CN102766025A - Method for preparing 3,3,3-trifluoro-propyl alcohol - Google Patents
Method for preparing 3,3,3-trifluoro-propyl alcohol Download PDFInfo
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- CN102766025A CN102766025A CN2012102863711A CN201210286371A CN102766025A CN 102766025 A CN102766025 A CN 102766025A CN 2012102863711 A CN2012102863711 A CN 2012102863711A CN 201210286371 A CN201210286371 A CN 201210286371A CN 102766025 A CN102766025 A CN 102766025A
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- trifluoro
- trifluoropropanol
- methyl ether
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Abstract
The invention discloses a method for preparing 3,3,3-trifluoro-propyl alcohol and aims at solving the problem of low reaction yield. 3,3,3-trifluoropropene-methyl ether serves as the raw material, and the method includes the following steps: adding 3,3,3-trifluoropropene-methyl ether, inorganic ester and activated Raney Ni catalysts into an autoclave, leading hydrogen pressure to be 5MPa, stirring to lead temperature to rise to 60-120 DEG C, and reacting for 4-8h, wherein mass ratio of 3,3,3-trifluoropropene-methyl ether: inorganic ester: catalysts is 1:(1.2-2.0):(0.05-0.2). The method is mainly used for preparing 3,3,3-trifluoro-propyl alcohol.
Description
Technical field
The present invention relates to a kind ofly 3,3, the preparation method of 3-trifluoropropanol relates in particular to a kind ofly with 3,3, and 3-trifluoro-propenyl methyl ether is 3,3 of a raw material, the preparation method of 3-trifluoropropanol.
Background technology
3,3, the 3-trifluoropropanol can be used as the midbody of synthetic medicine, agricultural chemicals, also can be used as the raw material or the midbody of synthesized high-performance material." Investigation of the factors controlling the regioselectivity of the hydroboration of fluoroolefins " Chemical communication, 2002,386～387 disclose a kind of 3; 3; The preparation method of 3-trifluoropropanol, this method are that raw material prepares 3,3 through two-step reaction with the trifluoro propene; The 3-trifluoropropanol, reactions step is following:
At first, trifluoro propene and the reaction of dibromo borine make boron cpd, and hydrolysis oxidation obtains trifluoropropanol again, overall yield of reaction 41%.But this method reaction yield is low more with step; And the reaction of second step is aqueous systems, and there are azeotropic in trifluoropropanol and water, and it is difficult that the product last handling process separates purification.
Summary of the invention
The technical problem that the present invention will solve is deficiency and the defective that overcomes in the background technology, provides a kind of not only reaction yield higher less with reactions step, and product separate simple 3,3, the preparation method of 3-trifluoropropanol.
Synthetic route of the present invention is:
In order to solve the problems of the technologies described above, of the present invention 3,3, the preparation method of 3-trifluoropropanol is with 3; 3,3-trifluoro-propenyl methyl ether is a raw material, comprises the steps: 3,3, and the Raney Ni catalyzer that 3-trifluoro-propenyl methyl ether, inorganic ester and activation are good adds autoclave; At hydrogen pressure is 5MPa, stirs down, is warming up to 60 ℃～120 ℃, and reaction 4h～8h is cooled to room temperature; Through filtering, distilling post-processing step, obtain 3,3, the 3-trifluoropropanol; Wherein 3,3,3-trifluoro-propenyl methyl ether: inorganic ester: the catalyst quality ratio is 1: 1.2～2.0: 0.05～0.2.
The present invention is preferred 3,3, and the preparation method of 3-trifluoropropanol comprises the steps: 50g 3; 3, the Raney Ni catalyzer that 3-trifluoro-propenyl methyl ether, 75g tributyl phosphate and 5g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa, stirs down; Be warming up to 100 ℃, reaction 6h, reaction solution is through filtration, distilation steps; Obtain 3,3, the 3-trifluoropropanol.
Beneficial effect of the present invention:
Of the present invention 3,3, the preparing method's of 3-trifluoropropanol reaction yield is higher, and 3,3,3-trifluoropropanol yield can reach 86%; And the method in the documents, 3,3,3-trifluoropropanol yield is 41%; Reactions step of the present invention is less, is merely single step reaction; And the method in the documents, reactions step was two steps.In addition, method of the present invention is to 3,3, and the aftertreatment of 3-trifluoropropanol is simple, and only common distillation can obtain the trifluoropropanol of purity 98%; And in the documents 3,3, the aftertreatment of 3-trifluoropropanol is loaded down with trivial details, must obtain the trifluoropropanol of purity 98% through azeotropic distillation.
Embodiment
Through specific embodiment the present invention is done further explain below, but protection scope of the present invention is not limited to this.
Analytical instrument: extra large glad GC-930 type gas chromatograph, the 30m DB-1 of the Agilent company (capillary chromatographic column of 50m * 0.32mm).
Analysis condition: 50 ℃ of post stove initial temperatures, 10 ℃/min temperature programming to 250 ℃, it is 250 ℃ with detector temperature that temperature of vaporization chamber is 280 ℃.
Raney Ni catalyst activation process: stir down, with in 150g alumino nickel and the 500g water adding reactor drum, heat temperature raising to 70 ℃; Under this temperature, drip 30% sodium hydroxide solution 1000g, after dripping, heat temperature raising to 80 ℃; Reaction 4h is cooled to room temperature, topples over the reaction solution upper strata and removes aqueous sodium hydroxide solution; Lower floor's catalyst layer is washed three times to neutral with 1000g, is stored in the water catalyzer subsequent use.
Embodiment 1
With 50g 3,3, the Raney Ni catalyzer that 3-trifluoro-propenyl methyl ether, 75g tributyl phosphate and 5g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa, stirs down; Heat temperature raising to 100 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution, filtering reacting liquid; Catalyzer is separated with reaction solution, and air distillation gained filtrating is collected 87 ℃～89 ℃ cuts, gets 3; 3,3-trifluoropropanol 39.7g, yield 86.0%, purity 98%.
Product structure is identified:
MS：m/z?114(M
+)，31(100)。
IR(KBr)，υ/cm
-1：3363，2962，1387，1256，1148，1003。
13CNMR(CDCl
3)，δ/ppm：127.57(CF
3，C3)，56.18(C，C1)，36.86(CH
2，C2)。
1HNMR(CDCl
3)，δ/ppm：3.90(m，2H)，2.38(m，2H)。
The said structure appraising datum confirms that method gained material of the present invention is 3,3 really, the 3-trifluoropropanol.
Embodiment 2
With 50g 3,3,3-trifluoro-propenyl methyl ether, the Raney Ni catalyzer that 60g dipropyl carbonate and 3g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 100 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 37.6g, yield 81.5%, purity 98%.
Embodiment 3
With 50g 3,3,3-trifluoro-propenyl methyl ether, the Raney Ni catalyzer that 64g diethyl carbonate and 2.5g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 70 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 35g, yield 75.8%, purity 98%.
Embodiment 4
With 50g 3,3,3-trifluoro-propenyl methyl ether, the Raney Ni catalyzer that 70g Ucar 35 carbonic ether and 3.5g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 90 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 37.8g, yield 81.9%, purity 98%.
Embodiment 5
With 50g 3,3,3-trifluoro-propenyl methyl ether, the Raney Ni catalyzer that 80g methylcarbonate and 4g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 80 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 38.7g, yield 83.8%, purity 98%.
Embodiment 6
With 50g 3,3,3-trifluoro-propenyl methyl ether, the Raney Ni catalyzer that 85g tributyl borate and 5.5g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 110 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 39.4g, yield 85.4%, purity 98%.
Embodiment 7
With 50g 3,3,3-trifluoro-propenyl methyl ether, the Raney Ni catalyzer that 90g triethyl phosphate and 6g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 120 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 39.5g, yield 85.6%, purity 98%.
Embodiment 8
With 50g 3,3,3-trifluoro-propenyl methyl ether, the Raney Ni catalyzer that 95g diethyl phosphoric acid and 10g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 100 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 39.1g, yield 84.7%, purity 98%.
Embodiment 9
With 50g 3,3,3-trifluoro-propenyl methyl ether, the Raney Ni catalyzer that 100g ethyl sulfate and 5g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 60 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 34.5g, yield 74.7%, purity 98%.
Embodiment 10
With 50g 3,3,3-trifluoro-propenyl methyl ether, the Raney Ni catalyzer that 80g amyl nitrate and 4g activation are good adds in the autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 70 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 36.2g, yield 78.4%, purity 98%.
Embodiment 11
With 50g 3,3,3-trifluoro-propenyl methyl ether, 75g reclaim and use tributyl phosphate and 4.8g to reclaim in the Raney Ni catalyzer adding autoclave, and filling hydrogen pressure is 5MPa; Stir down, heat temperature raising to 80 ℃, reaction 6h is cooled to room temperature, shifts out reaction solution; Filtering reacting liquid separates catalyzer with reaction solution, air distillation gained filtrating is collected 87～89 ℃ of cuts, gets 3; 3,3-trifluoropropanol 38.9g, yield 84.3%, purity 98%.
Claims (2)
1. one kind 3,3, the preparation method of 3-trifluoropropanol, the present invention is with 3,3; 3-trifluoro-propenyl methyl ether is a raw material, comprises the steps: 3,3, and the Raney Ni catalyzer that 3-trifluoro-propenyl methyl ether, inorganic ester and activation are good adds autoclave, is 5MPa at hydrogen pressure; Stir down, heat temperature raising to 60 ℃～120 ℃, reaction 4h～8h is cooled to room temperature; Through filtering, distilling post-processing step, obtain 3,3, the 3-trifluoropropanol; Wherein 3,3,3-trifluoro-propenyl methyl ether: inorganic ester: the catalyst quality ratio is 1: 1.2～2.0: 0.05～0.2.
2. according to claim 1 a kind of 3,3, the preparation method of 3-trifluoropropanol comprises the steps: to add in the autoclave 50g 3; 3, the Raney Ni catalyzer that 3-trifluoro-propenyl methyl ether, 75g tributyl phosphate and 5g activation are good is 5MPa at hydrogen pressure, stirs down; Heat temperature raising to 100 ℃, reaction 6h, reaction solution through filter, distilation steps; Obtain 3,3, the 3-trifluoropropanol.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02275829A (en) * | 1989-04-17 | 1990-11-09 | Central Glass Co Ltd | Production of 3,3,3-trifluoropropanol |
| JPH03249946A (en) * | 1990-02-28 | 1991-11-07 | Nard Inst Ltd | Production of raney ni-based catalyst |
| US5087775A (en) * | 1989-11-30 | 1992-02-11 | Bayer Aktiengesellschaft | Process for the preparation of partially fluorinated alcohols |
| JPH06212729A (en) * | 1993-01-19 | 1994-08-02 | Kajima Corp | Lighting system in ceiling |
| WO2007093567A1 (en) * | 2006-02-13 | 2007-08-23 | Solvay (Societe Anonyme) | Process for the manufacture of fluorinated alcohols |
| 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 |
-
2012
- 2012-08-09 CN CN2012102863711A patent/CN102766025A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02275829A (en) * | 1989-04-17 | 1990-11-09 | Central Glass Co Ltd | Production of 3,3,3-trifluoropropanol |
| US5087775A (en) * | 1989-11-30 | 1992-02-11 | Bayer Aktiengesellschaft | Process for the preparation of partially fluorinated alcohols |
| JPH03249946A (en) * | 1990-02-28 | 1991-11-07 | Nard Inst Ltd | Production of raney ni-based catalyst |
| JPH06212729A (en) * | 1993-01-19 | 1994-08-02 | Kajima Corp | Lighting system in ceiling |
| WO2007093567A1 (en) * | 2006-02-13 | 2007-08-23 | Solvay (Societe Anonyme) | Process for the manufacture of fluorinated alcohols |
| 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 |
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Application publication date: 20121107 |