CN105399607B - A kind of preparation method of 3,3,3 trifluoropropanol - Google Patents
A kind of preparation method of 3,3,3 trifluoropropanol Download PDFInfo
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- CN105399607B CN105399607B CN201510750757.7A CN201510750757A CN105399607B CN 105399607 B CN105399607 B CN 105399607B CN 201510750757 A CN201510750757 A CN 201510750757A CN 105399607 B CN105399607 B CN 105399607B
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- trifluoropropanols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/58—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of halogen, e.g. by hydrogenolysis, splitting-off
Abstract
The invention discloses a kind of preparation method of 3,3,3 trifluoropropanol.This method adds the trifluoropropanol of 2 bromine 3,3,3, solvent, catalyst, acid binding agent in autoclave, and pressurize 2~8Mpa, is warming up to 70~100 DEG C, and after reacting 2~6h, it is 85.7% to obtain 3,3,3 trifluoropropanols and calculate total recovery from 3,3,3 trifluoro propenes.Present invention is mainly used for the preparation of 3,3,3 trifluoropropanols.
Description
Technical field
The invention belongs to technical field of organic synthesis, there is provided for one kind with 2- bromo- 3,3,3- trifluoropropanols are raw material 3,3,3-
The preparation method of trifluoropropanol.
Background technology
The structural formula of 3,3,3- trifluoropropanols is CF3CH2CH2OH, it is widely used as medicine, agricultural chemicals and other fluorine materials
Intermediate, be also used as solvent, additive etc..
In the preparation method of 3,3,3- trifluoropropanols, reduced by 3,3,3- trifluoro propionic aldehyde and prepare 3,3,3- trifluoropropanols,
The selectivity and yield of this reaction are higher.3,3,3- trifluoros propionic aldehyde obtains generally by 3,3,3- trifluoro-propenyl methyl ethers
Arrive, be that initiation material needs to 3,3,3- trifluoropropanols, the higher synthetic method of document yield is prepared into 3,3,3- trifluoro propenes
To pass through the bromo- 3,3,3- trifluoros propane of intermediate 1,2- bis-, 3,3,3- trifluoro-propenyls methyl ether, 3,3,3- trifluoro propionic aldehyde.《Chemical industry
New material》, 33 (7), described in " 2- bromo- 3, the synthesis and application of 3,3- trifluoro propenes " delivered on 27~30 (2005)
One kind is catalyst using ferric trichloride, and 3,3,3- trifluoro propenes are passed through in bromine and obtain 1,2- bis- bromo- 3,3,3- trifluoro propane
Method, yield 95.2%.One kind is disclosed in CN102320938 using the bromo- 3,3,3- trifluoros propane of 1,2- bis- as raw material system
The method of standby 3,3,3- trifluoro-propenyl methyl ethers, yield 70%, one kind is disclosed with 3,3,3- trifluoropropyls in CN102010307
Alkenyl methyl ether prepares the method for 3,3,3- trifluoro propionic aldehyde, yield 95% for raw material.As from the foregoing from 3,3,3- trifluoro propene systems
The standby trifluoro propionic aldehyde of raw material 3,3,3- will typically pass through three-step reaction, and the reduction of the trifluoro propionic aldehyde of yield 63.3%, 3,3,3- prepares 3,
The yield of 3,3- trifluoropropanols is calculated by theoretical values 100%, and the total of 3,3,3- trifluoropropanols is calculated from 3,3,3- trifluoro propenes
Yield only has 63.3%.
The content of the invention
The technical problem to be solved in the present invention is the problem of presence for prior art, there is provided a kind of raw material is easy to get, always received
The high 3,3,3- trifluoropropanol preparation methods of rate.
The synthetic route of the 3,3,3- trifluoropropanols of the present invention is as follows：
For the present invention with 2- bromo- 3,3,3- trifluoropropanols are raw material, and 3,3,3- tri- are prepared through eliminating addition process single step reaction
Fluorine propyl alcohol.
The preparation method of 3,3, the 3- trifluoropropanols of the present invention, comprises the following steps：
This method adds 2- bromo- 3,3,3- trifluoropropanols, solvent, catalyst, acid binding agent in autoclave, and pressurization 2~
8Mpa, 70~100 DEG C are warming up to, after reacting 2~6h, obtain 3,3,3- trifluoropropanols.Wherein：The bromo- 3,3,3- trifluoropropanols of 2-：
The mol ratio of acid binding agent is 1.0:0.2~1.0；1.0~2.0 times of solvent load and the bromo- 3,3,3- trifluoropropanols quality of 2-；Urge
Agent dosage is the 15%~25% of the bromo- 3,3,3- trifluoropropanols quality of 2-.Wherein：Solvent be methanol, ethanol, ethyl acetate or
3,3,3- trifluoropropanols；Catalyst is Raney Ni catalyst, Pd/C catalyst or Ru/C catalyst.
Described acid binding agent is triethylamine, LiOH, LiCO3、Ca(OH)2、KOH、Na2CO3、CaCO3One of them.
Currently preferred 3, the preparation method of 3,3- trifluoropropanols, by 2- bromo- 3,3,3- trifluoropropanols, methanol, activation
Raney Ni catalyst well, potassium carbonate are added in autoclave, and pressurize 3~6Mpa, is warming up to 70~90 DEG C, reacts 2.5~4h
Afterwards, 3,3,3- trifluoropropanols are obtained.Wherein：The mol ratio of the bromo- 3,3,3- trifluoropropanols of 2- and acid binding agent is 1.0:0.3~0.8；
1.1~1.5 times of methanol usage and the bromo- 3,3,3- trifluoropropanols quality of 2-；Catalyst amount is the bromo- 3,3,3- trifluoropropanols of 2-
The 15%~20% of quality.
Advantages of the present invention：Compared with prior art, (1) is of the invention for the preparation method of 3,3, the 3- trifluoropropanols of the present invention
Method raw material 2- bromo- 3,3,3- trifluoropropanols can be prepared by the step of 3,3,3- trifluoro propene one, yield 90.2%
(disclosed in CN102664525), the trifluoro propionic aldehyde of documents raw material 3,3,3- are prepared by three steps, yield 63.3%；
(2) total recovery that the inventive method calculates 3,3,3- trifluoropropanols from 3,3,3- trifluoro propenes is 85.7%, and documents side
Method calculates total recovery from 3,3,3- trifluoro propenes and there was only 63.3%.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
The preparation of raw material 2- bromine 3,3,3- trifluoropropanols
4.0mol glacial acetic acids are added in reaction bulb, stirring is warming up to 90 DEG C, adds 0.4mol NBS and the 6.4g concentrated sulfuric acids,
Start simultaneously at and be passed through 3,3,3- trifluoro propenes, after reaction system clarification, add 0.20mol NBS and the 3.2g concentrated sulfuric acids, react
After system clarification, 0.40mol NBS and the 6.4g concentrated sulfuric acids are added, after reaction system clarification, 80 DEG C of reaction 2h, are warming up to 100
DEG C continue to react 2h, 3,3,3- trifluoro propenes it is common enter 1.3mol.40 DEG C are cooled to, adds the lower backflow of 7mol methanol stirring, instead
Answer 9h.Normal pressure steams methanol and methyl acetate, it is cooled filter out solid after, obtain 2- bromo- 3,3,3- trifluoropropyls in rectification under vacuum
Alcohol, yield 90.2%, content 99.1%.
Analytical instrument：The glad GC-930 types gas chromatograph in sea, chromatographic column Agilent company DB-5 (30m × 0.32mm).Point
Analysis condition：50 DEG C of initial temperature, initial time 3min, 10 DEG C/min temperature programmings are to 200 DEG C, and temperature of vaporization chamber is 250 DEG C, inspection
It is 250 DEG C to survey device temperature.
It is the specific embodiment that inventor provides below, it is necessary to which explanation, the invention is not restricted to these embodiments.
Embodiment 1
By 2- bromo- 3,3,3- trifluoropropanol 54g, methanol 64.8g, the Raney Ni catalyst 8.1g after activation, acid binding agent
Triethylamine 5.7g, add in 300mL autoclaves, close kettle stirring, after vacuumizing, after hydrogen displacement three times, pressurize 2Mpa, heating
To 80 DEG C, after reacting 2.5h, stop reaction, cool down, discharging, rectifying obtains 3,3,3- trifluoropropanols；Yield 85.2%.
Embodiment 2
By the trifluoropropanol 54g of 2- bromo- 3,3,3-, ethanol 71g, Pd/C catalyst 9.7g, LiOH 2.7g, it is high to add 300mL
Press in kettle, close kettle stirring, after vacuumizing, after hydrogen displacement three times, pressurize 4Mpa, is warming up to 90 DEG C, after reacting 5h, stops anti-
Should, cool down, discharging, rectifying obtains 3,3,3- trifluoropropanols；Yield 83.5%.
Embodiment 3
By the Raney Ni catalyst 9.7g after 2- bromo- 3,3,3- trifluoropropanol 54g, methanol 79g, activation, potassium carbonate
19.3g, add in 300mL autoclaves, close kettle stirring, after vacuumizing, after hydrogen displacement three times, pressurize 5Mpa, is warming up to 80
DEG C, after reacting 3.0h, stop reaction, cool down, discharging, rectifying obtains 3,3,3- trifluoropropanols；Yield 95.0%.
Embodiment 4
By the trifluoropropanol 54g of 2- bromo- 3,3,3-, ethyl acetate 80g, Ru/C catalyst 10.8g, LiCO312.4g add
In 300mL autoclaves, kettle stirring is closed, after vacuumizing, after hydrogen displacement three times, pressurize 6Mpa, is warming up to 90 DEG C, reacts 4h
Afterwards, stop reaction, cool down, discharging, rectifying obtains 3,3,3- trifluoropropanols；Yield 82.8%.
Embodiment 5
By the Raney Ni catalyst after 2- bromo- 3,3,3- trifluoropropanol 54g, 3,3,3- trifluoropropanol 108g, activation
12.4g、Ca(OH)216.5g, add in 300mL autoclaves, close kettle stirring, after vacuumizing, after hydrogen displacement three times, pressurization
8Mpa, 100 DEG C are warming up to, after reacting 6h, stop reaction, cool down, discharging, rectifying obtains 3,3,3- trifluoropropanols；Yield
66.6%.
Embodiment 6
By the Raney Ni catalyst 13.5g after 2- bromo- 3,3,3- trifluoropropanol 54g, methanol 87g, activation, acid binding agent
KOH 4.7g, add in 300mL autoclaves, close kettle stirring, after vacuumizing, after hydrogen displacement three times, pressurize 2Mpa, is warming up to
70 DEG C, after reacting 2h, stop reaction, cool down, discharging, rectifying obtains 3,3,3- trifluoropropanols；Yield 76.4%.
Embodiment 7
By 2- bromo- 3,3,3- trifluoropropanol 54g, methanol 72g, activation after Raney Ni catalyst 9.9g,
Na2CO314.8g, add in 300mL autoclaves, close kettle stirring, after vacuumizing, after hydrogen displacement three times, pressurize 4Mpa, heating
To 90 DEG C, after reacting 3h, stop reaction, cool down, discharging, rectifying obtains 3,3,3- trifluoropropanols；Yield 68.1%.
Embodiment 8
By 2- bromo- 3,3,3- trifluoropropanol 54g, methanol 79g, activation after Raney Ni catalyst 13.5g,
CaCO311.2g, add in 300mL autoclaves, close kettle stirring, after vacuumizing, after hydrogen displacement three times, pressurize 4Mpa, heating
To 95 DEG C, after reacting 5h, stop reaction, cool down, discharging, rectifying obtains 3,3,3- trifluoropropanols；Yield 56.4%.
Embodiment 9
By the Raney Ni catalyst 8.6g after 2- bromo- 3,3,3- trifluoropropanol 54g, methanol 64g, activation, potassium carbonate
19.3g, add in 300mL autoclaves, close kettle stirring, after vacuumizing, after hydrogen displacement three times, pressurize 4Mpa, is warming up to 80
DEG C, after reacting 2.5h, stop reaction, cool down, discharging, rectifying obtains 3,3,3- trifluoropropanols；Yield 94.9%.
Claims (3)
1. one kind 3,3, the preparation method of 3- trifluoropropanols, it is characterised in that comprise the following steps, by 2- bromo- 3,3,3- trifluoros
Propyl alcohol, solvent, catalyst, acid binding agent add in autoclave, are passed through pressurized with hydrogen 2Mpa~8Mpa, are warming up to 70 DEG C~100 DEG C,
After reacting 2h~6h, 3,3,3- trifluoropropanols are obtained；Wherein：The mol ratio of the bromo- 3,3,3- trifluoropropanols of 2- and acid binding agent is
1.0:0.2~1.0；1.0~2.0 times of solvent load and the bromo- 3,3,3- trifluoropropanols quality of 2-；Catalyst amount is that 2- is bromo-
The 15%~25% of 3,3,3- trifluoropropanol quality；Wherein：Solvent is methanol, ethanol, ethyl acetate or 3,3,3- trifluoropropanols；
Catalyst is Raney Ni catalyst, Pd/C catalyst or Ru/C catalyst.
2. as claimed in claim 13, the preparation method of 3,3- trifluoropropanols, it is characterised in that described acid binding agent is three second
Amine, LiOH, Li2CO3、Ca(OH)2、KOH、Na2CO3、K2CO3Or CaCO3。
3. as claimed in claim 13, the preparation method of 3,3- trifluoropropanols, it is characterised in that comprise the following steps, by 2-
Bromo- 3,3,3- trifluoropropanols, methanol, Raney Ni catalyst, potassium carbonate add autoclave in, be passed through pressurized with hydrogen 3Mpa~
6Mpa, 70 DEG C~90 DEG C are warming up to, after reacting 2.5h~4h, obtain 3,3,3- trifluoropropanols；Wherein：The bromo- 3,3,3- trifluoros of 2-
The mol ratio of propyl alcohol and potassium carbonate is 1.0:0.3~0.8；The 1.1 of methanol usage and the bromo- 3,3,3- trifluoropropanols quality of 2-~
1.5 again；Raney Ni catalyst amounts are the 15%~20% of the bromo- 3,3,3- trifluoropropanols quality of 2-.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6002053A (en) * | 1997-10-14 | 1999-12-14 | Bayer Aktiengesellschaft | Process for preparing pentafluoropentanol |
| EP2196449A1 (en) * | 2008-12-12 | 2010-06-16 | Saltigo GmbH | Method for producing perfluoralkyl or perfluoralkoxyalkanoles |
| CN102040480A (en) * | 2010-11-16 | 2011-05-04 | 巨化集团公司 | Synthetic method of 3,3,3-trifluoropropanol |
| CN102351651A (en) * | 2011-08-25 | 2012-02-15 | 西安近代化学研究所 | Preparation method of 3,3,3-trifluoropropanol |
| CN102372689A (en) * | 2011-11-18 | 2012-03-14 | 威海新元化工有限公司 | Preparation method of trifluoromethyl ethylene carbonate |
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2015
- 2015-11-06 CN CN201510750757.7A patent/CN105399607B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6002053A (en) * | 1997-10-14 | 1999-12-14 | Bayer Aktiengesellschaft | Process for preparing pentafluoropentanol |
| EP2196449A1 (en) * | 2008-12-12 | 2010-06-16 | Saltigo GmbH | Method for producing perfluoralkyl or perfluoralkoxyalkanoles |
| CN102040480A (en) * | 2010-11-16 | 2011-05-04 | 巨化集团公司 | Synthetic method of 3,3,3-trifluoropropanol |
| CN102351651A (en) * | 2011-08-25 | 2012-02-15 | 西安近代化学研究所 | Preparation method of 3,3,3-trifluoropropanol |
| CN102372689A (en) * | 2011-11-18 | 2012-03-14 | 威海新元化工有限公司 | Preparation method of trifluoromethyl ethylene carbonate |
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