CN1225440C - Conversion process of primary alcohol, hexamethylene glycol, tertiary amyl alcohol or cyclohexanol into halohydrocarbon in acid ionic liquid [Hmim] X,X==Cl,Br or I) - Google Patents
Conversion process of primary alcohol, hexamethylene glycol, tertiary amyl alcohol or cyclohexanol into halohydrocarbon in acid ionic liquid [Hmim] X,X==Cl,Br or I) Download PDFInfo
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- CN1225440C CN1225440C CN 03116131 CN03116131A CN1225440C CN 1225440 C CN1225440 C CN 1225440C CN 03116131 CN03116131 CN 03116131 CN 03116131 A CN03116131 A CN 03116131A CN 1225440 C CN1225440 C CN 1225440C
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- hmim
- ion liquid
- acidic ion
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Abstract
The present invention discloses a method for converting primary alcohol or cyclohexanol in Brphinsted acid ion liquid [Hmim]<+>X<->(X= Cl, Br, I), namely halogenating methylimidazole salts, into halogenated hydrocarbons, which belongs to the technical field of new methods of organic chemistry reaction. The ion liquid is mixed with primary alcohol or cyclohexanol, halogenated hydrocarbons are obtained by stir, heating, standing, gravity settling and liquid separation, and the yield is from 85 to 100%. In the reaction, the ionic liquid is also used as a catalyst, a halogenating reagent and a solvent. The method has the advantages of high yield, simple technology, reusable catalyst and solvent, environmental protection, etc.
Description
Technical field
The present invention relates to acidic ion liquid [Hmim]
+X
-, X=Cl, Br, I, i.e. primary alconol, hexylene glycol, tertiary amyl alcohol or hexalin are converted into the method for halohydrocarbon in the halogenation methylimidazole salt, exactly, relate to Br φ nsted acidic ion liquid [Hmim]
+X
-, X=Cl, Br, I, i.e. primary alconol, hexylene glycol, tertiary amyl alcohol or hexalin are converted into the method for halohydrocarbon in the halogenation methylimidazole salt, belong to the technical field of organic chemical reactions novel method.
Background technology
Halogenide is intermediate important in the medicine industry.The halo method of background technology is normally carried out alcohol and Halogen ionic inorganic salt under a large amount of sulphuric acid catalysis.The remaining spent acid in reaction back causes environmental pollution.Ionic liquid is a class environmental friendliness reagent that receives publicity day by day in recent years, has good stability, and is non-volatile, with advantage such as the organism solubility is adjustable.People such as calendar year 2001 R.X.Ren have reported halogenated method in the ionic liquid on Organic Letter.But in the document, still need to use inorganic or organic acid as catalyst, and long reaction time, yield is also unstable.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of Br φ nsted acidic ion liquid [Hmim]
+X
-, primary alconol, hexylene glycol, tertiary amyl alcohol or hexalin are converted into the method for halohydrocarbon among X=Cl, Br, the I.The present invention solves this technical problem by the following technical programs: with Br φ nsted acidic ion liquid [Hmim]
+X
-, X=Cl, Br, I and primary alconol, hexylene glycol, tertiary amyl alcohol or hexalin are inserted in the reaction flask, stir, and heating, reaction is left standstill, the gravity settling layering, high yield obtains halohydrocarbon.The ionic liquid of telling [Hmim]
+X
-, add used up haloid acid among X=Cl, Br, the I, remove then and anhydrate and can recycle.Br φ nsted acidic ion liquid [Hmim]
+X
-, X=Cl, Br, I double as catalyzer, halogenating agent and solvent.Halo circulating reaction skeleton symbol is:
Mim＝1-methylimidazole
Now describe technical scheme of the present invention in detail.A kind of Br φ nsted acidic ion liquid [Hmim]
+X
-, primary alconol, hexylene glycol, tertiary amyl alcohol or hexalin are converted into the method for halohydrocarbon among X=Cl, Br, the I, it is characterized in that,
Br φ nsted acidic ion liquid [Hmim] with 100 parts of weight
+X
-, primary alconol, hexylene glycol, tertiary amyl alcohol or the hexalin of X=Cl, Br, I and 8～10 parts of weight are inserted in the reaction flask, adopt nitrogen protection during iodide reaction, stir, heating, controlled temperature reacted 12～20 hours at 55～145 ℃, leave standstill, the gravity settling layering obtains halohydrocarbon;
Lower floor's Br φ nsted acidic ion liquid [Hmim]
+X
-, add used up haloid acid among X=Cl, Br, the I, remove then and anhydrate and can recycle.
Compare with background technology, the present invention has the following advantages:
1. Br φ nsted acidic ion liquid [Hmim] in reacting
+X
-, X=Cl, Br, I are both as catalyzer and solvent, again as halogenating agent.And this ionic liquid can be regenerated by adding used up haloid acid.
2. technology is simple, can high yield synthesizing halohydrocarbon, and catalyzer and solvent can recycle repeatedly, and environmental friendliness really realizes cleaner production.
Embodiment
Embodiment one:
With 100gBr φ nsted acidic ion liquid [Hmim]
+Cl
-Insert in the reaction flask with the 8.1g propyl carbinol, stir, heating, controlled temperature reacted 12 hours at 110 ℃, and reaction solution leaves standstill, gravity settling, layering obtains n-propylcarbinyl chloride yield 96%.The hydrochloric acid soln that adds 10.8g 37% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment two:
With 100gBr φ nsted acidic ion liquid [Hmim]
+Br
-Insert in the reaction flask with the 8.1g propyl carbinol, stir, heating, controlled temperature reacted 12 hours at 110 ℃, and reaction solution leaves standstill, gravity settling, layering obtains bromination of n-butane, yield 98%.The hydrobromic acid solution that adds 18.9g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment three:
With 100gBr φ nsted acidic ion liquid [Hmim]
+I
-Insert in the reaction flask with the 8.1g propyl carbinol, nitrogen protection is stirred, heating, and controlled temperature reacted 20 hours at 60 ℃, and reaction solution leaves standstill, gravity settling, layering obtains the iodo octane, yield 99%.The hydroiodic acid HI solution that adds 29.8g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment four:
With 100gBr φ nsted acidic ion liquid [Hmim]
+Cl
-Insert in the reaction flask with the 8.3g n-Octanol, stir, heating, controlled temperature reacted 12 hours at 140 ℃, and reaction solution leaves standstill, gravity settling, layering obtains the chloro octane, yield 95%.The hydrochloric acid soln that adds 6.3g 37% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment five:
With 100gBr φ nsted acidic ion liquid [Hmim]
+-Br
-Insert in the reaction flask with the 8.3g n-Octanol, stir, heating, controlled temperature reacted 12 hours at 140 ℃, and reaction solution leaves standstill, gravity settling, layering obtains n-octane bromide, yield 99%.The hydrobromic acid solution that adds 11.0g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment six:
With 100gBr φ nsted acidic ion liquid [Hmim]
+I
-Insert in the reaction flask with the 8.3g n-Octanol, nitrogen protection is stirred, heating, and controlled temperature reacted 20 hours at 100 ℃, and reaction solution leaves standstill, gravity settling, layering obtains the iodo octane, yield 98%.The hydroiodic acid HI solution that adds 17.4g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment seven:
With 100gBr φ nsted acidic ion liquid [Hmim]
+Cl
-Put into reaction flask with the 10g phenylcarbinol, stir, heating, controlled temperature reacted 15 hours at 90 ℃, and reaction solution leaves standstill, gravity settling, layering obtains chlorinated benzene methane, yield 97%.The hydrochloric acid soln that adds 9.1g37% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment eight:
With 100gBr φ nsted acidic ion liquid [Hmim]
+Br
-Put into reaction flask with the 10g phenylcarbinol, stir, heating, controlled temperature reacted 15 hours at 90 ℃, and reaction solution leaves standstill, gravity settling, layering obtains bromobenzene methane, yield 98%.The hydrobromic acid solution that adds 16.0g47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment nine:
With 100gBr φ nsted acidic ion liquid [Hmim]
+I
-Put into reaction flask with the 10g phenylcarbinol, nitrogen protection is stirred, heating, and controlled temperature reacted 15 hours at 90 ℃, and reaction solution leaves standstill, gravity settling, layering obtains phenyl-iodide methane, yield 100%.The hydroiodic acid HI solution that adds 25.2g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment ten:
With 100gBr φ nsted acidic ion liquid [Hmim]
+Cl
-Put into reaction flask with the 10g hexylene glycol, stir, heating, controlled temperature reacted 12 hours at 100 ℃, and reaction solution leaves standstill, gravity settling, layering obtains 1,6-dichloro hexane, yield 98%.The hydrochloric acid soln that adds 8.4g 37% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment 11:
With 100g Br φ nsted acidic ion liquid [Hmim]
+Br
-Put into reaction flask with the 10g hexylene glycol, stir, heating, controlled temperature reacted 12 hours at 100 ℃, and reaction solution leaves standstill, gravity settling, layering obtains 1,6-dibromo-hexane, yield 98%.The hydrobromic acid solution that adds 14.6g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment 12:
With 100g Br φ nsted acidic ion liquid [Hmim]
+I
-Put into reaction flask with the 10g hexylene glycol, nitrogen protection is stirred, heating, and controlled temperature reacted 12 hours at 68 ℃, and reaction solution leaves standstill, gravity settling, layering obtains 1,6-two iodohexanes, yield 100%.The hydroiodic acid HI solution that adds 23.1g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment 13:
With 100g Br φ nsted acidic ion liquid [Hmim]
+Cl
-Put into reaction flask with the 8.2g tertiary amyl alcohol, stir, heating, controlled temperature reacted 12 hours at 84 ℃, and reaction solution leaves standstill, and separatory obtains chloro uncle pentane, yield 95%.The hydrochloric acid soln that adds 9.2g 37% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment 14:
With 100gBr φ nsted acidic ion liquid [Hmim]
+Br
-Put into reaction flask with the 8.2g tertiary amyl alcohol, stir, heating, controlled temperature reacted 12 hours at 60 ℃, and reaction solution leaves standstill, and separatory obtains 2-bromoisopentane, yield 94%.The hydrobromic acid solution that adds 16.1g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment 15:
With 100gBr φ nsted acidic ion liquid [Hmim]
+I
-Put into reaction flask with the 8.2g tertiary amyl alcohol, nitrogen protection is stirred, heating, and controlled temperature reacted 12 hours at 60 ℃, and reaction solution leaves standstill, and separatory obtains iodo uncle pentane, yield 88%.The hydroiodic acid HI solution that adds 25.4g47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment 16:
With 100g Br φ nsted acidic ion liquid [Hmim]
+Cl
-Put into reaction flask with 9.5 hexalin, stir, heating, controlled temperature reacted 12 hours at 130 ℃, and reaction solution leaves standstill, gravity settling, layering obtains chlorocyclohexane, yield 96%.Add 9.4g hydrochloric acid in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment 17:
With 100gBr φ nsted acidic ion liquid [Hmim]
+Br
-Put into reaction flask with the 9.5g hexalin, stir, heating, controlled temperature reacted 12 hours at 130 ℃, and reaction solution leaves standstill, gravity settling, layering obtains bromocyclohexane, yield 96%.The hydrobromic acid solution that adds 16.4g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Embodiment 18:
With 100gBr φ nsted acidic ion liquid [Hmim]
+I
-Put into reaction flask with the 9.5g hexalin, nitrogen protection is stirred, heating, and controlled temperature reacted 12 hours at 70 ℃, and reaction solution leaves standstill, gravity settling, layering obtains iodocyclohexane, yield 85%.The hydroiodic acid HI solution that adds 25.9g 47% in the Br φ nsted of the lower floor acidic ion liquid, boil off water after the regenerated ionic liquid can be recycled.
Claims (1)
1.Br φ nsted acidic ion liquid [Hmim]
+X
-, primary alconol, hexylene glycol, tertiary amyl alcohol or hexalin are converted into the method for halohydrocarbon among X=Cl, Br, the I, it is characterized in that, with the Br φ nsted acidic ion liquid [Hmim] of 100 parts of weight
+X
-, primary alconol, hexylene glycol, tertiary amyl alcohol or the hexalin of X=Cl, Br, I and 8～10 parts of weight are inserted in the reaction flask, adopt nitrogen protection during iodide reaction, stir, heating, controlled temperature reacted 12～20 hours at 55～145 ℃, leave standstill, the gravity settling layering obtains halohydrocarbon;
Lower floor's Br φ nsted acidic ion liquid [Hmim]
+X
-, add used up haloid acid among X=Cl, Br, the I, remove then and anhydrate and can recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03116131 CN1225440C (en) | 2003-04-03 | 2003-04-03 | Conversion process of primary alcohol, hexamethylene glycol, tertiary amyl alcohol or cyclohexanol into halohydrocarbon in acid ionic liquid [Hmim] X,X==Cl,Br or I) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03116131 CN1225440C (en) | 2003-04-03 | 2003-04-03 | Conversion process of primary alcohol, hexamethylene glycol, tertiary amyl alcohol or cyclohexanol into halohydrocarbon in acid ionic liquid [Hmim] X,X==Cl,Br or I) |
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|---|---|
| CN1440958A CN1440958A (en) | 2003-09-10 |
| CN1225440C true CN1225440C (en) | 2005-11-02 |
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| CN 03116131 Expired - Fee Related CN1225440C (en) | 2003-04-03 | 2003-04-03 | Conversion process of primary alcohol, hexamethylene glycol, tertiary amyl alcohol or cyclohexanol into halohydrocarbon in acid ionic liquid [Hmim] X,X==Cl,Br or I) |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0422447D0 (en) * | 2004-10-08 | 2004-11-10 | Univ Cambridge Tech | Use of ionic liquids |
| DE102005008547B4 (en) * | 2005-02-23 | 2007-10-04 | Degussa Gmbh | Process for the preparation of alkyl chlorides |
| CN104447185B (en) | 2009-03-05 | 2016-06-22 | 蓝立方知识产权公司 | For liquid reactive method and apparatus |
| CN101768045B (en) * | 2010-01-12 | 2013-06-26 | 郑州大学 | Method for preparing halogenated hydrocarbons from strong acidic ionic liquid |
| CN104672053B (en) * | 2013-11-29 | 2016-08-24 | 上虞新和成生物化工有限公司 | Ionic liquid application in the preparation of bromoethane |
| CN113896614B (en) * | 2021-11-08 | 2024-04-02 | 山东绿色海洋化工研究院有限公司 | Method for continuously synthesizing chlorobutane in non-aqueous system |
| CN115745734A (en) * | 2022-12-14 | 2023-03-07 | 山东默锐科技有限公司 | Method for synthesizing n-bromobutane |
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Granted publication date: 20051102 Termination date: 20130403 |