EP2310347A2 - Process for the preparation of perfluorinated cis-alkene - Google Patents
Process for the preparation of perfluorinated cis-alkeneInfo
- Publication number
- EP2310347A2 EP2310347A2 EP09803441A EP09803441A EP2310347A2 EP 2310347 A2 EP2310347 A2 EP 2310347A2 EP 09803441 A EP09803441 A EP 09803441A EP 09803441 A EP09803441 A EP 09803441A EP 2310347 A2 EP2310347 A2 EP 2310347A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- perfluorinated
- cis
- process according
- aromatic amine
- hexafluoro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
Definitions
- Fluorocarbon based fluids have found widespread use in industry in a number of applications, including as refrigerants, aerosol propellants, blowing agents, heat transfer media, and gaseous dielectrics. Because of the suspected environmental problems associated with the use of some of these fluids, including
- alkynes to alkenes include Pd/C, Pd/BaSO 4 , Pd/BaCO 3 , and Pd/CaCO 3 .
- the use of quinoline as a catalyst modifier has been recommended whether the catalyst is Pd/C, Pd/BaSO 4 , or Lindlar's catalyst, Pd/CaCO 3 /Pb (M. Hudlicky, Reductions in Organic Chemistry, 2 nd Ed., ACS Monograph 188, 1996, p 8).
- the quality of the quinoline used may also affect the outcome.
- the PdVCaCO 3 ZPb catalyst, modified with pyridine, was successfully used in the reduction of an alkyne bearing a single fluorine on the carbon adjacent to the triple bond to give the corresponding cis-alkene (M. Prakesch, D. Gree, and R. Gree, J. Org. Chem., 66 (2001) 3146).
- the process is for the preparation of cis- 1,1,1, 4,4,4-hexafluoro-2- butene comprising: reducing hexafluoro-2-butyne with hydrogen over a palladium catalyst in the presence of a non-aromatic amine catalyst modifier to form a product comprising the cis- 1,1,1 ,4,4,4,-hexafluoro-2-butene.
- the starting material for this disclosure can be obtained by a variety of methods.
- the latter in turn can be prepared by the reductive dimerization of CF 3 CCI 3 (S Tomioka et al, Chemistry Letters, 1991, 1825).
- the pressure can vary considerably within the range of equipment capability. High pressures tend to speed up the reaction but may lead to overreduction. Hence the preferred pressures are 10 to 350 psig (72 to 2532 kPa) and more preferably 20-100 psig (145 to 723 kPa). In order to maximize the utilization of hydrogen, less than one equivalent may be added initially and more added as needed to complete the reaction or to maintain a desired hydrogen pressure.
- COMPARATIVE EXAMPLE A A pressure reactor was charged with 0.20 grams of 5 % palladium on carbon, 0.042 grams of reagent grade quinoline as catalyst poison and 25 mL of ethanol. After removing air as described in Example 1, 2.0 grams of hexafluoro-2- butyne was added. Hydrogenation was conducted at 20 psig (145 kPa) hydrogen pressure at room temperature. Workup and distillation as before gave 1.5 grams of CF 3 CH 2 CH 2 CF 3 ( 1 H NMR: 2.5 ppm; 19 F NMR: -66.8 ppm). Thus, even though the operating pressure was lower, over-reduction readily occurred to give the undesired butane.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US8507708P | 2008-07-31 | 2008-07-31 | |
PCT/US2009/051847 WO2010014548A2 (en) | 2008-07-31 | 2009-07-27 | Process for the preparation of perfluorinated cis-alkene |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2310347A2 true EP2310347A2 (en) | 2011-04-20 |
EP2310347A4 EP2310347A4 (en) | 2012-10-31 |
Family
ID=41610923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09803441A Withdrawn EP2310347A4 (en) | 2008-07-31 | 2009-07-27 | Process for the preparation of perfluorinated cis-alkene |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP2310347A4 (en) |
JP (1) | JP2011529893A (en) |
KR (1) | KR20110049820A (en) |
CN (1) | CN102112420A (en) |
MX (1) | MX2011000995A (en) |
WO (1) | WO2010014548A2 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2303818A1 (en) * | 2008-05-23 | 2011-04-06 | E. I. du Pont de Nemours and Company | High selectivity process to make dihydrofluoroalkenes |
US8461401B2 (en) * | 2010-03-26 | 2013-06-11 | Honeywell International Inc. | Method for making hexafluoro-2-butene |
US8530709B2 (en) * | 2010-05-21 | 2013-09-10 | Honeywell International Inc. | Process for the production of fluorinated alkenes |
US8524955B2 (en) * | 2010-05-21 | 2013-09-03 | Honeywell International Inc. | Process for the preparation of hexafluoro-2-butyne |
US8901360B2 (en) | 2010-05-21 | 2014-12-02 | Honeywell International Inc. | Process for cis 1,1,1,4,4,4-hexafluoro-2-butene |
JP5598910B2 (en) * | 2010-06-14 | 2014-10-01 | 独立行政法人産業技術総合研究所 | Method for producing fluorine compound |
WO2012079011A1 (en) * | 2010-12-10 | 2012-06-14 | E. I. Du Pont De Nemours And Company | Purification of cis-1,1,1,4,4,4-hexafluoro-2-butene via extractive distillation |
CN111018657B (en) * | 2014-02-07 | 2023-03-10 | 科慕埃弗西有限公司 | Integrated method for preparing Z-1,1,1,4,4,4-hexafluoro-2-butene |
CN106008147B (en) * | 2016-05-23 | 2018-11-02 | 北京宇极科技发展有限公司 | Z-1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene |
CN116060010B (en) * | 2023-03-31 | 2023-07-04 | 北京宇极科技发展有限公司 | Initiator, fluorination catalyst and process for the preparation of E-1, 4-hexafluoro-2-butene |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6014003B2 (en) * | 1978-11-08 | 1985-04-11 | 信越化学工業株式会社 | Method for selectively producing cis-olefin compounds |
JPS56133230A (en) * | 1980-03-21 | 1981-10-19 | Otsuka Pharmaceut Co Ltd | Preparation of cis-olefin |
US5587348A (en) * | 1995-04-19 | 1996-12-24 | Phillips Petroleum Company | Alkyne hydrogenation catalyst and process |
DE19526473A1 (en) * | 1995-07-20 | 1997-01-23 | Basf Ag | Process for the preparation of alkenes by partial hydrogenation of alkynes on fixed bed palladium catalysts |
DE19962907A1 (en) * | 1999-12-23 | 2001-07-05 | Basf Ag | Process for the preparation of C¶10¶-C¶30¶ alkenes by partial hydrogenation of alkynes on fixed bed supported palladium catalysts |
-
2009
- 2009-07-27 JP JP2011521221A patent/JP2011529893A/en active Pending
- 2009-07-27 EP EP09803441A patent/EP2310347A4/en not_active Withdrawn
- 2009-07-27 MX MX2011000995A patent/MX2011000995A/en not_active Application Discontinuation
- 2009-07-27 KR KR1020117004186A patent/KR20110049820A/en not_active Application Discontinuation
- 2009-07-27 CN CN2009801300180A patent/CN102112420A/en active Pending
- 2009-07-27 WO PCT/US2009/051847 patent/WO2010014548A2/en active Application Filing
Non-Patent Citations (5)
Title |
---|
BÜRGER H ET AL: "Vibrational spectra and normal coordinate analysis of cf3 compounds: Part XLI. Vibrational spectra, normal coordinate analysis and electron diffraction investigation of hexafluoroazomethane and of cis- and trans-1,1,1,4,4,4-hexafluorobut-2-ene", JOURNAL OF MOLECULAR STRUCTURE, ELSEVIER, AMSTERDAM, NL, vol. 84, no. 1-2, 1 September 1982 (1982-09-01), pages 49-68, XP002512757, ISSN: 0022-2860, DOI: 10.1016/0022-2860(82)85109-0 [retrieved on 2001-11-13] * |
HENNE A L ET AL: "Perfluoro-2-butyne and its hydrogenation products", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, ACS PUBLICATIONS, US, vol. 71, no. 1, 1 January 1949 (1949-01-01), pages 298-300, XP002512760, ISSN: 0002-7863, DOI: 10.1021/JA01169A080 * |
LINDLAR H: "Ein neuer Katalysator für selective Hydrierungen", HELVETICA CHIMICA ACTA, VERLAG HELVETICA CHIMICA ACTA, BASEL, CH, vol. 35, no. 2, 1 February 1952 (1952-02-01), pages 446-450, XP002512759, ISSN: 0018-019X, DOI: 10.1002/HLCA.19520350205 [retrieved on 2004-10-24] * |
See also references of WO2010014548A2 * |
SPEE, M. P. R.; BOERSMA, J. ET AL: "Selective Liquid-Phase Semihydrogenation of Functionalized Acetylenes and Propargylic Alcohols with Silica-Supported Bimetallic Palladium-Copper Catalysts", JOURNAL OF ORGANIC CHEMISTRY, vol. 66, 15 February 2001 (2001-02-15), pages 1647-1656, XP002683367, * |
Also Published As
Publication number | Publication date |
---|---|
WO2010014548A3 (en) | 2010-04-01 |
KR20110049820A (en) | 2011-05-12 |
MX2011000995A (en) | 2011-03-04 |
JP2011529893A (en) | 2011-12-15 |
EP2310347A4 (en) | 2012-10-31 |
CN102112420A (en) | 2011-06-29 |
WO2010014548A2 (en) | 2010-02-04 |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: MA, JING-JI Inventor name: VAN DER PUY, MICHAEL |
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DAX | Request for extension of the european patent (deleted) | ||
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C07C 21/18 20060101ALI20120917BHEP Ipc: B01J 23/745 20060101ALI20120917BHEP Ipc: B01J 23/04 20060101ALI20120917BHEP Ipc: C07C 17/354 20060101AFI20120917BHEP Ipc: B01J 23/44 20060101ALI20120917BHEP |
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A4 | Supplementary search report drawn up and despatched |
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STAA | Information on the status of an ep patent application or granted ep patent |
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18D | Application deemed to be withdrawn |
Effective date: 20150203 |