CN109438396A - A kind of preparation method of tetrahydrofuran -3- methylamine - Google Patents
A kind of preparation method of tetrahydrofuran -3- methylamine Download PDFInfo
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- CN109438396A CN109438396A CN201811290572.2A CN201811290572A CN109438396A CN 109438396 A CN109438396 A CN 109438396A CN 201811290572 A CN201811290572 A CN 201811290572A CN 109438396 A CN109438396 A CN 109438396A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The present invention provides a kind of preparation method of tetrahydrofuran -3- methylamine, including raw material, aminating reaction, hydrogenation reaction is added.Using tetrahydrofuran -3- formaldehyde as raw material, water is as reaction dissolvent, and under load type bimetal catalyst effect and aminating reaction occurs for liquefied ammonia, then is passed through hydrogen progress reduction reaction and obtains tetrahydrofuran -3- methylamine, and product purity is up to 99.8%, and yield is up to 99.1%.The preparation method of tetrahydrofuran -3- methylamine of the present invention has high income, and catalyst amount is few, advantage easy to operate, at low cost, is suitble to industrialized production.
Description
Technical field
The present invention relates to pesticide intermediate synthesis technical fields, and in particular to a kind of preparation side of tetrahydrofuran -3- methylamine
Method.
Background technique
Tetrahydrofuran -3- methylamine is to prepare one of important intermediate of dinotefuran, and there are mainly two types of existing production technologies:
(1), one is using tetrahydro 3 furanmethanol as raw material, tetrahydrofuran-is made by chloro, nitrile generation and hydrogenation three-step reaction
3- methylamine, but the process route is long, yield is low, and it is at high cost, and will use Cymag violent in toxicity, process safety is not high.
(2), another kind is then that tetrahydrofuran -3- first is made by amination and hydrogenation reaction using tetrahydrofuran -3- formaldehyde as raw material
Amine, it is also fewer about the report of the process route at present, technology be not it is very mature, be unsuitable for industrialized production.
Zhejiang Jetta is reported in patent CN106397372A, and using tetrahydrofuran -3- formaldehyde as raw material, 5%Pd/ C is to urge
Agent, catalyst usage amount are 9%-11wt%, and concentrated ammonia liquor is added, and are passed through 2.5Mpa hydrogen, and tetrahydro furan is made in 70 DEG C of reaction 2h
It mutters -3- methylamine, yield is only 89.93%.The technique uses ammonium hydroxide as ammonia source, but ammoniacal liquor mass concentration is only 25%, ammonia
Content is lower, needs to put into a large amount of ammonium hydroxide and is just able to achieve reaction；In post-processing, water is steamed by air-distillation, energy consumption
It is higher.Although the technique reaction time is shorter, its product yield is lower, and catalyst amount is larger, higher cost, and has
A large amount of waste water generate, and are unfavorable for industrialized production.
In patent CN107501213A, using ammonia methanol as ammonia source, the content of ammonia is still relatively low in ammonia methanol, only
It is 15%, also needs to consume a large amount of methanolic ammonia solutions.Although the catalyst system product yield is higher, reduction amination catalyst
Dosage be tetrahydrofuran -3- formaldehyde quality 10-20%, catalyst amount is big, and the reaction time is longer, is not suitable for big
Production.
It is preparing tetrahydrofuran -3- methylamine in the prior art, is having the disadvantage that
Reaction time shorter reaction system often has that product yield is low；
The problems such as it is big often to there is catalyst usage amount in the reaction system of high product yield, and the reaction time is longer；
Mostly in the prior art is using concentrated ammonia liquor or methanol ammonia, and the content of ammonia is lower, needs to be added large excess of concentrated ammonia liquor
Or methanol ammonia, the inventory of solvent are larger.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of preparation method of tetrahydrofuran -3- methylamine, with reality
Existing following goal of the invention:
Under the premise of guaranteeing tetrahydrofuran -3- methylamine high yield
(1) reaction time is reduced；
(2) usage amount of catalyst is reduced；
(3) dosage of solvent is reduced.
For achieving the above object, the present invention takes following technical scheme:
A kind of preparation method of tetrahydrofuran -3- methylamine, comprising the following steps: raw material, aminating reaction, hydrogenation reaction is added.
The addition raw material water, load type bimetal catalyst and tetrahydrofuran -3- formaldehyde is added in reaction kettle, nitrogen
After gas displacement, it is passed through liquefied ammonia.
Tetrahydrofuran -3- the formaldehyde, water, liquefied ammonia and load type bimetal catalyst mass ratio be 1:0.2-2:0.2-
2:0.01-0.1.
The load type bimetal catalyst is made of bimetallic and carrier metal oxide.
The first described bimetallic metal is Rh, and second of metal is one of Sn, Fe, Cu, Co, Ru, Ni；Carrier
Metal oxide is one of aluminium oxide, titanium oxide, silica.
The load capacity of the Rh is 0.1%- 5%；The load capacity of second of metal is 0.1%-5%.
The aminating reaction, reaction temperature are 50-140 DEG C, react and imine intermediate is made, until tetrahydrofuran -3- formaldehyde
GC detection level≤0.1%, aminating reaction terminate.
The hydrogenation reaction, reaction temperature are 50-140 DEG C, and Hydrogen Vapor Pressure is 1.0-4.0Mpa in reaction kettle, and the reaction was continued
To tetrahydrofuran -3- imines GC detection level≤0.3%, reaction was completed.
The preparation method further includes post-processing；The post-processing, cooling, reaction solution Filtration of catalyst, filters out
Catalyst continues to apply, and reaction solution rectifying obtains tetrahydrofuran -3- methylamine.
The preparation method, total reaction time 1-5h.
The yield of tetrahydrofuran -3- methylamine is 90.5-99.1%, purity 99.1-99.8%.
Preferred technical solution are as follows:
In above-mentioned steps one, the load type bimetal catalyst is made of bimetallic and carrier metal oxide, double gold
The first metal belonged to is Rh, and second of metal is one of Sn, Cu, Ru, and the load capacity of Rh is 2.8-3.5%, second of gold medal
The load capacity of category is 1-2%；
The carrier metal oxide is aluminium oxide；
Tetrahydrofuran -3- formaldehyde, water, liquefied ammonia and load type bimetal catalyst mass ratio be 1:0.5-1.5:0.4-0.6:
0.04-0.07。
Step 1 is consistent with the reaction temperature of step 2, and reaction temperature is 78-82 DEG C；
Step 2, Hydrogen Vapor Pressure is 1.9-2.1Mpa in reaction kettle；
Carrier metal oxide is aluminium oxide；
Preferred technical solution, the yield of tetrahydrofuran -3- methylamine are 95.4-99.1%；Purity is 99.4-99.8%；Overall reaction
Time is 2.1-3h.
Further preferred technical solution are as follows:
In above-mentioned steps one, the load type bimetal catalyst is made of bimetallic and carrier metal oxide, double gold
The first metal belonged to is Rh, and second of metal is Sn,
The load capacity of Rh is 3%, and the load capacity of second of metal is 1.5%；
The carrier metal oxide is aluminium oxide；
Tetrahydrofuran -3- formaldehyde, water, liquefied ammonia and load type bimetal catalyst mass ratio be 1:0.5:0.5:0.05.
Step 1 is consistent with the reaction temperature of step 2, and reaction temperature is 80 DEG C；
Step 2, Hydrogen Vapor Pressure is 2Mpa in reaction kettle；
Carrier metal oxide is aluminium oxide；
Further preferred technical solution, the yield of tetrahydrofuran -3- methylamine are 99.1%；Purity is 99.8%；Total reaction time
For 2.1h.
The preparation method of the tetrahydrofuran -3- methylamine, filters out catalyst after reaction, and catalyst can be used directly
In next secondary response.
Mostly in the prior art is using concentrated ammonia liquor or methanol ammonia, and the content of ammonia is lower, needs to be added large excess of dense
The inventory of ammonium hydroxide or methanol ammonia, solvent is larger, and using water as solvent in the present invention, the source using liquefied ammonia as ammonia,
The dosage of solvent can be greatly reduced, while guaranteeing that ammonia is enough.
The present invention by adopting the above technical scheme, obtains following technical effect:
(1) tetrahydrofuran -3- methylamine prepared by the present invention, yield 90.5-99.1%, purity 99.1-99.8% are preferably received
Rate is 95.4-99.1%；Purity is 99.4-99.8%；Yield is up to 99.1%, and product purity is up to 99.8%.
(2) present invention prepares tetrahydrofuran -3- methylamine using load type bimetal catalyst, and catalyst usage amount is few, urges
The dosage of agent is the 1-10%, preferably 4-7% of tetrahydrofuran -3- formaldehyde quality；And reaction is completed within 5 hours, instead
It answers efficiency to improve, is conducive to industrialized production.
(3) using liquefied ammonia as ammonia source, solvent usage amount is reduced, and post-processing rectification process amount reduces, and saves energy consumption；Tetrahydro furan
- 3- formaldehyde, water, liquid ammonia quality ratio mutter as 1:0.2-2:0.2-2.
Specific embodiment
A kind of preparation method of the tetrahydrofuran -3- methylamine of embodiment 1
The following steps are included:
(1) raw material is added
In autoclave, water 50g, 1.5%Sn-3%Rh/Al is added2O3Catalyst 5g, tetrahydrofuran -3- formaldehyde 100g；Nitrogen
Gas is replaced 3 times, and liquefied ammonia 50g is passed through.
(2) aminating reaction
80 DEG C are warming up to, reaction to tetrahydrofuran -3- formaldehyde GC detection level≤0.1%.
(3) hydrogenation reaction
It is passed through hydrogen 2.0Mpa, the reaction was continued, and reaction temperature is 80 DEG C；To tetrahydrofuran -3- imines GC detection level≤0.3%
Reaction was completed, total reaction time 2.1h.
(4) it post-processes
It is cooled to room temperature, Filtration of catalyst, reaction solution rectifying (20kpa, 100 DEG C of kettle temperature, 80 DEG C of top temperature) obtains tetrahydro furan
Mutter -3- methylamine 100.2g, yield 99.1%, purity 99.8%.
The experiment of embodiment 2-6 catalyst type single factor analysis
On the basis of embodiment 1, only change the type of second of metal, remaining operation carries out single factor analysis with embodiment 1
Experiment, the results are shown in Table 1.
1 different catalysts type of table reacts contrast table
Seen from table 1, embodiment 1,3,6 is preferred embodiment, and the type of second of metal is preferably Sn, Cu, Ru in catalyst,
For remaining condition with implementing 1, the yield of corresponding tetrahydrofuran -3- methylamine is 95.4-99.1%, purity 99.6-99.8%, total anti-
It is 2.1-2.4h between seasonable.
A kind of preparation method of the tetrahydrofuran -3- methylamine of embodiment 7
The following steps are included:
(1) raw material is added
In autoclave, water 150g, 1.5%Sn-3%Rh/Al is added2O3Catalyst 5g, tetrahydrofuran -3- formaldehyde 100g；
Nitrogen is replaced 3 times, and liquefied ammonia 50g is passed through.
(2) aminating reaction
80 DEG C are warming up to, tetrahydrofuran -3- formaldehyde G/C content≤0.1% is detected, aminating reaction terminates.
(3) hydrogenation reaction
It is passed through hydrogen 2.0Mpa, reaction temperature is 80 DEG C, and reaction was completed for detection tetrahydrofuran -3- imines G/C content≤0.3%, always
Reaction response 4.7h.
(4) it post-processes
It is cooled to room temperature；Reaction terminates, Filtration of catalyst, reaction solution rectifying (20kpa, 100 DEG C of kettle temperature, 80 DEG C of top temperature)
To tetrahydrofuran -3- methylamine 97.2g, yield 96.1%, purity 99.5%.
The dosage of water on the basis of embodiment 1, is only increased to 150g by 50g by embodiment 7, remaining with embodiment 1,
Yield is declined, and is reduced unobvious.
A kind of preparation method of tetrahydrofuran -3- methylamine of embodiment 8-11
Tetrahydrofuran -3- methylamine is prepared using different water and liquefied ammonia dosage, remaining operation is the same as embodiment 7.
The different water of table 2 and liquefied ammonia quantitative response contrast table
As can be seen from Table 2, embodiment 1,7,8 is preferred embodiment, i.e. tetrahydrofuran -3- formaldehyde: water: liquefied ammonia: the quality of catalyst
Ratio is preferably 100:50-150:50:5, and, with embodiment 1, corresponding yield is 95.2-99.1%, purity 99.5- for remaining
99.8%, total reaction time 2.1-2.8h.
A kind of preparation method of the tetrahydrofuran -3- methylamine of embodiment 12
The following steps are included:
(1) raw material is added
In autoclave, water 100g, 0.5%Sn-3%Rh/Al is added2O3Catalyst 5g, tetrahydrofuran -3- formaldehyde 100g；
Nitrogen is replaced 3 times, and liquefied ammonia 50g is passed through.
(2) aminating reaction
80 DEG C are warming up to, tetrahydrofuran -3- formaldehyde G/C content≤0.1% is detected.
(3) hydrogenation reaction
It is passed through hydrogen 2.0Mpa, 80 DEG C of reaction temperature, reaction was completed for detection tetrahydrofuran -3- imines G/C content≤0.3%, total anti-
It is 3.5h between seasonable.
(4) it post-processes
It is cooled to room temperature；Reaction terminates, Filtration of catalyst, reaction solution rectifying (20kpa, 100 DEG C of kettle temperature, 80 DEG C of top temperature)
To tetrahydrofuran -3- methylamine 91.5g, yield 90.5%, purity 99.0%.
Embodiment 12 increases to 100g on the basis of embodiment 1, by the dosage of water, while the load capacity of Sn being changed into
0.5%, the results show that embodiment 12 is compared with embodiment 1, the yield and purity of tetrahydrofuran -3- methylamine are significantly reduced；By
The result of above-described embodiment 7-11 is preferred dosage it is found that the dosage of water is 100g, will not be to tetrahydrofuran -3- methylamine
Yield and purity cause very big influence, therefore, when the load capacity for reducing Sn is 0.5%, can be substantially reduced the yield of product and pure
Degree.
Embodiment 13-15
On the basis of embodiment 12, change the content of Rh and the content of Sn, using different loads amount catalyst preparation tetrahydrofuran-
3- methylamine, remaining operation the results are shown in Table 3 with embodiment 12.
The catalyst reaction contrast table of 3 different loads amount of table
Embodiment 14-17 is the single factor analysis experiment of the content of Sn, it is seen then that embodiment 16 and 17 is preferred embodiment, that is, Sn
Content be preferably 1.2-1.8%, corresponding product yield is 97.4-98.1%, purity 99.4-99.6%, and total reaction time is
2.3-2.5h。
A kind of preparation method of the tetrahydrofuran -3- methylamine of embodiment 18
The following steps are included:
(1) raw material is added
In autoclave, water 100g, 1.5%Sn-3%Rh/Al is added2O3Catalyst 1g, tetrahydrofuran -3- formaldehyde 100g；
Nitrogen is replaced 3 times, and liquefied ammonia 50g is passed through.
(2) aminating reaction
80 DEG C are warming up to, tetrahydrofuran -3- formaldehyde G/C content≤0.1% is detected.
(3) hydrogenation reaction
It is passed through hydrogen 2.0Mpa, reaction temperature is 80 DEG C, and reaction was completed for detection tetrahydrofuran -3- imines G/C content≤0.3%, always
Reaction time is 3 h.
(4) it post-processes
It is cooled to room temperature；Reaction terminates, Filtration of catalyst, reaction solution rectifying (20kpa, 100 DEG C of kettle temperature, 80 DEG C of top temperature)
To tetrahydrofuran -3- methylamine 97.5g, yield 96.4%, purity 99.5%.
Embodiment 18 is to increase the dosage of water on the basis of embodiment 1 to 100g, reduces the dosage of catalyst to 1g,
Remaining is with embodiment 1, the results show that the dosage when water increases to 100g, the dosage of catalyst is reduced to tetrahydrofuran -3- formaldehyde
1% when, although yield and purity decrease, but it is not very big for reducing degree.
Embodiment 19-21
Different catalysts and its dosage prepare tetrahydrofuran -3- methylamine, remaining operation is the same as embodiment 18；
Table 4 changes catalyst amount and reacts contrast table
As it can be seen that embodiment 18,19 is preferred embodiment, i.e. the catalyst amount 4-7% that is preferably tetrahydrofuran -3- formaldehyde quality,
The yield of corresponding product is 96.4-97.5%, purity 99.5-99.7%, total reaction time 2.9-3h.
Comparative example 22 is tested using single-metal reforming catalyst
The following steps are included:
(1) raw material is added
In autoclave, water 50g, 5%Rh/Al is added2O3Catalyst 5g, tetrahydrofuran -3- formaldehyde 100g；Nitrogen displacement 3
It is secondary, it is passed through liquefied ammonia 50g.
(2) aminating reaction
80 DEG C are warming up to, tetrahydrofuran -3- formaldehyde G/C content≤0.1% is detected, aminating reaction terminates.
(3) hydrogenation reaction
It is passed through hydrogen 2.0Mpa, reaction temperature is 80 DEG C, and reaction was completed for detection tetrahydrofuran -3- imines G/C content≤0.3%, always
Reaction time 10.5h.
(4) it post-processes
It is cooled to room temperature；Reaction terminates, Filtration of catalyst, reaction solution rectifying (20kpa, 100 DEG C of kettle temperature, 80 DEG C of top temperature)
To tetrahydrofuran -3- methylamine 81.1g, yield 80.2%, purity 99.0%.
Comparative example 23-24
Tetrahydrofuran -3- methylamine is prepared using different monometallic supported catalysts, remaining operation is the same as comparative example 22.
5 different catalysts of table react contrast table
Comparative example 22-25's the results show that when using single-metal reforming catalyst prepare tetrahydrofuran -3- methylamine when, overall reaction
Time reaches 6-10.5h, and yield is only 84.3-87.5%, purity 99.0-99.1%.
The yield of tetrahydrofuran -3- methylamine of the present invention is calculated with tetrahydrofuran -3- formaldehyde.
Unless specifically indicated, the ratio that the present invention uses is mass ratio, and the percentage of use is quality percentage
Than.
Above embodiments are only used to illustrate the present invention, and are not intended as limitation of the invention.To institute of the embodiment of the present invention
Any simple modification, change and the equivalence changes made, within the scope of the present invention.
Claims (9)
1. a kind of preparation method of tetrahydrofuran -3- methylamine, it is characterised in that: anti-including raw material, aminating reaction plus hydrogen is added
It answers.
2. a kind of preparation method of tetrahydrofuran -3- methylamine according to claim 1, it is characterised in that: the addition is former
Water, load type bimetal catalyst and tetrahydrofuran -3- formaldehyde are added in reaction kettle material, after nitrogen displacement, are passed through liquefied ammonia.
3. a kind of preparation method of tetrahydrofuran -3- methylamine according to claim 2, it is characterised in that: the tetrahydro furan
Mutter -3- formaldehyde, water, liquefied ammonia and load type bimetal catalyst mass ratio be 1:0.2-2:0.2-2:0.01-0.1.
4. a kind of preparation method of tetrahydrofuran -3- methylamine according to claim 2, it is characterised in that: the support type
Bimetallic catalyst is made of bimetallic and carrier metal oxide.
5. a kind of preparation method of tetrahydrofuran -3- methylamine according to claim 4, it is characterised in that: the bimetallic
The first metal be Rh, second metal is one of Sn, Fe, Cu, Co, Ru, Ni；Carrier metal oxide is oxidation
One of aluminium, titanium oxide, silica.
6. a kind of preparation method of tetrahydrofuran -3- methylamine according to claim 5, it is characterised in that: the Rh's is negative
Carrying capacity is 0.1%- 5%；The load capacity of second of metal is 0.1%-5%.
7. a kind of preparation method of tetrahydrofuran -3- methylamine according to claim 1, it is characterised in that: the amination is anti-
It answers, reaction temperature is 50-140 DEG C, reacts and imine intermediate is made, until tetrahydrofuran -3- formaldehyde GC detection level≤0.1%, amine
Changing reaction terminates.
8. a kind of preparation method of tetrahydrofuran -3- methylamine according to claim 1, which is characterized in that described plus hydrogen is anti-
It answers, reaction temperature is 50-140 DEG C, and Hydrogen Vapor Pressure is 1.0-4.0Mpa in reaction kettle, and the reaction was continued to tetrahydrofuran -3- imines
Reaction was completed for GC detection level≤0.3%.
9. a kind of preparation method of tetrahydrofuran -3- methylamine according to claim 1, which is characterized in that the preparation side
Method, total reaction time 1-5h.
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| JPH09110848A (en) * | 1995-10-13 | 1997-04-28 | Mitsui Toatsu Chem Inc | Production of 3-(tetrahydrofuryl)methylamine |
| US5990323A (en) * | 1998-10-23 | 1999-11-23 | Eastman Chemical Company | Preparation of amines |
| CN106397372A (en) * | 2015-07-27 | 2017-02-15 | 浙江捷达科技有限公司 | 3-methylamine tetrahydrofuran preparation method |
| CN107501213A (en) * | 2017-08-23 | 2017-12-22 | 中国科学院兰州化学物理研究所 | A kind of synthetic method of 3 amino methyl tetrahydrofuran |
| CN107935970A (en) * | 2017-12-27 | 2018-04-20 | 浙江先锋科技股份有限公司 | A kind of preparation method of 3 methylamine tetrahydrofuran of high-purity low water content |
| CN108424406A (en) * | 2018-05-05 | 2018-08-21 | 湖北荆洪生物科技股份有限公司 | A kind of production technology of 3- aminomethyls tetrahydrofuran |
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2018
- 2018-10-31 CN CN201811290572.2A patent/CN109438396B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09110848A (en) * | 1995-10-13 | 1997-04-28 | Mitsui Toatsu Chem Inc | Production of 3-(tetrahydrofuryl)methylamine |
| US5990323A (en) * | 1998-10-23 | 1999-11-23 | Eastman Chemical Company | Preparation of amines |
| CN106397372A (en) * | 2015-07-27 | 2017-02-15 | 浙江捷达科技有限公司 | 3-methylamine tetrahydrofuran preparation method |
| CN107501213A (en) * | 2017-08-23 | 2017-12-22 | 中国科学院兰州化学物理研究所 | A kind of synthetic method of 3 amino methyl tetrahydrofuran |
| CN107935970A (en) * | 2017-12-27 | 2018-04-20 | 浙江先锋科技股份有限公司 | A kind of preparation method of 3 methylamine tetrahydrofuran of high-purity low water content |
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