CN102086155A - Method for synthesizing amine, alcohol, olefin and alkane through catalytic reduction by using supported gold - Google Patents

Method for synthesizing amine, alcohol, olefin and alkane through catalytic reduction by using supported gold Download PDF

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CN102086155A
CN102086155A CN2009102000077A CN200910200007A CN102086155A CN 102086155 A CN102086155 A CN 102086155A CN 2009102000077 A CN2009102000077 A CN 2009102000077A CN 200910200007 A CN200910200007 A CN 200910200007A CN 102086155 A CN102086155 A CN 102086155A
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electron
group
condensed ring
aromatic heterocycle
phenyl
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曹勇
娄夏冰
何林
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Fudan University
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Fudan University
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Abstract

The invention belongs to the field of chemical synthesis, and in particular relates to a method for synthesizing amine, alcohol, olefin and alkane through catalytic reduction by using supported gold. In the method, a nitro-compound, aldehyde ketone, alkyne and an olefin compound are taken as substrates, the supported gold is taken as a catalyst, formic acid and salt thereof are taken as a hydrogen transfer agent, and amine, alcohol, olefin and alkane compounds are prepared by catalyzing hydrogen transfer reaction through the supported gold catalyst at the temperature of between 30 and 80 DEG C under the protection of inert gas. The supported catalyst used in the method has the advantage that the supported catalyst is easy to separate and recycle; by the method, satisfying reaction speed and conversion rate can be achieved; and the method has high selectivity and obvious industrial production practical value.

Description

A kind of load type gold catalytic reduction synthesizes the method for amine, alcohol, alkene and alkane
Technical field
The invention belongs to the field of chemical synthesis, relate to the synthetic method of amine, alcohol, alkene and alkane.Be specifically related to the method for the synthetic amine of a kind of load type gold catalytic reduction, alcohol, alkene and alkane.
Background technology
The reaction that is reduced to corresponding amine, alcohol, alkene and alkane with nitro-compound, aldehyde ketone, alkynes and olefin(e) compound still is all very important the laboratory study aspect from the industrial application angle.Particularly it has very wide application in fields such as medicine, dyestuff, agricultural chemicals, liquid crystal material, rubber.
The disclosed method of reducing of prior art mainly contains: 1) active metal reduction method (as iron powder, zinc powder, tin grain etc.); 2) metal hydride reduction (as sodium borohydride, Lithium Aluminium Hydride etc.); 3) the catalytic hydrogenating reduction method (with noble metal platinum, palladium, and the skeleton nickel class be catalyzer).Have following many disadvantages and deficiency in the disclosed method of reducing of prior art: method 1), waste residue is many, corrodibility is strong, equipment attrition is serious; Method 2) in, major defect is the reductive agent costliness, and method 3) in, being subjected to the restriction of hydrogen source, security is low, generally under high pressure carries out, to the equipment requirements height.Compare above-mentioned traditional method, the hydrogen transference hydrogenation has actual and potential advantage.It adopts hydrogenous polyatomic molecule to make hydrogen source (the hydrogen donor is as formic acid and salt thereof, hydrazine, hydrocarbon, alcohol etc.), and hydrogen is transferred to reaction substrate (hydrogen acceptor) from the hydrogen donor in the reaction.Be hydrogen transfer agent with formic acid and salt thereof because cost is lower particularly, reaction is advantage such as control and receive art technology researchist's more concern easily.
Summary of the invention
The objective of the invention is provides a kind of load type gold catalytic reduction to synthesize the method for amine, alcohol, alkene and alkane for overcoming the shortcoming that the prior art catalyst system exists.The inventive method technology is simple, the reaction conditions gentleness, and the yield height, product performance are stable.
The inventive method is a substrate with nitro-compound, aldehyde ketone, alkynes and olefin(e) compound, is catalyzer with the load type gold, and formic acid and salt thereof are that hydrogen transfer agent carries out reduction reaction.
Particularly, the invention provides the method for load type gold catalytic reduction, and utilize this method to prepare amine, alcohol, alkene and alkane.The inventive method comprises: with nitro-compound, aldehyde ketone, alkynes and olefin(e) compound is substrate; with the load type gold is catalyzer; formic acid and salt thereof are hydrogen transfer agent; water or in aqueous phase system, add suitable solubility promoter; 30 ℃ ~ 80 ℃; protection of inert gas utilizes load type gold catalyst catalytic hydrogen transfer prepared in reaction amine, alcohol, alkene and alkane compound.
Among the present invention, employed catalyzer is a load type gold catalyst, and gold grain wherein is of a size of＜5nm; Carrier wherein is selected from CeO 2, TiO 2, ZrO 2Or Fe 2O 3In one or more.
Described load type gold catalyst must guarantee to be＜5nm gold grain, can prepare by the following method: deposition-precipitation method, colloid method or improved pickling process.The preferred deposition precipitator method.
Among the present invention, described nitro-compound, aldehyde ketone, alkynes or olefin(e) compound are:
Figure G2009102000077D00021
Wherein R is 4～10 carbon straight or branched alkyl, thiazolinyl, cycloalkyl or replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle;
Described substituted-phenyl, condensed ring or aromatic heterocycle substituting group can be one or more electron-donating groups and/or electron-withdrawing group, wherein said electron-donating group is an alkyl, alkoxyl group or amido, described electron-withdrawing group are fluorine, chlorine, bromine, iodine, cyano group, acyl group, aldehyde radical, ketone group, trifluoromethyl, nitro or the carboxyl that directly links to each other with aromatic ring;
Figure G2009102000077D00022
Wherein R is 4～10 carbon straight or branched alkyl, thiazolinyl, cycloalkyl, or replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle;
Described substituted-phenyl, condensed ring or aromatic heterocycle substituting group can be one or more electron-donating groups and/or electron-withdrawing group, wherein said electron-donating group is an alkyl, alkoxyl group or amido, described electron-withdrawing group are fluorine, chlorine, bromine, iodine or the trifluoromethyl that directly links to each other with aromatic ring;
Figure G2009102000077D00023
R wherein 1, R 2Be hydrogen, 4～10 carbon straight or branched alkyl, thiazolinyl, cycloalkyl, replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle;
Described substituted-phenyl, condensed ring or aromatic heterocycle substituting group can be one or more electron-donating groups and/or electron-withdrawing group, wherein said electron-donating group is an alkyl, alkoxyl group or amido, described electron-withdrawing group are fluorine, chlorine, bromine, iodine or the trifluoromethyl that directly links to each other with aromatic ring.R 1, R 2Can be the same or different;
R wherein 1, R 2Be hydrogen, 4～10 carbon straight or branched alkyl, thiazolinyl, cycloalkyl, replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle; Wherein substituted-phenyl, condensed ring or aromatic heterocycle substituting group can be one or more electron-donating groups and/or electron-withdrawing group, described electron-donating group is an alkyl, alkoxyl group or amido, described electron-withdrawing group are fluorine, chlorine, bromine, iodine or the trifluoromethyl that directly links to each other with aromatic ring.R 1, R 2Can be the same or different.
Figure G2009102000077D00032
R wherein 1, R 2Be hydrogen, 4～10 carbon straight or branched alkyl, thiazolinyl, cycloalkyl, replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle; Wherein substituted-phenyl, condensed ring or aromatic heterocycle substituting group can be one or more electron-donating groups and/or electron-withdrawing group, described electron-donating group is an alkyl, alkoxyl group or amido, described electron-withdrawing group are fluorine, chlorine, bromine, iodine or the trifluoromethyl that directly links to each other with aromatic ring.R 1, R 2Can be the same or different;
Among the present invention, add hydrogen transfer agent (hydrogen donor) in the reaction system, comprise formic acid and salt thereof.Preferred hydrogen donor is ammonium formiate or potassium formiate.Described its amount ranges of hydrogen donor is the 3-15 equivalent of substrate.Preferred amount ranges is the 5-10 equivalent of substrate.
Among the present invention, temperature of reaction is generally 30 ℃～80 ℃, can be according to substrate different adjustment optimal reaction temperature.
Among the present invention, be reflected in the protection of inert gas and carry out, described rare gas element is selected from argon gas, nitrogen or the helium a kind of, preferred nitrogen.
Pressure in the present invention's reaction is 0.1～1MPa, and preferred pressure is 0.5MPa.
The employed loaded catalyst of the inventive method has the easily separated advantage that recycles, and adopts the inventive method can obtain gratifying speed of response, transformation efficiency, and good selectivity is arranged, have significant industrial production practical value.
Embodiment
Below by embodiment in detail the present invention is described in detail, but content of the present invention is not limited thereto.
Embodiment 1
Capacity is the 1mmol oil of mirbane of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wt Au/ZrO 2Catalyzer, 7 equivalent ammonium formiates, 10mL ethanol, after using nitrogen replacement autoclave air then, the autoclave internal temperature is risen to 30 ℃, feed 0.5MPa nitrogen, stir 12h, with gc analysis as a result the oil of mirbane transformation efficiency that is converted into aniline be 99.8%, selectivity is 99%.
Embodiment 2
Capacity is the 1mmol nitrotoluene of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wtAu/TiO 2Catalyzer, 5 equivalent potassium formiates, 10mL ethanol, after using nitrogen replacement autoclave air then, the autoclave internal temperature is risen to 30 ℃, feed the 0.5MPa helium, stir 20h, with gc analysis as a result the transformation efficiency that is converted into amido toluene of nitrotoluene be 99.8%, selectivity is 99%.
Embodiment 3
Capacity is the 1mmol parachloronitrobenzene of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wtAu/CeO 2Catalyzer, 5 equivalent ammonium formiates, 10mL ethanol, after using nitrogen replacement autoclave air then, the autoclave internal temperature is risen to 30 ℃, feed the 0.5MPa argon gas, stir 14h, with gc analysis as a result the parachloronitrobenzene transformation efficiency that is converted into p-Chlorobenzoic acid amide be 98%, selectivity is 99%.
Embodiment 4
Capacity is the 1mmol 6-nitroquinoline of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wtAu/CeO 2Catalyzer, 5 equivalent ammonium formiates, 10mL ethanol, after using nitrogen replacement autoclave air then, the autoclave internal temperature is risen to 50 ℃, feed 0.5MPa nitrogen, stir 12h, the transformation efficiency that the 6-nitroquinoline is converted into 6-amido quinoline is 99.5%, and selectivity is 99%.
Embodiment 5
Capacity is the 1mmol nitro hexane of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wtAu/TiO 2Catalyzer, 5 equivalent ammonium formiates, 10mL ethanol, use nitrogen replacement autoclave air then after, the autoclave internal temperature is risen to 50 ℃, feed 0.5MPa nitrogen, stir 18h, the transformation efficiency that the nitro hexane is converted into the amido hexane is 99.5%, selectivity is 84%.
Embodiment 6
Capacity is the 1mmol phenylacetylene of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wtAu/TiO 2Catalyzer, 5 equivalent ammonium formiates, 10mL ethanol, use nitrogen replacement autoclave air then after, the autoclave internal temperature is risen to 60 ℃, feed 0.5MPa nitrogen, stir 6h, it is 97% that phenylacetylene is converted into cinnamic transformation efficiency, selectivity is 96%.
Embodiment 7
Capacity is the 1mmol vinylbenzene of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wtAu/CeO 2Catalyzer, 5 equivalent ammonium formiates, 10mL ethanol, use nitrogen replacement autoclave air then after, the autoclave internal temperature is risen to 60 ℃, feed 0.5MPa nitrogen, stir 17h, styrene conversion is that the transformation efficiency of phenylethane is 98%, selectivity is 99%.
Embodiment 8
Capacity is the 1mmol phenyl aldehyde of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wtAu/CeO 2Catalyzer, 5 equivalent ammonium formiates, 10mL ethanol, use nitrogen replacement autoclave air then after, the autoclave internal temperature is risen to 80 ℃, feed 0.5MPa nitrogen, stir 9h, the transformation efficiency that phenyl aldehyde is converted into phenylcarbinol is 99%, selectivity is 99%.
Embodiment 9
Capacity is the 1mmol methyl phenyl ketone of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wtAu/CeO 2Catalyzer, 5 equivalent ammonium formiates, 10mL ethanol, use nitrogen replacement autoclave air then after, the autoclave internal temperature is risen to 80 ℃, feed 0.5MPa nitrogen, stir 7h, the transformation efficiency that methyl phenyl ketone is converted into methylbenzyl alcohol is 99%, selectivity is 99%.
Embodiment 10
Capacity is the 1mmol p-Fluorobenzenecarboxaldehyde of packing in the stainless steel autoclave of 100mL, 0.05g 1.5%wtAu/CeO 2Catalyzer, 5 equivalent ammonium formiates, 10mL ethanol, use nitrogen replacement autoclave air then after, the autoclave internal temperature is risen to 80 ℃, feed 0.5MPa nitrogen, stir 6h, the transformation efficiency that p-Fluorobenzenecarboxaldehyde is converted into fluorophenyl methanol is 99%, selectivity is 99%.

Claims (17)

1. the method for the synthetic amine of a load type gold catalytic reduction, alcohol, alkene or alkane; it is characterized in that; this method comprises: with nitro-compound, aldehyde ketone, alkynes or olefin(e) compound is substrate; with the load type gold is catalyzer; formic acid and salt thereof are hydrogen transfer agent; under 30 ℃～80 ℃, adopt protection of inert gas, by load type gold catalyst catalytic hydrogen transfer prepared in reaction amine, alcohol, alkene or alkane compound.
2. method according to claim 1 is characterized in that, described load type gold catalyst, and its gold grain is of a size of＜5nm.
3. method according to claim 1 is characterized in that, its carrier of described load type gold catalyst is selected from CeO 2, TiO 2, ZrO 2Or Fe 2O 3In one or more.
4. according to claim 2 or 3 described methods, it is characterized in that described load type gold catalyst prepares by following method: deposition-precipitation method, colloid method or improved pickling process.
5. according to claim 2 or 3 described methods, it is characterized in that described load type gold catalyst prepares by deposition-precipitation method.
6. method according to claim 1 is characterized in that, described nitro-compound, aldehyde ketone, alkynes or olefin(e) compound are:
Figure F2009102000077C00011
R is 4～10 carbon straight or branched alkyl, thiazolinyl in the formula, cycloalkyl, and replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle;
Figure F2009102000077C00012
R is 4～10 carbon straight or branched alkyl, thiazolinyl in the formula, cycloalkyl, and replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle;
Figure F2009102000077C00013
R in the formula 1, R 2Be hydrogen, 4～10 carbon straight or branched alkyl, thiazolinyl, cycloalkyl, replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle;
Figure F2009102000077C00014
R in the formula 1, R 2Be hydrogen, 4～10 carbon straight or branched alkyl, thiazolinyl, cycloalkyl, replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle; Or,
Figure F2009102000077C00021
R in the formula 1, R 2Be hydrogen, 4～10 carbon straight or branched alkyl, thiazolinyl, cycloalkyl, replacement/unsubstituted phenyl, condensed ring or aromatic heterocycle.
7. method according to claim 6 is characterized in that, and is described
Figure F2009102000077C00022
Wherein said substituted-phenyl, condensed ring or aromatic heterocycle substituting group are one or more electron-donating groups and/or electron-withdrawing group; described electron-donating group is alkyl, alkoxyl group or amido, and described electron-withdrawing group is fluorine, chlorine, bromine, iodine, cyano group, acyl group, aldehyde radical, ketone group, trifluoromethyl, nitro or the carboxyl that directly links to each other with aromatic ring.
8. method according to claim 6 is characterized in that, and is described
Figure F2009102000077C00023
Wherein said substituted-phenyl, condensed ring or aromatic heterocycle substituting group are one or more electron-donating groups and/or electron-withdrawing group, described electron-donating group is an alkyl, alkoxyl group or amido, described electron-withdrawing group are fluorine, chlorine, bromine, iodine or the trifluoromethyl that directly links to each other with aromatic ring.
9. method according to claim 6 is characterized in that, and is described
Figure F2009102000077C00024
Wherein said substituted-phenyl, condensed ring or aromatic heterocycle substituting group are one or more electron-donating groups and/or electron-withdrawing group, described electron-donating group is alkyl, alkoxyl group or amido, and described electron-withdrawing group is fluorine, chlorine, bromine, iodine, the trifluoromethyl that directly links to each other with aromatic ring; R 1, R 2Identical or different.
10. method according to claim 6 is characterized in that, and is described
Figure F2009102000077C00025
Wherein said substituted-phenyl, condensed ring or aromatic heterocycle substituting group are one or more electron-donating groups and/or electron-withdrawing group, described electron-donating group is alkyl, alkoxyl group or amido, and described electron-withdrawing group is fluorine, chlorine, bromine, iodine or the trifluoromethyl that directly links to each other with aromatic ring; R 1, R 2Identical or different.
11. method according to claim 6 is characterized in that, and is described
Figure F2009102000077C00026
Wherein said substituted-phenyl, condensed ring or aromatic heterocycle substituting group are one or more electron-donating groups and/or electron-withdrawing group, described electron-donating group is alkyl, alkoxyl group or amido, and described electron-withdrawing group is fluorine, chlorine, bromine, iodine or the trifluoromethyl that directly links to each other with aromatic ring; R 1, R 2Identical or different.
12. method according to claim 1 is characterized in that, described hydrogen transfer agent is selected from ammonium formiate or potassium formiate.
13. method according to claim 1 is characterized in that, the 3-15 equivalent that described hydrogen transfer agent amount ranges is a substrate.
14. method according to claim 1 is characterized in that, the 5-10 equivalent that described hydrogen transfer agent amount ranges is a substrate.
15. method according to claim 1 is characterized in that, described rare gas element is selected from argon gas, nitrogen or helium.
16. method according to claim 15 is characterized in that, described protection of inert gas pressure is 0.1～1MPa.
17. method according to claim 15 is characterized in that, described protection of inert gas pressure is 0.5MPa.
CN2009102000077A 2009-12-04 2009-12-04 Method for synthesizing amine, alcohol, olefin and alkane through catalytic reduction by using supported gold Pending CN102086155A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103193567A (en) * 2013-04-02 2013-07-10 复旦大学 Method for controllable reduction of unsaturated organic compound from catalysis of formic acid by nanogold
CN103641673A (en) * 2013-12-12 2014-03-19 上海交通大学 Method for catalytic reduction of carbon-carbon double bond by carbon nitride supported metal nanoparticles
CN110204466A (en) * 2019-05-17 2019-09-06 东华大学 A kind of cis- olefinic amine compound and its preparation method and application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103193567A (en) * 2013-04-02 2013-07-10 复旦大学 Method for controllable reduction of unsaturated organic compound from catalysis of formic acid by nanogold
CN103641673A (en) * 2013-12-12 2014-03-19 上海交通大学 Method for catalytic reduction of carbon-carbon double bond by carbon nitride supported metal nanoparticles
CN110204466A (en) * 2019-05-17 2019-09-06 东华大学 A kind of cis- olefinic amine compound and its preparation method and application

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Application publication date: 20110608