CN103044283A - Method for preparing oxime ether - Google Patents
Method for preparing oxime ether Download PDFInfo
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- CN103044283A CN103044283A CN2012103777338A CN201210377733A CN103044283A CN 103044283 A CN103044283 A CN 103044283A CN 2012103777338 A CN2012103777338 A CN 2012103777338A CN 201210377733 A CN201210377733 A CN 201210377733A CN 103044283 A CN103044283 A CN 103044283A
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- ethyl
- methylimidazole
- ether
- oxime ether
- propyl ether
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Abstract
The invention relates to a method for preparing oxime ether, comprising the following steps: (1) adding 5-10 M of 1-ethyl-3-methylimidazole tetrafluoroborate into 1 M of methyl ethyl ketoxime and then adding 3-5 M of sodium carbonate, potassium carbonate or sodium hydroxide; and finally, adding 2-3 M of chloroethane and reacting at a room temperature for 3-5 hours; and (2) filtering the solution and adding 1-2 M of propyl ether into a filtering solution to extract, and then rectifying to obtain the oxime ether. The method has the advantages that 1, the 1-ethyl-3-methylimidazole tetrafluoroborate is used as a reaction agent, is low in cost, is not volatilized, does not generate harmful gas and does not generate wastewater; and on the aspect of environmental improvement, the method is obviously improved when being compared with other technologies; 2, the method is simple in process and convenient to operate; the processing cost is lower on the post-period treatment and the cost is saved; and 3, the product yield is high and the quality is good.
Description
Technical field
The present invention relates to a kind of preparation method of oxime ether, it uses ketoxime and alkylating reagent reaction to obtain.
Background technology
Oxime ether and derivative thereof are at agricultural chemicals and very important purposes is pharmaceutically arranged, and also are simultaneously the important intermediate of the important agricultural chemicals of preparation, medicine intermediate alcoxyl amine, and the method for synthesizing oxime ether mainly contains following several method commonly used at present:
Bull.Acad.Sci.USSR, Div.Chen.Sci. (Engl.Transl.), EN, the 28th volume, 121-128 page or leaf (1979) have described the oxime alkylated reaction that uses azo alkane, haloalkane and sulfuric acid dialkyl; Special experimental study the competition between o-alkylation and the N-alkylation.Described in acetone, ethanol, water or Anaesthetie Ether, prepared a with general productive rate, the O-alkyl oxide of a '-two carbonyl oximes.In order to be conducive to the O-alkylation, because nitrone is heat-labile, high as far as possible temperature is adopted in suggestion, or alkylating reagent is large as far as possible.
WO-AOO/18726 has described the alkylated reaction of oxime in all kinds of SOLVENTS, and reaction also can be carried out in the mixture of these solvents.
EPO158159 has introduced first with ketoxime and sodium hydroxide reaction, carry out the O-alkylated reaction with alkylating agent again with forming oxime sodium after the methylbenzene azeotropic dehydration, then carry out acid out, saltout, the aftertreatment such as extraction, underpressure distillation, decolouring, rectifying obtains product, yield is not all about 71-72% with product.The method technique relative complex operates more loaded down with trivial detailsly, and preparation process produces reluctant sewage waste residue etc., causes the post-processed cost higher, is unfavorable for controlling cost.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of simple to operate, and is with low cost, and yield is higher, and pollutes the lower method for preparing oxime ether.
Content of the present invention is may further comprise the steps:
(1), in the 1M methyl ethyl ketone oxime, add the 1-ethyl-3-methylimidazole a tetrafluoro borate of 5-10M, then add yellow soda ash, salt of wormwood or the sodium hydroxide of 3-5M, add at last the monochloroethane of 2-3M, normal-temperature reaction 3-5 hour;
(2), filter mentioned solution, the propyl ether that adds 1-2M in the filtrate extracts, then rectifying gets oxime ether.
M represents molar equivalent.
The structural formula of oxime ether of the present invention can be:
Wherein, R is C
2H
5R
1Be methyl, R
2Be ethyl.
Employing by the ketoxime compound of general formula (II) and alkylating agent in ionic liquid with alkaline condition under reaction and getting:
Wherein, R
1Be methyl, R
2Be ethyl.
Described 1-ethyl-3-methylimidazole a tetrafluoro borate is 1-ethyl-3-methylimidazole potassium tetrafluoroborate.
The add-on of described 1-ethyl-3-methylimidazole a tetrafluoro borate is 6-7M.
Extraction divides to be carried out for 2-3 time.
After having filtered in the step (2), wash filter residue with propyl ether, the propyl ether of described extraction usefulness comprises the propyl ether washings that washs usefulness.
The invention has the beneficial effects as follows, the present invention compared with prior art, advantage is, 1, to adopt 1-ethyl-3-methylimidazole a tetrafluoro borate be reagent in the present invention, and its price is low, and is non-volatile, do not produce obnoxious flavour, do not produce waste water, in environmental improvement, it is obvious to compare the other technologies progress, 2, technique of the present invention is simple, and is easy to operate, in the processing in later stage, processing cost of the present invention is cheaper, has saved cost; 3, product yield is high, and quality is good, specifically sees the embodiment analysis.
Embodiment
Embodiment 1
In with the container of thermometer, prolong, add 100kg1-ethyl-3-methylimidazole potassium tetrafluoroborate, 99% the methyl ethyl ketone oxime of 9kg, then the yellow soda ash of 30kg99% drip the monochloroethane of 23kg under the normal temperature, drip 1.5h, drip rear normal-temperature reaction 1h.With reacting liquid filtering, filter residue (salinity) is drained, filter residue divides 3 equivalent washings with propyl ether as far as possible, and filter residue is cast out, the propyl ether washings is used as extraction, the reaction solution that removes by filter behind the salinity is used respectively 5kg (comprising above-mentioned washings), the extraction of 5kg propyl ether, merges upper layer of extraction liquid, Distillation recovery propyl ether solvent, 112-116 ℃ of fraction collected in rectifying again, collect to get the O-ethyl-methyl ethyl ketoxime (product of the present invention) of 11.3g, yield 94.2%, vapor detection product purity 99.5%.The 1-of lower floor ethyl-3-methylimidazole potassium tetrafluoroborate after the extraction reclaims solvent and steam except volatile solvent 1h the 98kg that weighs to get, reuse under 60 ℃ of 50mmHg.
Embodiment 2
In with the container of thermometer, prolong, add 200kg1-ethyl-3-methylimidazole potassium tetrafluoroborate, 99% the methyl ethyl ketone oxime of 9kg, then the sodium hydroxide of 20kg99% drip the monochloroethane of 16kg under the normal temperature, drip 1h, drip rear normal-temperature reaction 2h.With reacting liquid filtering, filter residue (salinity) is drained, filter residue divides 4 equivalent washings with propyl ether as far as possible, and filter residue is cast out, the propyl ether washings is used as extraction, the reaction solution that removes by filter behind the salinity is used respectively 8kg (comprising above-mentioned washings), the extraction of 8kg propyl ether, merges upper layer of extraction liquid, Distillation recovery propyl ether solvent, 112-116 ℃ of fraction collected in rectifying again, collect to get the O-ethyl-methyl ethyl ketoxime of 10.2g, yield 85.0%, vapor detection product purity 99.3%.The 1-of lower floor ethyl-3-methylimidazole potassium tetrafluoroborate after the extraction reclaims solvent and steam except volatile solvent 1h the 196kg that weighs to get, reuse under 60 ℃ of 50mmHg.
Embodiment 3
In with the container of thermometer, prolong, add 150kg1-ethyl-3-methylimidazole potassium tetrafluoroborate, 99% the methyl ethyl ketone oxime of 9kg, then the salt of wormwood of 55kg99% drip the monochloroethane of 28kg under the normal temperature, drip 0.5h, drip rear normal-temperature reaction 2h.With reacting liquid filtering, filter residue (salinity) is drained, filter residue divides 5 equivalent washings with propyl ether as far as possible, and filter residue is cast out, the propyl ether washings is used as extraction, the reaction solution that removes by filter behind the salinity is used respectively 6kg (comprising above-mentioned washings), the extraction of 6kg propyl ether, merges upper layer of extraction liquid, Distillation recovery propyl ether solvent, 112-116 ℃ of fraction collected in rectifying again, collect to get the O-ethyl-methyl ethyl ketoxime of 10.8g, yield 89.9%, vapor detection product purity 99.2%.The 1-of lower floor ethyl-3-methylimidazole potassium tetrafluoroborate after the extraction reclaims solvent and steam except volatile solvent 1h the 145kg that weighs to get, reuse under 60 ℃ of 50mmHg.
Claims (5)
1. a method for preparing oxime ether is characterized in that, may further comprise the steps:
(1), in the 1M methyl ethyl ketone oxime, add the 1-ethyl-3-methylimidazole a tetrafluoro borate of 5-10M, then add yellow soda ash, salt of wormwood or the sodium hydroxide of 3-5M, add at last the monochloroethane of 2-3M, normal-temperature reaction 3-5 hour;
(2), filter mentioned solution, the propyl ether that adds 1-2M in the filtrate extracts, then rectifying gets oxime ether.
2. the method for preparing oxime ether according to claim 1 is characterized in that, described 1-ethyl-3-methylimidazole a tetrafluoro borate is 1-ethyl-3-methylimidazole potassium tetrafluoroborate.
3. the method for preparing oxime ether according to claim 1 and 2 is characterized in that, the add-on of described 1-ethyl-3-methylimidazole a tetrafluoro borate is 6-7M.
4. the method for preparing oxime ether according to claim 1 and 2 is characterized in that, extraction divides to be carried out for 2-3 time.
5. the method for preparing oxime ether according to claim 1 and 2 is characterized in that, after having filtered in the step (2), washs filter residue with propyl ether, and the propyl ether of described extraction usefulness comprises the propyl ether washings that washs usefulness.
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| CN2012103777338A CN103044283A (en) | 2012-09-07 | 2012-09-07 | Method for preparing oxime ether |
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| CN2012103777338A CN103044283A (en) | 2012-09-07 | 2012-09-07 | Method for preparing oxime ether |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369449A (en) * | 2018-12-25 | 2019-02-22 | 浙江工业大学 | A kind of method of synthesizing oxime ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0158159A1 (en) * | 1984-04-12 | 1985-10-16 | AlliedSignal Inc. | Process for the synthesis of o-substituted oxime compounds and the conversion thereof into the corresponding hydroxylamine o-substituted |
| US5488162A (en) * | 1994-01-03 | 1996-01-30 | Buckland; Paul R. | Process for preparing o-alkylhydroxylamine salts without the isolation of intermediates |
| CN1321144A (en) * | 1998-09-30 | 2001-11-07 | 巴斯福股份公司 | Method for preparing trion-bis (oxime ether) derivs. and trion-mono and trio-bis (oxime ether) derivs. obtained therewith |
| CN101565386A (en) * | 2009-05-18 | 2009-10-28 | 浙江大学宁波理工学院 | Method for synthesizing oxime ether |
-
2012
- 2012-09-07 CN CN2012103777338A patent/CN103044283A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0158159A1 (en) * | 1984-04-12 | 1985-10-16 | AlliedSignal Inc. | Process for the synthesis of o-substituted oxime compounds and the conversion thereof into the corresponding hydroxylamine o-substituted |
| US5488162A (en) * | 1994-01-03 | 1996-01-30 | Buckland; Paul R. | Process for preparing o-alkylhydroxylamine salts without the isolation of intermediates |
| CN1321144A (en) * | 1998-09-30 | 2001-11-07 | 巴斯福股份公司 | Method for preparing trion-bis (oxime ether) derivs. and trion-mono and trio-bis (oxime ether) derivs. obtained therewith |
| CN101565386A (en) * | 2009-05-18 | 2009-10-28 | 浙江大学宁波理工学院 | Method for synthesizing oxime ether |
Non-Patent Citations (1)
| Title |
|---|
| 张胜建 等: "离子液体中酮肟O-烷基化反应的研究", 《有机化学》, vol. 30, no. 4, 31 December 2010 (2010-12-31), pages 606 - 610 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369449A (en) * | 2018-12-25 | 2019-02-22 | 浙江工业大学 | A kind of method of synthesizing oxime ether |
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Application publication date: 20130417 |