CN102626645B - Application of fluorgypsum in ketoxime Beckmann rearrangement - Google Patents
Application of fluorgypsum in ketoxime Beckmann rearrangement Download PDFInfo
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- CN102626645B CN102626645B CN2012100837869A CN201210083786A CN102626645B CN 102626645 B CN102626645 B CN 102626645B CN 2012100837869 A CN2012100837869 A CN 2012100837869A CN 201210083786 A CN201210083786 A CN 201210083786A CN 102626645 B CN102626645 B CN 102626645B
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- fluorgypsum
- ketoxime
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Abstract
The invention relates to an applied research of fluorgypsum in ketoxime Beckmann rearrangement reaction. A catalyst of fluorgypsum is a main by-product generated in fluorine chemical industry and is solid waste which is difficult to treat. According to an application, fluorgypsum can be directly used as a catalyst or used as a catalyst carrier, and then is modified by sulfuric acid or chlorosulfonic acid so as to serve as a catalyst and be applied in ketoxime Beckmann rearrangement reaction. The application of the fluorgypsum in the ketoxime Beckmann rearrangement can be used for organic synthesis, particularly Beckmann conversion reaction of cyclohexanone-oxime and cyclododecanone-oxime.
Description
Technical field
The present invention relates to the application study of solid waste fluorgypsum in ketoxime Beckmann rearrangement reaction.
Background technology
The reasonable utilization of industrial residue is an important content of national economy sustainable development.Along with developing rapidly of aluminium industry, fluorine chemical and organic chemical industry, very fast to the demand increase of hydrofluoric acid and fluoride salt, the byproduct fluorgypsum is corresponding increase also, and the accumulating amount of China's waste slag of fluorine gypsum ranks first in the world.But, up to the present, domestic processing and the problem of complex utilization that solves not yet preferably fluorgypsum.Most of fluorgypsum, after neutralisation treatment, just as a kind of solid waste, storing up a little, is directly stored up not only landed property, goes back contaminated soil and groundwater environment.
On November 6th, 2009, Hunan Province Science and Technology Department held the great special project of Hunan Province's science and technology " the steel metallurgy of aluminium important auxiliary material in industrial area, Xiangxiang are produced energy-conserving and emission-cutting technology exploitation and demonstration (2009) " Launching Ceremony in Xiangxiang City, and include " Xiangjiang River basin Heavy Metal Pollution Control " project in as sub-project, obtained great special subsidy of country's " 12 " energy-saving and emission-reduction.National " 863 " plan on June 1 key project in 2010 " fluorgypsum harmless treatment and the research and development of recycling key technology and demonstration " formally starts in Wuhan University.
It is the important functional group's conversion reaction of a class that the acid catalysis of oxime transforms, and wherein the Beckmann of ketoxime rearrangement is the important reaction of synthesizing amide, has the stereocpecificity of height, has been successfully applied to the industrial production of epsilon-caprolactams and lauric lactam at present.
Summary of the invention
The object of the invention is to the solid waste fluorgypsum is prepared into to catalyst, be applied to ketoxime Beckmann rearrangement reaction.
Implementing process of the present invention comprises fluorgypsum pretreatment process and catalytic reaction process.
The pretreatment process specifically comprises and first adopts organic solvent to carry out impregnation process to solid waste, removes the organic impurities contained in fluorgypsum, dries or directly stand-by (fluorgypsum catalyst A); Or, by the fluorgypsum after the organic solvent dipping, through sulfuric acid or chlorosulfonic acid modification, be prepared into pellet type catalyst, stand-by.Be called fluorgypsum catalyst B and C.
Catalytic reaction process comprises two kinds of fronts catalyst for the Beckmann rearrangement reaction, concrete operations technique is: oxime is dissolved in to suitable organic solvent, add a certain amount of catalyst, stir at a certain temperature, TLC monitors reaction end, isolated by filtration, remove organic solvent, obtains the acid amides crude product.
Reaction yield is usually very high, adopts the means such as solvent wash, crystallization or rapid column chromatography of certain polarity can obtain sterling, thereby has improved the operability of technique of the present invention, is conducive to suitability for industrialized production.
The fluorgypsum used refers to the solid waste of fluorine chemical, comprises fresh fluorgypsum and is long placed in old fluorgypsum.
The organic solvent of fluorgypsum pretreatment refers to aromatic hydrocarbon, halogenated hydrocarbons or their mixed solvent, wherein aromatic hydrocarbon refers to benzene,toluene,xylene, chlorobenzene, halogenated hydrocarbons refers to carrene, chloroform, carbon tetrachloride, 1,2-dichloroethanes, preferred pretreatment solvent are toluene, chloroform.
Ketoxime comprises non-cyclic ketoxime and ring-type ketoxime.
The non-annularity ketoxime refers to the structure with following general formula (I)
, R wherein
1And R
2Identical or different, comprise various substituted aryls, thick aryl, alkyl or cycloalkyl, various substituted radicals refer to alkyl, aryl, alkoxyl, halogen, nitro, cyano group, trifluoromethyl.
The preferred cyclohexanone oxime of ring-type ketoxime and cyclododecanone oxime.
Catalyst refers to the fluorgypsum after pretreatment processing, and its quality consumption is generally 5 ~ 50% of oxime, and preferable amount is 10 ~ 30% of oxime.
The organic solvent that catalytic reaction is suitable refers to aromatic hydrocarbons, halogenated hydrocarbons etc., typically refer to benzene,toluene,xylene, chlorobenzene, chloroform, 1,2-dichloroethanes etc., preferred toluene, solvent load guarantees to dissolve oxime at least, be generally 5 ~ 50 mL/mmol oximes, preferable amount is 10 ~ 20 mL/mmol oximes.
The uniform temperature of catalytic reaction refers to the temperature that guarantees to dissolve oxime, typically refers to room temperature to the solvent refluxing temperature, and preferably temperature is reflux temperature.
The specific embodiment
Embodiment 1 diphenyl-ketoxime Beckmann rearrangement reaction
1.97 g diphenyl-ketoximes are dissolved in 10 mL toluene solvants, and magnetic agitation, treat whole dissolvings, adds 0.2 g fluorgypsum catalyst A, is warming up to backflow.By TLC monitoring reaction process, react complete, suction filtration, filter cake 5mL toluene wash, the filtrate desolventizing, thick product petroleum ether, vacuum drying, obtain white solid 1.67 g, yield 85%, m.p 163 ~ 164
oC.
1H NMR (400 MHz, CDCl
3) δ 7.87 (d,
J=7.6 Hz, 2 H), 7.83 (br s, 1 H), 7.64 (d,
J=7.6 Hz, 2 H), 7.57-7.54 (m, 1 H), 7.49 (t,
J=7.6 Hz, 2 H), 7.38 (t,
J=7.6 Hz, 2 H), 7.72 (t,
J=7.6 Hz, 1 H).
Embodiment 2 diphenyl-ketoxime Beckmann rearrangement reactions
After using the fluorgypsum catalyst A in example 1 instead B or C, yield all reaches 93%, m.p 163 ~ 164
oC.
Embodiment 3 diphenyl-ketoxime Beckmann rearrangement reactions
Make the solvent toluene in example 1 into 1,2-dichloroethanes, catalyst is used C instead, yield 92%, and m.p 163 ~ 164
oC.
Embodiment 4 diphenyl-ketoxime Beckmann rearrangement reactions
The amount of fluorgypsum catalyst C in example 2 is adjusted into to 0.3g, yield 95%, m.p 163 ~ 164
oC.
Embodiment 5 diphenyl-ketoxime Beckmann rearrangement reactions
The amount of fluorgypsum catalyst C in example 2 is adjusted into to 0.1g, yield 91%, m.p 163 ~ 164
oC.
Embodiment 6 acetophenone oxime Beckmann rearrangement reactions
1.35 g acetophenone oximes are dissolved in 5 mL toluene solvants, and magnetic agitation, treat whole dissolvings, adds 0.1 g fluorgypsum catalyst C, is warming up to backflow.By TLC monitoring reaction process, react complete, suction filtration, filter cake washs with 10 mL benzene, the filtrate desolventizing, thick product petroleum ether, vacuum drying, obtain white solid 1.25 g, yield 93%, m.p 114 ~ 115
oC.
1H NMR (400 MHz, CDCl
3) δ 8.44 (br s, 1 H), 7.51 (d,
J=8.5 Hz, 2 H), 7.24 (t,
J=7.8 Hz, 2 H), 7.06 (t,
J=7.2 Hz, 1 H), 2.09 (s, 3 H).
Embodiment 7 using cyclohexanone-oxime Beckmann rearrangement reactions
1.13 g cyclohexanone oximes are dissolved in 10 mL toluene solvants, and magnetic agitation, treat whole dissolvings, adds 0.1g fluorgypsum catalyst C, is warming up to backflow.By TLC monitoring reaction process, react complete, suction filtration, filter cake 5mL toluene wash, the filtrate desolventizing, thick product petroleum ether, vacuum drying, obtain white solid 1.0 g, yield 88%, m.p 69 ~ 70
oC.
1H NMR (400 MHz, CDCl
3) δ 7.46 (br s, 1 H), 3.21-3.16 (m, 2 H), 2.45-2.41 (m, 2 H), 1.75-1.72 (m, 2 H), 1.68-1.61 (m, 4 H).
Claims (7)
1.
As the fluorgypsum of the fluorine chemical solid waste purposes as catalyst in ketoxime Beckmann rearrangement reaction, wherein the fluorgypsum catalyst is by obtaining as the solvent impregnated pretreatment of fresh fluorgypsum of fluorine chemical solid waste, or by will be as after the solvent impregnated pretreatment of the old fluorgypsum of being long placed in of fluorine chemical solid waste, through the concentrated sulfuric acid or chlorosulfonic acid, process and obtain, the pretreatment solvent for use is benzene,toluene,xylene, chlorobenzene, carrene, chloroform, carbon tetrachloride, 1, the 2-dichloroethanes.
2.
According to purposes claimed in claim 1, it is characterized in that: ketoxime is non-cyclic ketoxime, cyclohexanone oxime or cyclododecanone oxime.
3.
According to purposes claimed in claim 1, it is characterized in that: rearrangement reaction, at the benzene,toluene,xylene as solvent, chlorobenzene, chloroform, 1, is carried out in the 2-dichloroethanes.
4.
According to purposes claimed in claim 3, it is characterized in that: rearrangement reaction is carried out in the toluene as solvent.
5.
According to purposes claimed in claim 1, it is characterized in that: the temperature of rearrangement reaction is that room temperature arrives the solvent refluxing temperature.
6.
According to purposes claimed in claim 5, it is characterized in that: the temperature of rearrangement reaction is 80 ~ 100 o C.
7.
According to purposes claimed in claim 5, it is characterized in that: the temperature of rearrangement reaction is the solvent refluxing temperature.
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19520271A1 (en) * | 1995-06-02 | 1996-12-05 | Basf Ag | Process for the preparation of cyclohexanone oxime and caprolactam |
| CN1142147C (en) * | 2001-03-30 | 2004-03-17 | 清华大学 | Method for synthesizing hexanolactam by using titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime |
| CN101468792B (en) * | 2007-12-28 | 2013-03-20 | 尹小林 | Novel technique for producing sulfur from industrial waste gypsum |
| CN102020429A (en) * | 2010-07-06 | 2011-04-20 | 长沙理工大学 | Waste fluorine gypsum activating technique |
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