CN105753632A - Preparation method of 4-bromo-1, 1, 2-trifluoro-1-butene - Google Patents
Preparation method of 4-bromo-1, 1, 2-trifluoro-1-butene Download PDFInfo
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- CN105753632A CN105753632A CN201410781045.7A CN201410781045A CN105753632A CN 105753632 A CN105753632 A CN 105753632A CN 201410781045 A CN201410781045 A CN 201410781045A CN 105753632 A CN105753632 A CN 105753632A
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Abstract
The invention discloses a preparation method of 4-bromo-1, 1, 2-trifluoro-1-butene. According to the preparation method, in water as a solvent, 1, 4-dibromo-2-chloro-1, 1, 2-trifluorobutylene and zinc, iron, magnesium, aluminum, tin, copper or manganese as a dehalogenation agent undergo a dehalogenation reaction to produce 4-bromo-1, 1, 2-trifluoro-1-butene. The preparation method has the advantages of high yield, simple separation process, no need of solvent recovery and low cost.
Description
Technical field
The invention belongs to fluorine-containing field of fine chemical, the preparation method relating to a kind of bromo-1,1,2-tri-fluoro-1-butylene of 4-.
Background technology
Bromo-1,1, the 2-tri-fluoro-1-butylene of 4-(4-Bromo-1,1,2-trifluoro-1-butene, abridge BTFB) is a kind of important fluorine-containing organic intermediate, it is possible to for fields such as pesticide, medicine, materials.Such as at pesticide field, patent US3562341, WO2004020399, EP410551, CN1359379, WO2003049541, DE19544674, CN87104606, WO2003039258, US5514717, CN1064479, WO9321150, WO9304049 and EP506269 etc. report with 4-bromo-1,1, the fluoro-1-butylene of 2-tri-is intermediate, by reacting introducing-CH2CH2CF=CF2Functional group, the pesticide of gained has particularly pertinent performance in nematicide, has anthelmintic concurrently, kills the effects such as acarid.
In prior art, the preparation method of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-there is is following report:
US Patent No. 2003181615 discloses with CTFE for initiation material, through bromination addition, telomerize, dehalogenation three-step reaction prepares 4-bromo-1,1, the fluoro-1-butylene of 2-tri-, it may be assumed that the first step prepares 1,2-bis-bromo-2-chloro-1 with CTFE with bromine addition, 2,2-HFC-143as；The bromo-2-of second step 1,2-bis-chloro-1,2,2-HFC-143a and ethylene carry out telomerisation under catalyst action and prepare the chloro-1,1,2-trifluorobutane of the bromo-2-of 1,4-bis-；The bromo-2-of 3rd step 1,4-bis-chloro-1,1,2-trifluorobutane carries out the dehalogenation reaction and prepares the fluoro-1-butylene of the bromo-1,1,2-of 4-tri-.For the 3rd step dehalogenation reaction, embodiment 3 discloses concrete preparation process, stirs at the band being connected to condenser and adds 21.34g (0.326mol) zinc powder and 6.62g (0.048mol) ZnCl in two neck reactors2With 130g dimethyl sulfoxide, it is warming up to 40 DEG C then by 90.3g (0.297mol) 1, the bromo-2-of 4-bis-chloro-1,1, the solution of 2-trifluorobutane and 40g dimethyl sulfoxide is added dropwise in reactor, drips post-heating and is incubated 4 hours to 90 DEG C, after reaction terminates, first process with the hydrochloric acid solution of 10%, followed by NaHCO3Neutralize, then wash with water, finally extract and MgSO with trifluorotrichloroethane (CFC-113)4Dry, trifluorotrichloroethane is distilled off and obtains bromo-1,1, the 2-tri-fluoro-1-butylene of 20.2g4-, reaction yield only 36%.This three-step reaction adopts zinc/organic polar solvent reaction system, namely must use a large amount of polar organic solvent and zinc salt, and zinc salt is prone to form complex with target product and organic solvent, so that thick product later separation purifies, difficult solvent recovery.
The above-mentioned 3rd step dehalogenation reaction is typically in zinc/organic polar solvent reaction system to carry out, and polar solvent includes alcohol, ketone, ether, ester, amide, sulfone etc..At synthesis 4-bromo-1,1, during 2-tri-fluoro-1-butylene, except adopting dimethyl sulfoxide (DMSO) solvent except US2003181615 report, within 2005, J.Guio report uses N ' dinethylformamide (DMF) (JournalofPolymerScience:PartA:PolymerChemistry, 2005,43,917 935.) as reaction dissolvent, US20060052640 then adopts many carbon high boiling alcohol as reaction dissolvent.When adopting these polar solvents, need distillation to be separated by product or wash when separating product and organic solvent is removed.As adopted distillation, easily form complex owing to reaction produces substantial amounts of zinc salt with product and solvent, cause and be difficult to steam completely product, it is impossible to realize product and reactant liquor efficiently separates；As adopted washing, owing to the polar solvent water solublity adopted is better so that solvent recovery is more difficult.So, the zinc/organic polar solvent reaction system adopted at present is all extremely disadvantageous for industrialization and environmental protection.
Accordingly, it would be desirable to the method developing bromo-1,1, the 2-tri-fluoro-1-butylene of a kind of new preparation 4-.
Summary of the invention
The preparation method that present invention aim at providing a kind of bromo-1,1,2-tri-fluoro-1-butylene of 4-, there is yield height, separate simple, without the low advantage of solvent recovery and cost.
For reaching goal of the invention the technical solution used in the present invention it is:
The preparation method of a kind of bromo-1,1,2-tri-fluoro-1-butylene of 4-, with water for solvent, with metallic zinc, ferrum, magnesium, aluminum, stannum, copper or manganese for agent, chloro-1,1, the 2-trifluorobutane of the bromo-2-of Isosorbide-5-Nitrae-two prepares bromo-1,1, the 2-tri-fluoro-1-butylene of 4-through the dehalogenation reaction.
The solvent that the present invention uses is water, it is possible to be deionized water, tap water or clean Natural Water.What be preferably used is tap water.
The agent that the present invention adopts is metal, if ferrum, zinc, magnesium, aluminum, stannum, copper or manganese are suitable.What be preferably used is zinc.The shape of zinc can be granular, lamellar or Powdered, it is preferable that Powdered.
The mol ratio of chloro-1,1, the 2-trifluorobutane of the bromo-2-of Isosorbide-5-Nitrae-two, agent and water that the present invention adopts is preferably 1:1～5:5～30, more preferably 1:1～1.5:8～15.
The reaction temperature preferably 0～100 DEG C that the present invention adopts, more preferably 50～90 DEG C.
In preparation method of the present invention, as the preferred mode of one, it is preferable that 1, chloro-1,1, the 2-trifluorobutane of the bromo-2-of 4-bis-adds reaction system in the way of dropping, time for adding is 0.5～3.0h, and controlling temperature of reaction system during dropping is 0～100 DEG C, is incubated 0.1～3h after dropwising；As it is preferred that mode, the time for adding of described chloro-1,1, the 2-trifluorobutane of the bromo-2-of Isosorbide-5-Nitrae-two is 0.5～1.5h, during dropping control temperature of reaction system be 50～90 DEG C, after dropwising be incubated 0.5～1.5h.
The present invention adopts water as solvent, it is to avoid when using organic solvent, product and solvent are difficult to the shortcoming reclaimed, and reaction product liquid can obtain 4-bromo-1 through separatory operation, 1,2-tri-fluoro-1-butylene crude product, can obtain the purity 4-more than 99% bromo-1 after rectification, 1,2-tri-fluoro-1-butylene.The inventive method is simple to operate, and yield is high, it is adaptable to industrialized production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these detailed description of the invention.One skilled in the art would recognize that and present invention encompasses all alternatives, improvement project and the equivalents potentially included in Claims scope.
The synthesis of the fluoro-1-butylene of the bromo-1,1,2-of embodiment 1:4-tri-
Equipped with, in the there-necked flask of agitating device, adding zinc powder 9.8g (0.15mol) and water 24g (1.33mol), stirring is warming up to 50 DEG C.Dropping chloro-1,1, the 2-trifluorobutane 46g (0.15mol, 99.4%) of the bromo-2-of Isosorbide-5-Nitrae-two, period controls rate of addition, makes reaction temperature maintain 50～60 DEG C, and 60min drips complete.50 DEG C of insulation reaction 3h.Zinc powder disappears substantially.Filtering, filtrate stratification, separatory obtains crude product 24.2g.GC analyzes, and in crude product, the content of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-is 96.8%, yield 82.7%.
The synthesis of the fluoro-1-butylene of the bromo-1,1,2-of embodiment 2:4-tri-
Equipped with, in the there-necked flask of agitating device, adding zinc powder 14.7g (0.225mol) and water 24g (1.33mol), stirring is warming up to 60 DEG C.Dropping chloro-1,1, the 2-trifluorobutane 46g (0.15mol, 99.4%) of the bromo-2-of Isosorbide-5-Nitrae-two, period controls rate of addition, makes reaction temperature maintain 60～70 DEG C, and 70min drips complete.60 DEG C of insulation reaction 0.5h.Zinc powder has residue.Filter, reclaim zinc powder 4.4g.Filtrate stratification, separatory obtains crude product 24.5g.GC analyzes, and in crude product, the content of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-is 98.6%, yield 85.2%.
The synthesis of the fluoro-1-butylene of the bromo-1,1,2-of embodiment 3:4-tri-
Equipped with, in the there-necked flask of agitating device, adding zinc powder 10.8g (0.165mol) and water 32g (1.78mol), stirring is warming up to 70 DEG C.Dropping chloro-1,1, the 2-trifluorobutane 46g (0.15mol, 99.4%) of the bromo-2-of Isosorbide-5-Nitrae-two, period controls rate of addition, makes reaction temperature maintain 70-80 DEG C, and 45min drips complete.70 DEG C of insulation reaction 1.0h.Zinc powder has a small amount of residue.Filter, reclaim zinc powder 0.7g.Filtrate stratification, separatory obtains crude product 24.7g.GC analyzes, and in crude product, the content of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-is 98.9%, yield 86.1%.
The synthesis of the fluoro-1-butylene of the bromo-1,1,2-of comparative example 1:4-tri-
Equipped with, in the there-necked flask of agitating device, adding zinc powder 10.8g (0.165mol) and N ' dinethylformamide 30.2g (32ml), stirring is warming up to 70 DEG C.Dropping chloro-1,1, the 2-trifluorobutane 46g (0.15mol, 99.4%) of the bromo-2-of Isosorbide-5-Nitrae-two, period controls rate of addition, makes reaction temperature maintain 70-80 DEG C, and 60min drips complete.70 DEG C of insulation reaction 1.0h.Zinc powder has residue.Decompression product of distillation, to steaming liquid (external heat temperature 70～140 DEG C, vacuum-0.05～-0.08MPa), obtains crude product 16.4g.GC analyzes, and in crude product, the content of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-is 96.2%, yield 55.6%.
The synthesis of the fluoro-1-butylene of the bromo-1,1,2-of comparative example 2:4-tri-
Equipped with, in the there-necked flask of agitating device, adding zinc powder 10.8g (0.165mol) and diethylene glycol 35.8g (32ml), stirring is warming up to 70 DEG C.Dropping chloro-1,1, the 2-trifluorobutane 46g (0.15mol, 99.4%) of the bromo-2-of Isosorbide-5-Nitrae-two, period controls rate of addition, makes reaction temperature maintain 70-80 DEG C, and 60min drips complete.70 DEG C of insulation reaction 1.0h.Zinc powder has residue.Decompression product of distillation, to steaming liquid (external heat temperature 70～150 DEG C, vacuum-0.05～-0.08MPa), obtains crude product 20.5g.GC analyzes, and in crude product, the content of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-is 98.4%, yield 71.2%.
Claims (9)
1. the preparation method of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-, it is characterised in that with water for solvent, with metallic zinc, ferrum, magnesium, aluminum, stannum, copper or manganese for agent, the bromo-2-of Isosorbide-5-Nitrae-two chloro-1,1,2-trifluorobutane prepares bromo-1,1, the 2-tri-fluoro-1-butylene of 4-through the dehalogenation reaction.
2. the preparation method of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-described in claim 1, it is characterised in that described agent is zinc.
3. the preparation method of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-described in claim 1, it is characterised in that the mol ratio of described chloro-1,1, the 2-trifluorobutane of the bromo-2-of Isosorbide-5-Nitrae-two, agent and water is 1:1～5:5～30.
4. the preparation method of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-described in claim 3, it is characterised in that the mol ratio of described chloro-1,1, the 2-trifluorobutane of the bromo-2-of Isosorbide-5-Nitrae-two, agent and water is 1:1～1.5:8～15.
5. the preparation method of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-described in claim 1, it is characterised in that reaction temperature is 0～100 DEG C.
6. the preparation method of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-described in claim 6, it is characterised in that described reaction temperature is 50～90 DEG C.
7. the 4-bromo-1 described in claim 1,1, the preparation method of the fluoro-1-butylene of 2-tri-, it is characterized in that the described bromo-2-of Isosorbide-5-Nitrae-two chloro-1,1,2-trifluorobutane adds reaction system in the way of dropping, time for adding is 0.5～3.0h, and controlling temperature of reaction system during dropping is 0～100 DEG C, is incubated 0.1～3h after dropwising.
8. the preparation method of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-described in claim 7, it is characterized in that the described bromo-2-of Isosorbide-5-Nitrae-two chloro-1,1, the time for adding of 2-trifluorobutane is 0.5～1.5h, and controlling temperature of reaction system during dropping is 50～90 DEG C, is incubated 0.5～1.5h after dropwising.
9. the preparation method of bromo-1,1, the 2-tri-fluoro-1-butylene of 4-described in claim 1, it is characterised in that bromo-1,1, the 2-tri-fluoro-1-butylene of described 4-obtains bromo-1,1, the 2-tri-fluoro-1-butylene of the purity 4-more than 99% after separatory and distillation procedure.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233619A (en) * | 2020-03-17 | 2020-06-05 | 河北师范大学 | Method for synthesizing 4-halogenated-1, 1, 2-trifluoro-1-butene |
| CN114805010A (en) * | 2022-06-08 | 2022-07-29 | 河北桑迪亚医药技术有限责任公司 | Preparation method of 4-halogenated-1, 1, 2-trifluoro-1-butene |
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| US2774798A (en) * | 1954-11-23 | 1956-12-18 | Kellogg M W Co | Process for dehalogenation of organic compounds in the presence of a detergent |
| JPS5726629A (en) * | 1980-07-23 | 1982-02-12 | Daikin Ind Ltd | Preparation of trifluoroethylene |
| US20050222461A1 (en) * | 2002-05-13 | 2005-10-06 | Peter Wolfrum | Method for the production of substituted trifluoroethylenes |
| US20060052640A1 (en) * | 2002-05-13 | 2006-03-09 | Peter Wolfrum | Method for the production of substituted trifluroethylenses |
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2014
- 2014-12-16 CN CN201410781045.7A patent/CN105753632A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2774798A (en) * | 1954-11-23 | 1956-12-18 | Kellogg M W Co | Process for dehalogenation of organic compounds in the presence of a detergent |
| JPS5726629A (en) * | 1980-07-23 | 1982-02-12 | Daikin Ind Ltd | Preparation of trifluoroethylene |
| US20050222461A1 (en) * | 2002-05-13 | 2005-10-06 | Peter Wolfrum | Method for the production of substituted trifluoroethylenes |
| US20060052640A1 (en) * | 2002-05-13 | 2006-03-09 | Peter Wolfrum | Method for the production of substituted trifluroethylenses |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233619A (en) * | 2020-03-17 | 2020-06-05 | 河北师范大学 | Method for synthesizing 4-halogenated-1, 1, 2-trifluoro-1-butene |
| CN114805010A (en) * | 2022-06-08 | 2022-07-29 | 河北桑迪亚医药技术有限责任公司 | Preparation method of 4-halogenated-1, 1, 2-trifluoro-1-butene |
| CN114805010B (en) * | 2022-06-08 | 2023-08-04 | 河北桑迪亚医药技术有限责任公司 | Preparation method of 4-halogenated-1, 2-trifluoro-1-butene |
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