CN106083528B - A kind of preparation method of 2,2- difluoroethanols - Google Patents
A kind of preparation method of 2,2- difluoroethanols Download PDFInfo
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- CN106083528B CN106083528B CN201610385525.0A CN201610385525A CN106083528B CN 106083528 B CN106083528 B CN 106083528B CN 201610385525 A CN201610385525 A CN 201610385525A CN 106083528 B CN106083528 B CN 106083528B
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- difluoroethanols
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Abstract
The invention discloses a kind of preparation method of 2,2 difluoroethanols, the preparation method is through the following steps that realize：With acetate and 1 chlorine, 2,2 Difluoroethane for raw material, higher boiling alcohols adjusts pH value with acetic acid, according to specific rate of charge, 2,2 difluoroethanols of production is reacted under particular temperature gradient as solvent.The present invention replaces traditional sulfoxide type, amide solvent using high boiling solvent of the boiling point higher than 150 DEG C, can one-step method prepare 2,2 difluoroethanols, raw material, which is dirt cheap, to be easy to get, simple for process easy to operate, and conversion ratio, yield are double high, by-product is few, is suitble to industrialized production；2,2 difluoroethanol purity >=98.5 prepared by the present invention, conversion ratio >=96%, yield >=92%.
Description
Technical field
The invention belongs to technical field of fluorine chemical industry, and in particular to the preparation method of one kind 2,2- difluoroethanols.
Background technology
2,2- difluoroethanols extensively should as fluorine-containing organic synthesis intermediate in pesticide, medicine, fluoropolymer field
With being the important synthesis material such as Insecticides (tech) ＆ Herbicides (tech).
Since difluoroethanol is in the important function of medicine and pesticide field, lot of domestic and international R＆D institution and scholar to it
Effort was made in synthesis, and method route also differs widely.2298723 A1 of European patent EP discloses ethyl difluoro as original
Material, tetrahydrofuran do catalysis for solvent ruthenium and add standby difluoroethanol, this method yield only 66% and catalyst ruthenium are precious metal,
It is of high cost, be not suitable for large-scale industrial production.1820789 A1 of European patent EP is equally announced a kind of to be urged with Noble Metal Rhodium carbon
Agent is catalyzed, and prepares difluoroethanol method with hydrogen reducing methyl difluoroacetate, catalyst amount is more, and cost is higher.China
Patent CN 104098444 A, CN 102553614 A, CN 10276602 A be using difluoro acetate as raw material, using hydrogen entirely
Gas is catalyzed in noble metal agent or is synthetically prepared difluoroethanol as reducing agent by the use of Li-Al hydrogen, boron hydride.In conclusion
Difluoroethanol is synthesized by catalytic material reduction method of difluoro acetate, needs noble metal catalyst and special reducing agent mostly, and
And yield is not mostly high, cost is higher in industrialization, and operation difficulty is big.103687831 A of Chinese patent CN are disclosed with 1-
Chloro- 2,2- Difluoroethanes are raw material, and the first step, which occurs, with formic acid, acetate in the solvent of non-alcohols reacts production 2,2- difluoros
Ethyl ester or 2,2- bis-fluoro ethyls acetic acid esters, then transesterification synthesizes difluoroethanol in alcohol and arbitrary alkali.This method is anti-
Answer step more, generated time is longer, and total recovery is less than 85%.
Invention content：
In view of the problems of the existing technology, passed through the present invention provides one kind with chloro- 2, the 2- Difluoroethanes of 1- for raw material
The method that one-step method prepares 2,2- difluoroethanols, this method raw material, which is dirt cheap, to be easy to get, simple for process easy to operate, conversion ratio, yield
Double height, by-product is few, is suitble to industrialized production.
The used to achieve these goals technical solution of the present invention is：
The present invention provides the preparation methods of one kind 2,2- difluoroethanols, include the following steps：
（1）Acetate is dissolved in water and high boiling solvent, glacial acetic acid adjusts PH, adds in autoclave, takes out true
Sky, N2Displacement adds in chloro- 2, the 2- Difluoroethanes of 1-, and feed intake middle acetate：Water：Higher boiling alcohols：The chloro- 2,2- Difluoroethanes of 1-
It is 1:0.1~0.5：4~8:0.5~1.5；Segmentation reaction 2.5h；
（2）After reaction, rectification and purification obtains water and difluoroethanol azeotropic product, is removed water with toluene, finally obtains pure
The 2,2- difluoroethanols of degree >=98.5.
Further, step（1）In, the mass ratio of chloro- 2, the 2- dichloroethanes of the acetate, water, high boiling solvent, 1-
It is 1:0.1~0.5：4~8:0.5~1.5.
Above-mentioned acetate is preferably potassium acetate or sodium acetate.
Further, step（1）Described in high boiling solvent be more than 150 DEG C of monohydric alcohol, dihydric alcohol or ternary for boiling point
Alcohol.
High boiling solvent used in the present invention is preferably glycerine, propylene glycol, ethylene glycol or diethylene glycol (DEG).
Further, step（1）In, the glacial acetic acid adjusts PH to 5-6.
Further, step（1）In, the segmentation reaction is carries out under two temperature gradients：First 180~250
0.5h is reacted at DEG C, then reacts 2h at 60~90 DEG C.
The chloro- 2,2- Difluoroethanes purity requirements of raw material 1- used in the present invention are more than 90%.
Beneficial effects of the present invention are：
（1）The present invention replaces traditional sulfoxide type, amide solvent, energy using high boiling solvent of the boiling point higher than 150 DEG C
Enough one-step method prepare 2,2- difluoroethanols, and raw material, which is dirt cheap, to be easy to get, simple for process easy to operate, and conversion ratio, yield are double high, by-product
Object is few, is suitble to industrialized production；
（2）2,2- difluoroethanols purity >=98.5 prepared by the present invention, conversion ratio >=96%, yield >=92%.
Specific embodiment
Below by embodiment, the present invention will be further elaborated, and the description below is only for explaining the present invention, not
Its content is defined.
Embodiment 1
1.1 weigh 200g potassium acetates, 60g water, 800g glycerine, add in glacial acetic acid adjusting PH to 5, add in stirring
In 2L autoclaves, kettle cover is closed, is replaced 3 times with nitrogen, is evacuated as negative pressure, by chloro- 2, the 2- Difluoroethanes of 1- that purity is 92%
240g is added in kettle, is opened stirring, is begun to warm up, and when temperature rises to 210 DEG C, then timing heat preservation 0.5h, temperature is dropped
It is 70 DEG C, insulation reaction 2h under stirring condition；
1.2 after reaction, releases material, separating-purifying obtains the azeotropic of water and difluoroethanol in glass rectifier unit
Azeotropic product is added in 500ml three-necked flasks by object, and three-necked flask top adds a water knockout drum, and 200g toluene is added in and is burnt
In bottle, temperature is controlled, removes water, rectifying again finally obtains concentration（Purity）For 98.9% 2,2- difluoroethanols 158g.
Embodiment 2
2.1 weigh 200g potassium acetates, 50g water, 1200g ethylene glycol, add in glacial acetic acid adjusting PH to 6, add in stirring
2L autoclaves in, close kettle cover, with nitrogen replace 3 times, evacuate as negative pressure.By the chloro- 2,2- Difluoroethanes of 1- that purity is 92%
240g is added in kettle.Stirring is opened, is begun to warm up.When temperature rises to 220 DEG C, timing heat preservation 0.5h.Then, temperature is dropped
It is 90 DEG C, heats while stirring, keeps the temperature 2h;
2.2 after reaction, releases material, separating-purifying obtains the azeotropic of water and difluoroethanol in glass rectifier unit
Object.Azeotropic product is added in 500ml three-necked flasks, three-necked flask top adds a water knockout drum, and 200g toluene is added in and is burnt
In bottle, temperature is controlled, removes water, rectifying again obtains concentration（Purity）For 98.5% 2,2- difluoroethanols 162g.
Embodiment 3
3.1 weigh 200g sodium acetates, 20g water, 1600g propylene glycol, add in glacial acetic acid adjusting PH to 6, add in stirring
2L autoclaves in, close kettle cover, with nitrogen replace 3 sides, evacuate as negative pressure.By the chloro- 2,2- Difluoroethanes of 1- that purity is 92%
160g is added in kettle.Stirring is opened, is begun to warm up.When temperature rises to 250 DEG C, timing heat preservation 0.5h.Then, temperature is dropped
It is 90 DEG C, heats while stirring, keeps the temperature 2h;
3.2 after reaction, releases material, separating-purifying obtains the azeotropic of water and difluoroethanol in glass rectifier unit
Object.Azeotropic product is added in 500ml three-necked flasks, three-necked flask top adds a water knockout drum, and 200g toluene is added in and is burnt
In bottle, temperature is controlled, removes water, rectifying again obtains concentration（Purity）For 98.7% 2,2- difluoroethanol 115g. yields
94.50%。
Embodiment 4
4.1 weigh 200g sodium acetates, 100g water, 1600g diethylene glycol (DEG)s, add in glacial acetic acid adjusting PH to 6, add in stirring
2L autoclaves in, close kettle cover, with nitrogen replace 3 sides, evacuate as negative pressure.By the chloro- 2,2- Difluoroethanes of 1- that purity is 92%
300g is added in kettle.Stirring is opened, is begun to warm up.When temperature rises to 180 DEG C, timing heat preservation 0.5h.Then, temperature is dropped
It is 60 DEG C, heats while stirring, keeps the temperature 2h;
4.2 after reaction, releases material, separating-purifying obtains the azeotropic of water and difluoroethanol in glass rectifier unit
Object.Azeotropic product is added in 500ml three-necked flasks, three-necked flask top adds a water knockout drum, and 200g toluene is added in and is burnt
In bottle, temperature is controlled, removes water, rectifying again obtains concentration（Purity）For 99% 2,2- difluoroethanols 186g.
Embodiment 5
5.1 weigh 200g potassium acetates, 60g water, 800g octanols, add in glacial acetic acid adjusting PH to 5, add in the 2L with stirring
In autoclave, kettle cover is closed, is replaced 3 times with nitrogen, is evacuated as negative pressure, by chloro- 2, the 2- Difluoroethanes 240g of 1- that purity is 92%
It is added in kettle, opens stirring, begin to warm up, when temperature rises to 210 DEG C, then temperature, is reduced to 70 by timing heat preservation 0.5h
DEG C, insulation reaction 2h under stirring condition；
5.2 after reaction, releases material, separating-purifying obtains the azeotropic of water and difluoroethanol in glass rectifier unit
Azeotropic product is added in 500ml three-necked flasks by object, and three-necked flask top adds a water knockout drum, and 200g toluene is added in and is burnt
In bottle, temperature is controlled, removes water, rectifying again finally obtains concentration（Purity）For 98.5% 2,2- difluoroethanols 160g.
Effect example
1st, the preparation method for providing embodiment 1-5 carries out yield and conversion ratio, reaction time count, and sets control group,
With patent（CN103687831A）Prepared by the method for offer, concrete outcome is shown in Table 1.
Table 1
In addition, prepared using other boiling points higher than 150 DEG C of monohydric alcohol, dihydric alcohol or trihydroxylic alcohol as solvent 2,2-
Difluoroethanol purity >=98.5, yield >=92%, obvious technical effects.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not limited by embodiment
System, it is other it is any without departing from the present invention Spirit Essences with made under principle change, modification, combine, replacement, simplification should be
Equivalence replacement mode, is included within protection scope of the present invention.
Claims (1)
1. one kind 2, the preparation method of 2- difluoroethanols, it is characterised in that：Include the following steps：
（1）Acetate is dissolved in water and high boiling solvent, glacial acetic acid adjusts pH to 5-6, adds in autoclave, takes out true
Sky, N2Displacement adds in chloro- 2, the 2- Difluoroethanes of 1-, and feed intake middle acetate：Water：High boiling solvent：The chloro- 2,2- Difluoroethanes of 1-
Mass ratio be 1:0.1~0.5：4~8:0.5~1.5；Segmentation reaction 2.5h；
（2）After reaction, rectification and purification obtains water and difluoroethanol azeotropic product, is removed water with toluene, finally obtain purity >=
98.5 2,2- difluoroethanols；
The acetate is potassium acetate or sodium acetate；
The high boiling solvent is glycerine, propylene glycol, ethylene glycol or diethylene glycol (DEG)；
The segmentation reaction is carries out under two temperature gradients：0.5h is reacted at 180~250 DEG C first, then 60~
2h is reacted at 90 DEG C.
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| CN107353179A (en) * | 2017-06-17 | 2017-11-17 | 南通宝凯化工有限公司 | A kind of preparation technology of difluoroethanol |
| CN108046992B (en) * | 2017-12-29 | 2021-02-02 | 山东华安新材料有限公司 | Method and equipment for purifying 2, 2-difluoroethanol |
| CN116023267A (en) * | 2022-12-14 | 2023-04-28 | 南通宝凯药业有限公司 | Preparation process of difluoroethyl acetate |
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| US2868846A (en) * | 1956-01-05 | 1959-01-13 | Pennsalt Chemicals Corp | Preparation of 2, 2, 2-trifluoroethanol |
| WO2013010985A1 (en) * | 2011-07-19 | 2013-01-24 | Bayer Intellectual Property Gmbh | Process for preparing 2,2-difluoroethanol |
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