CN1042528C - Hydrodehalogenation reaction catalyzed by halohydrocarbon - Google Patents
Hydrodehalogenation reaction catalyzed by halohydrocarbon Download PDFInfo
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- CN1042528C CN1042528C CN93111071A CN93111071A CN1042528C CN 1042528 C CN1042528 C CN 1042528C CN 93111071 A CN93111071 A CN 93111071A CN 93111071 A CN93111071 A CN 93111071A CN 1042528 C CN1042528 C CN 1042528C
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- reaction
- halohydrocarbon
- catalyzer
- add
- hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a hydrodehalogenation reaction catalyzed by halohydrocarbon under a mild condition, which uses palladium chromium compounds of soluble macromolecule carriers loaded on nitrogen-containing coordination atoms as catalysts to react in alcohol solvent under normal pressure at low temperature. The reaction system has the advantages of simplicity, high efficiency of catalysts, easy preparation and high activity, and is a practical halohydrocarbon dehalogenation method.
Description
The present invention relates to the shortening-dehalogenation reaction of halohydrocarbon, specifically in the presence of the macromolecule loading palladium catalyst of the nitrogenous ligating atom of solubility, hydrodehalogenation reaction catalyzed in halohydrocarbon and hydrogen that normal pressure, cold condition are realized down.
The dehalogenation reaction of halohydrocarbon is not only the important reaction in the Minute Organic Synthesis, and important use (be used for and will be difficult to the high toxicity of handling with ordinary method or cause that the halohydrocarbon of serious environmental pollution is converted into easy processing or recycling compound) is also arranged in environmental protection.The existing many patent reports of relevant this class reaction.Normally use the 8th family's metal (being carried on the inorganic carrier) or title complex to make catalyzer, make hydrogen source with alcohol, organic acid salt or hydrogen, and add a certain amount of alkali (oxyhydroxide of basic metal, alkaline-earth metal or weak acid strong alkali salt etc.).For example European patent (1990, EP352,164) is with Pd (OAc)
2Be catalyzer, at Pph
3And NEt
3Exist down, make chlorobenzene and hydrogen reaction generation benzene, transformation efficiency only 41%.United States Patent (USP) (1986, US4,618,686) is a catalyzer with Pd/C, and the interpolation phosphoric acid salt of still needing can make the polychlorinated biphenyl dehalogenation.Be reflected at 50 ℃, K
2CO
3Carry out under existing.United States Patent (USP) (1971, US3,595,931) is used Pd/Al
2O
3(0.6%) make catalyzer, make 2-chloro-p-Xylol and hydrogen carry out the High Temperature Gas phase reaction in the presence of KOH, generate dimethylbenzene, transformation efficiency is near 100%.Transformation efficiency is low during low temperature.At present, common dehalogenation catalyst system is a hydrogen source and be hydrogen source with alcohols or organic acid salt without hydrogen when adding alkali.If do not add alkali when being hydrogen source again with hydrogen, like this since the two activity all not high.
The purpose of this invention is to provide have active high, good stability, simple, easily synthetic, the dehalogenate activator that cost is low and reaction conditions is gentle is realized the hydrodehalogenation reaction of Organohalogen compounds.
The present invention adopts the palladium complex (PdCl of the soluble high-molecular carrier (PVP) that is carried on nitrogenous ligating atom
2) be that catalyzer is (with PVP-PdCl
2Expression), halohydrocarbon is reacted in normal pressure, low temperature, alcoholic solvent, and add the HCl that appropriate bases is generated with neutralization.Reaction can be expressed from the next:
Polymer carrier (PVP) the best is polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide etc.Catalyzer usage quantity in reaction is 5.0 * 10
-2-1.0 * 10
-5M.The temperature of reaction that halohydrocarbon carries out in alcoholic solvent (as methyl alcohol, ethanol, n-propyl alcohol, Virahol) can be controlled in 20～80 ℃, and the reaction hydrogen pressure can be controlled in normal pressure or is higher than normal pressure.Alkali or strong base-weak acid salt add-on are with OH in the catalyzer
-The halogen ratio is 1～5, and the adding method can adopt once and add in advance, and also graded splashes into.Catalyzer be alcoholic solvent or contain alcohol mixed solvent in react.
The present invention has catalyzer and easily prepares, and palladium easily reclaims, and active high, selectivity is good, the reaction conditions gentleness, and cost is low, and reaction system is simple, and raw material is easy to get, and does not need characteristics such as specific installation.
This class catalyzer has very high activity to the dehalogenation of halogenated aryl hydrocarbon, benzyl halides and allyl halide.High reactivity as chlorobenzene dechlorination reaction can reach 100mol Cl/molPdmin.The consumption (by Pd) of this catalyzer in reaction is 5.0 * 10
-2～1.0 * 10
-5M.Mol ratio (the OH of alkali and substrate
-/ X) be advisable with 1～5.Below by example the dehalogenation reaction of the present invention is elaborated.
The reaction of example 1 chlorobenzene dechlorination
In 50ml glass reaction bottle, add dehydrated alcohol 5.5ml, PVP-PdCl
2Ethanolic soln 14.5ml (3.4 * 10
-3M), Mg (OH)
20.3g (5mmol) with chlorobenzene 0.5ml (5mmol).Be reflected in the normal pressure hydrogen and carry out, temperature of reaction is 65 ℃, and through the 4h reaction, chlorobenzene 100% is converted into benzene, does not have other by products and generates.
Example 2-6
Carry out example 2-6 by example 1 described experiment condition and step, the results are shown in Table 1.
The dehalogenation reaction of some halohydrocarbon of table 1
By above-mentioned example, when adopting PVP-Pdcl provided by the invention
2, can make the halohydrocarbon generation dehalogenation reaction at atmospheric low-temperature.This reaction does not need specific installation, and reaction system is simple, and catalyzer easily prepares, and is active high, is a kind of economical and practical dehalogenation method.
| Example | Halohydrocarbon | Alkali | Pd consumption mol/l | Reaction times min | Transformation efficiency % | Product % |
| ?2 ?3 ?4 ?5 ?6 | Chlorobenzene bromobenzene benzyl chloride p-dichlorobenzene m-dichlorobenzene | NaOH Mg(OH) 2Mg(OH) 2Mg(OH) 2Mg(OH) 2 | ?2.3×10 -3?2.3×10 -3?2.3×10 -3?2.3×10 -3?2.3×10 -3 | ?60 ?90 ?10 ?180 ?300 | ?100 ?100 ?100 ?95.6 ?87.3 | Benzene (100) benzene (100) toluene (100) chlorobenzene (0), benzene (100) chlorobenzene (4,3), benzene (95.7) |
Claims (4)
1. hydrodehalogenation reaction catalyzed by halohydrocarbon, the palladium complex that it is characterized in that adopting the soluble high-molecular carrier that is carried on nitrogenous ligating atom is a catalyzer, make halogenated aryl hydrocarbon and benzyl halides in normal pressure, 20～80 ℃, alcoholic solvent and add appropriate bases and in the presence of hydrogen, react, be expressed from the next:
Catalyzer usage quantity in reaction is 5.0 * 10
-2～1.0 * 10
-5M.
2. according to the described dehalogenation reaction of claim 1, it is characterized in that said polymer carrier is polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide.
3. according to the described dehalogenation reaction of claim 1, it is characterized in that in the catalyzer that alkali or strong base-weak acid salt add-on are with OH
-/ halogen rope ratio is 1～5, and the adding method can adopt once and add in advance, and also graded splashes into.
4. according to the described dehalogenation reaction of claim 1, it is characterized in that alcoholic solvent can select methyl alcohol, ethanol, n-propyl alcohol, Virahol for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93111071A CN1042528C (en) | 1993-04-24 | 1993-04-24 | Hydrodehalogenation reaction catalyzed by halohydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93111071A CN1042528C (en) | 1993-04-24 | 1993-04-24 | Hydrodehalogenation reaction catalyzed by halohydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1094022A CN1094022A (en) | 1994-10-26 |
| CN1042528C true CN1042528C (en) | 1999-03-17 |
Family
ID=4988877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93111071A Expired - Fee Related CN1042528C (en) | 1993-04-24 | 1993-04-24 | Hydrodehalogenation reaction catalyzed by halohydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1042528C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465140C (en) * | 2006-12-01 | 2009-03-04 | 华南理工大学 | Hydrogen catalyzed alkyl halide dehaloginating reducton process for preparing hydrocarbon |
| CN101475428B (en) * | 2009-01-16 | 2012-11-21 | 大连理工大学 | Room temperture nickel catalysis dechlorination method for chlorinated aromatic hydrocarbons |
| CN105503706A (en) * | 2015-12-28 | 2016-04-20 | 衢州学院 | Dehalogenation degradation method for halogenated pyridine compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068484A (en) * | 1989-11-02 | 1991-11-26 | Uop | Process for the hydroconversion of a feedstock comprising organic compounds having a tendency to readily form polymer compounds |
| EP0479116A1 (en) * | 1990-10-04 | 1992-04-08 | The Dow Chemical Company | Vapor phase hydrogenation of carbon tetrachloride |
-
1993
- 1993-04-24 CN CN93111071A patent/CN1042528C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068484A (en) * | 1989-11-02 | 1991-11-26 | Uop | Process for the hydroconversion of a feedstock comprising organic compounds having a tendency to readily form polymer compounds |
| EP0479116A1 (en) * | 1990-10-04 | 1992-04-08 | The Dow Chemical Company | Vapor phase hydrogenation of carbon tetrachloride |
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| Publication number | Publication date |
|---|---|
| CN1094022A (en) | 1994-10-26 |
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