CN105085315B - Method for preparing nitrile compounds by catalytic oxidation of amine - Google Patents
Method for preparing nitrile compounds by catalytic oxidation of amine Download PDFInfo
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- CN105085315B CN105085315B CN201410184610.1A CN201410184610A CN105085315B CN 105085315 B CN105085315 B CN 105085315B CN 201410184610 A CN201410184610 A CN 201410184610A CN 105085315 B CN105085315 B CN 105085315B
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Abstract
A method for preparing nitrile compounds by catalytic oxidation of amine can catalyze amine to oxidize and synthesize the nitrile compounds high efficiently and high selectively under the condition of normal pressure and normal temperature by using peroxide as an oxidizing agent. The method for preparing nitrile compounds by catalytic oxidation of amine has mild operation condition. The conversion rate of amine can be reached to 92%, and the selectivity of the nitrile compounds can be reached to 95%.
Description
Technical field
The present invention relates to chemical field is and in particular to a kind of side preparing nitrile compounds for amine catalysis oxidation
Method.
Background technology
Nitrile compounds are that a kind of demand is big, broad-spectrum chemicals, can live as medical and nitrogenous class is biological
The synthetic intermediate of property compound.Traditional synthetic method is related to halide and is reacted with the metering of inorganic cyanide, high cost,
Course of reaction not environmental protection, product is complicated, isolate and purify difficulty.
Preparing nitrile compounds by amine catalysis oxidation is a kind of new raw material road with important application prospect, high-efficiency environment friendly
Line and synthetic method.Recently, Mizuno etc. is achieved by aminated compounds to nitrile chemical combination with the catalyst that noble ruthenium loads
The conversion of thing, but this reaction mechanism mechanism of reaction needs the more harsh reaction condition such as high temperature, using noble metal, high cost, and ruthenium catalysis
Agent easily inactivates, and needs to improve further in recycling property.
Content of the invention
Prepare the application of nitrile compounds in order to realize amine direct efficient oxidation conversion, need invention a kind of for amine catalysis
The synthetic method of nitrile is prepared in oxidation, under catalyst action, using oxygen source, under temperate condition synthesizes amine efficiently catalyzing and oxidizing
Nitrile.
A kind of method preparing nitrile compounds for amine catalysis oxidation, under catalyst action, using peroxide be
Oxidant, primary amine catalysis oxidation is synthesized nitrile compounds；
Described catalyst is metal-doped phosphate aluminium molecular sieve.
Described phosphate aluminium molecular sieve is one of AlPO-3, AlPO-4, AlPO-5, AlPO-31 or two or more；Doping
Metal is one of Fe, Mn, Co, Ni, Cu or two or more；
In metal-doped phosphate aluminium molecular sieve, doping metals and the mol ratio of phosphate aluminium molecular sieve are 1:50-1:20.
At 0 DEG C -100 DEG C, the reaction time is 0.2-12 hour to reaction temperature；
60 DEG C of preferable reaction temperature, 0.2 hour reaction time.
Substrate primary amine is aromatic series or Armeen；
Described primary aromatic amine is benzylamine, to chlorobenzylamine, 4-Fluorobenzylamine, and to bretylium tosylate, o-chlorine benzylamine, to methylbenzylamine,
To trifluoromethyl benzylamine, one of 4-Methoxybenzylamine or two or more；
Described Armeen is n-butylamine, one of phenyl ethylamine or two or more.
Reaction medium adopts liquid solvent；Solvent is：Water, acetonitrile, 1,4- dioxane, oxolane, chlorobenzene, N, N- bis-
One of NMF, dimethyl sulfoxide (DMSO) or more than two kinds；
Every 0.5 mM of primary amine solvent load is 0.005-2 milliliter, preferably 2 milliliters.
Catalytic conversion process is with peroxide as oxygen source；Oxygen source is：Cyclohexyl hydroperoxide, hydrogen peroxide, the tert-butyl group
One of hydrogen peroxide, phenethyl hydrogen peroxide, hyperis or more than two kinds；Its consumption is substrate molecule of primary amine
Mole 1-10 times, preferably 2 times.
Every 0.5 mM of primary amine adopt 0.01 gram -1 gram of catalyst amount, preferably 0.02 gram.
According to the present invention, for improving the activity and selectivity of catalytic reaction, need to choose suitably metal-doped molecular sieve
Make catalyst.The performance of catalytic reaction is relevant with the species of active component in catalyst, the effect to reactivity worth for the different metal
Difference, therefore will choose suitable metal.Variety classes molecular sieve has different apertures, has confinement to substrate molecule,
There are different catalytic performances.The performance of catalytic reaction is relevant with different metal in metal-doped molecular sieve, the property of metal surface
Matter difference leads to metal different from the effect of substrate molecule and oxygen source.The molecular sieve of different metal doping, such as MnAPO- are investigated
5, FeAPO-5, CoAPO-5, CuAPO-5, NiAPO-5 etc., investigate same metal-doped different molecular sieve simultaneously and this are urged
Change the impact of reaction, such as MnAPO-3, MnAPO-4, MnAPO-5.
Substrate molecule is primary amine or secondary amine for amine.As benzylamine, to chlorobenzylamine, 4-Fluorobenzylamine, to bretylium tosylate, adjacent benzyl chloride
Amine, to methylbenzylamine, to trifluoromethyl benzylamine, 4-Methoxybenzylamine, n-butylamine, phenyl ethylamine.
According to the present invention, for making reaction condition environmental protection, pollution-free, reaction condition is gentle, does oxygen using peroxide
Source.Using oxygen source it is：Cyclohexyl hydroperoxide, hydrogen peroxide, TBHP, phenethyl hydrogen peroxide, isopropyl mistake
Hydrogen oxide.
Different medium has Different Effects to the performance of catalytic reaction, so the effect of different solvents to be investigated.Solvent is：
Water, acetonitrile, Isosorbide-5-Nitrae-dioxane, oxolane, chlorobenzene, DMF, dimethyl sulfoxide (DMSO).
According to the present invention, it is reduces cost, improves efficiency, select TBHP to be oxygen source in oxidizing process, instead
Should be at 0 DEG C -100 DEG C, the reaction time is 0.5-12 hour, and amine efficiently catalyzing and oxidizing is nitrile product, and the method not only has
High selectivity, and with low cost, method is simple, Efficient Conversion.
Brief description
Fig. 1 is embodiment 1 product structure nmr analysis figure.
Specific embodiment
The following example will be helpful to understand the present invention, but present invention is not limited to this.
Embodiment 1
0.5 mM of benzylamine, 0.05 gram of MnAPO-3,2 milliliters of acetonitriles are added pressure bottle, adds 1 mM of tert-butyl group
Hydrogen peroxide, under normal temperature and pressure, reacts 4 hours, product is analyzed using GC-MS, and amine conversion ratio is 66%, and nitrile is
The selectivity of benzonitrile is 98%.
The following Fig. 1 of product structure nmr analysis.
Embodiment 2
0.5 mM is added pressure bottle to chlorobenzylamine, 0.10 gram of MnAPO-4,2 milliliters of chlorobenzenes, adds 1 mM of uncle
Butylhydroperoxide, under normal temperature and pressure, reacts 6 hours, product is analyzed using GC-MS, and amine conversion ratio is 72%, nitrile
Class is p-Cyanochlorobenzene is selectively 76%.
Embodiment 3
1 mM is added pressure bottle to Methoxyamine, 0.02 gram of MnAPO-5,2 milliliters of acetonitriles, adds 1 mM of ring
Hexyl hydrogen peroxide, under 50 DEG C of normal pressures, reacts 12 hours, product is analyzed using GC-MS, and amine conversion ratio is 73%,
Nitrile is i.e. selective to methoxy benzonitrile to be 97%.
Embodiment 4
0.5 mM of 4-Fluorobenzylamine, 0.05 gram of FeAPO-3,2 milliliters of oxolanes are added pressure bottle, adds 1 mmoles
That phenethyl hydrogen peroxide, under 60 DEG C of normal pressures, reacts 8 hours, product is analyzed using GC-MS, and amine conversion ratio is
87%, nitrile is p-Cyanochlorobenzene is selectively 95%.
Embodiment 5
0.5 mM of o-chlorine benzylamine, 0.05 gram of CoAPO-3,2 milliliters of Isosorbide-5-Nitrae-dioxane are added pressure bottle, adds 1
MM hyperis, under 30 DEG C of normal pressures, react 3 hours, product is analyzed using GC-MS, amine conversion ratio
For 57%, nitrile is o-chlorobenzonitrile is selectively 93%.
Embodiment 6
By 0.5 mM of n-butylamine, 0.20 mM gram, 2 milliliters of acetonitriles addition pressure bottles, add 1 mM of tertiary fourth
Base hydrogen peroxide, under normal temperature and pressure, reacts 4 hours, product is analyzed using GC-MS, and amine conversion ratio is 25%, nitrile
I.e. n-Butyronitrile is selectively 90%.
Embodiment 7
0.5 mM of benzylamine, 0.5 gram of CuAPO-3,2 milliliters of acetonitriles are added pressure bottle, adds 1 mM of tert-butyl group
Hydrogen peroxide, under normal temperature and pressure, reacts 6 hours, product is analyzed using GC-MS, and amine conversion ratio is 60%, and nitrile is
Benzonitrile is selectively 90%.
Embodiment 8
0.5 mM is added pressure bottle to bretylium tosylate, 0.07 gram of FeAPO-4,2 milliliters of water, adds 1 mM of peroxide
Change hydrogen, under 30 DEG C of normal pressures, react 7 hours, product is analyzed using GC-MS, amine conversion ratio is 71%, and nitrile is i.e. to bromine
Benzonitrile is selectively 95%.
Embodiment 9
0.5 mM of phenyl ethylamine, 0.05 gram of ZnAPO-5,2 milliliters of acetonitriles are added pressure bottle, adds 1 mM of tertiary fourth
Base hydrogen peroxide, under 0 DEG C of normal pressure, reacts 10 hours, product is analyzed using GC-MS, and amine conversion ratio is 68%, nitrile
I.e. benzene acetonitrile is selectively 90%.
Embodiment 10
0.5 mM is added pressure bottle to methylbenzylamine, 0.02 gram of MnAPO-3,2 milliliters of DMFs,
Add 1 mM of TBHP, under 100 DEG C of normal pressures, react 3 hours, product is analyzed using GC-MS,
Amine conversion ratio is 99%, and nitrile is i.e. selective to methyl benzonitrile to be 71%.
Embodiment 11
0.5 mM of 4-Methoxybenzylamine, 1 gram of MnAPO-5,2 milliliters of acetonitriles are added pressure bottle, adds 1 mM
Phenethyl hydrogen peroxide, under 70 DEG C of normal pressures, reacts 2 hours, product is analyzed using GC-MS, and amine conversion ratio is 81%,
Nitrile is i.e. selective to methoxy benzonitrile to be 89%.
Embodiment 12
0.5 mM is added pressure bottle to trifluoromethyl benzylamine, 0.05 gram of MnAPO-5,2 milliliters of acetonitriles, adds 1 milli
Mole cyclohexyl hydroperoxide, under normal temperature and pressure, reacts 7 hours, product is analyzed using GC-MS, and amine conversion ratio is
81%, nitrile is i.e. selective to trifluoromethylbenzonitrile to be 89%.
Embodiment 13
0.5 mM is added pressure bottle to methylbenzylamine, 0.01 gram of MnAPO-5,2 milliliters of water, adds 1 mM of ring
Hexyl hydrogen peroxide, under normal temperature and pressure, reacts 7 hours, product is analyzed using GC-MS, and amine conversion ratio is 90%, nitrile
Class is i.e. selective to methyl benzonitrile to be 95%.
Embodiment 14
0.5 mM is added pressure bottle to methylbenzylamine, 0.25 gram of MnAPO-5,2 milliliters of Isosorbide-5-Nitrae-dioxane, then plus
Enter 1 mM of cyclohexyl hydroperoxide, under normal temperature and pressure, react 7 hours, product is analyzed using GC-MS, amine converts
Rate is 71%, and nitrile is i.e. selective to methyl benzonitrile to be 89%.
Claims (9)
1. a kind of for amine catalysis oxidation prepare nitrile compounds method it is characterised in that：Under catalyst action, using
Oxide is oxidant, and primary amine catalysis oxidation is synthesized nitrile compounds；
Described catalyst is metal-doped phosphate aluminium molecular sieve；
Described phosphate aluminium molecular sieve is one of AlPO-3, AlPO-4, AlPO-5, AlPO-31 or two or more；Doping metals
For one of Fe, Mn, Co, Ni, Cu or two or more；
In metal-doped phosphate aluminium molecular sieve, doping metals and the mol ratio of phosphorus and aluminium sum in phosphate aluminium molecular sieve are 1:50-1：
20.
2. in accordance with the method for claim 1 it is characterised in that：
At 0 DEG C -100 DEG C, the reaction time is 0.2-12 hour to reaction temperature.
3. in accordance with the method for claim 1 it is characterised in that：Substrate primary amine is aromatic series or Armeen；
Described primary aromatic amine is benzylamine, and to chlorobenzylamine, 4-Fluorobenzylamine, to bretylium tosylate, o-chlorine benzylamine, to methylbenzylamine, to three
Methyl fluoride benzylamine, one of 4-Methoxybenzylamine or two or more；
Described Armeen is n-butylamine, one of phenyl ethylamine or two or more.
4. in accordance with the method for claim 1 it is characterised in that：Reaction medium adopts liquid solvent；Solvent is：Water, acetonitrile,
One of 1,4- dioxane, oxolane, chlorobenzene, N,N-dimethylformamide, dimethyl sulfoxide (DMSO) or more than two kinds；
Every 0.5 mM of primary amine solvent load is 0.005-2 milliliter.
5. in accordance with the method for claim 1 it is characterised in that：Catalytic conversion process is with peroxide as oxygen source；Oxygen source
For：In cyclohexyl hydroperoxide, hydrogen peroxide, TBHP, phenethyl hydrogen peroxide, hyperis one
Plant or more than two kinds；Its consumption is 1-10 times of substrate molecule of primary amine mole.
6. in accordance with the method for claim 1 it is characterised in that：Every 0.5 mM of primary amine adopt 0.01 gram of catalyst amount-
1 gram.
7. in accordance with the method for claim 2 it is characterised in that：
60 DEG C of reaction temperature, 0.2 hour reaction time.
8. in accordance with the method for claim 5 it is characterised in that：Catalytic conversion process is with peroxide as oxygen source；Oxygen source
For：In cyclohexyl hydroperoxide, hydrogen peroxide, TBHP, phenethyl hydrogen peroxide, hyperis one
Plant or more than two kinds；Its consumption is 2 times of substrate molecule of primary amine mole.
9. in accordance with the method for claim 6 it is characterised in that：Every 0.5 mM of primary amine adopts 0.02 gram of catalyst amount.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351989A (en) * | 2000-11-15 | 2002-06-05 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing benzonitrile |
| KR100720834B1 (en) * | 2005-11-29 | 2007-05-23 | 한국화학연구원 | Methods to prepare oxygenated hydrocarbons using nickel containing porous materials |
| CN102802791A (en) * | 2009-04-17 | 2012-11-28 | 约翰逊马西有限公司 | Small Pore Molecular Sieve Supported Copper Catalysts Durable Against Lean/rich Aging For The Reduction Of Nitrogen Oxides |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351989A (en) * | 2000-11-15 | 2002-06-05 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing benzonitrile |
| KR100720834B1 (en) * | 2005-11-29 | 2007-05-23 | 한국화학연구원 | Methods to prepare oxygenated hydrocarbons using nickel containing porous materials |
| CN102802791A (en) * | 2009-04-17 | 2012-11-28 | 约翰逊马西有限公司 | Small Pore Molecular Sieve Supported Copper Catalysts Durable Against Lean/rich Aging For The Reduction Of Nitrogen Oxides |
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