CN104926594A - Preparation method for 2,4- dichloro-2-fluorobutane derivative - Google Patents
Preparation method for 2,4- dichloro-2-fluorobutane derivative Download PDFInfo
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- CN104926594A CN104926594A CN201510220911.XA CN201510220911A CN104926594A CN 104926594 A CN104926594 A CN 104926594A CN 201510220911 A CN201510220911 A CN 201510220911A CN 104926594 A CN104926594 A CN 104926594A
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Abstract
The invention discloses a preparation method for a 2,4-dichloro-2-fluorobutane derivative. The method comprises the following steps: using dichlorofluoroethane (CH3CFCl2) and CH2=CHR as raw materials; and preparing the 2,4-dichloro-2-fluorobutane derivative in the presence of a telomeric catalyst, a catalytic additive and a solvent, wherein the telomeric catalyst is elemental copper, copper chloride or cuprous chloride; the catalytic additive is 2,2-dipyridyl, pentamethyldiethylenetriamine, tris(2-pyridyl methyl) amine or tris(2-dimethylamino ethyl)amine; and the solvent is acetonitrile, methanol or dimethyl sulfoxide. The preparation method provided by the invention provides a synthetic route with cheap raw materials and little three-wastes, and is mainly applied in preparation of the 2,4-dichloro-2-fluorobutane derivative.
Description
Technical field
The present invention relates to a kind of preparation method of fluorochemicals, be specifically related to the preparation method of a kind of 2,4-bis-chloro-2-fluorine butane derivative.
Background technology
In the past few decades, the study on the synthesis for fluorochemicals is the hot fields that chemists pay close attention to always.Fluorine is the element that electron-withdrawing power is the strongest, can form the very strong C-F key of bond energy, and its atomic radius is close with hydrogen atom, after atom is introduced organism, significantly can change physicochemical property and the biological activity of compound with carbon atom.
Organic fluorocompound is widely used in chemicals, agricultural chemicals, the fields such as photoelectric material, and existing most of organic fluoride-containing thing, be not present in occurring in nature, need synthetic.Therefore, for the study on the synthesis of organic fluorocompound matter, kind and the means of fluorine-containing material can be enriched.
Freon-type material as important fluorine-containing organic raw material, wide material sources, cheap.With this kind of material for Material synthesis organic fluorocompound, there is important prospects for commercial application and learning value.With the telomerization method that dichloro fluorine Lyons is raw material, be the important means preparing fluorine-containing cyclopropane derivative, document Org.Lett.2012,14 (24), 6214-6217 report with vinylbenzene (2mmol) and CF
3cHCl
2(4mL) at Cu (3mmol) and Et
2under NH (10mmol) catalysis, carry out purifying synthesis with column chromatography and obtain the chloro-triRuorobutyl benzene of 2,4-bis-, it is comparatively large to there is catalyst levels in the method, and the reaction three wastes are many.
Summary of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, provides a kind of catalyst levels little, the preparation method of 2, the 4-bis-chloro-2-fluorine butane derivatives that the three wastes are few.
The preparation feedback equation of 2,4-bis-chloro-2-fluorine butane derivatives of the present invention is as follows:
The present invention, with the preparation method of 2,4-bis-chloro-2-fluorine butane derivative, is characterized in that dichloro one fluoroethane (CH
3cFCl
2) and CH
2=CHR is raw material, and telomerizing under catalyzer and catalyst aid existence, in polar solvent, synthesis obtains 2,4-bis-chloro-2-fluorine butane derivative, and reaction equation is as follows:
Raw material CH of the present invention
2=CHR is ethene derivatives, comprises alkene, aryl ethylene, haloolefin, vinyl alcohol, and in raw material and product, R is alkyl, aryl, perfluoroalkyl or alkyl alcohol, preferred n-hexylene, isooctene, vinylbenzene, vinylchlorid, naphthalene ethene or vinylcarbinol.
Of the present invention telomerize catalyzer adopt copper simple substance or 1, the mantoquita of divalent, comprise that elemental copper, halo copper, halo are cuprous, Cupric salicylate, cupric oxalate or acetylacetone copper, preferred cuprous chloride or cupric chloride.
Catalyst aid of the present invention is organic amine, many pyridine compounds and theirs, add catalyst aid and can improve the solvability telomerizing catalyzer, reduce redox-potential, for reaching higher transformation efficiency and selectivity, preferred catalytic auxiliary agent 2,2-dipyridyl, pentamethyl-diethylenetriamine, three (2-pyridylmethyl) amine or three (2-dimethylaminoethyl) amine.
Solvent of the present invention is polar solvent, comprising: alcohols, ketone, nitrile, amides, sulfone class, and adding polar solvent can effectively improve speed of reaction and selectivity of product, and preferred solvent is acetonitrile, methyl alcohol or dimethyl sulfoxide (DMSO).
The invention has the advantages that:
(1) catalyst levels used in reaction is 1% ~ 10% of alkene mole number, and in documents, catalyst levels is 150% of alkene, and usage quantity obviously reduces.(2) reaction is with distillation purifying, raw material, and solvent and catalyzer all can be recycled, and therefore the three wastes are few, and documents uses column chromatography purification to cause material to be difficult to recycling.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but not any pro forma restriction is done to the present invention.
Embodiment 1:
Stir in autoclave to 500mL Ti Alloy Strip and add 2.8 grams of cupric chlorides, 6.2 gram of 2,2-dipyridyl, be dissolved in 100mL acetonitrile, with air in nitrogen replacement still, be pressed into 261 grams of CH with nitrogen
3cFCl
2with 62 grams of vinylchlorid, temperature of reaction 140 DEG C, 10 hours reaction times, after reaction, crude product air distillation removes CH
3cFCl
2and acetonitrile, and recycle, continue underpressure distillation and collect the chloro-2-fluorine butane of product 2,4,4-tri-, transformation efficiency 58.3%, selectivity 91.7%.
Embodiment 2 ~ 6:
Embodiment 2 ~ 6 prepares 2,4,4-tri-chloro-2-fluorine butane according to preparation method identical in embodiment 1, and difference is the catalysts in embodiment 1 is cupric chloride, and is respectively copper simple substance in embodiment 2 ~ 6, cupric chloride, cuprous chloride, cupric bromide.The reaction result of embodiment 2 ~ 6 is as shown in table 1.
Table 1 catalyzer and catalyst aid impact
Embodiment 7 ~ 12:
Embodiment 7 ~ 12 prepares 2,4-bis-chloro-2-fluorine butane derivative according to preparation method identical in embodiment 1, and difference is raw material with vinylchlorid in embodiment 1, and in embodiment 7 ~ 12, adopt raw material to be respectively naphthalene ethene, vinyl toluene, n-hexylene, isooctene, vinylbenzene and vinylcarbinol.The reaction result of embodiment 7 ~ 12 is as shown in table 2.
The reaction result of table 2 different sorts alkene
| Embodiment | Alkene | Temperature of reaction DEG C | Solvent | Transformation efficiency % | Selectivity % |
| 7 | N-hexylene | 130 | Acetonitrile | 82.5 | 93.5 |
| 8 | Naphthalene ethene | 130 | Acetonitrile | 73.1 | 80.2 |
| 9 | Vinyl toluene | 120 | Acetonitrile | 75.6 | 91.4 |
| 10 | Isooctene | 150 | Acetonitrile | 71.8 | 90.2 |
| 11 | Vinylbenzene | 130 | Methyl alcohol | 80.1 | 76.5 |
| 12 | Vinylcarbinol | 140 | Methyl-sulphoxide | 20.5 | 79.7 |
Embodiment 13 ~ 18:
Embodiment 13 ~ 18 prepares 2,4,4-tri-chloro-2-fluorine butane according to preparation method identical in embodiment 1, and difference telomerizes catalyzer and CH in embodiment 1
3cFCl
2mol ratio is 0.01:1, and the catalyst ratio in embodiment 13 ~ 18 is 0.001:1,0.005:1,0.02:1,0.05:1,0.1:1 and 0.5:1.The reaction result of embodiment 13 ~ 18 is as shown in table 3.
Table 3 catalyst levels affects
| Embodiment | Catalyst ratio | Transformation efficiency % | Selectivity % |
| 13 | 0.001:1 | 20.5 | 80.6 |
| 14 | 0.005:1 | 40.2 | 85.8 |
| 15 | 0.02:1 | 60.2 | 92.4 |
| 16 | 0.05:1 | 61.0 | 93.6 |
| 17 | 0.1:1 | 60.5 | 89.2 |
| 18 | 0.5:1 | 65.3 | 79.3 |
Embodiment 19 ~ 23:
Embodiment 19 ~ 23 prepares 2,4,4-tri-chloro-2-fluorine butane according to preparation method identical in embodiment 1, and difference is that in embodiment 1, temperature of reaction is 140 DEG C, and in embodiment 19 ~ 23, temperature of reaction is respectively 60,100,120,160,180 DEG C.The reaction result of embodiment 19 ~ 23 is as shown in table 4.
Table 4 reaction temperatures affect
| Embodiment | Catalyzer % | Temperature of reaction | Transformation efficiency % | Selectivity % |
| 19 | 2 | 60 | 30.6 | 74.1 |
| 20 | 2 | 100 | 57.4 | 90.3 |
| 21 | 2 | 120 | 59.2 | 91.7 |
| 22 | 2 | 160 | 61.5 | 93.4 |
| 23 | 2 | 180 | 62.0 | 65.3 |
Embodiment 24 ~ 29:
Embodiment 24 ~ 29 prepares 2,4,4-tri-chloro-2-fluorine butane according to preparation method identical in embodiment 1, difference be in embodiment 1 reaction times be 10 hours, and in embodiment 24 ~ 29 reaction times be respectively 1,8,12,24,36,48 hour.The reaction result of embodiment 24 ~ 29 is as shown in table 5.
Table 5 reaction times is on reaction impact
| Embodiment | Temperature of reaction DEG C | Reaction times h | Transformation efficiency % | Selectivity % |
| 24 | 70 | 1 | 10.1 | 70.5 |
| 25 | 70 | 8 | 56.7 | 90.2 |
| 26 | 70 | 12 | 58.9 | 91.3 |
| 27 | 70 | 24 | 62.1 | 93.5 |
| 28 | 70 | 36 | 63.2 | 87.4 |
| 29 | 70 | 48 | 65.7 | 76.0 |
Claims (6)
1. the preparation method of bis-chloro-2-fluorine butane derivatives, 2,4-bis-chloro-2-fluorine butane derivative general formula is such as formula shown in (I):
Comprise the following steps: with dichloro one fluoroethane and CH
2=CHR is raw material, and telomerizing under catalyzer and catalyst aid exist, in polar solvent, synthesis obtains 2,4-bis-chloro-2-fluorine butane derivative, and wherein, in raw material and product, R is alkyl, aryl, halogen or alkyl alcohol; Telomerize catalyzer be copper simple substance or 1, the mantoquita of divalent, catalyst aid is organic amine, many pyridine compounds and theirs, and polar solvent is alcohols, ketone, nitrile, amides or sulfone class, and reaction conditions is by dichloro one fluoroethane and CH
2=CHR mol ratio 1 ~ 5:1, telomerizes catalyzer and dichloro one fluoroethane mol ratio 0.001 ~ 0.5:1, temperature of reaction 60 ~ 180 DEG C, reaction times 1 ~ 48h.
2. the preparation method of 2,4-bis-chloro-2-fluorine butane derivatives according to claim 1, is characterized in that raw material CH
2=CHR is n-hexylene, isooctene, vinylbenzene, vinylchlorid, naphthalene ethene or vinylcarbinol.
3. the preparation method of 2,4-bis-chloro-2-fluorine butane derivatives according to claim 1, telomerizing catalyzer described in it is characterized in that is elemental copper, cuprous halide, copper halide, Cupric salicylate, cupric oxalate or acetylacetone copper.
4. according to claim 12, the preparation method of 4-bis-chloro-2-fluorine butane derivative, it is characterized in that catalyst aid is 2,2-dipyridyl, pentamethyl-diethylenetriamine, three (2-pyridylmethyl) amine or three (2-dimethylaminoethyl) amine.
5. the preparation method of 2,4-bis-chloro-2-fluorine butane derivatives according to claim 1, is characterized in that polar solvent is acetonitrile, methyl alcohol, acetone, dimethyl formamide or dimethyl sulfoxide (DMSO).
6. the preparation method of 2,4-bis-chloro-2-fluorine butane derivatives according to claim 1, is characterized in that reaction conditions is dichloro one fluoroethane and CH
2=CHR mol ratio 2 ~ 3:1, telomerizes catalyzer and dichloro one fluoroethane mol ratio 0.01 ~ 0.05:1, temperature of reaction 100 ~ 160 DEG C, reaction times 8 ~ 24h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879903A (en) * | 2017-11-06 | 2018-04-06 | 宿迁德威化工有限公司 | A kind of 1,1 difluoro compounds |
| CN110015946A (en) * | 2018-11-28 | 2019-07-16 | 大连理工大学 | A kind of preparation method of 1,5- diaryl -4- amylene-1-ol compound |
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| GB2188929A (en) * | 1986-04-10 | 1987-10-14 | Ceskoslovenska Akademie Ved | Production of halogenated organic compounds |
| CN103209944A (en) * | 2010-11-17 | 2013-07-17 | 纳幕尔杜邦公司 | Catalytical synthesis of hydrohalocarbons |
| CN104326862A (en) * | 2014-11-20 | 2015-02-04 | 西安近代化学研究所 | Preparation method of 2,4-dichloro-1,1,1-trifluorobutane derivative |
| CN104447186A (en) * | 2014-11-20 | 2015-03-25 | 西安近代化学研究所 | Preparation method of 2,4,4-trichloro-1,1,1-trifluorobutane |
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2015
- 2015-05-04 CN CN201510220911.XA patent/CN104926594A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2188929A (en) * | 1986-04-10 | 1987-10-14 | Ceskoslovenska Akademie Ved | Production of halogenated organic compounds |
| CN103209944A (en) * | 2010-11-17 | 2013-07-17 | 纳幕尔杜邦公司 | Catalytical synthesis of hydrohalocarbons |
| CN104326862A (en) * | 2014-11-20 | 2015-02-04 | 西安近代化学研究所 | Preparation method of 2,4-dichloro-1,1,1-trifluorobutane derivative |
| CN104447186A (en) * | 2014-11-20 | 2015-03-25 | 西安近代化学研究所 | Preparation method of 2,4,4-trichloro-1,1,1-trifluorobutane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879903A (en) * | 2017-11-06 | 2018-04-06 | 宿迁德威化工有限公司 | A kind of 1,1 difluoro compounds |
| CN110015946A (en) * | 2018-11-28 | 2019-07-16 | 大连理工大学 | A kind of preparation method of 1,5- diaryl -4- amylene-1-ol compound |
| CN110015946B (en) * | 2018-11-28 | 2021-08-10 | 大连理工大学 | Preparation method of 1, 5-diaryl-4-pentene-1-alcohol compound |
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Application publication date: 20150923 |