CN105906513A - Preparation method of trifluoroethylamine - Google Patents
Preparation method of trifluoroethylamine Download PDFInfo
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- CN105906513A CN105906513A CN201610263119.7A CN201610263119A CN105906513A CN 105906513 A CN105906513 A CN 105906513A CN 201610263119 A CN201610263119 A CN 201610263119A CN 105906513 A CN105906513 A CN 105906513A
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- trifluoroethylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of trifluoroethylamine. The preparation method comprises the following steps: amination reaction: taking CHF2CH2X as a raw material, and feeding ammonia gas in the presence of a solvent and a catalyst to ammonify so as to generate trifluoroethylamine; and rectification: rectifying the ammonified product to obtain a finished product, filtering kettle liquid to obtain ammonium chloride as a by-product, and recycling filtrate used as the solvent of amination reaction. The catalyst is inorganic iodide, and the solvent is a frequently used organic solvent DMF or NMP. The purity of the prepared finished product is greater than or equal to 99.5%, and the yield of the finished product is greater than or equal to 90%.
Description
Technical field
The invention belongs to the field of organic intermediate, be specifically related to the preparation method of a kind of trifluoroethylamine.
Background technology
Trifluoroethylamine is important organic intermediate, is widely used in the industry such as pesticide, medication chemistry.At pesticide field
In, can be with the high insecticide of synthesizing activity, acaricide, ovicide, and synthetic herbicide.In field of medicaments, can conduct
The medicine 1 of medicine intermediate preparation treatment diabetes, 2-replaces biguanide and derivant thereof.
It synthesizes mainly following several routes:
Within 1934, Henry Gilman is with sodium trifluoroacetate as raw material, generates trifluoro second through esterification, amidatioon, five phosphine oxide dehydrations
Nitrile, last platinum catalysis hydrogenation obtains target product trifluoroethylamine.This route steps is longer, and operation complexity, and total recovery is relatively low, does not has
There is industrialization meaning.
Within 1954, method 1 is improved by GB717232, and with trifluoroacetamide as raw material, the reduction of hydrogenated aluminum lithium prepares mesh
Mark product.The method route is succinct, but raw material is costly, is difficulty with industrialization.
Reacting generation imines with trifluoro acetaldehyde for raw material and benzylamine, then reset, finally hydrolysis obtains trifluoroethylamine.This route
Design comparison is ingenious, and yield is the highest, but raw material trifluoro acetaldehyde is gas and costly, and industrial cost is more high-leveled and difficult with industry
Change.
Method 4 is improved with trifluoroacetic acid as raw material by V.A. Soloshonok in 2002 etc., through acylated, benzylamine Asia
Amination, 3 rearrangements, dehalogenation and last hydrolysis obtain target product trifluoroethylamine.Although this route cost of material is relatively cheap,
But route is various, operating difficulties and yield relatively low, the most difficult industrialization.
Summary of the invention
Goal of the invention: in order to solve the deficiencies in the prior art, the invention provides the preparation method of a kind of trifluoroethylamine.
Technical scheme: the preparation method of a kind of trifluoroethylamine, comprises the steps:
The first step, aminating reaction: with CHF2CH2X is raw material, and in the presence of solvent and catalyst, logical ammonia ammonification generates trifluoro second
Amine, reaction equation is as follows:
CHF2CH2X + 2NH3 →CF3CH2NH2 +NH4X；
Second step, rectification: the product after amination obtains finished product through rectification, still liquid obtains side product sodium chloride, filtrate after filtering
Solvent reclaiming as aminating reaction；Catalyst is inorganic iodide, and solvent is conventional organic solvent DMF or NMP.
As optimization: in the described first step, aminating reaction, described CHF2CH2X is particularly as follows: CHF2CH2Cl、CHF2CH2Br、
CHF2CH2I。
As optimization: in the described first step, aminating reaction, described solvent is: NMP；DMF；DMSO；Alkyl diol: the third two
Alcohol or ethylene glycol.
As optimization: the described first step, aminating reaction concrete operations are as follows: use batch technology, equipped with tail gas absorption
Being sequentially added into solvent, liquefied ammonia and proper catalyst in the autoclave of device, start stirring, heat temperature raising, at 30 DEG C-100
DEG C, CHF slowly it is passed through by fixing speed2CH2X reacts, and observes temperature situation in still, when still temperature rise to about 110 DEG C-210 DEG C, now
Still is pressed in 2.0-6.0MPa, insulation reaction 16-36 hour, and reaction terminates substantially, is then cooled to room temperature, opens tail gas and inhales
Receive tower, open exhaust-valve and carry out excess of ammonia gas absorption operation.
As optimization: after the tail gas Water spray tower absorption after the described first step, aminating reaction processes, deposed ammonia is transported
To sewage plant.
As optimization: in described second step, distillation process, reaction mass carries out distillation operation at 2L glass rectifier unit,
Fractionate out qualified finished product.
As optimization: in described second step, distillation process, still internal solvent and by-product isolated by vacuum filtration after cooling,
Obtain side product sodium chloride, filtrate namely solvent reclaiming.
Beneficial effect: finished product purity >=99.5% that the present invention prepares, product yield >=90%.
The present invention compares additive method, and the cost of raw material is low and is easy to get, operation is simple, mild condition, be prone to industry
Metaplasia is produced；Yield and conversion ratio all improve a lot.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
As it is shown in figure 1, the preparation method of a kind of trifluoroethylamine, comprise the steps:
The first step, aminating reaction: with CHF2CH2X is raw material, and in the presence of solvent and catalyst, logical ammonia ammonification generates trifluoro second
Amine, reaction equation is as follows:
CHF2CH2Cl + 2NH3 →CF3CH2NH2 +NH4Cl；
Described solvent is: NMP or DMF.
Aminating reaction concrete operations are as follows: use batch technology, depend in equipped with the autoclave of device for absorbing tail gas
Secondary addition solvent, liquefied ammonia and proper catalyst, start stirring, heat temperature raising, at 30 DEG C, be slowly passed through by fixing speed
CHF2CH2Cl reacts, and observes temperature situation in still, and when still temperature rise to about 110 DEG C, now still is pressed in 2.0MPa, insulation reaction 16
Hour, reaction terminates substantially, is then cooled to room temperature, opens tail gas absorber, opens exhaust-valve and carry out excess of ammonia aspiration receipts
Operation.
After tail gas after aminating reaction processes with Water spray tower absorption, deposed ammonia is transported to sewage plant.
Second step, rectification: the product after amination obtains finished product through rectification, still liquid obtains side product sodium chloride after filtering,
Filtrate is as the solvent reclaiming of aminating reaction；Catalyst is inorganic iodide, and solvent is conventional organic solvent DMF or N
MP.In distillation process, reaction mass carries out distillation operation at 2L glass rectifier unit, fractionates out qualified finished product；Still internal solvent
And by-product isolated by vacuum filtration after cooling, obtain side product sodium chloride, filtrate namely solvent reclaiming.
Embodiment 2
As it is shown in figure 1, the preparation method of a kind of trifluoroethylamine, comprise the steps:
The first step, aminating reaction: with CHF2CH2Br is raw material, and in the presence of solvent and catalyst, logical ammonia ammonification generates trifluoro
Ethamine, reaction equation is as follows:
CHF2CH2Br + 2NH3 →CF3CH2NH2 +NH4Br；
Described solvent is: DMSO.
Aminating reaction concrete operations are as follows: use batch technology, depend in equipped with the autoclave of device for absorbing tail gas
Secondary addition solvent, liquefied ammonia and proper catalyst, start stirring, heat temperature raising, at 100 DEG C, be slowly passed through by fixing speed
CHF2CH2Br reacts, and observes temperature situation in still, and when still temperature rise to about 210 DEG C, now still is pressed in 6.0MPa, insulation reaction 36
Hour, reaction terminates substantially, is then cooled to room temperature, opens tail gas absorber, opens exhaust-valve and carry out excess of ammonia aspiration receipts
Operation.
After tail gas after aminating reaction processes with Water spray tower absorption, deposed ammonia is transported to sewage plant.
Second step, rectification: the product after amination obtains finished product through rectification, still liquid obtains side product sodium chloride after filtering,
Filtrate is as the solvent reclaiming of aminating reaction；Catalyst is inorganic iodide, and solvent is conventional organic solvent DMF or N
MP.In distillation process, reaction mass carries out distillation operation at 2L glass rectifier unit, fractionates out qualified finished product；Still internal solvent
And by-product isolated by vacuum filtration after cooling, obtain side product sodium chloride, filtrate namely solvent reclaiming.
Embodiment 3
As it is shown in figure 1, the preparation method of a kind of trifluoroethylamine, comprise the steps:
The first step, aminating reaction: with CHF2CH2I is raw material, and in the presence of solvent and catalyst, logical ammonia ammonification generates trifluoro second
Amine, reaction equation is as follows:
CHF2CH2I + 2NH3 →CF3CH2NH2 +NH4I；
Described solvent is: alkyl diol: propylene glycol or ethylene glycol.
Aminating reaction concrete operations are as follows: use batch technology, depend in equipped with the autoclave of device for absorbing tail gas
Secondary addition solvent, liquefied ammonia and proper catalyst, start stirring, heat temperature raising, at 80 DEG C, be slowly passed through by fixing speed
CHF2CH2I reacts, and observes temperature situation in still, and when still temperature rise to about 170 DEG C, now still is pressed in 4.0MPa, and insulation reaction 27 is little
Time, reaction terminates substantially, is then cooled to room temperature, opens tail gas absorber, opens exhaust-valve and carries out excess of ammonia aspiration and bring drill to an end
Make.
After tail gas after aminating reaction processes with Water spray tower absorption, deposed ammonia is transported to sewage plant.
Second step, rectification: the product after amination obtains finished product through rectification, still liquid obtains side product sodium chloride after filtering,
Filtrate is as the solvent reclaiming of aminating reaction；Catalyst is inorganic iodide, and solvent is conventional organic solvent DMF or N
MP.In distillation process, reaction mass carries out distillation operation at 2L glass rectifier unit, fractionates out qualified finished product；Still internal solvent
And by-product isolated by vacuum filtration after cooling, obtain side product sodium chloride, filtrate namely solvent reclaiming.
The present invention is not limited to above-mentioned preferred forms, and anyone can show that under the enlightenment of the present invention other are various
The product of form, no matter but in its shape or structure, make any change, every have same as the present application or akin skill
Art scheme, within all falling within protection scope of the present invention.
Claims (7)
1. the preparation method of a trifluoroethylamine, it is characterised in that: comprise the steps:
The first step, aminating reaction: with CHF2CH2X is raw material, and in the presence of solvent and catalyst, logical ammonia ammonification generates trifluoro second
Amine, reaction equation is as follows:
CHF2CH2X + 2NH3 →CF3CH2NH2 +NH4X；
Second step, rectification: the product after amination obtains finished product through rectification, still liquid obtains side product sodium chloride, filtrate after filtering
Solvent reclaiming as aminating reaction；Catalyst is inorganic iodide, and solvent is conventional organic solvent DMF or NMP.
The synthesis technique of difluoroethylamine the most according to claim 1, it is characterised in that: in the described first step, aminating reaction,
Described CHF3CH2X is particularly as follows: CHF3CH2Cl、CHF3CH2Br、CHF3CH2I。
The synthesis technique of difluoroethylamine the most according to claim 1, it is characterised in that: in the described first step, aminating reaction,
Described solvent is: NMP；DMF；DMSO；Alkyl diol: propylene glycol or ethylene glycol.
The preparation method of trifluoroethylamine the most according to claim 1, it is characterised in that: the described first step, aminating reaction have
Gymnastics is made as follows: use batch technology, is sequentially added into solvent, liquefied ammonia and fits in equipped with the autoclave of device for absorbing tail gas
Amount catalyst, starts stirring, heat temperature raising, at 30 DEG C-100 DEG C, is slowly passed through CHF by fixing speed3CH2X reacts, and observes still
Interior temperature situation, when still temperature rise to about 110 DEG C-210 DEG C, now still is pressed in 2.0-6.0MPa, insulation reaction 16-36 hour,
Reaction terminates substantially, is then cooled to room temperature, opens tail gas absorber, opens exhaust-valve and carry out excess of ammonia gas absorption operation.
The preparation method of trifluoroethylamine the most according to claim 1, it is characterised in that: after the described first step, aminating reaction
Tail gas with Water spray tower absorption process after, deposed ammonia is transported to sewage plant.
The preparation method of trifluoroethylamine the most according to claim 1, it is characterised in that: in described second step, distillation process,
Reaction mass carries out distillation operation at 2L glass rectifier unit, fractionates out qualified finished product.
The preparation method of trifluoroethylamine the most according to claim 1, it is characterised in that: in described second step, distillation process,
Still internal solvent and by-product isolated by vacuum filtration after cooling, obtains side product sodium chloride, filtrate namely solvent reclaiming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610263119.7A CN105906513A (en) | 2016-04-26 | 2016-04-26 | Preparation method of trifluoroethylamine |
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| CN201610263119.7A CN105906513A (en) | 2016-04-26 | 2016-04-26 | Preparation method of trifluoroethylamine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3650437A1 (en) * | 2018-11-08 | 2020-05-13 | Fujian Yongjing Technology Co., Ltd. | New process for the manufacture of 1,1,1-trifluoro-2-chloroethane (hcfc-133a) and/or trifluoroethylamine (tfea) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003137844A (en) * | 2001-10-30 | 2003-05-14 | Tosoh F-Tech Inc | Method for producing fluoroalkylamine |
| CN101973888A (en) * | 2010-10-30 | 2011-02-16 | 西安近代化学研究所 | Preparation method of 2,2,2-trifluoroethylamine |
-
2016
- 2016-04-26 CN CN201610263119.7A patent/CN105906513A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003137844A (en) * | 2001-10-30 | 2003-05-14 | Tosoh F-Tech Inc | Method for producing fluoroalkylamine |
| CN101973888A (en) * | 2010-10-30 | 2011-02-16 | 西安近代化学研究所 | Preparation method of 2,2,2-trifluoroethylamine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3650437A1 (en) * | 2018-11-08 | 2020-05-13 | Fujian Yongjing Technology Co., Ltd. | New process for the manufacture of 1,1,1-trifluoro-2-chloroethane (hcfc-133a) and/or trifluoroethylamine (tfea) |
| JP2021508668A (en) * | 2018-11-08 | 2021-03-11 | 福建永晶科技股▲ふん▼有限公司Ｆｕｊｉａｎ Ｙｏｎｇｊｉｎｇ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ | New method for producing 1,1,1-trifluoro-2-chloroethane (HCFC-133a) and / or trifluoroethylamine (TFEA) |
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