CN104258904A - Lewis acid-amine salt/ammonium salt mixed catalyst and applications thereof in hydrogenation and hydrosilation of carbon oxides - Google Patents
Lewis acid-amine salt/ammonium salt mixed catalyst and applications thereof in hydrogenation and hydrosilation of carbon oxides Download PDFInfo
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- CN104258904A CN104258904A CN201410415316.7A CN201410415316A CN104258904A CN 104258904 A CN104258904 A CN 104258904A CN 201410415316 A CN201410415316 A CN 201410415316A CN 104258904 A CN104258904 A CN 104258904A
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Abstract
A Lewis acid-amine salt/ammonium salt mixed catalyst and applications thereof in hydrogenation and hydrosilation of carbon oxides are disclosed. The catalyst is a mixture of a Lewis acid, and an amine salt or an ammonium salt. The Lewis acid is any one selected from tris(pentafluorophenyl)boron, tris(tetrafluorophenyl)boron, tris(trifluorophenyl)boron, tris(difluorophenyl)boron, tris(fluorophenyl)boron and triphenylboron. The catalyst is suitable for hydrogenation and hydrosilation of any carbon oxides. Aldehydes and acetones can be completely reduced into alkanes under actions of the catslyst. Reactions can be rapidly performed at room temperature under normal pressure, the using amount of hydrogenated silane is small, the conversion rate is high, and the product yield is high. The catalyst is free of heavy metals, so that problems such as heavy metal pollution can be avoided. After the reactions are finished, products can be separated by distillation, extraction, column chromatography and other separation methods according to characteristics of the products, and post-treatment is free of use of hydrofluoric acid or concentrated sulfuric acid and NH4F.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, be specifically related at least containing the amine salt of a H atom or the mixed catalyst of ammonium salt in a kind of lewis acid and atom N, and the application of this catalyst in hydrogenation and hydrosilation hydrocarbon.
Background technology
Hydrogenation adds on organic compound by hydrogen, and such as, ketone compounds can be reduced into alcohol compound.Prior art, needs relatively high Hydrogen Vapor Pressure and reaction temperature usually, also has the heterogeneous catalysts such as solid catalyst Pt, Rh, Pd, Ni.Silicon hydrogenation relates to and silane containing hydrogen is added to ketone, aldehyde, ester form elementary siloxanes.Prior art, hydrosilylation process also needs rare metal Rh, Pt, Pd as catalyst.Although it has good catalytic activity to carbonyl hydrosilation, substantially catalytic activity is not had for the SA oxygen-bearing organic matter such as ester, ether.
As far back as late nineteen seventies bibliographical information mistake, utilize the method for fluoride salt activation Si-H key under heterogeneous conditions, the carbonyl of selective catalysis hydrosilation reduction aldehyde, ketone, ester obtains silicon ether or its hydrolysate alcohol, and other group (as C=C, NO
2, Br ,-CONH
2) unaffected.Carbonyl (ketone, aldehydes) thoroughly can be reduced to methylene by Clemmensen and Wolff-Kishner-Huang ring dragon two kinds of reduction reactions, but Clemmensen reducing process exists shortcomings such as heavy metal pollution, productive rate are low, strong acid condition; Wolff-Kishner-huang-Minlon reduction exists that material toxicity is high, hot environment, productive rate are low, the shortcoming of basic conditions.Clemmensen and Wolff-Kishner-Huang Min-lon reduction method all can not reduce the oxygen-containing organic compound beyond aldehyde ketone in addition.
In recent years bibliographical information some at lewis acid as B (C
6f
5)
3under the participation of (being called for short BCF), hydrogen silane can by the oxygen-containing organic compound hydrogenations such as aldehyde, ketone, carboxylic acid, ester, ether, alcohol or hydrosilation reduction, and obtain alkane or silicon ether reduzate, silicon ether can be hydrolyzed further and obtain alcohol.But, the having some limitations property of method reported: (1) can not thoroughly by ketone and aromatic aldehyde reduction; (2) silane reagent of 3 or 6 times is needed; (3) hydrofluoric acid or dense H is needed
2sO
4with NH
4f is as functional group conversions's reagent during post processing; (4) the usual reaction needed long period.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of in a mild condition can the lewis acid of efficient catalytic hydrosilanes reduction hydrocarbon and amine salt or ammonium salt mixed catalyst, and the application of this catalyst in hydrogenation and hydrosilation hydrocarbon.
Solving the problems of the technologies described above adopted technical scheme is: this catalyst is mixed for 1:0.1 ~ 10 in molar ratio by amine salt or ammonium salt and lewis acid, wherein said lewis acidic structure is such as formula shown in A, in formula, shown in "-" representative, atom can connect arbitrary group or atom, concrete as three (pentafluorophenyl group) boron, three (tetrafluoro phenyl) boron, three (trifluorophenyl) boron, three (difluorophenyl) boron, three (fluorophenyl) boron, triphenyl borine etc., wherein preferred three (pentafluorophenyl group boron).
Described amine salt or ammonium salt are the amine salt or the ammonium salt that the atom N of structure as shown in above formula B at least contain a H atom, and in formula, X-represents arbitrary anion, and ammonium salt is concrete as ammonium chloride, ammonium bromide, iodate amine, ammonium sulfate, ammonium nitrate, ammonium fluosilicate, ammonium phosphate, ammonium acetate etc., amine salt is concrete as methyl chloride amine, methyl bromide amine, dimethylammonium chloride amine, dimethyl iodate amine, ethylmercury chloride amine, ethyl phosphonium bromide amine, ethyl phosphonium iodide amine, diethyl ammonium chloride, diethyl amine bromide, triethylammonium chloride, propyl group ammonium chloride, propyl group amine bromide, dipropyl ammonium chloride, dipropyl amine bromide, n-butylmagnesium chloride amine, three n-butylmagnesium chloride amine, tert-butyl group ammonium chloride, tetraphenylphosphonium chloride amine, diphenyl ammonium chloride, phenyl methyl ammonium chloride, piperidine hydrochlorate, 2,2,6,6-tetramethyl piperidine hydrochloride, benzimidazole hydrochloride, imidazole hydrochloride, pyridine hydrochloride, triazolium salt hydrochlorate, any one in thiazole hydrochloride, the wherein preferred ammonium chloride of ammonium salt, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium phosphate, any one in ammonium nitrate, amine salt preferred tertiary butyl ammonium chloride or piperidine hydrochlorate.
In above-mentioned catalyst, amine salt or ammonium salt and lewis acidic mol ratio are preferably 1:0.8 ~ 1.2.
The purposes in alkane or silicon ether prepared by catalyst of the present invention at catalytic hydrogenation silane reduction hydrocarbon, concrete grammar is: under inert gas shielding, by hydrosilanes, hydrocarbon joins in organic solvent, then catalyst is added, in hydrosilanes and catalyst, lewis acidic mol ratio is 1:0.001 ~ 0.2, stirring at room temperature 10 ~ 60 minutes, described hydrosilanes and the mol ratio of hydrocarbon are 2n/m ~ 3n/m:1, obtain alkane, the mol ratio of hydrosilanes and hydrocarbon is 0.8n/m ~ 2n/m:1, obtain siloxanes, wherein m is the number of the hydrogen atom be connected with silicon atom in per molecule hydrosilanes, n is the number of oxygen atom in per molecule hydrocarbon.
The purposes in methane or methyl alcohol prepared by catalyst of the present invention at catalytic hydrogenation silane reducing carbon dioxide, concrete grammar is: add in toluene by hydrosilanes, catalyst, in hydrosilanes and catalyst, lewis acidic mol ratio is 1:0.001 ~ 0.2, then carbon dioxide is passed into, the pressure controlling carbon dioxide is 0.1 ~ 0.2MPa, 20 ~ 100 DEG C are reacted 5 ~ 12 hours, and reaction terminates rear hydrolysis, obtains methyl alcohol or methane.
In above-mentioned hydrosilanes and catalyst, lewis acidic mol ratio is preferably 1:0.01 ~ 0.1.
Above-mentioned hydrocarbon is aldehyde, ketone, carboxylic acid, acid anhydrides, carboxylic acid halides, ester, ether, alcohol, siloxanes etc.; Organic solvent is aprotic solvent that is oxygen-free or fluorine element, concrete as carrene, chloroform, carbon tetrachloride, n-hexane, pentane, dichloroethanes, benzene, chlorobenzene, dichloro benzene,toluene,xylene, ethylo benzene etc.; A H atom is had at least to be connected with Si atom in hydrosilanes, specifically if silane, phenylsilane, diphenyl silane, tri-phenyl-silane, phenyl methyl silane, triethyl silicane, phenyldimethylsilane, dichloro hydrogen silicon, trichlorosilane, triethoxysilane, diethoxymethylsilane, trimethyl silica dimethylsilane, number-average molecular weight are the polymethyl hydrogen siloxane etc. of 222 ~ 642, wherein preferred phenylsilane, diphenyl silane or triethyl silicane.
The reaction mechanism that catalyst hydrosilanes reduction hydrocarbon of the present invention prepares alkane or silicon ether is as follows: the lewis acid first in catalyst is (as three (pentafluorophenyl group) boron, be abbreviated as BCF) react with ammonium salt or amine salt and generate boronation amine salt or hydroboration ammonium salt (A), then lewis acid and hydrosilanes are reacted and (as phenylsilane, are abbreviated as PhSiH
3) generate reactive intermediate (B); The reaction of reactive intermediate (B) and aldehyde, ketone is through two steps, and first step hydrosilation reduction I, generates silicon ether (2); Second step silicon ether (2) thoroughly reduces II, generates alkane (3).The reaction mechanism of the similar aldehyde ketone of reduction of carboxylic acid, the reduction reaction of ether and alcohol is mainly through second step reduction mechanism.
Compared with the prior art, beneficial effect of the present invention is as follows:
1, this catalyst is applicable to hydrogenation and the hydrosilation of any hydrocarbon, as: aldehyde, ketone, carboxylic acid, acid anhydrides, carboxylic acid halides, ester, alcohol, ether, siloxanes, CO
2etc., and can be thoroughly alkane by aldehyde, ketone body powder.
2, the reaction of catalyst hydrosilanes of the present invention and aldehyde, ketone, carboxylic acid, acid anhydrides, carboxylic acid halides, ester, alcohol, ether, siloxanes etc. can complete fast under the condition of normal temperature and pressure, and the consumption of hydrosilanes is few, conversion ratio is high, and the productive rate of product is high.
3, do not contain heavy metal in catalyst of the present invention, there is not the problems such as heavy metal pollution.
4, after the present invention's reaction terminates, the separation method separated products such as distillation, extraction, column chromatography can be used according to the difference of product property, not need hydrofluoric acid or dense H
2sO
4with NH
4f carries out post processing.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiments.
Embodiment 1
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 11mg (0.1mmol) tert-butyl group ammonium chloride are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is as follows:
Be dissolved in 10mL chloroform by 216mg (2.0mmol) phenylsilane, 364mg (2.0mmol) benzophenone, then add above-mentioned catalyst, stirring at room temperature 10 minutes, benzophenone is reduced to diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 100%, and the productive rate of diphenyl methane is 80%.
Three (pentafluorophenyl group) boron of the present embodiment also can with equimolar three (tetrafluoro phenyl) boron, three (trifluorophenyl) boron, three (difluorophenyl) boron, three (fluorophenyl) boron or triphenyl borine are replaced, phenylsilane also can use equimolar silane, diphenyl silane, tri-phenyl-silane, phenyl methyl silane, triethyl silicane, phenyldimethylsilane, dichloro hydrogen silicon, trichlorosilane, triethoxysilane, diethoxymethylsilane, trimethyl silica dimethylsilane or number-average molecular weight are the polymethyl hydrogen siloxane replacement of 222 ~ 642, chloroform also can use isopyknic carrene, carbon tetrachloride, n-hexane, pentane, dichloroethanes, benzene, chlorobenzene, dichloro-benzenes, toluene, dimethylbenzene or ethylo benzene are replaced.
Embodiment 2
The purposes in ethylbenzene prepared by catalyst prepared by embodiment 1 at catalysis phenylsilane reduction of acetophenones, its using method is as follows:
In embodiment 1, the equimolar acetophenone of benzophenone used is replaced, and other steps are identical with embodiment 1, and acetophenone is reduced to ethylbenzene.Warp
1the conversion ratio that H NMR detects phenylsilane is 100%, and the productive rate of ethylbenzene is 70%.
Embodiment 3
The purposes in toluene prepared by catalyst prepared by embodiment 1 at catalysis phenylsilane reduction benzaldehyde, its using method is as follows:
In embodiment 1, the equimolar benzaldehyde of benzophenone used is replaced, and other steps are identical with embodiment 1, and benzaldehyde is reduced to toluene.Warp
1the conversion ratio that H NMR detects phenylsilane is 95%, and the productive rate of toluene is 70%.
Embodiment 4
The purposes in cyclohexane prepared by catalyst prepared by embodiment 1 at catalysis phenylsilane reduction cyclohexanone, its using method is as follows:
In embodiment 1, the equimolar cyclohexanone of benzophenone used is replaced, and other steps are identical with embodiment 1, and cyclohexanone is reduced to cyclohexane.Warp
1the conversion ratio that H NMR detects phenylsilane is 80%, and the productive rate of cyclohexane is 70%.
Embodiment 5
The purposes in pentane prepared by catalyst prepared by embodiment 1 at catalysis phenylsilane reduction propione, its using method is as follows:
In embodiment 1, the equimolar propione of benzophenone used is replaced, and other steps are identical with embodiment 1, and propione is reduced to pentane.Warp
1the conversion ratio that H NMR detects phenylsilane is 95%, and the productive rate of pentane is 70%.
Embodiment 6
The purposes in propane prepared by catalyst prepared by embodiment 1 at catalysis phenylsilane reduction acetone, its using method is as follows:
In embodiment 1, the equimolar acetone of benzophenone used is replaced, and other steps are identical with embodiment 1, and acetone is reduced to propane.Warp
1the conversion ratio that H NMR detects phenylsilane is 95%, and the productive rate of propane is 85%.
Embodiment 7
The purposes in diphenyl hexichol methoxy silane prepared by catalyst prepared by embodiment 1 at catalysis diphenyl silane reduction benzophenone, its using method is as follows:
In embodiment 1, the equimolar diphenyl silane of phenylsilane used is replaced, and other steps are identical with embodiment 1, and benzophenone hydrosilation obtains diphenyl hexichol methoxy silane.Warp
1the conversion ratio that H NMR detects diphenyl silane is 100%, and the productive rate of diphenyl hexichol methoxy silane is 95%.
Embodiment 8
The purposes in diphenyl-methane prepared by catalyst prepared by embodiment 1 at catalysis diphenyl silane reduction benzophenone, its using method is as follows:
Identical in embodiment 1, the phenylsilane used diphenyl silane of 1.5 times of moles is replaced, and other steps are identical with embodiment 1, and benzophenone is reduced to diphenyl-methane.Warp
1the conversion ratio that H NMR detects diphenyl silane is 95%, and the productive rate of diphenyl-methane is 67%.
Embodiment 9
The purposes in triphenyl hexichol methoxy silane prepared by catalyst prepared by embodiment 1 at catalysis tri-phenyl-silane reduction benzophenone, its using method is as follows:
In embodiment 1, the phenylsilane used tri-phenyl-silane of its mole 2 times is replaced, and other steps are identical with embodiment 1, and benzophenone hydrosilation obtains triphenyl hexichol methoxy silane.Warp
1the conversion ratio that H NMR detects tri-phenyl-silane is 98%, and the productive rate of triphenyl hexichol methoxy silane is 69%.
Embodiment 10
The purposes in triethyl group hexichol methoxy silane prepared by catalyst prepared by embodiment 1 at catalysis triethyl silicane reduction benzophenone, its using method is as follows:
In embodiment 1, the phenylsilane used triethyl silicane of its mole 2 times is replaced, and other steps are identical with embodiment 1, and benzophenone hydrosilation obtains triethyl group hexichol methoxy silane.Warp
1the conversion ratio that H NMR detects triethyl silicane is 99%, and the productive rate of triethyl group hexichol methoxy silane is 89%.
Embodiment 11
The purposes in triethoxy hexichol methoxy silane prepared by catalyst prepared by embodiment 1 at catalysis triethoxysilane reduction benzophenone, its using method is as follows:
In embodiment 1, the equimolar triethoxysilane of phenylsilane used is replaced, and other steps are identical with embodiment 1, and benzophenone hydrosilation obtains triethoxy hexichol methoxy silane.Warp
1the conversion ratio that H NMR detects triethoxysilane is 86%, and the productive rate of triethoxy hexichol methoxy silane is 92%.
Embodiment 12
The purposes in toluene and ethane prepared by catalyst prepared by embodiment 1 at catalysis phenylsilane reduction ethyl benzoate, its using method is as follows:
In embodiment 1, the benzophenone used ethyl benzoate of its mole 0.5 times is replaced, and other steps are identical with embodiment 1, and ethyl benzoate is reduced to toluene and ethane.Warp
1the conversion ratio that H NMR detects triethoxysilane is 95%, and the productive rate of toluene is 70%.
Embodiment 13
Embodiment 1 prepare catalyst catalysis phenylsilane also ethyl orthoacetate prepare the purposes in ethane, its using method is as follows:
In embodiment 1, the benzophenone used ethyl acetate of its mole 0.5 times is replaced, and other steps are identical with embodiment 1, and ethyl acetate is reduced to ethane.Warp
1the conversion ratio that H NMR detects phenylsilane is 100%, and the productive rate of ethane is 99%.
Embodiment 14
The purposes in ethane prepared by catalyst prepared by embodiment 1 at catalysis phenylsilane Hai Yuan diox, its using method is as follows:
In embodiment 1, benzophenone used its mole 0.5 times of diox is replaced, and other steps are identical with embodiment 1, and dioxanes is reduced to ethane.Warp
1the conversion ratio that H NMR detects phenylsilane is 95%, and the productive rate of ethane is 94%.
Embodiment 15
The purposes in ethane prepared by catalyst prepared by embodiment 1 at catalysis quadrosilan reduction ether, its using method is as follows:
In embodiment 1, the equimolar ether of benzophenone used is replaced, and phenylsilane is replaced with waiting mole quadrosilan, and other steps are identical with embodiment 1, and ether is reduced to ethane.Warp
1the conversion ratio that H NMR detects quadrosilan is 95%, and the productive rate of ethane is 93%.
Embodiment 16
Embodiment 1 prepare catalyst catalysis triethyl silicane also ethyl orthoacetate prepare the purposes in ethane, its using method is as follows:
In embodiment 1, the benzophenone used ethyl acetate of its mole 0.5 times is replaced, and the phenylsilane triethyl silicane of its mole 3 times is replaced, and other steps are identical with embodiment 1, and ethyl acetate is reduced to ethane.Warp
1the conversion ratio that H NMR detects quadrosilan is 89%, and the productive rate of ethane is 88%.
Embodiment 17
The purposes in propane prepared by catalyst prepared by embodiment 1 at catalysis triethyl silicane reduction acetone, its using method is as follows:
In embodiment 1, the equimolar acetone of benzophenone used is replaced, and the phenylsilane triethyl silicane of its mole 2 times is replaced, and other steps are identical with embodiment 1, and acetone is reduced to propane.Warp
1the conversion ratio that H NMR detects quadrosilan is 95%, and the productive rate of propane is 90%.
Embodiment 18
The purposes in propane prepared by catalyst prepared by embodiment 1 at catalysis phenylsilane reduction glycerine, its using method is as follows:
In embodiment 1, the glycerine of benzophenone equimolar amounts used is replaced, and the consumption of phenylsilane is 3 times in embodiment 1, and other steps are identical with embodiment 1, and glycerine is reduced to propane.Warp
1the conversion ratio that H NMR detects quadrosilan is 95%, and the productive rate of propane is 87%.
Embodiment 19
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 17.7mg (0.1mmol) 2,2,6,6-tetramethyl piperidine hydrochloride are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is identical with embodiment 1, obtains diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 99%, and the productive rate of diphenyl methane is 50%.
Embodiment 20
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 10.9mg (0.1mmol) diethyl ammonium chloride are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is identical with embodiment 1, obtains diphenyl methane.Its warp
1the conversion ratio that H NMR detects phenylsilane is 72%, and the productive rate of diphenyl methane is 96%.
Embodiment 21
The purposes in toluene prepared by catalyst prepared by embodiment 20 at catalysis phenylsilane reduction benzaldehyde, its using method is as follows:
In embodiment 20, the equimolar benzaldehyde of benzophenone used is replaced, and other steps are identical with embodiment 20, obtain toluene.Warp
1the conversion ratio that H NMR detects phenylsilane is 98%, and the productive rate of toluene is 69%.
Embodiment 22
The purposes in ethylbenzene prepared by catalyst prepared by embodiment 20 at catalysis phenylsilane reduction of acetophenones, its using method is as follows:
In embodiment 20, the equimolar acetophenone of benzophenone used is replaced, and other steps are identical with embodiment 20, obtain ethylbenzene.Warp
1the conversion ratio that H NMR detects phenylsilane is 98%, and the productive rate of ethylbenzene is 67%.
Embodiment 23
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 5.3mg (0.1mmol) ammonium chloride are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is identical with embodiment 1, obtains diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 86%, and the productive rate of diphenyl methane is 99%.
Embodiment 24
The purposes in toluene prepared by catalyst prepared by embodiment 23 at catalysis phenylsilane reduction benzaldehyde, its using method is as follows:
In embodiment 23, the equimolar benzaldehyde of benzophenone used is replaced, and other steps are identical with embodiment 23, obtain toluene.Warp
1the conversion ratio that H NMR detects phenylsilane is 99%, and the productive rate of toluene is 70%.
Embodiment 25
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 14.5mg (0.1mmol) ammonium iodide are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is identical with embodiment 1, obtains diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 91%, and the productive rate of diphenyl methane is 100%.
Embodiment 26
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 13.7mg (0.1mmol) triethylammonium chloride are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is identical with embodiment 1, obtains diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 99%, and the productive rate of diphenyl methane is 48%.
Embodiment 27
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 14.3mg (0.1mmol) benzyimag iesium chloride amine are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is identical with embodiment 1, obtains diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 90%, and the productive rate of diphenyl methane is 80%.
Embodiment 28
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 11.8mg (0.1mmol) glyoxal ethyline hydrochloride are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and except the reaction time extends to 60 minutes, other steps are identical with embodiment 1, obtain diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 80%, and the productive rate of diphenyl methane is 75%.
Embodiment 29
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 15.4mg (0.1mmol) benzimidazole hydrochloride are mixed, is prepared into catalyst.
2, the purposes in toluene prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzaldehyde, and except the reaction time extends to 30 minutes, other steps are identical with embodiment 1, obtain toluene.Warp
1the conversion ratio that H NMR detects phenylsilane is 87%, and the productive rate of toluene is 80%.
Embodiment 30
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 8.0mg (0.1mmol) ammonium nitrate are mixed, is prepared into catalyst.
2, the purposes in ethane prepared by above-mentioned catalyst at catalysis phenylsilane reduction ether, and its using method is identical with embodiment 1, obtains ethane.Warp
1the conversion ratio that H NMR detects phenylsilane is 90%, and the productive rate of ethane is 90%.
Embodiment 31
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 13.2mg (0.1mmol) ammonium sulfate are mixed, is prepared into catalyst.
2, the purposes in ethane prepared by above-mentioned catalyst at catalysis phenylsilane reduction ether, and its using method is identical with embodiment 1, obtains ethane.Warp
1the conversion ratio that H NMR detects phenylsilane is 90%, and the productive rate of ethane is 89%.
Embodiment 32
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 17.8mg (0.1mmol) ammonium fluosilicate are mixed, is prepared into catalyst.
2, the purposes in ethane prepared by above-mentioned catalyst at catalysis phenylsilane reduction ether, and its using method is identical with embodiment 1, obtains ethane.Warp
1the conversion ratio that H NMR detects phenylsilane is 90%, and the productive rate of ethane is 88%.
Embodiment 33
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 7.8mg (0.1mmol) ammonium acetate are mixed, is prepared into catalyst.
2, the purposes in ethane prepared by above-mentioned catalyst at catalysis phenylsilane reduction ether, and its using method is identical with embodiment 1, obtains ethane.Warp
1the conversion ratio that H NMR detects phenylsilane is 90%, and the productive rate of ethane is 88%.
Embodiment 34
1, Kaolinite Preparation of Catalyst
24.2mg (0.11mmol) triphenyl borine and 11mg (0.1mmol) tert-butyl group ammonium chloride are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is identical with embodiment 1, obtains diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 90%, and the productive rate of diphenyl methane is 84%.
Embodiment 35
1, Kaolinite Preparation of Catalyst
5.3mg (0.01mmol) three (pentafluorophenyl group) boron and 11mg (0.1mmol) tert-butyl group ammonium chloride are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is identical with embodiment 1, obtains diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 90%, and the productive rate of diphenyl methane is 84%.
Embodiment 36
1, Kaolinite Preparation of Catalyst
53mg (0.1mmol) three (pentafluorophenyl group) boron and 1.1mg (0.01mmol) tert-butyl group ammonium chloride are mixed, is prepared into catalyst.
2, the purposes in diphenyl methane prepared by above-mentioned catalyst at catalysis phenylsilane reduction benzophenone, and its using method is identical with embodiment 1, obtains diphenyl methane.Warp
1the conversion ratio that H NMR detects phenylsilane is 91%, and the productive rate of diphenyl methane is 85%.
Embodiment 37
The purposes in ethane prepared by catalyst prepared by embodiment 1 at catalysis phenylsilane reduction methyl triethoxy phenylsilane, its using method is as follows:
In embodiment 1, the equimolar triethoxy phenylsilane of benzophenone used is replaced, and the consumption of phenylsilane is 2 times in embodiment 1, and other steps are identical with embodiment 1, obtain ethane.Warp
1the conversion ratio that H NMR detects phenylsilane is 95%, and the productive rate of ethane is 90%.
Embodiment 38
1, Kaolinite Preparation of Catalyst
By 10.6mg (0.02mmol) three (pentafluorophenyl group) boron and 3.5mg (0.1mmol) 2,2,6,6 ,-tetramethyl piperidine hydrochloride mixes, and is prepared into catalyst.
2, catalyst catalysis phenylsilane reducing carbon dioxide at 100 DEG C prepares the purposes in methane, and its using method is as follows:
Be dissolved in 1mL toluene by above-mentioned catalyst, add 43.2mg (0.4mmol) phenylsilane, freezing vacuum is drained, and passes into CO under an atmospheric pressure
2, the pressure controlling carbon dioxide is 0.2MPa, and 100 DEG C are heated 8 hours, adds watery hydrochloric acid hydrolysis, warp
1h NMR detects CO
298% changes into methane.
Three (pentafluorophenyl group) boron of the present embodiment also can be replaced with equimolar three (tetrafluoro phenyl) boron, three (trifluorophenyl) boron, three (difluorophenyl) boron, three (fluorophenyl) boron or triphenyl borine, and phenylsilane also can be replaced with the polymethyl hydrogen siloxane that equimolar silane, diphenyl silane, tri-phenyl-silane, phenyl methyl silane, triethyl silicane, phenyldimethylsilane, dichloro hydrogen silicon, trichlorosilane, triethoxysilane, diethoxymethylsilane, trimethyl silica dimethylsilane or number-average molecular weight are 222 ~ 642.
Embodiment 39
The purposes in methane prepared by catalyst prepared by embodiment 38 at catalysis phenylsilane reducing carbon dioxide, its using method is as follows:
Be dissolved in 1mL toluene by above-mentioned catalyst, add 43.2mg (0.4mmol) phenylsilane, freezing vacuum is drained, and passes into CO under an atmospheric pressure
2, the pressure controlling carbon dioxide is 0.1MPa, places 8 hours for 20 DEG C, adds watery hydrochloric acid hydrolysis, warp
1h NMR detects CO
295% changes into methane.
Embodiment 40
The purposes in methyl alcohol prepared by catalyst prepared by embodiment 38 at catalysis phenylsilane reducing carbon dioxide, its using method is as follows:
Be dissolved in 1mL toluene by above-mentioned catalyst, add 43.2mg (0.4mmol) phenylsilane, freezing vacuum is drained, and passes into CO under an atmospheric pressure
2, the pressure controlling carbon dioxide is 0.1MPa, and 80 DEG C are heated 8 hours, adds watery hydrochloric acid hydrolysis, warp
1h NMR detects CO
283% changes into methyl alcohol.
Embodiment 41
1, Kaolinite Preparation of Catalyst
10.6mg (0.02mmol) three (pentafluorophenyl group) boron and 2.7mg (0.02mmol) diisopropyl ammonium chloride are mixed, is prepared into catalyst.
2, the purposes in methane prepared by catalyst at catalysis phenylsilane reducing carbon dioxide, and its using method is as follows:
Be dissolved in 1mL toluene by above-mentioned catalyst, add 43.2mg (0.4mmol) phenylsilane, freezing vacuum is drained, and passes into CO under an atmospheric pressure
2, 100 DEG C are heated 8 hours, add watery hydrochloric acid hydrolysis, warp
1h NMR detects CO
297% changes into methane.
Embodiment 42
The purposes in methane prepared by catalyst prepared by embodiment 41 at catalysis phenylsilane reducing carbon dioxide, its using method is as follows:
Be dissolved in 1mL toluene by above-mentioned catalyst, add 43.2mg (0.4mmol) phenylsilane, freezing vacuum is drained, and passes into CO under an atmospheric pressure
2, place 8 hours for 25 DEG C, add watery hydrochloric acid hydrolysis, warp
1h NMR detects CO
293% changes into methane.
Embodiment 43
The purposes in methyl alcohol prepared by catalyst prepared by embodiment 41 at catalysis phenylsilane reducing carbon dioxide, its using method is as follows:
Be dissolved in 1mL toluene by lewis acid base catalyst, add 43.2mg (0.4mmol) phenylsilane, freezing vacuum is drained, and passes into CO under an atmospheric pressure
2, 80 DEG C are heated 8 hours, add watery hydrochloric acid hydrolysis, warp
1h NMR detects CO
281% changes into methyl alcohol.
Claims (9)
1. lewis acid and amine salt or an ammonium salt mixed catalyst, is characterized in that: it is mixed for 1:0.1 ~ 10 in molar ratio by amine salt or ammonium salt and lewis acid, and wherein said lewis acid is three (pentafluorophenyl group) boron, three (tetrafluoro phenyl) boron, three (trifluorophenyl) boron, three (difluorophenyl) boron, three (fluorophenyl) boron, any one in triphenyl borine, described ammonium salt is ammonium chloride, ammonium bromide, iodate amine, ammonium sulfate, ammonium nitrate, ammonium fluosilicate, ammonium phosphate, any one in ammonium acetate, described amine salt is methyl chloride amine, methyl bromide amine, dimethylammonium chloride amine, dimethyl iodate amine, ethylmercury chloride amine, ethyl phosphonium bromide amine, ethyl phosphonium iodide amine, diethyl ammonium chloride, diethyl amine bromide, triethylammonium chloride, propyl group ammonium chloride, propyl group amine bromide, dipropyl ammonium chloride, dipropyl amine bromide, n-butylmagnesium chloride amine, three n-butylmagnesium chloride amine, tert-butyl group ammonium chloride, tetraphenylphosphonium chloride amine, diphenyl ammonium chloride, phenyl methyl ammonium chloride, piperidine hydrochlorate, 2,2,6,6-tetramethyl piperidine hydrochloride, benzimidazole hydrochloride, imidazole hydrochloride, pyridine hydrochloride, triazolium salt hydrochlorate, any one in thiazole hydrochloride.
2. lewis acid according to claim 1 and amine salt or ammonium salt mixed catalyst, is characterized in that: described amine salt or ammonium salt and lewis acidic mol ratio are 1:0.8 ~ 1.2.
3. lewis acid according to claim 1 and 2 and amine salt or ammonium salt mixed catalyst, it is characterized in that: described lewis acid is three (pentafluorophenyl group boron), described ammonium salt is any one in ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium phosphate, ammonium nitrate, and described amine salt is tert-butyl group ammonium chloride or piperidine hydrochlorate.
4. the purposes in alkane or siloxanes prepared by lewis acid according to claim 1 and amine salt or ammonium salt mixed catalyst at catalytic hydrogenation silane reduction hydrocarbon, and its using method is as follows:
Under inert gas shielding, hydrosilanes, hydrocarbon are joined in organic solvent, add catalyst, in hydrosilanes and catalyst, lewis acidic mol ratio is 1:0.001 ~ 0.2, stirring at room temperature 10 ~ 60 minutes, described hydrosilanes and the mol ratio of hydrocarbon are 2n/m ~ 3n/m:1, obtain alkane, the mol ratio of hydrosilanes and hydrocarbon is 0.8n/m ~ 2n/m:1, obtain siloxanes, wherein m is the number of the hydrogen atom be connected with silicon atom in per molecule hydrosilanes, and n is the number of oxygen atom in per molecule hydrocarbon;
Above-mentioned hydrosilanes is silane, phenylsilane, diphenyl silane, tri-phenyl-silane, phenyl methyl silane, triethyl silicane, phenyldimethylsilane, dichloro hydrogen silicon, trichlorosilane, triethoxysilane, diethoxymethylsilane, trimethyl silica dimethylsilane, number-average molecular weight are any one in the polymethyl hydrogen siloxane of 222 ~ 642; Hydrocarbon is any one in aldehyde, ketone, carboxylic acid, acid anhydrides, carboxylic acid halides, ester, ether, alcohol, siloxanes; Organic solvent is any one in carrene, chloroform, carbon tetrachloride, n-hexane, pentane, dichloroethanes, benzene, chlorobenzene, dichloro benzene,toluene,xylene, ethylo benzene.
5. lewis acid according to claim 4 and amine salt or ammonium salt mixed catalyst prepare purposes in alkane or siloxanes at catalytic hydrogenation silane reduction hydrocarbon, it is characterized in that: in described hydrosilanes and catalyst, lewis acidic mol ratio is 1:0.01 ~ 0.1.
6. the lewis acid according to claim 4 or 5 and ammonium salt or amine salt mixed catalyst prepare purposes in alkane or siloxanes at catalytic hydrogenation silane reduction hydrocarbon, it is characterized in that: described hydrosilanes is any one in phenylsilane, diphenyl silane, triethyl silicane.
7. the purposes in methane or methyl alcohol prepared by the lewis acid of claim 1 and amine salt or ammonium salt mixed catalyst at catalytic hydrogenation silane reducing carbon dioxide, and its using method is as follows:
Hydrosilanes, catalyst are added in toluene, in hydrosilanes and catalyst, lewis acidic mol ratio is 1:0.001 ~ 0.2, then carbon dioxide is passed into, the pressure controlling carbon dioxide is 0.1 ~ 0.2MPa, 20 ~ 100 DEG C are reacted 5 ~ 12 hours, reaction terminates rear hydrolysis, obtains methane or methyl alcohol;
Above-mentioned hydrosilanes is silane, phenylsilane, diphenyl silane, tri-phenyl-silane, phenyl methyl silane, triethyl silicane, phenyldimethylsilane, dichloro hydrogen silicon, trichlorosilane, triethoxysilane, diethoxymethylsilane, trimethyl silica dimethylsilane, number-average molecular weight are any one in the polymethyl hydrogen siloxane of 222 ~ 642.
8. lewis acid according to claim 7 and ammonium salt or amine salt mixed catalyst prepare purposes in methane or methyl alcohol at catalytic hydrogenation silane reducing carbon dioxide, it is characterized in that: in described hydrosilanes and catalyst, lewis acidic mol ratio is 1:0.01 ~ 0.1.
9. the lewis acid according to claim 7 or 8 and ammonium salt or amine salt mixed catalyst prepare purposes in methane or methyl alcohol at catalytic hydrogenation silane reducing carbon dioxide, it is characterized in that: described hydrosilanes is any one in phenylsilane, diphenyl silane, triethyl silicane.
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| CN108325562A (en) * | 2018-02-11 | 2018-07-27 | 乐山师范学院 | A kind of support type borane catalyst |
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| CN108676023A (en) * | 2018-05-22 | 2018-10-19 | 乐山师范学院 | One kind efficiently preparing boron hydride ion [RnH4-nB]-Method |
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| CN109438151A (en) * | 2018-09-28 | 2019-03-08 | 乐山师范学院 | A kind of method that aldehyde and ketone are reduced to alcohol |
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| CN108690198B (en) * | 2018-05-15 | 2021-01-15 | 杭州师范大学 | Method for preparing methyl phenyl silicone oil by catalyzing tris (pentafluorophenyl) borane |
| CN108676023A (en) * | 2018-05-22 | 2018-10-19 | 乐山师范学院 | One kind efficiently preparing boron hydride ion [RnH4-nB]-Method |
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| CN111303930B (en) * | 2020-02-08 | 2022-02-08 | 河北工业大学 | Method for hydrosilylation reaction of carbonyl compound in biological oil |
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