CN103641684B - High-purity chloro ethanol and preparation method thereof - Google Patents
High-purity chloro ethanol and preparation method thereof Download PDFInfo
- Publication number
- CN103641684B CN103641684B CN201310697872.3A CN201310697872A CN103641684B CN 103641684 B CN103641684 B CN 103641684B CN 201310697872 A CN201310697872 A CN 201310697872A CN 103641684 B CN103641684 B CN 103641684B
- Authority
- CN
- China
- Prior art keywords
- ozonization
- preparation
- chloroethanol
- purity
- raw material
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to industrial chemicals synthesis field, disclose a kind of method preparing high-purity chloro ethanol, this preparation method comprises the steps: step a: by raw material 1,4-dichloro-2-butene and ozonization solvent, stir, access ozone carries out ozonization, and gas-chromatography follows the tracks of reaction, until raw material disappears, stop ozonization; Step b: logical nitrogen discharges the ozone in reaction flask, adds reductive agent, reduction reaction temperature-10 ~ 30 DEG C, stirs, recycling design under condition of normal pressure, and air distillation is collected, and cut obtains product.Present invention process route is simple and direct, it is little to pollute, yield is high, speed of response is fast, aftertreatment is simple, and product purity is high by more than 99%, has industrial value.
Description
Technical field
The present invention relates to industrial chemicals synthesis field, specifically a kind of method preparing high-purity chloro ethanol.
Background technology
Chloroethanol is important organic solvent and industrial chemicals, high-purity chloro ethanol is widely used in the industries such as chemical industry, medicine, agricultural chemicals, rubber and dyestuff, in medicine industry, feed oxazolone, pentoxiverin, caramiphen, benactyzine and Intensain, Propranololum and PROCAINE HCL, PHARMA GRADE etc. in order to preparing phosphoric acid piperazine, furan, in pesticide industry, make the raw material of 1059 sterilants, Niran (1068) sterilant and Systox etc.Current industry is prepared chloroethanol and is mainly contained hypochlorous acid method and hydrochloric acid method 2 kinds of methods.Hypochlorous acid method, passes in water by ethene and chlorine simultaneously, and chlorine and water react and generates hypochlorous acid, and hypochlorous acid and Addition on ethylene generate chloroethanol.The chloroethanol aqueous solution initial content that hypochlorous acid method obtains is lower, is generally only 4-7% (massfraction), need removes moisture through continuous rectification, can obtain the chloroethanol product that massfraction is 32%.The further azeotropic distillation of chloroethanol of high density except anhydrating, then removes residual benzene and some high boiling material through rectification under vacuum, just can obtain the chloroethanol that massfraction is 90-95%.This technological reaction is simultaneously inevitable generates by product ethylene dichloride and dichloro-diethyl ether, and the chlorine absorption amount of technique low, consume energy large, seriously polluted, make it apply and be subject to a definite limitation.Hydrochloric acid method is for raw material production high concentration cl ethanol with oxyethane and hydrogenchloride.Hydrochloric acid salting-out distillation is first prepared high-purity hydrogen chloride by this technique, then by itself and oxyethane under certain condition liquid phase synthesis again through to neutralize and rectifying just can obtain purity and can reach about 98% chloroethanol.This technique has relative to hypochlorous acid method that technique is simple, constant product quality, product purity high advantage, but reaction raw materials HC1 gas purification process costly, and it is large, seriously polluted to consume energy.
Summary of the invention
The present invention is directed to problems of the prior art, provide a kind of preparation method polluting little, that cost is low, purity is high chloroethanol.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals:
The preparation method of high-purity chloro ethanol, preparation method comprises the steps:
Step a: by raw material Isosorbide-5-Nitrae-dichloro-2-butene and ozonization solvent, stirs, and access ozone carries out ozonization, and gas-chromatography follows the tracks of reaction, until raw material disappears, stops ozonization;
Step b: logical nitrogen discharges the ozone in reaction flask, adds reductive agent, reduction reaction temperature-10 ~ 30 DEG C, stirs, recycling design under condition of normal pressure, and air distillation is collected, and cut obtains product.
Isosorbide-5-Nitrae-dichloro-2-butene restores through ozone oxidation and obtains target product chloroethanol, and its synthetic route is as follows:
As preferably, described ozonization solvent select methyl alcohol, ethanol, Virahol any one.
As preferably, the mole dosage of described reductive agent be the 0.9-1.5 of Isosorbide-5-Nitrae-dichloro-2-butene mole dosage doubly.
As preferably, described reductive agent selects sodium borohydride or POTASSIUM BOROHYDRIDE.
As preferably, described ozonization temperature is-25 ~ 5 DEG C.
As preferably, in described step b, in reduction reaction, churning time is 1-2 hour.
As preferably, described cut temperature controls to choose 128 ~ 129 DEG C.
Present invention also offers a kind of high-purity chloro ethanol utilizing above-mentioned method to prepare.
The present invention, owing to have employed above technical scheme, has significant technique effect:
The present invention is with 1,4-dichloro-2-butene is raw material, restore can prepare chloroethanol through ozone oxidation, this operational path is simple and direct, pollute the trend that the advantage such as little, yield is high, speed of response is fast, aftertreatment is simple meets current green chemical industry, and product purity is high by more than 99%, the shortcoming of the restriction that existing handicraft product purity causes chemical industry to use not can be made up very well, have industrial value.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
The instrument and equipment used in embodiment: ozonizer, GF-G-3-010G(Qingdao Guolin Industry Co., Ltd.); Nuclear magnetic resonance analyser, mark in AVANCEDMX II I 400M(TMS, Bruker company); Gas-chromatography, section GC1690 dawn.
Embodiment 1
Join in 500mL four-hole bottle by 125 grams of Isosorbide-5-Nitrae-dichloro-2-butenes (1mol) and 200 ml methanol, mechanical stirring is at-25 DEG C, ozonization is carried out after regulating oxygen flow, gas-chromatography follows the tracks of reaction, and within about 3 hours, raw material disappears, and reaction terminates to stop ozonize.Ozone in reaction flask is caught up with by logical nitrogen, keep Nei Wen about-10 DEG C, be added dropwise to containing in 40.0 grams of sodium borohydride (1.05mol) 150 ml methanol solution, add and continue stirring reaction afterwards after 1 hour, react complete, normal pressure recycling design, air distillation is collected 128 ~ 129 DEG C of cuts and is obtained colourless transparent liquid 136.8 grams, gas phase content 99.4%, yield 84.5%.
Product structure confirms:
1HNMR(δppm,400MHz,CDCl
3):3.60-3.74(m,2H,-CH
2Cl);3.82-3.96(m,2H,-CH*
2OH);2.41(s,1H,OH).
13CNMR(δppm,100MHz,CDCl
3):45.42;62.88.
Embodiment 2
Join in 500mL four-hole bottle by 125 grams of Isosorbide-5-Nitrae-dichloro-2-butenes (1mol) and 200 milliliters of ethanol, mechanical stirring is at-10 DEG C, ozonization is carried out after regulating oxygen flow, gas-chromatography follows the tracks of reaction, and within about 3 hours, raw material disappears, and reaction terminates to stop ozonize.Ozone in reaction flask is caught up with by logical nitrogen, temperature about 0 DEG C in keeping, be added dropwise to containing in 66.0 grams of POTASSIUM BOROHYDRIDE (1.2mol), 150 milliliters of ethanolic solns, add and continue stirring reaction afterwards after 1.5 hours, react complete, normal pressure recycling design, air distillation is collected 128 ~ 129 DEG C of cuts and is obtained colourless transparent liquid 140.3 grams, gas phase content 99.7%, yield 86.9%.Product nuclear magnetic spectrogram is identical with embodiment 1.
Embodiment 3
Join in 500mL four-hole bottle by 125 grams of Isosorbide-5-Nitrae-dichloro-2-butenes (1mol) and 200 milliliters of Virahols, mechanical stirring is at 5 DEG C, ozonization is carried out after regulating oxygen flow, gas-chromatography follows the tracks of reaction, and within about 3 hours, raw material disappears, and reaction terminates to stop ozonize.Ozone in reaction flask is caught up with by logical nitrogen, temperature about 10 DEG C in keeping, be added dropwise to containing in 50.0 grams of POTASSIUM BOROHYDRIDE (0.91mol), 150 milliliters of ethanolic solns, add and continue stirring reaction afterwards after 2 hours, react complete, normal pressure recycling design, air distillation is collected 128 ~ 129 DEG C of cuts and is obtained colourless transparent liquid 138.7 grams, gas phase content 99.5%, yield 85.7%.Product nuclear magnetic spectrogram is identical with embodiment 1.
In a word, the foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (5)
1. purity higher than 99% the preparation method of chloroethanol, it is characterized in that, described preparation method comprises the steps:
Step a: by raw material 1,4-dichloro-2-butene and ozonization solvent, stir, access ozone carries out ozonization, gas-chromatography follows the tracks of reaction, until raw material disappears, stops ozonization, described ozonization solvent select methyl alcohol, ethanol, Virahol any one, described ozonization temperature is-25 ~ 5 DEG C;
Step b: logical nitrogen discharges the ozone in reaction flask, adds reductive agent, reduction reaction temperature-10 ~ 30 DEG C, stirs, recycling design under condition of normal pressure, and air distillation is collected, and cut obtains product.
2. purity according to claim 1 is higher than the preparation method of chloroethanol of 99%, it is characterized in that: the mole dosage of described reductive agent be the 0.9-1.5 of Isosorbide-5-Nitrae-dichloro-2-butene mole dosage doubly.
3. purity according to claim 1 is higher than the preparation method of chloroethanol of 99%, it is characterized in that: described reductive agent selects sodium borohydride or POTASSIUM BOROHYDRIDE.
4. purity according to claim 1 is higher than the preparation method of chloroethanol of 99%, it is characterized in that: in described step b, in reduction reaction, churning time is 1-2 hour.
5. purity according to claim 1 is higher than the preparation method of chloroethanol of 99%, it is characterized in that: described cut temperature controls to choose 128 ~ 129 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310697872.3A CN103641684B (en) | 2013-12-18 | 2013-12-18 | High-purity chloro ethanol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310697872.3A CN103641684B (en) | 2013-12-18 | 2013-12-18 | High-purity chloro ethanol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103641684A CN103641684A (en) | 2014-03-19 |
| CN103641684B true CN103641684B (en) | 2016-04-06 |
Family
ID=50247017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310697872.3A Expired - Fee Related CN103641684B (en) | 2013-12-18 | 2013-12-18 | High-purity chloro ethanol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103641684B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105527363A (en) * | 2014-09-29 | 2016-04-27 | 蚌埠丰原涂山制药有限公司 | Method for rapidly detecting 2-chloroethanol residues in gelatin |
| CN115960065A (en) * | 2023-01-06 | 2023-04-14 | 山东鲁西药业有限公司 | Preparation method of flavoxate hydrochloride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222136A (en) * | 1996-06-19 | 1999-07-07 | 陶氏化学公司 | Process for making 2,3-dihalopropanols |
| CN101698632A (en) * | 2009-11-09 | 2010-04-28 | 无锡市银杏塑业科技有限公司 | High-purity 2-ethylene chlorohydrin production method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0720901B2 (en) * | 1987-07-23 | 1995-03-08 | 旭電化工業株式会社 | (4S) -2-Chloro-4-methylhexanol |
-
2013
- 2013-12-18 CN CN201310697872.3A patent/CN103641684B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222136A (en) * | 1996-06-19 | 1999-07-07 | 陶氏化学公司 | Process for making 2,3-dihalopropanols |
| CN101698632A (en) * | 2009-11-09 | 2010-04-28 | 无锡市银杏塑业科技有限公司 | High-purity 2-ethylene chlorohydrin production method |
Non-Patent Citations (1)
| Title |
|---|
| 环氧乙烷法合成高浓度氯乙醇的研究;徐波等;《天津化工》;20020131(第1期);第20-21页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103641684A (en) | 2014-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103641684B (en) | High-purity chloro ethanol and preparation method thereof | |
| CN103787883B (en) | A kind of preparation method of 4-chloroacetyl acetacetic ester | |
| CN102602892B (en) | Method for preparing chlorine gas through catalytic oxidation of hydrogen chloride | |
| CN104610035A (en) | Method for preparing high-purity 4,4'-difluorobenzophenone | |
| CN109534975B (en) | Catalytic synthesis method of 2-hydroxybenzophenone compound | |
| CN113015714B (en) | Continuous Flow Synthesis of Cannabidiol | |
| CN103641722B (en) | A kind of production method of adjacent nitro bromobenzyl | |
| JP2018501205A (en) | Method for producing methyldichlorophosphane | |
| CN107674044A (en) | A kind of method using carbon dioxide, amine and aryldiazonium acetic acid esters synthesis of carbamates | |
| CN103666770B (en) | Preparation method of epoxy modified castor oil | |
| CN117720106A (en) | Purification method of dichloromethane | |
| CN101659611A (en) | Method for preparing 2, 4, 5-trifluoro-phenylacetic-acid | |
| CN108558916A (en) | A kind of synthesis technology to benzene butoxybenzoic acid | |
| CN105481695A (en) | Method for preparing carboxylate compounds | |
| CN102076644A (en) | Process for production of 1, 2, 3, 4-tetrachlorohexafluorobutane | |
| CN104209144A (en) | Catalytic system, preparation method thereof, and preparation method of vinyl acetylene by the same | |
| CN103524333B (en) | The preparation method of 2,6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acid | |
| Zhang et al. | Ionic liquids and relative process design | |
| CN110818527A (en) | Continuous process for preparing high-purity 1,1, 1-trichlorotrifluoroethane by reactive distillation | |
| CN100409942C (en) | Method for extending life of catalyst used in preparation of methyl chloride by carbon tetrachloride alcoholysis | |
| CN101381286A (en) | Method for synthesizing triphenylphosphine onium salts and halomethyl benzyl ethers compounds | |
| CN107915571A (en) | A kind of production technology of Benzene Chloride | |
| CN104478768A (en) | Trifluoromethylsulfo fluorobenzene compound | |
| CN104744233B (en) | A kind of purification process of glacial acetic acid | |
| CN102363614A (en) | Method for synthesizing 2-bromothiophene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160406 Termination date: 20181218 |