about 1 hour, the pH value of souring soln is 4-6, stir after 1 hour, still about 4-6, the frame that re-packs gets 2-chloro-6-hydroxyl quinoline woods to the pH value of repetition measurement solution, clarify with 60 ℃ of hot wash sheet frame to filtrates, the oven dry product, surveying content with liquid chromatography is 98.2%, yield is 92.5%.
Embodiment 2
The ring-closure reaction stage:
In the 3000L reactor, drop into 180kg potassium hydroxide solid and 800kg acetone soln, open stirring, be mixed with basic solvent, logical cooling water temperature to 25 ± 5 ℃, drop into 260kg then to the adjacent nitro alpha.-acetylacetanilide of chlorine, reacted 3 hours down at 25 ± 5 ℃, slowly be warming up to 60-65 ℃ then, reacted 2 hours, get the tracking sample, with liquid-phase chromatographic analysis whether the adjacent nitro alpha.-acetylacetanilide of chlorine is reacted completely, if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＜0.1%, then can handle, if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＞0.1%, then need to prolong the reaction times, follow the tracks of again.Till reactant reaches requirement to the adjacent nitro alpha.-acetylacetanilide of chlorine content.
The reduction reaction stage:
In reactor, drop into 200kg Sodium sulfhydrate and 500kg acetone, slowly be warming up to 65 ℃, reach reflux state, about reaction 15h, after reaction finishes, logical water coolant is reduced to room temperature, feed cold salt then and reduce to 5 ℃ again, be incubated 2 hours, making the whole crystallizations of whole generation material is sodium salt, the frame that re-packs then obtains the crystallisate sodium salt.
The acidification reaction stage:
Gained sodium salt 2000L, hot water dissolving about 60 ℃ changes still, adding the 50Kg gac decoloured 1 hour under 60 ℃ of temperature, frame re-packs, get filtrate, drip concentrated hydrochloric acid in reactor, temperature is being controlled at about 40 ℃, and rate of addition was controlled at about 1 hour, the pH value of souring soln is 4-6, stir after 1 hour, still about 4-6, the frame that re-packs gets 2-chloro-6-hydroxyl quinoline woods to the pH value of repetition measurement solution, clarify with 60 ℃ of hot wash sheet frame to filtrates, the oven dry product, surveying content with liquid chromatography is 97.7%, yield is 91.5%.
Solvent cycle is utilized:
In the 5000L reactor, drop into the 300kg sodium hydrate solid, the acetone mother liquor that 1000kg reclaims is opened stirring, be mixed with basic solvent, logical cooling water temperature to 25 ± 5 ℃, drop into 400kg then to the adjacent nitro alpha.-acetylacetanilide of chlorine, reacted 3 hours down at 25 ± 5 ℃, slowly be warming up to 60-65 ℃ then, reacted 2 hours.Following steps are with above-mentioned operation, and acetone mother liquor of the present invention can recycle, can overlap in the production of using next batch and go, and does not influence the content and the yield of product.
The recovery of solvent:
Drop into the waste water of reduction phase in the 3000L reactor, the acetone solvent that atmospheric pressure or vacuum distillate out reclaims, and can overlap and use in the production.
Embodiment 3
The ring-closure reaction of preparation alkali lye:
In the 3000L reactor, measure the 800Kg methyl tertiary butyl ether, drive agitator, drop into sodium hydroxide 150Kg, logical cooling water temperature is to 20-30 ℃, drop into 400Kg again to the adjacent nitro alpha.-acetylacetanilide of chlorine, 20-30 ℃ of insulation reaction 3 hours, logical steam slowly was warming up to 50 ℃, insulation reaction 2 hours;
Reduction reaction:
Drop into 500Kg methyl tertiary butyl ether and 150Kg POTASSIUM BOROHYDRIDE in reactor, logical steam slowly is warming up to 60 ℃, little back flow reaction 20 hours, be cooled to room temperature after logical colder salt reduce to 5 ℃, the frame that re-packs filters out metal-salt;
The acidification reaction stage:
The acidification reaction stage adopts existing souring method to carry out acidifying, and surveying product content with liquid chromatography is 97.1%, and yield is 90.2%.
Comparative example (adopting the solvent of water) as reaction
The ring-closure reaction of preparation alkali lye:
Measure 1400L water in the 5000L reactor, start to stir, drop into 375kg sodium hydroxide, be mixed with aqueous sodium hydroxide solution, logical cold salt was reduced to 25 ± 5 ℃, drops into 400kg then to the adjacent nitro alpha.-acetylacetanilide of chlorine, 25 ± 5 ℃ of insulation reaction 3 hours.It is 110 ℃ towards the material temperature that logical steam slowly is warming up to nature, insulation reaction 5 hours.
Reduction reaction:
Continuation drops into 800kg water and 300kg Sodium sulfhydrate in reactor, logical steam is warming up to 115 ℃-118 ℃ insulations 18 hours, sampling is surveyed and is followed the tracks of, with liquid-phase chromatographic analysis whether the adjacent nitro alpha.-acetylacetanilide of chlorine is reacted completely, if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＜0.1, then can handle, if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＞0.1, then needing to prolong the reaction times is 2 hours, follows the tracks of again.Till reactant reaches requirement to the adjacent nitro alpha.-acetylacetanilide of chlorine content.After reaction finished, logical water coolant was reduced to room temperature, feeds cold salt then and reduces to 5 ℃ again, is incubated 2 hours, and making the whole crystallizations of whole generation material is sodium salt, and the frame that re-packs then obtains the crystallisate sodium salt.
The acidification reaction stage:
Gained sodium salt 2000L, hot water dissolving about 60 ℃ changes still, adding the 50kg gac decoloured 1 hour under 60 ℃ of temperature, frame re-packs, get filtrate, drip concentrated hydrochloric acid in reactor, temperature is being controlled at about 40 ℃, and rate of addition was controlled at about 1 hour, the pH value of souring soln is 4-6, stir after 1 hour, still about 4-6, the frame that re-packs gets 2-chloro-6-hydroxyl quinoline woods to the pH value of repetition measurement solution, clarify with 60 ℃ of hot wash sheet frame to filtrates, the oven dry product, surveying content with liquid chromatography is 95.8%, yield is 80.7%.
By the comparison of above embodiment and comparative example, all to be higher than with the aqueous solution be the reaction conditions of solvent for content, the yield of product when visible the present invention adopted organic solvent to be reaction solvent, and can recycle, reduces production cost, reduces quantity of wastewater effluent.
Claims (6)
1. the synthetic method of a 2-chloro-6-hydroxy quinoxaline comprises that it is characterized in that: described closed loop and reducing process are as follows to be closed loop, reduction and the acidification reaction of starting raw material to the adjacent nitro alpha.-acetylacetanilide of chlorine:
The first step: ring-closure reaction
In reactor, add the organic solvent that contains alkaline matter, add then the adjacent nitro alpha.-acetylacetanilide of chlorine, under 20-30 ℃, initiation reaction 2.5-3.5 hour, be warmed up to 50 ℃-solvent boiling point temperature then and carry out ring-closure reaction, reaction times is 2.5-3.5 hour, sampling, follow the tracks of the adjacent nitro alpha.-acetylacetanilide of chlorine content with liquid chromatography, if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＜0.1%, then can descend the step to handle, if tracking results is to the adjacent nitro alpha.-acetylacetanilide of chlorine content＞0.1%, then need to prolong the reaction times, up to reactant to the adjacent nitro alpha.-acetylacetanilide of chlorine content＜step processing down in 0.1% o'clock;
Second step: reduction reaction
In above-mentioned reactor, add reductive agent, be warming up to about 50-150 ℃, insulation reaction 5-15 hour, get the tracking sample, whether react completely, if tracking results is amount of nitrogen oxides＜0.1% with the liquid-phase chromatographic analysis oxynitride, then can carry out the back step handles, if tracking results is amount of nitrogen oxides＞0.1%, then need to prolong the reaction times, carry out repetition measurement again till the reactant amount of nitrogen oxides reaches requirement; After reaction finished, logical water coolant was reduced to room temperature, feeds cold salt then and reduces to 5 ℃ again, is incubated 2 hours, and making the whole crystallizations of whole generation material is metal-salt, and the frame that re-packs then obtains the crystallisate metal-salt;
Wherein said mol ratio to the adjacent nitro alpha.-acetylacetanilide of chlorine, alkali and reductive agent is 1: 3-6: 1-2, be according to referring to that the hydrogen-oxygen radical that the monoatomic base metal is provided converts wherein, be meant according to providing the reductive agent that shifts 1 mole of electronics to convert with the mol ratio of reductive agent with the mole number of alkali.
2. synthetic method according to claim 1 is characterized in that: described acidification reaction is:
The metal-salt that will obtain through the reactant crystallisation by cooling of reduction reaction, the hot water dissolving is used in dry back, adds activated carbon decolorizing, get filtrate and carry out acidifying, drip acid solution in filtrate, regulating the pH value is 4-6, the washing desalination, the filter cake oven dry had both got 2-chloro-6-hydroxy quinoxaline.
3. synthetic method according to claim 1 and 2, it is characterized in that: described organic solvent uses alcohols or ethers or ketone or its mixture, wherein alcohols is selected from methyl alcohol or ethanol or propyl alcohol, and ethers is selected from ether or methyl tertiary butyl ether, and ketone is selected from acetone.
4. synthetic method according to claim 1 and 2 is characterized in that: described alkaline matter is selected from potassium hydroxide or sodium hydroxide or salt of wormwood or its mixture.
5. synthetic method according to claim 1 and 2 is characterized in that: described reductive agent is sodium sulphite or sodium polysulphide or S-WAT or sodium bisulfite or its mixture.
6. synthetic method according to claim 2 is characterized in that: described acid solution is the concentrated hydrochloric acid or the vitriol oil.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108065A (en) * | 2011-03-23 | 2011-06-29 | 浙江禾田化工有限公司 | Method for preparing 2-quinoxalinol |
| CN102180840A (en) * | 2011-03-15 | 2011-09-14 | 安徽丰乐农化有限责任公司 | New preparation process of 6-chloro-2-hydroxyquinoxaline |
| CN102584723A (en) * | 2012-01-19 | 2012-07-18 | 江苏丰山集团有限公司 | Method for synthetizing 2,6-dichloroquinoxaline by using diketene |
| CN102675233A (en) * | 2012-05-25 | 2012-09-19 | 安徽丰乐农化有限责任公司 | New high-yield production process of 6-chloro-2-hydroxyquinoxaline |
| CN102675231A (en) * | 2012-05-15 | 2012-09-19 | 江苏丰山集团有限公司 | Method for removing sulfur content impurity in synthesis technology of 2, 6-dichloro-quinoxaline |
| CN113788786A (en) * | 2021-09-14 | 2021-12-14 | 京博农化科技有限公司 | Quizalofop-p-ethyl intermediate impurity and preparation method thereof |
| CN114369069A (en) * | 2022-01-21 | 2022-04-19 | 江苏丰山集团股份有限公司 | Preparation method of quizalofop-p-ethyl cyclic compound intermediate |
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| CN102180840A (en) * | 2011-03-15 | 2011-09-14 | 安徽丰乐农化有限责任公司 | New preparation process of 6-chloro-2-hydroxyquinoxaline |
| CN102108065A (en) * | 2011-03-23 | 2011-06-29 | 浙江禾田化工有限公司 | Method for preparing 2-quinoxalinol |
| CN102108065B (en) * | 2011-03-23 | 2012-11-28 | 浙江禾田化工有限公司 | Method for preparing 2-quinoxalinol |
| CN102584723A (en) * | 2012-01-19 | 2012-07-18 | 江苏丰山集团有限公司 | Method for synthetizing 2,6-dichloroquinoxaline by using diketene |
| CN102584723B (en) * | 2012-01-19 | 2015-03-04 | 江苏丰山集团股份有限公司 | Method for synthetizing 2,6-dichloroquinoxaline by using diketene |
| CN102675231A (en) * | 2012-05-15 | 2012-09-19 | 江苏丰山集团有限公司 | Method for removing sulfur content impurity in synthesis technology of 2, 6-dichloro-quinoxaline |
| CN102675233A (en) * | 2012-05-25 | 2012-09-19 | 安徽丰乐农化有限责任公司 | New high-yield production process of 6-chloro-2-hydroxyquinoxaline |
| CN102675233B (en) * | 2012-05-25 | 2016-03-09 | 安徽丰乐农化有限责任公司 | A kind of production technique of 6-chlorine-2-hydroxyl quinoxaline |
| CN113788786A (en) * | 2021-09-14 | 2021-12-14 | 京博农化科技有限公司 | Quizalofop-p-ethyl intermediate impurity and preparation method thereof |
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