CN105461600A - Method for preparing ethyl methyl sulfone - Google Patents
Method for preparing ethyl methyl sulfone Download PDFInfo
- Publication number
- CN105461600A CN105461600A CN201510949854.9A CN201510949854A CN105461600A CN 105461600 A CN105461600 A CN 105461600A CN 201510949854 A CN201510949854 A CN 201510949854A CN 105461600 A CN105461600 A CN 105461600A
- Authority
- CN
- China
- Prior art keywords
- reaction
- preparation
- hydrogen peroxide
- methylethyl sulfone
- sulfone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing ethyl methyl sulfone. According to the method, ethyl methyl sulfide serves as a raw material, glacial acetic acid serves as a catalyst, hydrogen peroxide serves as an oxidant, the stirring reaction is performed for 4-5 h at 60-80 DEG C; and after the reaction is over, reaction fluid undergoes aftertreatment to obtain ethyl methyl sulfone. According to the method, the homogeneous catalysis glacial acetic acid is adopted and is low in cost, and the reaction is easy to operate. The reaction conditions are mild, the production cycle is short, and the yield can be 90% or above.
Description
Technical field
The invention belongs to technical field of fine, be specifically related to a kind of preparation method of methylethyl sulfone.
Background technology
Methylethyl sulfone is a kind of water white liquid, and its derivative can be used for the preparation etc. of sterilant, antiviral.In the industry, methylethyl sulfone is not only a kind of important solvent, can be used for the fractionation etc. of raceme, is also important organic synthesis intermediate, is widely used in the reactions such as molecular recombination.Therefore the preparation of methylethyl sulfone and derivative thereof arouses widespread concern.
Methylethyl sulfone is reduced by two sulfones at first and obtains (CanadianJournalofChemistry, 57 (10), 1206-13; 1979), its reaction equation is as follows.The method adopts the strong reductants such as lithium aluminum hydride, and operational requirement is higher, has suitable danger, and aftertreatment technology is complicated, and yield is low, is not suitable for scale operation.
。
Present stage, methylethyl sulfone is be that raw material prepares through oxidizing reaction with methyl ethyl sulfide mostly.Oxygenant changes the Green Oxidant of environmental sound into gradually by initial metal composite, organic oxidizing agent, inorganic oxidizer, such as ozone, oxygen, immobilized oxide compound, hydrogen peroxide etc.Wherein, hydrogen peroxide oxidation after product is water, easy to use, is the generally acknowledged practical oxygenant of environmental protection.But hydrogen peroxide only has medium oxidation capacity, therefore need to set up the object that efficient catalyst system realizes its green oxidation.
。
Document (Org.Lett.2005,7:5015-5018; Tetrahedron2001,57:9669-9676) adopt the oxidizing reaction of heterogeneous catalyst catalysis thioether, but long reaction time, productive rate are low, the large usage quantity of hydrogen peroxide.Chinese patent CN101798277 reaches using immobilized double-deck ionic liquid-tungstate as catalyzer and improves yield, the object that recycles, but this kind of solid-carried catalyst prepares loaded down with trivial details and access times are limited.Compared with heterogeneous catalyst, the catalytic efficiency of homogeneous catalyst is high, and reaction easily controls.In addition, mostly use the organic solvents such as methyl alcohol, acetone, methylene dichloride in existing processes, which increases the removal process of solvent and the consumption of solvent, be unfavorable for that environmental protection is produced.
Summary of the invention
The object of the invention is to overcome prior art defect, provides a kind of preparation method of methylethyl sulfone, the method cost is low, yield is high, clean environment firendly and easy and simple to handle.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for methylethyl sulfone, it take methyl ethyl sulfide as raw material, and Glacial acetic acid is catalyzer, and hydrogen peroxide is oxygenant, and at 60-80 DEG C of stirring reaction 4-5h, reaction terminates rear reaction solution through aftertreatment and get final product.
Concrete, the mol ratio of methyl ethyl sulfide and Glacial acetic acid is 1:0.01-0.04.
Concrete, hydrogen peroxide is with H
2o
2meter, methyl ethyl sulfide and H
2o
2mol ratio be 1:2.0-2.5.
Hydrogen peroxide sectional drips, as, hydrogen peroxide can drip all at twice, in first time dropping process, control temperature is no more than 50 DEG C, after first time drips and terminates, then be warming up to temperature of reaction and carry out second time and drip (twice dropping all controls to dropwise within half an hour), this addresses the problem the problem that the rising of Yin Wendu in existing production technique causes peroxide decomposition, thus decrease the consumption of hydrogen peroxide, save cost.
Above-mentioned aftertreatment is specially: in reaction solution, add alkali be adjusted to pH in neutral, extract with organic solvent (as chloroform etc.), organic phase air distillation removing organic solvent, more namely concentrating under reduced pressure obtains methylethyl sulfone product, methylethyl sulfone yield can reach more than 90%.Alkali selected by neutralization reaction liquid can be sodium hydroxide, potassium hydroxide, sodium carbonate or solution of potassium carbonate etc., wherein preferred sodium hydroxide, potassium hydroxide.
The reaction equation of the inventive method is as follows:
。
Compared to the prior art, the beneficial effect of the inventive method:
1) adopt homogeneous catalyst Glacial acetic acid, low price, reacts easy to operate;
2) reaction is solvent with raw material, without the need to additionally using solvent, decreases the problem of solvent recuperation and consumption in preparation process;
3) reaction conditions is gentle, and with short production cycle, yield can reach more than 90%;
4) adopt the mode dripping hydrogen peroxide stage by stage to prepare methylethyl sulfone, solve Yin Wendu in existing technique and raise the problem causing peroxide decomposition, thus decrease the consumption of hydrogen peroxide, saved cost;
5) pollution-free in production process, extract the organic solvents, chloroform selected and can be recycled, recoverable after a small amount of by product acetate condensing crystal.
Embodiment
Do to introduce in detail further to technical scheme of the present invention below in conjunction with embodiment, but protection scope of the present invention is not limited thereto.
comparative example
A preparation method for methylethyl sulfone, is specially: in 2000mL reactor, add 380g methyl ethyl sulfide and 30% hydrogen peroxide (referring to mass percent, lower same) 1360g, control temperature of reaction between 65-75 DEG C, be incubated 10 hours.React complete, in reactor, add chloroform extraction 3 times, organic phase less than 100 DEG C air distillation removing chloroforms.Then slow vacuum distillation, cut when collecting 157 DEG C, common 420g(colourless transparent liquid), content 97%, yield 78%.
embodiment 1
A preparation method for methylethyl sulfone, is specially: in 2000mL reactor, add 380g methyl ethyl sulfide and 5.9g Glacial acetic acid, slowly drips 30% hydrogen peroxide 680g, keep still temperature in dropping process below 50 DEG C under room temperature.Be warming up to 65 DEG C after dropping terminates, and then drip 30% hydrogen peroxide 680g, control temperature of reaction between 65-75 DEG C, be incubated 5 hours.React complete, in reactor, stir the sodium hydroxide solution adding 32% be adjusted to pH in neutral, then use chloroform extraction 3 times, organic phase less than 100 DEG C air distillations remove chloroforms.Then slow vacuum distillation, cut when collecting 157 DEG C, common 488g(colourless transparent liquid), content 99%, yield 90.5%.
embodiment 2
A preparation method for methylethyl sulfone, is specially: in 2000mL reactor, add 228g methyl ethyl sulfide and 5g Glacial acetic acid, slowly drips 30% hydrogen peroxide 408g, keep still temperature in dropping process below 50 DEG C under room temperature.Be warming up to 65 DEG C after dropping terminates, and then drip 30% hydrogen peroxide 408g, control temperature of reaction between 65-75 DEG C, be incubated 4 hours.React complete, in reactor, stirring adds the sodium hydroxide solution of 32% is neutrality to pH value, then uses chloroform extraction 3 times, organic phase less than 100 DEG C air distillations removing chloroforms.Then slow vacuum distillation, cut when collecting 157 DEG C, common 295g(colourless transparent liquid), content 99%, yield 91.2%.
As can be seen from above-mentioned: the situation of not adding Glacial acetic acid with reference examples and once adding hydrogen peroxide is compared, adopt the reaction times of the embodiment 1 and 2 of the inventive method significantly to shorten (foreshortening to 4-5h from 10h) than the reaction times of reference examples, and content, the especially yield of methylethyl sulfone product all increase.
Claims (5)
1. a preparation method for methylethyl sulfone, is characterized in that, take methyl ethyl sulfide as raw material, and Glacial acetic acid is catalyzer, and hydrogen peroxide is oxygenant, and at 60-80 DEG C of stirring reaction 4-5h, reaction terminates rear reaction solution through aftertreatment and get final product.
2. the preparation method of methylethyl sulfone as claimed in claim 1, it is characterized in that, the mol ratio of methyl ethyl sulfide and Glacial acetic acid is 1:0.01-0.04.
3. the preparation method of methylethyl sulfone as claimed in claim 1, it is characterized in that, hydrogen peroxide is with H
2o
2meter, methyl ethyl sulfide and H
2o
2mol ratio be 1:2.0-2.5.
4. the preparation method of methylethyl sulfone as claimed in claim 3, it is characterized in that, hydrogen peroxide drips all at twice, and in first time dropping process, control temperature is no more than 50 DEG C, after first time drips and terminates, then is warming up to temperature of reaction and carries out second time dropping.
5. the preparation method of methylethyl sulfone as claimed in claim 1, it is characterized in that, described aftertreatment is specially: in reaction solution, add alkali be adjusted to pH in neutral, extract with organic solvent, organic phase air distillation removing organic solvent, more namely concentrating under reduced pressure obtains methylethyl sulfone product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510949854.9A CN105461600B (en) | 2015-12-18 | 2015-12-18 | A kind of preparation method of Methylethyl sulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510949854.9A CN105461600B (en) | 2015-12-18 | 2015-12-18 | A kind of preparation method of Methylethyl sulfone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105461600A true CN105461600A (en) | 2016-04-06 |
| CN105461600B CN105461600B (en) | 2018-03-16 |
Family
ID=55599818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510949854.9A Active CN105461600B (en) | 2015-12-18 | 2015-12-18 | A kind of preparation method of Methylethyl sulfone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105461600B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107473994A (en) * | 2016-06-08 | 2017-12-15 | 郑州大学 | The synthetic method of Methylethyl sulfone |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029028A (en) * | 2007-01-24 | 2007-09-05 | 华中农业大学 | Chemical synthesis of albendazole-2-amino-sulphone |
| CN101100450A (en) * | 2007-08-06 | 2008-01-09 | 湖南化工研究院 | Method for preparing ethylsulfonyl acetonitrile |
| JP2008238490A (en) * | 2007-03-26 | 2008-10-09 | Canon Inc | Image outputting apparatus and image outputting method |
| CN102285927A (en) * | 2011-06-29 | 2011-12-21 | 青岛康地恩药业股份有限公司 | Method for preparing ponazuril serving as anticoccidiosis medicament |
| CN102459161A (en) * | 2009-06-09 | 2012-05-16 | 住友精化株式会社 | Process for preparation of alkyl sulfone compounds |
| CN104488895A (en) * | 2014-12-18 | 2015-04-08 | 广西田园生化股份有限公司 | Compound composition containing methanesulphonyl myclobutanil and trichloroisocyanuric acid |
-
2015
- 2015-12-18 CN CN201510949854.9A patent/CN105461600B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029028A (en) * | 2007-01-24 | 2007-09-05 | 华中农业大学 | Chemical synthesis of albendazole-2-amino-sulphone |
| JP2008238490A (en) * | 2007-03-26 | 2008-10-09 | Canon Inc | Image outputting apparatus and image outputting method |
| CN101100450A (en) * | 2007-08-06 | 2008-01-09 | 湖南化工研究院 | Method for preparing ethylsulfonyl acetonitrile |
| CN102459161A (en) * | 2009-06-09 | 2012-05-16 | 住友精化株式会社 | Process for preparation of alkyl sulfone compounds |
| CN102285927A (en) * | 2011-06-29 | 2011-12-21 | 青岛康地恩药业股份有限公司 | Method for preparing ponazuril serving as anticoccidiosis medicament |
| CN104488895A (en) * | 2014-12-18 | 2015-04-08 | 广西田园生化股份有限公司 | Compound composition containing methanesulphonyl myclobutanil and trichloroisocyanuric acid |
Non-Patent Citations (4)
| Title |
|---|
| D.T.HICALLAN等: "The Preparation and Properties of Sulfur Compounds Related to Petroleum.I The Dialkyl Sulfides and Disulfides", 《PREPARATIOOFN D IALKYLS ULFIDEASN D DISULFIDES》 * |
| 张明森主编: "《精细有机化工中间体全书》", 31 March 2008 * |
| 石先莹等: "甲基乙基砜的制备方法催化H2O2选择性氧化硫醚", 《高等学校化学学报》 * |
| 陈明等: "乙磺酰基乙腈的一种制备方法", 《精细化工中间体》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107473994A (en) * | 2016-06-08 | 2017-12-15 | 郑州大学 | The synthetic method of Methylethyl sulfone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105461600B (en) | 2018-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6704597B2 (en) | Simultaneous saccharification and fermentation method of lignocellulose improved by using surfactant | |
| CN103086891B (en) | The preparation method of elasticizer diethylene glycol dibenzoate | |
| CN104176968B (en) | The production method of the high dense water reducer of a kind of naphthalene system | |
| CN109225198A (en) | A kind of preparation method of bismuth doped stannum oxide photochemical catalyst that capableing of efficient degradation dyestuff and antibiotic waste water | |
| CN101245467A (en) | Stripping liquid and stripping method for stripping titanium and titanium alloy anodized film | |
| CN103242158B (en) | Technological method for synthesizing ethyl acetate | |
| CN105461600A (en) | Method for preparing ethyl methyl sulfone | |
| CN103113250A (en) | Preparation method of D-para hydroxybenzene glycine methyl ester | |
| CN109336789A (en) | A kind of preparation method of 3- hydroxy-propanesulfonic acid | |
| CN105363352A (en) | Method for synthesizing high acid resistant MOR zeolite molecular sieve membrane from fluorine-containing dilute solution | |
| CN112079721A (en) | Production process of ethyl difluorobromoacetate | |
| CN104817480B (en) | Reuse of Bunte salt in sodium hydrosulfite waste residue | |
| CN103508916A (en) | Preparation technology for paracetamol | |
| CN101709055A (en) | Method for synthesizing ionic liquid | |
| CN103274912B (en) | Green preparation technology of phthalic dicarboxaldehyde | |
| CN103506126B (en) | A kind of preparation method of copper radical synthesizing methanol catalyst | |
| CN102584726B (en) | Method for preparing penconazole serving as bacteriacide | |
| CN102531858B (en) | Preparation method of lyral | |
| CN103468755B (en) | Method for enzymatic synthesis of phenethyl caffeate in complexation extraction agent/ionic liquid system | |
| CN101698632B (en) | High-purity 2-ethylene chlorohydrin production method | |
| CN106749165B (en) | A kind of preparation method of butylene sulfite | |
| CN103877838B (en) | A kind of method for improving the nitric acid rate of recovery in Glucurolactone production | |
| CN100439511C (en) | Process for catalytic extraction of yam saponin by using modified cellulase | |
| CN104447329A (en) | Preparation method of 2-chloroacetoacetic acid ethyl ester | |
| CN110635049A (en) | Method for preparing perovskite film with assistance of gas phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |