CN103641684A - High-purity chlorohydrins and preparation method thereof - Google Patents
High-purity chlorohydrins and preparation method thereof Download PDFInfo
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- CN103641684A CN103641684A CN201310697872.3A CN201310697872A CN103641684A CN 103641684 A CN103641684 A CN 103641684A CN 201310697872 A CN201310697872 A CN 201310697872A CN 103641684 A CN103641684 A CN 103641684A
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- 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
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- 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
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- 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
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- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to the field of synthesis of chemical raw materials, and discloses a method for preparing high-purity chlorohydrins. The preparation method comprises the following steps: a, mixing a raw material 1, 4-dichloro-2-butene and an ozonization reaction solvent; agitating; charging ozone to perform ozonization reaction; tracking the reaction through gas chromatography; and stopping the ozonization reaction until raw materials disappear; and b, charging nitrogen to remove the ozone from a reaction flask; adding a reducing agent to reduce at -10-30 DEG C; agitating; recovering the solvent under a normal pressure condition; and distilling and collecting fractions under normal pressure to obtain the high-purity chlorohydrins. The preparation method is simple and convenient in process route, small in pollution, high in yield, fast in reaction speed, and simple in post-treatment; the chlorohydrins have the purity exceeding 99%, and thus the industrial value is relatively high.
Description
Technical field
The present invention relates to industrial chemicals synthetic field, specifically a kind of method of 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, in order to preparing phosphoric acid piperazine, furan, feed oxazolone, pentoxiverin, caramiphen, benactyzine and Intensain, Propranololum and PROCAINE HCL, PHARMA GRADE etc., in pesticide industry, make the raw material of 1059 sterilants, Niran (1068) sterilant and Systox etc.Industry is at present prepared chloroethanol and is mainly contained hypochlorous acid method and 2 kinds of methods of salt acid system.Hypochlorous acid method, is about to ethene and chlorine and passes in water simultaneously, and chlorine reacts with water 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 remove moisture through continuous rectification, can obtain massfraction and be 32% chloroethanol product.The further azeotropic distillation of chloroethanol of high density removes and anhydrates, 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 pollutedly, make its application be subject to certain limitation.Salt acid system is that to take oxyethane and hydrogenchloride be raw material production high concentration cl ethanol.This technique is first prepared high-purity hydrogen chloride by hydrochloric acid salting-out distillation, then liquid phase is synthetic under certain condition through neutralization and rectifying, just can obtain purity 98% left and right chloroethanol again by itself and oxyethane.This technique with respect to hypochlorous acid method have that technique is simple, constant product quality, the high advantage of product purity, but reaction raw materials HC1 gas purification process expense is higher, and it is large, seriously polluted to consume energy.
Summary of the invention
The present invention is directed to problems of the prior art, a kind of preparation method little, chloroethanol that cost is low, purity is high that pollutes is provided.
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, stir, access ozone carries out ozonization, and gas-chromatography is followed the tracks of reaction, until raw material disappears, stops ozonization;
Step b: logical nitrogen is discharged the ozone in reaction flask, adds reductive agent, stir reduction reaction temperature-10～30 ℃, under condition of normal pressure, reclaims solvent, and air distillation is collected, and cut obtains product.
Isosorbide-5-Nitrae-dichloro-2-butene restores and obtains target product chloroethanol through ozone oxidation, and its synthetic route is as follows:
As preferably, described ozonization solvent select methyl alcohol, ethanol, Virahol any.
As preferably, the mole dosage of described reductive agent be Isosorbide-5-Nitrae-dichloro-2-butene mole dosage 0.9-1.5 doubly.
As preferably, described reductive agent is selected sodium borohydride or POTASSIUM BOROHYDRIDE.
As preferably, described ozonization temperature is-25～5 ℃.
As preferably, in described step b, in reduction reaction, churning time is 1-2 hour.
As preferably, described cut temperature is controlled and is chosen 128～129 ℃.
The present invention also provides a kind of high-purity chloro ethanol that utilizes above-mentioned method to prepare.
The present invention, owing to having adopted above technical scheme, has significant technique effect:
The present invention is with 1,4-dichloro-2-butene is raw material, through ozone oxidation, restore and can prepare chloroethanol, 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 more than 99%, can finely make up the shortcoming that existing handicraft product purity causes the restriction of chemical industry use not, have industrial value.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
The instrument and equipment using in embodiment: ozonizer, GF-G-3-010G(Qingdao Guolin Industry Co., Ltd.); Nuclear magnetic resonance analyser, mark in AVANCE DMX II I 400M(TMS, Bruker company); Gas-chromatography, GC1690 dawn of section.
Embodiment 1
125 grams of Isosorbide-5-Nitrae-dichloro-2-butenes (1mol) and 200 ml methanol are joined in 500mL four-hole bottle, and mechanical stirring is at-25 ℃, after regulating oxygen flow, carry out ozonization, gas-chromatography is followed the tracks of reaction, and within approximately 3 hours, raw material disappears, and reaction finishes to stop ozonize.Logical nitrogen is caught up with ozone in reaction flask, keep ℃ left and right, Nei Wen-10, be added dropwise to containing in 40.0 grams of sodium borohydrides (1.05mol), 150 ml methanol solution, after adding, continue stirring reaction after 1 hour, react complete, normal pressure reclaims solvent, and air distillation is collected 128～129 ℃ of cuts and obtained 136.8 grams of colourless transparent liquids, gas phase content 99.4%, yield 84.5%.
Product structure is confirmed:
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
125 grams of Isosorbide-5-Nitrae-dichloro-2-butenes (1mol) and 200 milliliters of ethanol are joined in 500mL four-hole bottle, and mechanical stirring is at-10 ℃, after regulating oxygen flow, carry out ozonization, gas-chromatography is followed the tracks of reaction, and within approximately 3 hours, raw material disappears, and reaction finishes to stop ozonize.Logical nitrogen is caught up with ozone in reaction flask, 0 ℃ of left and right of temperature in keeping, be added dropwise to containing in 150 milliliters of ethanolic solns of 66.0 grams of POTASSIUM BOROHYDRIDE (1.2mol), after adding, continue stirring reaction after 1.5 hours, react complete, normal pressure reclaims solvent, and air distillation is collected 128～129 ℃ of cuts and obtained 140.3 grams of colourless transparent liquids, gas phase content 99.7%, yield 86.9%.Product nuclear magnetic spectrogram is identical with embodiment 1.
Embodiment 3
125 grams of Isosorbide-5-Nitrae-dichloro-2-butenes (1mol) and 200 milliliters of Virahols are joined in 500mL four-hole bottle, and mechanical stirring is at 5 ℃, after regulating oxygen flow, carry out ozonization, gas-chromatography is followed the tracks of reaction, and within approximately 3 hours, raw material disappears, and reaction finishes to stop ozonize.Logical nitrogen is caught up with ozone in reaction flask, 10 ℃ of left and right of temperature in keeping, be added dropwise to containing in 150 milliliters of ethanolic solns of 50.0 grams of POTASSIUM BOROHYDRIDE (0.91mol), after adding, continue stirring reaction after 2 hours, react complete, normal pressure reclaims solvent, and air distillation is collected 128～129 ℃ of cuts and obtained 138.7 grams of colourless transparent liquids, 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 of doing 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 (8)
1. the preparation method of high-purity chloro ethanol, is characterized in that, described preparation method comprises the steps:
Step a: by raw material Isosorbide-5-Nitrae-dichloro-2-butene and ozonization solvent, stir, access ozone carries out ozonization, and gas-chromatography is followed the tracks of reaction, until raw material disappears, stops ozonization;
Step b: logical nitrogen is discharged the ozone in reaction flask, adds reductive agent, stir reduction reaction temperature-10～30 ℃, under condition of normal pressure, reclaims solvent, and air distillation is collected, and cut obtains product.
2. the preparation method of high-purity chloro ethanol according to claim 1, is characterized in that: described ozonization solvent select methyl alcohol, ethanol, Virahol any.
3. the preparation method of high-purity chloro ethanol according to claim 1, is characterized in that: the mole dosage of described reductive agent is 0.9-1.5 times of Isosorbide-5-Nitrae-dichloro-2-butene mole dosage.
4. the preparation method of high-purity chloro ethanol according to claim 1, is characterized in that: described reductive agent is selected sodium borohydride or POTASSIUM BOROHYDRIDE.
5. the preparation method of high-purity chloro ethanol according to claim 1, is characterized in that: described ozonization temperature is-25～5 ℃.
6. the preparation method of high-purity chloro ethanol according to claim 1, is characterized in that: in described step b, in reduction reaction, churning time is 1-2 hour.
7. the preparation method of high-purity chloro ethanol according to claim 1, is characterized in that: described cut temperature is controlled and chosen 128～129 ℃.
8. the high-purity chloro ethanol that utilizes the method as described in as arbitrary in claim 1-7 to prepare.
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Cited By (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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6429330A (en) * | 1987-07-23 | 1989-01-31 | Adeka Argus Chemical Co Ltd | (4s)-2-chloro-4-methylhexanol |
| 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 |
-
2013
- 2013-12-18 CN CN201310697872.3A patent/CN103641684B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6429330A (en) * | 1987-07-23 | 1989-01-31 | Adeka Argus Chemical Co Ltd | (4s)-2-chloro-4-methylhexanol |
| 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 |
|---|
| 徐波等: "环氧乙烷法合成高浓度氯乙醇的研究", 《天津化工》, no. 1, 31 January 2002 (2002-01-31), pages 20 - 21 * |
Cited By (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 |
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| CN103641684B (en) | 2016-04-06 |
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Granted publication date: 20160406 Termination date: 20181218 |