CN1020864C - Catalysts for olefination of aldehyde and their application - Google Patents
Catalysts for olefination of aldehyde and their application Download PDFInfo
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- CN1020864C CN1020864C CN 88105578 CN88105578A CN1020864C CN 1020864 C CN1020864 C CN 1020864C CN 88105578 CN88105578 CN 88105578 CN 88105578 A CN88105578 A CN 88105578A CN 1020864 C CN1020864 C CN 1020864C
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Abstract
The present invention relates to dialkyl arsine, trialkyl or dialkyl catalysts, and cocatalysts of phosphorous acid trialkyl ester, etc., which are used in ethenoid reactions of aldehyde. The present invention also relates to a method for preparing corresponding alkene compounds from aldehyde or aldehyde with vinylogy radicals and alkyl halide with electron withdrawing groups or vinylogy radicals. The present invention has the advantages of mild condition of a catalytic reaction, simple operation, good yield and favorable stereo selectivity; the method of the present invention is suitable for industrialized production.
Description
The invention belongs to organic catalyst and the application in the olefination of aldehyde thereof.Further say it is under trialkyl-arsine, trialkyl or co-catalyst catalysis such as dialkyl catalyst and phosphorous acid trialkyl, aldehyde reacts the preparation method who generates corresponding alkene with the alkyl halide of band electron withdraw group or vinylogy base, that is to say Wei Tixi (Wittig) type reaction of catalysis.
The witig reaction (Liebig.Ann.Chem., 580,44, (1953)) that nineteen fifty-three is found is one of most popular method of preparation alkene, has obtained commercial Application (Angew.Chem.Int.Ed.Eng.16,423～429(1977)) seventies.But the phosphonium ylide and the carbonyls reactivity that have electron withdraw group are poor, and the accessory substance triphenyl phosphine oxide is difficult to reclaim to be reused, and will triphenyl phosphine oxide be converted into triphenyl phasphine with poisonous phosgene industrial.Once reported triphenyl phosphine oxide is made sulfonium salt, electrolysis is a triphenyl phasphine again, wherein need use the dimethyl suflfate of severe toxicity.
Huang Yao once waited the p π-d π according to the p track of the 4d track of arsenic atom and carbon atom to hand over the corresponding phosphorus atoms of the ability of covering poor, arsenic ylide ionic more, high this characteristic of reactivity, developed arsenic ylide (Adv.Organomet.Chem.20,115(1982).Shi Lilan, yellow credit once waited the method (chemical journal, 44,421, (1986)) that successfully adopts the solid-liquid phase transfer.Feasible reaction need not prepare arsenic ylide, thereby simplifies the operation, and byproduct of reaction oxidation triphenylarsine can be through multiple reducing agent such as triphenyl phosphite (Lu Xiyan etc., the chemistry journal, 43,450～453(1985)) etc. change into triphenylarsine and reuse, for the applications expanding of arsine reagent prospect.But above-mentioned reaction costs an arm and a leg owing to use equivalent arsenic ylide reagent, is difficult to realize suitability for industrialized production.So the reaction that realizes forming the Wei Tixi type of two keys with the arsine reagent of catalytic amount is still the problem that people thirst for solving.
The purpose of this invention is to provide the catalyst of a class major element and, the olefination of aldehyde can be carried out under room temperature or lower temperature, reduce reagent dosage in the middle application of the olefination of aldehyde.Shorten reactions steps, make it to be applicable to suitability for industrialized production.
The present invention propose a class can catalysis aldehyde and alkyl halide carry out the catalyst of the olefination of aldehyde.This class catalyst is to be made of catalyst and co-catalyst bi-component.Catalyst is that molecular formula is trialkyl-arsine, the trialkyl of RnM
Or Er Ting Ji Di, wherein R is aryl, substituted aryl, C
2-C
12Alkyl, the cyclic hydrocarbon radical of straight or branched, n equals 3 or 2, M is arsenic, antimony or tellurium.Co-catalyst is that molecular formula is (R
1O)
3Tricresyl phosphite hydrocarbyl carbonate, sodium sulfite, sodium hydrogensulfite, vulcanized sodium, sodium dithionate or the sodium thiosulfate etc. of P, wherein R
1Be aryl, substituted aryl, C
2-C
12Alkyl or alkyl, cycloalkyl etc.
Adopting bicomponent catalyst of the present invention to be particularly useful for molecular formula is R
2The aldehyde of CHO and molecular formula are XCH
2It is R that the alkenyl catalytic reaction that the halogenated hydrocarbons of Y carries out aldehyde generates corresponding molecular formula
2The alkene of CH=CHY.R wherein
2Be C
2-C
10Alkyl or substituted hydrocarbon radical, aryl, substituted aryl, heteroaryl, cycloalkyl or corresponding vinylogy base, Y is an electron withdraw group, as-CHO ,-COR
2,-CO
2R
2,-COC
6H
5,-CN ,-SO
2R
2,-SOR
2,-POR
2R
2,-CONR
2R
2Or its corresponding vinylogy base, wherein R
3=R
2Or R
3≠ R
2
When catalytic reaction of the present invention is made co-catalyst with the phosphorous acid trialkyl, can do following description:
Only need little amount of catalyst among the present invention and, catalytic reaction is carried out with the reactant equivalent or near the co-catalyst of equivalent.The mole ratio of reactant, catalyst and co-catalyst is 1: 0.03-0.03: 0.7-2.0 increases catalyst amount and helps improving reaction speed and productive rate.Comprehensive benefit analysis, optimal proportion are 1: 0.05-0.20: 0.8-1.2.
Catalytic reaction of the present invention is to carry out in the presence of alkali, used alkali can be carbonate, fluoride, the hydroxide of a kind of lithium, sodium or potassium, also can be above-mentioned alkali and two kinds of alkali that mix of aluminium oxide, as mixture of potash, sodium carbonate, lithium carbonate, potassium fluoride, sodium fluoride, lithium fluoride, potassium hydroxide, NaOH and above-mentioned alkali and aluminium oxide etc.The mole ratio of two kinds of mixed bases is 1: 0.2-5.0, the variation of the intensity of alkali is little to reaction speed influence of the present invention.The alkali consumption can be the mole ratio 1 ' 1.0-5.0 of reactant and alkali.The conversion ratio of reactant is not only relevant with the character of reactant, catalyst and co-catalyst, and also relevant with reaction temperature and reaction time.Reaction temperature adopts room temperature to 80 ℃, and the reaction time is 2-50 hour.Although along with the rising reaction speed of reaction temperature is obviously accelerated, in most cases room temperature can satisfy reaction needed.
Catalytic reaction of the present invention can be carried out under the solvent-free existence at a kind of or two kinds of polar solvents, preferably adopts oxolane, acetonitrile, formamide, chloroform, carrene or ethanol, and the mixture of above-mentioned two kinds of solvents.
Catalytic reaction of the present invention is preferably under agitation carried out.
The present invention has realized the catalytic amount arsine first,
The class witig reaction of Huo Di reagent, and opened up new way for utilizing organic major element compound to carry out catalytic reaction.The inventive method mild condition, easy and simple to handle, can high yield and highly-solid selectively ground by synthetic α of one step of aldehyde, beta-unsaturated acid, ester, ketone or the like.Used inexpensive being easy to get such as co-catalyst tricresyl phosphite hydrocarbyl carbonate, accessory substance tricresyl phosphate hydrocarbyl carbonate is again industrial useful reagent.The arsine of the inventive method employing catalytic amount,
The reagent of Huo Di has reduced the three wastes, makes it these reagent and is applicable to industrial application.
To help further to understand the present invention by following example.
Embodiment 1
In the dry reaction pipe, add 1mmol aldehyde, 1.2mmol potash is filling N then
2Under the condition, add 0.5ml oxolane, 2ml acetonitrile, 1.2mmole alkyl halide, 0.2mmole tributyl arsine and 1.5mmole tricresyl phosphite phenylester.The stirring at room reaction.Filtration is finished in reaction, extracts solvent.Product is identified through nuclear magnetic resoance spectrum.Determine by capillary chromatography along inverse proportion.(table is seen the literary composition back)
Embodiment 2
Reaction condition except that changing with embodiment 1.(table is seen the literary composition back)
Embodiment 3
In reactor, add 100mmole aldehyde, the potash of mole ratios such as 120mmole and aluminium oxide add 100mmole bromacetone, 5mmole tributyl behind the inflated with nitrogen
With 100mmole vulcanized sodium, add thermal agitation, filtration is finished in reaction, desolventizes.(table is seen the literary composition back)
Embodiment 4
In reactor, add 120mmole aldehyde, 150mmole potassium fluoride and aluminium oxide (mole ratio is 0.8: 2) add 120mmole alkyl halide, 15mmol tributyl arsine and 150mmole sodium dithionate, 100ml oxolane, 300ml acetonitrile behind the inflated with nitrogen.Stirring at room is filtered, is desolventized.(table is seen the literary composition back)
Embodiment 5
In reactor, add 50mmole aldehyde, 60mmole sodium carbonate, the 50mmole alkyl halide, the 5mmole triphenylarsine, the 60mmole triphenyl phosphite, 200mm ethanol adds thermal agitation in the time of 50 ℃, and filtration is finished in reaction, desolventizes.(table is seen the literary composition back)
Embodiment 6
Except that doing the solvent with carrene, condition is with embodiment 5.(table is seen the literary composition back)
Embodiment 7
Add 50mmole aldehyde in reactor, 50mmole potash adds the 50mmole alkyl halide, 100ml solvent, 5mmole catalyst and 55mmole co-catalyst, stirring at room.
Claims (5)
1, a kind of catalyst that is used for the alkenyl of aldehyde is characterized in that being made up of catalyst and the two components of co-catalyst, and described catalyst is that molecular formula is the trialkyl-arsine of RnM, trialkyl
Or Er Ting Ji Di, wherein R is aryl, substituted aryl, C
2-C
12Alkyl, the cyclic hydrocarbon radical of straight or branched, M is arsenic, antimony or tellurium, n equals 3 or 2, described co-catalyst is that molecular formula is (R
1O)
3The tricresyl phosphite hydrocarbyl carbonate of P, sodium sulfite, sodium hydrogensulfite, vulcanized sodium, sodium dithionate or sodium thiosulfate, wherein R
2Be aryl, substituted aryl, C
2-C
12Alkyl or alkyl, cycloalkyl, the mole ratio of catalyst and co-catalyst is 1: 2.3-66.7.
2, a kind of catalyst that is used for the alkenyl of aldehyde as claimed in claim 1, the mole ratio that it is characterized in that described catalyst and co-catalyst is 1: 4-24.
3, the alkenyl catalyst that is used for aldehyde as claimed in claim 1 is characterized in that catalyst tributyl arsine wherein, triphenylarsine, thricyclohexyl arsine or three (p-methylphenyl) arsine.
4, the alkenyl catalyst that is used for aldehyde as claimed in claim 1 is characterized in that co-catalyst wherein is tricresyl phosphite phenylester, phosphorous acid isobutyl or tricresyl phosphite cyclohexyl ester.
5, a kind of purposes of catalyst as claimed in claim 1 is characterized in that aldehyde and the alkyl halide that has electron withdraw group carry out the olefination of aldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105578 CN1020864C (en) | 1988-09-14 | 1988-09-14 | Catalysts for olefination of aldehyde and their application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105578 CN1020864C (en) | 1988-09-14 | 1988-09-14 | Catalysts for olefination of aldehyde and their application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1032654A CN1032654A (en) | 1989-05-03 |
| CN1020864C true CN1020864C (en) | 1993-05-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105578 Expired - Fee Related CN1020864C (en) | 1988-09-14 | 1988-09-14 | Catalysts for olefination of aldehyde and their application |
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|---|---|
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|---|---|---|---|---|
| MX2012005759A (en) | 2009-11-18 | 2012-10-03 | Fab Pharma S A S | Novel heterocyclic acrylamides and their use as pharmaceuticals. |
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1988
- 1988-09-14 CN CN 88105578 patent/CN1020864C/en not_active Expired - Fee Related
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| CN1032654A (en) | 1989-05-03 |
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