CN109336923A - A method of alpha-aminonitriles are synthesized using mesoporous molecular sieve catalyst - Google Patents
A method of alpha-aminonitriles are synthesized using mesoporous molecular sieve catalyst Download PDFInfo
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- CN109336923A CN109336923A CN201811306743.6A CN201811306743A CN109336923A CN 109336923 A CN109336923 A CN 109336923A CN 201811306743 A CN201811306743 A CN 201811306743A CN 109336923 A CN109336923 A CN 109336923A
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
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Abstract
The invention discloses a kind of methods using mesoporous molecular sieve catalyst synthesis alpha-aminonitriles, and using phosphine aldehyde, ammonium chloride, Cymag as raw material, using ammonium hydroxide as reaction dissolvent, using mesoporous molecular sieve catalyst as catalyst, alpha-aminonitriles are made in one kettle way.Present invention employs mesoporous molecular sieve catalysts to catalyze and synthesize alpha-aminonitriles, and reaction condition is mild, and the reaction time is shorter, up to 85% or more, the rate of recovery of catalyst may be reused repeatedly yield 95% or more, and lost without obvious catalytic activity, there is preferable prospects for commercial application.
Description
Technical field
The present invention relates to a kind of synthetic methods of glufosinate-ammonium intermediate, and in particular to is synthesized using mesoporous molecular sieve catalyst
The method of alpha-aminonitriles
Background technique
2- amino -4- (methyl ethoxy) phosphono butyronitrile (alpha-aminonitriles, structure is as shown in formula II) is glufosinate-ammonium preparation
An important intermediate in the process.Strecker reaction is to synthesize an important reaction of alpha-aminonitriles, reaction equation
It is as follows:
Strecker reaction process is mature, and reaction condition is of less demanding, stable yield, is suitable for industrialized production.Due to
It is related to the use of Cymag extremely toxic substance, in order to ensure process efficient is low useless, therefore seems especially to the control of reaction yield
It is important, and the yield of existing synthesis alpha-aminonitriles method is generally lower than 70%, raw material sources are difficult, easily pollute the environment.
Summary of the invention
The purpose of the present invention is for the reaction time is longer, reaction selectivity is not high, yield is lower in existing synthetic method
The case where, a kind of method using mesoporous molecular sieve catalyst synthesis alpha-aminonitriles is provided, the conversion ratio of reaction is reached
100%, selectivity is also up to 90%.
Technical scheme is as follows:
A method of alpha-aminonitriles being synthesized using mesoporous molecular sieve catalyst, this method is with phosphine aldehyde, ammonium chloride, Cymag
For raw material, using ammonium hydroxide as reaction dissolvent, using mesoporous molecular sieve catalyst as catalyst, alpha-aminonitriles are made in one kettle way.
The method of synthesis alpha-aminonitriles of the present invention, specifically includes: by ammonium chloride, Cymag, ammonium hydroxide and mesoporous point
Sub- sieve catalyst is put into reaction kettle, cooling, is passed through nitrogen protection and reaction product is avoided to aoxidize, phosphine aldehyde (structure is slowly added dropwise
As shown in formula I), slight exotherm is reacted, to prevent local temperature excessively high, control dropping temperature is no more than 20 DEG C；After being added dropwise,
Reaction temperature is controlled at 20~80 DEG C, is stirred to react 2~10h, after reaction, deamination is depressurized, obtains 2- amino -4- (methyl
Ethyoxyl) phosphono butyronitrile aqueous solution.
The molar ratio of the phosphine aldehyde, Cymag and ammonium chloride is 1:1~1.5:1~3.5, preferably 1:1.1~1.2:
1.3~3.5.
The concentration of the ammonium hydroxide is 18~22%；The weight ratio of ammonium hydroxide and phosphine aldehyde is 3~6:1.
The mesoporous molecular sieve catalyst and phosphine aldehyde weight ratio is 0.2~5:100, preferably 1~4:100.
The mesoporous molecular sieve catalyst is sequential silicon-based mesoporous point of sequential silicon-based mesopore molecular sieve or metal-modified
Son sieve；The sequential silicon-based mesopore molecular sieve is MCM-41 molecular sieve, MCM-48 molecular sieve, SBA-n molecular sieve, n=3,15；
The metal is one of Al, Ni, Fe, Zr, Cu, Ti, Co etc. or a variety of mixing；Sequential silicon-based mesoporous point of metal-modified
Son sieve is successively made through metal salt solution immersion load, dry, roasting by sequential silicon-based mesopore molecular sieve.What the present invention used
Mesoporous molecular sieve catalyst specific surface area with higher, the pore distribution and higher hydro-thermal of macropore capacity and rule
Stability, and be easily recycled, it is suitable for industrialized production.
Preferably, the mesoporous molecular sieve catalyst is Zr-MCM-41 mesopore molecular sieve, Zr-MCM-48 mesoporous molecular
Sieve, Zr-SBA-3 mesopore molecular sieve, Ti-SBA-15 mesopore molecular sieve；Wherein, the Zr-MCM-41 mesopore molecular sieve, Zr-
The load capacity of Zr is 0.1~0.6%, Ti-SBA-15 mesoporous molecular in MCM-48 mesopore molecular sieve, Zr-SBA-3 mesopore molecular sieve
The load capacity of Ti is 0.2~0.5% in sieve.
Preferably, phosphine aldehyde is added dropwise in 0.5~1h；After being added dropwise, reaction temperature is 30~50 DEG C, and the reaction time is
2~5h.
Compared to the prior art, beneficial effects of the present invention:
The present invention uses one kettle way, selects efficiently be catalyzed with reusable mesoporous molecular sieve catalyst for the first time
Strecker reacts synthesizing amino nitrile compounds, and simple process, reaction condition is mild, and the reaction time is shorter, and conversion ratio reaches
100%, significantly improve reaction yield, yield is up to 85% or more.Catalyst easily recycles, the rate of recovery 95% or more, and
It may be reused repeatedly, and lost without obvious catalytic activity, there is preferable prospects for commercial application.
Specific embodiment
The present invention is described in further details below in conjunction with specific embodiment.These embodiments are merely to illustrate this hair
Bright, the present invention is not limited by the following examples.All equivalent change or modifications made according to the present invention should all cover at this
Within the protection scope of invention.Implementation condition unless otherwise instructed is usually the condition in routine experiment.
Embodiment 1
By 49g Cymag, 107g ammonium chloride, 492g ammonium hydroxide (mass fraction 20%, similarly hereinafter) and 1.64g Zr-MCM-41
Mesopore molecular sieve (load capacity of Zr is 0.2%) is put into reaction kettle, is cooled to 15 DEG C and subsequent reactions heat release is avoided to prevent temperature
Height is spent, stirring is opened, is passed through nitrogen protection, 164g phosphine aldehyde is slowly added dropwise, control dropping temperature is no more than 20 DEG C；It is added dropwise
Control temperature is stirred to react 5h at 30 DEG C afterwards, and gas-chromatography monitors phosphine aldehyde conversion ratio up to 100%, and reaction terminates, and depressurizes deamination,
Obtain the aqueous solution of 2- amino -4- (methyl ethoxy) phosphono butyronitrile, yield 87.3%.
Embodiment 2
By 49g Cymag, 107g ammonium chloride, 680g ammonium hydroxide and the 3.8g Zr-MCM-41 mesopore molecular sieve (load capacity of Zr
0.2%) to put into reaction kettle, stirring is opened, 15 DEG C is cooled to, is passed through nitrogen protection, 164g phosphine aldehyde is slowly added dropwise, is controlled
Dropping temperature is no more than 20 DEG C；Temperature is controlled after being added dropwise at 30 DEG C, is stirred to react 3h, after reaction, is depressurized deamination, is obtained
To the aqueous solution of 2- amino -4- (methyl ethoxy) phosphono butyronitrile, yield 91.2%.
Embodiment 3
By 51g Cymag, 60g ammonium chloride, 492g ammonium hydroxide and 3.8g Zr-MCM-41 mesopore molecular sieve, (load capacity of Zr is
0.2%) it puts into reaction kettle, is cooled to 15 DEG C, open stirring, be passed through nitrogen protection, 164g phosphine aldehyde, control drop is slowly added dropwise
Heating degree is no more than 20 DEG C；Temperature is controlled after being added dropwise at 50 DEG C, is stirred to react 3h, after reaction, is depressurized deamination, is obtained
The aqueous solution of 2- amino -4- (methyl ethoxy) phosphono butyronitrile, yield 85.4%.
Embodiment 4
By 49g Cymag, 160g ammonium chloride, 680g ammonium hydroxide and the 3.8g Zr-MCM-48 mesopore molecular sieve (load capacity of Zr
0.2%) to put into reaction kettle, 15 DEG C are cooled to, stirring is opened, is passed through nitrogen protection, 164g phosphine aldehyde is slowly added dropwise, is controlled
Dropping temperature is no more than 20 DEG C；Temperature is controlled after being added dropwise at 30 DEG C, is stirred to react 2h, after reaction, is depressurized deamination, is obtained
To the aqueous solution of 2- amino -4- (methyl ethoxy) phosphono butyronitrile, yield 85.6%.
Embodiment 5
By 51g Cymag, 107g ammonium chloride, 550g ammonium hydroxide and the 4.0g Ti-SBA-15 mesopore molecular sieve (load capacity of Ti
0.3%) to put into reaction kettle, 15 DEG C are cooled to, stirring is opened, is passed through nitrogen protection, 164g phosphine aldehyde is slowly added dropwise, is controlled
Dropping temperature is no more than 20 DEG C；Temperature is controlled after being added dropwise at 30 DEG C, is stirred to react 3h, after reaction, is depressurized deamination, is obtained
To the aqueous solution of 2- amino -4- (methyl ethoxy) phosphono butyronitrile, yield 89.1%.
Embodiment 6
By 51g Cymag, 60g ammonium chloride, 550g ammonium hydroxide and 6.0g Zr-MCM-48 mesopore molecular sieve, (load capacity of Zr is
0.2%) it puts into reaction kettle, is cooled to 15 DEG C, open stirring, be passed through nitrogen protection, 164g phosphine aldehyde, control drop is slowly added dropwise
Heating degree is no more than 20 DEG C；Temperature is controlled after being added dropwise at 30 DEG C, is stirred to react 2h, after reaction, is depressurized deamination, is obtained
The aqueous solution of 2- amino -4- (methyl ethoxy) phosphono butyronitrile, yield 86.3%.
Embodiment 7
By 51g Cymag, 107g ammonium chloride, 550g ammonium hydroxide and 3.8g Zr-SBA-3 mesopore molecular sieve, (load capacity of Zr is
0.2%) it puts into reaction kettle, is cooled to 15 DEG C, open stirring, be passed through nitrogen protection, 164g phosphine aldehyde, control drop is slowly added dropwise
Heating degree is no more than 20 DEG C；Temperature is controlled after being added dropwise at 30 DEG C, is stirred to react 3h, after reaction, is depressurized deamination, is obtained
The aqueous solution of 2- amino -4- (methyl ethoxy) phosphono butyronitrile, yield 89.0%.
Embodiment 8
By 51g Cymag, 107g ammonium chloride, 550g ammonium hydroxide and the 4.0g Ti-SBA-15 mesopore molecular sieve (load capacity of Ti
It is 0.3%, is reused through 5 times) it puts into reaction kettle, 15 DEG C are cooled to, stirring is opened, is passed through nitrogen protection, is slowly dripped
Add 164g phosphine aldehyde, control dropping temperature is no more than 20 DEG C；Temperature is controlled after being added dropwise at 30 DEG C, is stirred to react 3h, reaction knot
Shu Hou depressurizes deamination, obtains the aqueous solution of 2- amino -4- (methyl ethoxy) phosphono butyronitrile, yield 88.8%.
Embodiment 9
49g Cymag, 107g ammonium chloride, 680g ammonium hydroxide are put into reaction kettle, are cooled to 15 DEG C, opens stirring, is led to
Enter nitrogen protection, 164g phosphine aldehyde is slowly added dropwise, control dropping temperature is no more than 20 DEG C；After being added dropwise control temperature at 30 DEG C,
It is stirred to react 3h, after reaction, deamination is depressurized, obtains the aqueous solution of 2- amino -4- (methyl ethoxy) phosphono butyronitrile, receive
Rate 70.0%.
Claims (10)
1. a kind of method using mesoporous molecular sieve catalyst synthesis alpha-aminonitriles, it is characterised in that this method is with phosphine aldehyde, chlorination
Ammonium, Cymag are raw material, and using ammonium hydroxide as reaction dissolvent, using mesoporous molecular sieve catalyst as catalyst, alpha-amido is made in one kettle way
Nitrile.
2. the method for synthesis alpha-aminonitriles according to claim 1, characterized by comprising: by ammonium chloride, Cymag, ammonia
Water and mesoporous molecular sieve catalyst mixing, it is cooling, phosphine aldehyde is added dropwise under nitrogen protection, control dropping temperature is no more than 20 DEG C；Drop
After adding, 20~80 DEG C of 2~10h of reaction obtain 2- amino -4- (methyl ethoxy) phosphono butyronitrile after reaction
Aqueous solution.
3. the method for synthesis alpha-aminonitriles according to claim 1 or 2, it is characterised in that the phosphine aldehyde, Cymag with
The molar ratio of ammonium chloride is 1:1~1.5:1~3.5.
4. the method for synthesis alpha-aminonitriles according to claim 3, it is characterised in that phosphine aldehyde, Cymag and the chlorination
The molar ratio of ammonium is 1:1.1~1.2:1.3~3.5.
5. it is according to claim 1 or 2 synthesis alpha-aminonitriles method, it is characterised in that the ammonia concn be 18~
22%；The weight ratio of ammonium hydroxide and phosphine aldehyde is 3~6:1.
6. the method for synthesis alpha-aminonitriles according to claim 1 or 2, it is characterised in that the mesopore molecular sieve catalysis
Agent is the sequential silicon-based mesopore molecular sieve of sequential silicon-based mesopore molecular sieve or metal-modified；The mesoporous molecular sieve catalyst with
Phosphine aldehyde weight ratio is 0.2~5:100, preferably 1~4:100.
7. the method for synthesis alpha-aminonitriles according to claim 6, it is characterised in that the sequential silicon-based mesoporous molecular
Sieve is MCM-41 molecular sieve, MCM-48 molecular sieve, SBA-n molecular sieve；N=3,15；The metal be Al, Ni, Fe, Zr, Cu,
One of Ti, Co etc. or a variety of mixing.
8. the method for synthesis alpha-aminonitriles according to claim 7, it is characterised in that the mesoporous molecular sieve catalyst
For Zr-MCM-41 mesopore molecular sieve, Zr-MCM-48 mesopore molecular sieve, Zr-SBA-3 mesopore molecular sieve, mesoporous point of Ti-SBA-15
Son sieve；Wherein, the Zr-MCM-41 mesopore molecular sieve, Zr-MCM-48 mesopore molecular sieve, in Zr-SBA-3 mesopore molecular sieve
The load capacity that the load capacity of Zr is Ti in 0.1~0.6%, Ti-SBA-15 mesopore molecular sieve is 0.2~0.5%.
9. the method for synthesis alpha-aminonitriles according to claim 2, it is characterised in that after being added dropwise, reaction temperature 30
~50 DEG C, the reaction time is 2~5h.
10. the method for synthesis alpha-aminonitriles according to claim 1 or 2, it is characterised in that after reaction, reaction solution subtracts
Pressure-off ammonia.
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| CN201811306743.6A CN109336923B (en) | 2018-11-05 | 2018-11-05 | Method for synthesizing alpha-aminonitrile by adopting mesoporous molecular sieve catalyst |
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| CN201811306743.6A CN109336923B (en) | 2018-11-05 | 2018-11-05 | Method for synthesizing alpha-aminonitrile by adopting mesoporous molecular sieve catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426502A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Process for producing nitrile |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399240A (en) * | 2011-12-27 | 2012-04-04 | 江苏优士化学有限公司 | Improved synthesis method for glufosinate and analogue thereof |
| CN105481894A (en) * | 2015-11-27 | 2016-04-13 | 浙江新安化工集团股份有限公司 | New method or preparing glufosinate ammonium salt |
| CN107880072A (en) * | 2017-10-26 | 2018-04-06 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of glufosinate-ammonium |
-
2018
- 2018-11-05 CN CN201811306743.6A patent/CN109336923B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399240A (en) * | 2011-12-27 | 2012-04-04 | 江苏优士化学有限公司 | Improved synthesis method for glufosinate and analogue thereof |
| CN105481894A (en) * | 2015-11-27 | 2016-04-13 | 浙江新安化工集团股份有限公司 | New method or preparing glufosinate ammonium salt |
| CN107880072A (en) * | 2017-10-26 | 2018-04-06 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of glufosinate-ammonium |
Non-Patent Citations (2)
| Title |
|---|
| GREENLEE, W. J.: "Synthesis of β,γ-unsaturated amino acids by the Strecker reaction", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| 尹科等: "新型氰化物在Strecker反应合成α-氨基腈中的应用", 《化学通报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426502A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Process for producing nitrile |
| CN114426502B (en) * | 2020-10-13 | 2024-02-09 | 中国石油化工股份有限公司 | Process for the preparation of nitriles |
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