EP2215097A1 - Synthesis of hydrofluoroalkanols and hydrofluoroalkenes - Google Patents
Synthesis of hydrofluoroalkanols and hydrofluoroalkenesInfo
- Publication number
- EP2215097A1 EP2215097A1 EP08851477A EP08851477A EP2215097A1 EP 2215097 A1 EP2215097 A1 EP 2215097A1 EP 08851477 A EP08851477 A EP 08851477A EP 08851477 A EP08851477 A EP 08851477A EP 2215097 A1 EP2215097 A1 EP 2215097A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- metal
- reactive metal
- anhydride
- reaction
- 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- Withdrawn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
- 230000015572 biosynthetic process Effects 0.000 title description 9
- 238000003786 synthesis reaction Methods 0.000 title description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 98
- 239000002184 metal Substances 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 75
- 230000008569 process Effects 0.000 claims abstract description 64
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 24
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 20
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 20
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 71
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 67
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 150000001299 aldehydes Chemical class 0.000 claims description 37
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 36
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- -1 perfluoro-n-propyl Chemical group 0.000 claims description 24
- 239000000203 mixture Chemical class 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 230000002829 reductive effect Effects 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 12
- 150000003751 zinc Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000008246 gaseous mixture Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 150000003222 pyridines Chemical class 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical class C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical group 0.000 claims description 5
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 4
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000001273 butane Substances 0.000 claims description 4
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 4
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 claims description 4
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical class C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical class C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims 4
- 230000002140 halogenating effect Effects 0.000 claims 2
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 50
- 239000011541 reaction mixture Substances 0.000 description 46
- 239000002904 solvent Substances 0.000 description 25
- 229930040373 Paraformaldehyde Natural products 0.000 description 17
- BAMUEXIPKSRTBS-UHFFFAOYSA-N 1,1-dichloro-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Cl)Cl BAMUEXIPKSRTBS-UHFFFAOYSA-N 0.000 description 16
- 229920002866 paraformaldehyde Polymers 0.000 description 16
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000010354 integration Effects 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- ZGDAIZKZNKWBTM-UHFFFAOYSA-N 2-chloro-2,3,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(Cl)C(F)(F)F ZGDAIZKZNKWBTM-UHFFFAOYSA-N 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- FAOACLKUNWKVPH-UHFFFAOYSA-N 2,3,3,4,4,4-hexafluorobut-1-ene Chemical compound FC(=C)C(F)(F)C(F)(F)F FAOACLKUNWKVPH-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- FMKLGBFKHKIUKZ-UHFFFAOYSA-N 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(Cl)Cl FMKLGBFKHKIUKZ-UHFFFAOYSA-N 0.000 description 3
- PUFSJRPTJJPPJP-UHFFFAOYSA-N 3-chloro-1,1,1,2,2,3-hexafluoropropane Chemical compound FC(Cl)C(F)(F)C(F)(F)F PUFSJRPTJJPPJP-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DMUPYMORYHFFCT-UHFFFAOYSA-N 1,2,3,3,3-pentafluoroprop-1-ene Chemical compound FC=C(F)C(F)(F)F DMUPYMORYHFFCT-UHFFFAOYSA-N 0.000 description 2
- KEGQZXLRQSXPJU-UHFFFAOYSA-N 1,3-difluoro-1,3-bis(trifluoromethyl)cyclobutane Chemical compound FC(F)(F)C1(F)CC(F)(C(F)(F)F)C1 KEGQZXLRQSXPJU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzenecarbonitrile Natural products N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- QHNXEVRKFKHMRL-UHFFFAOYSA-N dimethylazanium;acetate Chemical compound CNC.CC(O)=O QHNXEVRKFKHMRL-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical group COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JXLLSNNXICBZIS-UHFFFAOYSA-N (2-chloro-2,3,3,3-tetrafluoropropyl) acetate Chemical compound CC(=O)OCC(F)(Cl)C(F)(F)F JXLLSNNXICBZIS-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- IBKYGQGEWCSHPJ-UHFFFAOYSA-N 1,3-difluoro-1,3-bis(1,1,2,2,2-pentafluoroethyl)cyclobutane Chemical compound FC(F)(F)C(F)(F)C1(F)CC(F)(C(F)(F)C(F)(F)F)C1 IBKYGQGEWCSHPJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RQBSYMINZKITIR-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoropropan-1-ol Chemical compound OCC(Cl)C(F)(F)F RQBSYMINZKITIR-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N anhydrous dimethyl-acetamide Natural products CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JFDZBHWFFUWGJE-KWCOIAHCSA-N benzonitrile Chemical group N#[11C]C1=CC=CC=C1 JFDZBHWFFUWGJE-KWCOIAHCSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical class 0.000 description 1
- 150000001930 cyclobutanes Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
- C07C17/363—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms by elimination of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
- C07C23/02—Monocyclic halogenated hydrocarbons
- C07C23/06—Monocyclic halogenated hydrocarbons with a four-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/63—Halogen-containing esters of saturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
Definitions
- This disclosure relates in general to a process for the production of hydrofluoroalkanols, and a process for the production of hydrofluoroalkenes, and in particular a process for the production of 2,3,3,3-tetrafluoro-1 -propene, from hydrofluoroalkanols and hydrofluoroalkanol esters.
- the present invention provides for the manufacture of hydrofluoroalkanols and hydrofluoroalkenes. Described herein is a process for the manufacture of hydrofluoroalkanols of the structure R f CFXCHROH, comprising reacting a halofluorocarbon of the structure RfCFX 2 , wherein each X is independently selected from Cl, Br, and I, with an aldehyde and a reactive metal in a reaction solvent to generate a reaction product comprising a metal hydrofluoroalkoxide, neutralizing said the metal hydrofluoroalkoxide to produce a hydrofluoroalkanol, and, optionally, recovering the hydrofluoroalkanol.
- the reductive dehydroxyhalogenation comprises reacting the metal hydrofluoroalkoxide with a carboxylic acid anhydride and a reactive metal to form the hydrofluoroalkene.
- the reductive dehydroxyhalogenation comprises neutralizing the metal hydrofluoroalkoxide to produce a hydrofluoroalkanol, mixing a dehydrating agent with said hydrofluoroalkanol thereby forming a gaseous mixture, and contacting a catalyst with said gaseous mixture, thereby forming the hydrofluoroalkene.
- the methods comprise the steps of manufacturing hydrofluoroalkenes as described above, wherein R f is CF 3 .
- Also disclosed is a method for the manufacture of hydrofluoroalkenes of the structure RfCF CHR, comprising reacting a hydrofluoroalkanol of structure RfCFXCHROH or a hydrofluoroalkoxide of structure RfCFXCHROMX, wherein M is a reactive metal in the +2 oxidation state and wherein X is selected from Cl, Br, and I, with a carboxylic acid anhydride and a reactive metal in a reaction solvent to form a hydrofluoroalkene, and isolating the hydrofluoroalkene.
- R f is a perfluoroalkyl group having from one to four carbon atoms
- X is selected from Cl, Br, and I
- R is CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 21 (CHs) 2 CH Or H.
- reactive metal refers to reactive metals such as magnesium turnings, activated zinc powder, aluminum, and a powder of any of the following metals: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium, and also zinc(ll) salts.
- Magnesium turnings are pieces of magnesium which are cut to produce small pieces with higher surface areas and generally low amounts of surface oxides (which reduce reactivity).
- the reactive metal powders of magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium are Rieke metals, which are prepared by a specific procedure which produces high surface area metal powders which are very reactive in reactions such as those of the present invention. Without wishing to be bound by any particular theory, Rieke metals are thought to be highly reactive because they have high surface areas and lack passivating surface oxides.
- a dehydrating agent is a gas or gaseous mixture containing at least one gas selected from the group consisting of: methane, ethane, propane, butane, natural gas, alcohols, aldehydes, and carbon monoxide.
- natural gas refers to a gaseous mixture having methane as the major component, but also comprising quantities of ethane, butane, propane, carbon dioxide, nitrogen.
- dehydroxyhalogenating refers to removing a hydroxyl group and a halogen atom, chosen from Cl, Br and I, from adjacent carbon atoms of a hydrofluoroalkanol to form a hydrofluoroalkene.
- hydrofluoroalkanols of the formula RfCFXCHROH such as 1 ,1 ,1 ,2-tetrafluoro-2-chloropropanol, an intermediate that may be converted into 2,3,3,3-tetrafluoro-1 -propene (HFC-1234yf), are prepared.
- R is selected from the group consisting of CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 2 , (CH 3 ) 2 CH or H.
- R f is a perfluoroalkyl group having from one to four carbon atoms.
- R f is selected from the group consisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, perfluoro-n-butyl and perfluoro-i-butyl, respectively, i.e., CF 3 -, CF 3 CF 2 -, CF 3 CF 2 CF 2 -, (CFs) 2 CF-, CF 3 CF 2 CF 2 - and CF 3 CF(CF 3 )CF 2 -, respectively.
- R f is CF 3 and R is H.
- X is selected from Cl, Br, and I. In another embodiment, X is Cl.
- halofluorocarbons of the formula RfCFX 2 wherein each X is independently selected from Cl, Br, and I, are reacted with an aldehyde, and a reactive metal in a reaction solvent to generate a metal hydrofluoroalkoxide.
- the metal hydrofluoroalkoxide is neutralized to provide a hydrofluoroalkanol, which can be isolated.
- the neutralization comprises dilution with an organic solvent, and reaction with a dilute aqueous solution of an acid, including without limitation dilute aqueous hydrochloric acid or dilute aqueous sulfuric acid.
- the organic solvent phase is washed further with an aqueous salt solution.
- the organic solvent phase is then dried and the solvent removed by evaporation or distillation to provide the hydrofluoroalkanol product.
- the metal hydrofluoroalkoxide may be used in further reactions as described later to produce a hydrofluoroalkene without neutralization.
- the halofluorocarbon is 1 ,1 ,dichlorotetrafluoroethane and the hydrofluoroalkanol is 2-chloro- 2,3,3,3-tetrafluoro-1 -propanol.
- Halofluorocarbons of the formula RfCFX 2 wherein each X is independently selected from Cl, Br, and I may be prepared by halogenation of the corresponding hydrofluorocarbons R f CFH 2 .
- Rf is CF 3 and X is Cl
- 1 ,1 ,1 ,2- tetrafluoroethane (HFC-134a) is chlorinated to prepare 1 ,1 ,1 ,2-tetrafluoro- 2,2-dichloroethane (CFC-114a).
- a zinc salt is added to the mixture comprising the reaction of the halofluorocarbon.
- Suitable zinc salts include zinc acetate, zinc bromide, zinc chloride, zinc citrate, zinc sulfate and mixtures thereof.
- the zinc salt is zinc acetate.
- the amount of zinc salt added is from 0.1 to 1.0 mole per mole of halofluorocarbon.
- the amount of zinc salt added is from 0.25 to 0.7 mole per mole of halofluorocarbon.
- the amount of zinc salt added is from 0. 5 to 0.6 mole per mole of halofluorocarbon.
- the aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.
- the mole ratio of reactive metal to halofluorocarbon is about 1 :1. In another embodiment, the mole ratio of reactive metal to halofluorocarbon is about 2:1. In yet another embodiment, the mole ratio of reactive metal to halofluorocarbon is about 2.5:1. In one embodiment, the mole ratio of aldehyde to halofluorocarbon is about 1 :1. In another embodiment, the mole ratio of aldehyde to halofluorocarbon is about 2:1.
- the mole ratio of aldehyde to halofluorocarbon is about 3:1.
- a quaternary ammonium salt is added to the reaction.
- the quaternary ammonium salt is a bis-alkyldimethyl ammonium acetate. Without wishing to be bound by any particular theory, such quaternary ammonium salts are believed to promote the decomposition of paraformaldehyde to formaldehyde.
- the amount of quaternary ammonium salt added is from about 1 % to about 20% by weight of the amount of paraformaldehyde. In other embodiments, the amount of quaternary ammonium salt added is from about 5% to about 10% by weight of the amount of paraformaldehyde.
- reaction solvent is selected from the group consisting of alkyl, dialkyl, and trialkyl linear or cylic amines, N-methylpyrrolidine, N-methylpipehdine, sulfoxides, ethers, pyridine or alkyl-substituted pyridines, pyrazine or pyhmidine, alkyl and aromatic nitriles, hexamethylphosphoramide, alcohols, esters, and mixtures thereof.
- an alcohol solvent is methanol.
- an ester solvent is methyl formate.
- a sulfoxide solvent is dimethylsulfoxide.
- an alkyl nitrile solvent is acetonitrile.
- an aromatic nitrile solvent is benzonitrile.
- the reaction solvent is selected from the group consisting of trialkylamines, N-methylpyrrolidine, N-methylpiperidine, pyridine, alkyl-substituted pyridines, dimethylformamide, pyrazine or pyrimidine, and mixtures thereof.
- the reaction solvent is selected from the group consisting of dimethylformamide, tetrahydrofuran, pyridine, dimethylacetamide, 1 ,4-dioxane, N-methyl pyrrolidone, diethyl ether, and mixtures thereof.
- the reaction solvent is pyridine or alkyl-substituted pyridines, or mixtures thereof.
- the reaction solvent is a mixture of pyridine or alkyl- substituted pyridines, and dimethylformamide.
- the amount of water present in the reaction of the halofluorocarbon with an aldehyde and reactive metal is less than 1000 ppm. In another embodiment, the amount of water present in the reaction of the halofluorocarbon with an aldehyde and reactive metal is about 500 ppm. In yet another embodiment, the amount of water present in the reaction of the halofluorocarbon with an aldehyde and reactive metal is from about 100 to about 300 ppm. In one embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed at a temperature of from about 30 0 C to about 100 0 C.
- the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed at a temperature of from about 50°C to about 80°C. In one embodiment, the reaction is conducted for from about 3 to about 10 hours. In another embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is conducted for from about 4 to about 8 hours. In yet another embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is conducted for from about 4 to about 6 hours.
- the aldehyde is pre-treated with the reaction solvent for a period of time before the reaction.
- paraformaldehyde is pre-treated in pyridine for four hours at 60 0 C prior to reaction with halofluorocarbon and reactive metal.
- the pre-treatment occurs for two hours.
- the pre- treatment occurs for six hours.
- there is no pre- treatment and the reaction is commenced upon charging all of the reactants and reaction solvent to the reaction vessel sequentially.
- the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed in a closed vessel or other reactor.
- reaction of the halofluorocarbon with an aldehyde and reactive metal is performed under autogenous pressure.
- the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed in an open vessel or reactor, equipped with a suitable condenser to prevent escape of unreacted halofluorocarbon.
- R f is a perfluoroalkyl group having from one to four carbon atoms.
- R f is CF 3 and R is H.
- the process for producing a hydrofluoroalkene comprises neutralizing the reaction product to produce a hydrofluoroalkanol; mixing a dehydrating agent with the hydrofluoroalkanol, thereby forming a gaseous mixture; and contacting a catalyst with the gaseous mixture, thereby forming the hydrofluoroalkene .
- the reaction product of a chlorofluoroalkane, an aldehyde and a reactive metal is neutralized by diluting the reaction product mixture with a mixture of a solvent, ice, and an aqueous solution of an acid.
- the solvent can be any commonly used organic solvent, such as diethyl ether.
- the aqueous solution of an acid is an aqueous solution of a common mineral acid, such as hydrochloric acid.
- the layer comprising the organic solvent is separated.
- the organic solvent layer can be subsequently washed with a dilute aqueous solution of an acid, followed by a brine solution.
- the organic layer is then dried.
- the drying is accomplished by stirring the organic layer over and anhydrous salt, such as anhydrous magnesium sulfate or anhydrous sodium sulfate.
- the organic solvent can then be evaporated to afford the hydrofluoroalkanol.
- the hydrofluoroalkanol is at least one selected from the group consisting of: fluoroalkanols having the general formula R f 'CH2OH wherein R f ' is selected from the group consisting of: CF 3 CFCI-, CF 3 CF 2 CFCI-, CF 3 CF 2 CF 2 CFCI- and CF 3 CF 2 CF 2 CFCI-.
- the hydrofluoroalkanol is 2,3,3,3-tetrafluoro-2-chloro-1 - propanol.
- the catalyst is at least one transition metal.
- the metal is selected from the group consisting of: nickel (Ni), palladium (Pd), and platinum (Pt).
- the catalyst is a supported catalyst which comprises a transition metal and a support material.
- the support material is at least one selected from the group consisting of activated carbon and /-alumina.
- the dehydrating agent is at least one gas selected from the group consisting of: methane, ethane, propane, butane, natural gas, alcohols, aldehydes, and carbon monoxide.
- the mixing step takes place at a temperature in the range between about 65-80 0 C.
- the process further comprises preheating the gaseous mixture prior to the contacting step.
- the preheating takes place at a temperature in the range between about 250 to about 450 0 C.
- the contacting step preferably takes place at a temperature in the range between about 400 to about 700°C.
- the contacting step also preferably takes place for between about 20 to about 25 seconds.
- the process further comprises the step of neutralizing any residual HF contained in the hydrofluoroalkene product, wherein the HF is neutralized by passing the hydrofluoroalkene product through a KOH solution.
- the gaseous mixture may further comprise at least one diluent inert gas selected from the group consisting of: nitrogen, helium, and argon.
- the conversion of the hydrofluoroalkanol to hydrofluoroalkene is in the range between about 50 to about 100%.
- the selectivity of hydrofluoroalkanol to hydrofluoroalkene is in the range between about 29 to about 100%.
- the pressure during the contacting step is in the range between about 1 to about 100 psig.
- the reductive dehydroxyhalogenation comprises reacting the metal hydrofluoroalkoxide with a carboxylic acid anhydride and a reactive metal.
- the hydrofluoroalkanol of structure RfCFXCHROH or a hydrofluoroalkoxide of structure R f CFXCHROMX, wherein M is a reactive metal in the +2 oxidation state react first with the carboxylic acid anhydride to form an ester as described below. This ester then reacts with the reactive metal to form a hydrofluoroalkene.
- R f is selected from the group consisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, perfluoro-n-butyl and perfluoro-i-butyl
- X is selected from Cl, Br, and I
- R is selected from the group consisting of H, CH 3 , C 2 H 5 , n-CsH / , and i- C 3 H 7 , and in particular R f is CF 3
- X is Cl and R is H.
- the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, and formic anhydride.
- the reactive metal powder is as described above.
- the reductive dehydroxyhalogenation can be done without neutralizing the product mixture from the reaction of a halofluorocarbon with a reactive metal and an aldehyde.
- the reductive dehydroxyhalogenation is done after first isolating the hydrofluoroalkanol, and then reacting it with a carboxylic acid anhydride and a reactive metal.
- the reductive dehydroxyhalogenation is done without isolating the ester. In other embodiments, the reductive dehydroxyhalogenation is done with the ester being isolated from the solvent and metal salts, and then reacted with the reactive metal.
- the product of the reductive dehydroxyhalogenation further comprises a substituted cyclobutane of the formula cyclo-(-CF(R f )CHRCF(R f )CHR-), wherein R f is a perfluoroalkyl group having from one to four carbon atoms and R is CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 2 , (CH 3 ) 2 CH or H. In one particular embodiment, R f is CF 3 and R is H.
- the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, and formic anhydride.
- the carboxylic acid anhydride is acetic anhydride.
- the mole ratio of carboxylic acid anhydride to hydrofluoroalkanol is from about 1 :1 to about 2:1.
- the mole ratio of carboxylic acid anhydride to hydrofluoroalkanol is from about 1.4:1 to about 1.8:1.
- the mole ratio of reactive metal to hydrofluoroalkanol is about 1 :1.
- the mole ratio of reactive metal to hydrofluoroalkanol is about 2:1. In yet another embodiment, the mole ratio of reactive metal to hydrofluoroalkanol is about 2.5:1.
- R f is CF 3
- R is H
- X is Cl
- R' is CH 3 .
- the reductive dehydroxyhalogenation is conducted in a reaction solvent which is the same solvent in which the reaction of a halofluorocarbon with reactive metal and an aldehyde is conducted in.
- the reductive dehydroxyhalogenation is conducted in a reaction solvent which is a different solvent than the reaction of a halofluorocarbon with reactive metal and an aldehyde is conducted in.
- the reductive dehydroxyhalogenation is conducted in a mixture of pyridine or an alkyl-substituted pyridine, and dimethylformamide.
- the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
- a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
- “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
- Example 1 demonstrates the preparation of 2-chloro-3,3,3- trifluoropropanol from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane.
- Example 2 demonstrates the conversion of 2-chloro-2, 3,3,3- tetrafluoropropanol to 2,3,3,3- tetrafluoroi -propene.
- Example 3 demonstrates the synthesis of 2,3,3,3- tetrafluoro-1 - propene from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane.
- a 400 ml Hastelloy C shaker tube was charged with 20 g (0.315 mol) of activated Zinc powder, 7.5g (0.25 mol) of paraformaldehyde and 130 ml anhydrous DMF under N 2 . The tube was cooled down to -15 0 C and 43 g (0.25 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 60 0 C for 6 hours.
- Example 4 demonstrates the synthesis of 2-chloro-2, 3,3,3- tetrafluoropropanol (CF 3 CCIFCH 2 OH) in pyridine.
- Example 5 demonstrates the synthesis of 2-chloro-2, 3,3,3- tetrafluoropropanol CF 3 CCIFCH 2 OH in dimethylacetamide.
- Example 6 demonstrates the synthesis of 2-chloro-2, 3,3,3- tetrafluoropropanol CF 3 CCIFCH 2 OH in pyridine, with pre-treatment of formaldehyde.
- a 80 ml Fisher Porter tube was charged with 1.82g (0.06 mol) of paraformaldehyde and 30 ml anhydrous pyridine under N 2 .
- the tube was heated up to 60 0 C and stirred at 60 0 C for 4hr. Then it was cooled down to room temp and 2.24 g (0.034 mol) of activated Zinc powder were added. After purging with N 2 for 15 min, the tube was cooled down to -15 0C and 5 g (0.029 mol) of 1 ,1 -dichlorotetrafluoroethane were added.
- CF 3 CCIFCH 2 OZnCI (analyzed as CF 3 CCIFCH 2 OH) increased to 78.7%.
- Example 7 illustrates the esterification of 2,3,3, 3-tetrafluoro-2- chloropropanol with acetic anhydride to produce 2,3,3,3-tetrafluoro-2- chloropropyl acetate.
- Example 8 illustrates the direct esterification of CF 3 CCIFCH 2 OZnCI to CF 3 CCIFCH 2 OAC. 10 ml of a pyridine solution containing about 14%
- CF 3 CCIFCH 2 OZnCI was vacuum evaporated at room temp to remove the majority of the pyridine. Then 2.Og acetic anhydride and 1 ml DMF were added into the resultant solid. The mixture was stirred at 60 0 C for 7hr.
- Example 9 illustrates the conversion of CF 3 CCIFCH 2 OAC to 2,3,3,3- tetrafluoropropene.
- Example 10 demonstrates the reaction of 1 ,1 - dichlorotetrafluoroethane with paraformaldehyde in a mixed solvent of dimethylformamide and pyridine to produce CF 3 CCIFCH 2 OZnCI.
- a 80 ml Fisher Porter tube was charged with 2.2g Zn (0.037 mol), 0.3g Zinc acetate (0.0016mol), 2g (0.067 mol) of paraformaldehyde, 15g of anhydrous pyridine and 15g of dimethylformamide under N 2 . After N 2 purge for 15 min, the tube was cooled down to -15 0 C and 5 g (0.029 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 50 0 C for 2 hours. The pressure of the reactor dropped to 5 psig at end of reaction from 25 psig. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS.
- Example 11 illustrates esterification of CF 3 CCIFCH 2 OZnCI directly to CF 3 CCIFCH 2 OAC with acetic anhydride in a solvent mixture.
- Example 12 illustrates the synthesis of 2,3,3,3- tetrafluoroi -propene from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane in 3:1 pyridine:DMF solvent.
- Solvent pyridine was excluded from integration. The data is reported in Table 11 by area percent of GC-MS. The selectivity of 1 ,1 -dichlorotetrafluoroethane to CF 3 CCIFCH 2 OZnCI (analyzed as CF 3 CCIFCH 2 OH) is 81 % based on GC-MS analysis.
- Example 13 illustrates the synthesis of 2,3,3,3- tetrafluoro-1- propene from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane in 1 :1 pyridine:DMF solvent.
- a 80 ml Fisher Porter tube was charged with 2.1 g Zn (0.032), 0.3g
- the reaction mix above was treated with 2g Na 2 CO 3 in 80 ml Fisher Porter tube. After Na 2 CO 3 was filtrated off, activated Zinc powder (1g, 0.015mol) was added. The reaction was run in an 80ml Fisher Porter tube at 60 0 C for 4hr with stirring. The pressure of the reactor increased from 5 psig to 18 psig. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. The data is reported by area percent of GC-MS. The result of vapor phase was listed in Table 17 and the result of liquid phase was reported in Table 18 (solvent DMF and pyridine was excluded from integration).
- Example 14 illustrates the synthesis of 2,3,3,4,4,4- hexafluoro-1 - butene from 1 ,1 ,1 ,2,2,3-hexafluoro-3,3-dichloropropane in 1 :1 pyhdine:DMF solvent.
- a 80 ml Fisher Porter tube is charged with 2.1 g Zn (0.032), 0.3g Zinc acetate (0.0016mol), 2g (0.067 mol) of paraformaldehyde, 0.2g Bis(hydrogenated alkyl) dimethyl ammonium acetate and 3Og anhydrous pyridine under N 2 . After purging with N 2 for 15 min, the tube is cooled down to -15 0 C and 6.4 g (0.029 mol) of 1 ,1 ,1 , 2,2,3-hexafluoro-3,3- dichloropropane was added. Then the reaction mixture is stirred at 50 0 C for 3 hours. The pressure of the reactor drops to 5.5 psig at end of reaction from 23 psig.
- reaction mixture After the reaction mixture cooled down to room temperature, it is analyzed by GC-MS.
- GC-MS analysis a portion of the reaction mixture is acidified with a 10% solution of HCI in acetone. Solvents DMF and pyridine are excluded from integration. The data is reported in Table 18 by area percent of GC-MS.
- the selectivity of 216cb to CF 3 CF 2 CCIFCH 2 OZnCI (analyzed as CF 3 CF 2 CCIFCH 2 OH) is about 85% based on GC-MS analysis.
- the reaction mix above is then treated with 2g Na 2 CO 3 in an 80 ml Fisher Porter tube. After Na 2 CO 3 is filtrated off, activated Zinc powder (1g, 0.015mol) is added. The reaction is run in an 80ml Fisher Porter tube at 60 0 C for 4hr with stirring. The pressure of the reactor increases from 5 psig to 18 psig. After the reaction mixture is cooled down to room temperature, it is analyzed by GC-MS. The data is reported by area percent of GC-MS. The result of vapor phase is listed in Table 20 and the result of liquid phase is reported in Table 21 (solvent DMF and pyridine was excluded from integration).
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Abstract
Described herein is a process for the manufacture of hydrofluoroalkanols of the structure RfCFClCHROH, comprising reacting a halofluorocarbon of the structure RfCFX2, wherein each X is independently selected from Cl, Br, and I, with an aldehyde and a reactive metal in a reaction solvent to generate a reaction product comprising a metal hydrofluoroalkoxide, neutralizing said metal hydrofluoroalkoxide to produce a hydrofluoroalkanol, and recovering the hydrofluoroalkanol. Also described herein are methods of manufacturing hydrofluoroalkenes of the structure RfCF=CHR from halofluorocarbons of the structure RfCFX2, wherein each X is independently selected from Cl, Br, and I, comprising (1) reacting halofluorocarbons of the structure RfCFX2, wherein each X is independently selected from Cl, Br, and I, with an aldehyde and a reactive metal to generate a reaction product comprising a metal hydrofluoroalkoxide, and reductively dehydroxyhalogenating said metal hydrofluoroalkoxide to produce a hydrofluoroalkene or (2) reacting a hydrofluoroalkanol of the structure RfCFXCHROH or a hydrofluoroalkoxide of the structure RfCFXCHROMX, wherein M is a reactive metal in the +2 oxidation state, with a carboxylic acid anhydride and a reactive metal in a reaction solvent to form a hydrofluoroalkene and isolating the hydrofluoroalkene. In particular, 2,3,3,3,-tetrafluoro-1-propene may be manufactured with this process. Also described are compounds of the formula RfCFClCHROC(=O)R'.
Description
TITLE
SYNTHESIS OF HYDROFLUOROALKANOLS AND HYDROFLUOROALKENES
BACKGROUND
Field of the Disclosure
This disclosure relates in general to a process for the production of hydrofluoroalkanols, and a process for the production of hydrofluoroalkenes, and in particular a process for the production of 2,3,3,3-tetrafluoro-1 -propene, from hydrofluoroalkanols and hydrofluoroalkanol esters. Description of the Related Art
The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. HFC's, however, are now being regulated due to concerns related to global warming. There is always a need for new and better processes for the preparation of halocarbons that may be useful as refrigerants or in other applications such as foam expansion agents, aerosol propellants, fire suppression or extinguishing agents, solvents, and sterilants to name a few. SUMMARY OF THE INVENTION
The present invention provides for the manufacture of hydrofluoroalkanols and hydrofluoroalkenes. Described herein is a process for the manufacture of hydrofluoroalkanols of the structure RfCFXCHROH, comprising reacting a halofluorocarbon of the structure RfCFX2, wherein each X is independently selected from Cl, Br, and I, with an aldehyde and a reactive metal in a reaction solvent to generate a reaction product comprising a metal hydrofluoroalkoxide, neutralizing said the metal hydrofluoroalkoxide to produce a hydrofluoroalkanol, and, optionally, recovering the hydrofluoroalkanol.
Also described herein are methods of manufacturing hydrofluoroalkenes from halofluorocarbons of the structure RfCFX2, wherein each X is independently selected from Cl, Br, and I, comprising reacting halofluorocarbons of the structure RfCFX2, wherein each X is independently selected from Cl, Br, and I with an aldehyde and a reactive metal in a reaction solvent to generate a reaction product comprising a metal hydrofluoroalkoxide, and reductively dehydroxyhalogenating the metal hydrofluoroalkoxide to produce a hydrofluoroalkene, and, optionally, recovering the hydrofluoroalkene. In one embodiment, the reductive dehydroxyhalogenation comprises reacting the metal hydrofluoroalkoxide with a carboxylic acid anhydride and a reactive metal to form the hydrofluoroalkene. In another embodiment, the reductive dehydroxyhalogenation comprises neutralizing the metal hydrofluoroalkoxide to produce a hydrofluoroalkanol, mixing a dehydrating agent with said hydrofluoroalkanol thereby forming a gaseous mixture, and contacting a catalyst with said gaseous mixture, thereby forming the hydrofluoroalkene.
Also described herein are methods of manufacturing 2,3,3,3- tetrafluoro-1 -propene. The methods comprise the steps of manufacturing hydrofluoroalkenes as described above, wherein Rf is CF3.
Also disclosed herein are novel hydrofluoroalkanol esters of the formula RfCFXCH2OC(=O)R, where Rf is a perfluoroalkyl group having from one to four carbon atoms, R is CH3, CH3CH2, CH3CH2CH2, (CH3)2CH or H, X is selected from Cl, Br, and I, and R' is selected from the group consisting of -CH3, -C2H5, -CH2CH2CH3, CH2CH2CO2H, CH2CH2CH2CO2H, CH2CH2CH2CH2CO2H and H, and novel hydrofluorocarbons of the formula cyclo-(-CF(Rf)CHRCF(Rf)CHR-).
Also disclosed is a method for the manufacture of hydrofluoroalkenes of the structure RfCF=CHR, comprising reacting a hydrofluoroalkanol of structure RfCFXCHROH or a hydrofluoroalkoxide of structure RfCFXCHROMX, wherein M is a reactive metal in the +2 oxidation state and wherein X is selected from Cl, Br, and I, with a carboxylic acid anhydride and a reactive metal in a reaction solvent to form a hydrofluoroalkene, and isolating the hydrofluoroalkene.
Also disclosed herein is a compound having the formula RfCFXCHRO-Zn-X, where Rf is a perfluoroalkyl group having from one to four carbon atoms, X is selected from Cl, Br, and I, and R is CH3, CH3CH2, CH3CH2CH21 (CHs)2CH Or H.
Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention. Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description and from the claims.
DETAILED DESCRIPTION
Before addressing details of embodiments described below, some terms are defined or clarified.
As used herein, formaldehyde refers to the compound having the structure H2C=O, which is also known to occur in the form of a cyclic trimer 1 ,3,5-trioxane, and also as paraformaldehyde or polyoxymethylene.
As used herein, reactive metal refers to reactive metals such as magnesium turnings, activated zinc powder, aluminum, and a powder of any of the following metals: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium, and also zinc(ll) salts. Magnesium turnings are pieces of magnesium which are cut to produce small pieces with higher surface areas and generally low amounts of surface oxides (which reduce reactivity). The reactive metal powders of magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium are Rieke metals, which are prepared by a specific procedure which produces high surface area metal powders which are very reactive in reactions such as those of the present invention. Without wishing to be bound by any particular theory, Rieke metals are thought to be highly reactive because they have high surface areas and lack passivating surface oxides.
As used herein, a dehydrating agent is a gas or gaseous mixture containing at least one gas selected from the group consisting of: methane, ethane, propane, butane, natural gas, alcohols, aldehydes, and
carbon monoxide. As used herein, natural gas refers to a gaseous mixture having methane as the major component, but also comprising quantities of ethane, butane, propane, carbon dioxide, nitrogen.
As used herein dehydroxyhalogenating refers to removing a hydroxyl group and a halogen atom, chosen from Cl, Br and I, from adjacent carbon atoms of a hydrofluoroalkanol to form a hydrofluoroalkene.
In one embodiment, hydrofluoroalkanols of the formula RfCFXCHROH, such as 1 ,1 ,1 ,2-tetrafluoro-2-chloropropanol, an intermediate that may be converted into 2,3,3,3-tetrafluoro-1 -propene (HFC-1234yf), are prepared. In one embodiment, R is selected from the group consisting of CH3, CH3CH2, CH3CH2CH2, (CH3)2CH or H. In one embodiment, Rf is a perfluoroalkyl group having from one to four carbon atoms. In another embodiment, Rf is selected from the group consisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, perfluoro-n-butyl and perfluoro-i-butyl, respectively, i.e., CF3-, CF3CF2-, CF3CF2CF2-, (CFs)2CF-, CF3CF2CF2CF2- and CF3 CF(CF3)CF2-, respectively. In one embodiment, Rf is CF3 and R is H. In one embodiment X is selected from Cl, Br, and I. In another embodiment, X is Cl.
In one embodiment, halofluorocarbons of the formula RfCFX2, wherein each X is independently selected from Cl, Br, and I, are reacted with an aldehyde, and a reactive metal in a reaction solvent to generate a metal hydrofluoroalkoxide. In one embodiment the metal hydrofluoroalkoxide is neutralized to provide a hydrofluoroalkanol, which can be isolated. In some embodiments, the neutralization comprises dilution with an organic solvent, and reaction with a dilute aqueous solution of an acid, including without limitation dilute aqueous hydrochloric acid or dilute aqueous sulfuric acid. Upon separation of the organic solvent phase from the aqueous phase, in some embodiments, the organic solvent phase is washed further with an aqueous salt solution. The organic solvent phase is then dried and the solvent removed by evaporation or distillation to provide the hydrofluoroalkanol product. In other embodiments, the metal hydrofluoroalkoxide may be used in further
reactions as described later to produce a hydrofluoroalkene without neutralization. In one embodiment, the halofluorocarbon is 1 ,1 ,dichlorotetrafluoroethane and the hydrofluoroalkanol is 2-chloro- 2,3,3,3-tetrafluoro-1 -propanol. Halofluorocarbons of the formula RfCFX2, wherein each X is independently selected from Cl, Br, and I may be prepared by halogenation of the corresponding hydrofluorocarbons RfCFH2. For example, in one embodiment where Rf is CF3 and X is Cl, 1 ,1 ,1 ,2- tetrafluoroethane (HFC-134a) is chlorinated to prepare 1 ,1 ,1 ,2-tetrafluoro- 2,2-dichloroethane (CFC-114a).
In some embodiments, in addition to the reactive metal, a zinc salt is added to the mixture comprising the reaction of the halofluorocarbon. Suitable zinc salts include zinc acetate, zinc bromide, zinc chloride, zinc citrate, zinc sulfate and mixtures thereof. In one embodiment, the zinc salt is zinc acetate. In one embodiment, the amount of zinc salt added is from 0.1 to 1.0 mole per mole of halofluorocarbon. In another embodiment, the amount of zinc salt added is from 0.25 to 0.7 mole per mole of halofluorocarbon. In another embodiment, the amount of zinc salt added is from 0. 5 to 0.6 mole per mole of halofluorocarbon. In one embodiment, the aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde. In one embodiment, the mole ratio of reactive metal to halofluorocarbon is about 1 :1. In another embodiment, the mole ratio of reactive metal to halofluorocarbon is about 2:1. In yet another embodiment, the mole ratio of reactive metal to halofluorocarbon is about 2.5:1. In one embodiment, the mole ratio of aldehyde to halofluorocarbon is about 1 :1. In another embodiment, the mole ratio of aldehyde to halofluorocarbon is about 2:1. In yet another embodiment, the mole ratio of aldehyde to halofluorocarbon is about 3:1. In some embodiments where paraformaldehyde is used as the aldehyde, a quaternary ammonium salt is added to the reaction. In one embodiment, the quaternary ammonium salt is a bis-alkyldimethyl ammonium acetate. Without wishing to be bound by any particular theory, such quaternary ammonium salts are believed to promote the
decomposition of paraformaldehyde to formaldehyde. In some embodiments the amount of quaternary ammonium salt added is from about 1 % to about 20% by weight of the amount of paraformaldehyde. In other embodiments, the amount of quaternary ammonium salt added is from about 5% to about 10% by weight of the amount of paraformaldehyde.
The reaction of the halofluorocarbon with an aldehyde and reactive metal is conducted in a reaction solvent. In one embodiment, the reaction solvent is selected from the group consisting of alkyl, dialkyl, and trialkyl linear or cylic amines, N-methylpyrrolidine, N-methylpipehdine, sulfoxides, ethers, pyridine or alkyl-substituted pyridines, pyrazine or pyhmidine, alkyl and aromatic nitriles, hexamethylphosphoramide, alcohols, esters, and mixtures thereof. In one embodiment, an alcohol solvent is methanol. In one embodiment, an ester solvent is methyl formate. In one embodiment, a sulfoxide solvent is dimethylsulfoxide. In one embodiment, an alkyl nitrile solvent is acetonitrile. In one embodiment, an aromatic nitrile solvent is benzonitrile. In another embodiment, the reaction solvent is selected from the group consisting of trialkylamines, N-methylpyrrolidine, N-methylpiperidine, pyridine, alkyl-substituted pyridines, dimethylformamide, pyrazine or pyrimidine, and mixtures thereof. In another embodiment, the reaction solvent is selected from the group consisting of dimethylformamide, tetrahydrofuran, pyridine, dimethylacetamide, 1 ,4-dioxane, N-methyl pyrrolidone, diethyl ether, and mixtures thereof. In yet another embodiment, the reaction solvent is pyridine or alkyl-substituted pyridines, or mixtures thereof. In yet another embodiment, the reaction solvent is a mixture of pyridine or alkyl- substituted pyridines, and dimethylformamide.
In one embodiment, the amount of water present in the reaction of the halofluorocarbon with an aldehyde and reactive metal is less than 1000 ppm. In another embodiment, the amount of water present in the reaction of the halofluorocarbon with an aldehyde and reactive metal is about 500 ppm. In yet another embodiment, the amount of water present in the reaction of the halofluorocarbon with an aldehyde and reactive metal is from about 100 to about 300 ppm.
In one embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed at a temperature of from about 300C to about 1000C. In another embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed at a temperature of from about 50°C to about 80°C. In one embodiment, the reaction is conducted for from about 3 to about 10 hours. In another embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is conducted for from about 4 to about 8 hours. In yet another embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is conducted for from about 4 to about 6 hours.
In one embodiment, the aldehyde is pre-treated with the reaction solvent for a period of time before the reaction. In one embodiment paraformaldehyde is pre-treated in pyridine for four hours at 600C prior to reaction with halofluorocarbon and reactive metal. In one embodiment, the pre-treatment occurs for two hours. In another embodiment, the pre- treatment occurs for six hours. In still other embodiments, there is no pre- treatment, and the reaction is commenced upon charging all of the reactants and reaction solvent to the reaction vessel sequentially. In one embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed in a closed vessel or other reactor. In one embodiment the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed under autogenous pressure. In another embodiment, the reaction of the halofluorocarbon with an aldehyde and reactive metal is performed in an open vessel or reactor, equipped with a suitable condenser to prevent escape of unreacted halofluorocarbon.
According to another aspect of the present invention, there is provided a process for the manufacture of hydrofluoroalkenes of the structure RfCF=CHR. This process comprises reacting a halofluorocarbon of the structure RfCFX2 with an aldehyde and a reactive metal to generate a metal hydrofluoroalkoxide, reductively dehydroxyhalogenating said reaction product in a second step to produce a hydrofluoroalkene, and then isolating the hydrofluoroalkene.
In one embodiment, Rf is a perfluoroalkyl group having from one to four carbon atoms. In a particular embodiment, Rf is CF3 and R is H.
In one embodiment, the process for producing a hydrofluoroalkene comprises neutralizing the reaction product to produce a hydrofluoroalkanol; mixing a dehydrating agent with the hydrofluoroalkanol, thereby forming a gaseous mixture; and contacting a catalyst with the gaseous mixture, thereby forming the hydrofluoroalkene . In one embodiment, the reaction product of a chlorofluoroalkane, an aldehyde and a reactive metal is neutralized by diluting the reaction product mixture with a mixture of a solvent, ice, and an aqueous solution of an acid. In one embodiment, the solvent can be any commonly used organic solvent, such as diethyl ether. In one embodiment, the aqueous solution of an acid is an aqueous solution of a common mineral acid, such as hydrochloric acid. After stirring the resulting mixture for a period of time, the layer comprising the organic solvent is separated. In one embodiment, the organic solvent layer can be subsequently washed with a dilute aqueous solution of an acid, followed by a brine solution. The organic layer is then dried. In some embodiments, the drying is accomplished by stirring the organic layer over and anhydrous salt, such as anhydrous magnesium sulfate or anhydrous sodium sulfate. In some embodiments, the organic solvent can then be evaporated to afford the hydrofluoroalkanol.
In this embodiment, the hydrofluoroalkanol is at least one selected from the group consisting of: fluoroalkanols having the general formula Rf'CH2OH wherein Rf' is selected from the group consisting of: CF3CFCI-, CF3CF2CFCI-, CF3CF2CF2CFCI- and CF3CF2CF2CF2CFCI-. In one embodiment, the hydrofluoroalkanol is 2,3,3,3-tetrafluoro-2-chloro-1 - propanol.
In one embodiment, the catalyst is at least one transition metal. The metal is selected from the group consisting of: nickel (Ni), palladium (Pd), and platinum (Pt). In one embodiment, the catalyst is a supported catalyst which comprises a transition metal and a support material. The support material is at least one selected from the group consisting of activated carbon and /-alumina.
The dehydrating agent is at least one gas selected from the group consisting of: methane, ethane, propane, butane, natural gas, alcohols, aldehydes, and carbon monoxide.
The mixing step takes place at a temperature in the range between about 65-800C.
The process further comprises preheating the gaseous mixture prior to the contacting step. The preheating takes place at a temperature in the range between about 250 to about 4500C.
The contacting step preferably takes place at a temperature in the range between about 400 to about 700°C. The contacting step also preferably takes place for between about 20 to about 25 seconds.
The process further comprises the step of neutralizing any residual HF contained in the hydrofluoroalkene product, wherein the HF is neutralized by passing the hydrofluoroalkene product through a KOH solution.
The hydrofluoroalkene product comprises at least one hydrofluoroalkene selected from the group consisting of: 2,3,3,3- tetrafluoro-1-propene or any hydrofluoroalkene selected from the group consisting of compounds represented by the formula: RfCF=CH2 wherein Rf is selected from the group consisting of: CF3, CF3CF2, CF3CF2CF2, (CFs)2CF-, CF3CF2CF2CF2- and CF3 CF(CF3)CF2-.
The gaseous mixture may further comprise at least one diluent inert gas selected from the group consisting of: nitrogen, helium, and argon.
The conversion of the hydrofluoroalkanol to hydrofluoroalkene is in the range between about 50 to about 100%. The selectivity of hydrofluoroalkanol to hydrofluoroalkene is in the range between about 29 to about 100%.
The pressure during the contacting step is in the range between about 1 to about 100 psig. Further in accordance with the present invention, there is provided a process for the manufacture of hydrofluoroalkenes of the structure RfCF=CHR, comprising reacting a hydrofluoroalkanol of structure RfCFXCHROH or a hydrofluoroalkoxide of structure RfCFXCHROMX, wherein M is a reactive metal in the +2 oxidation state, with a carboxylic
acid anhydride and a reactive metal in a reaction solvent to form a hydrofluoroalkene, and isolating the hydrofluoroalkene.
In another embodiment, the reductive dehydroxyhalogenation comprises reacting the metal hydrofluoroalkoxide with a carboxylic acid anhydride and a reactive metal. In this embodiment, hydrofluoroalkenes of the structure RfCF=CHR are manufactured by reacting a hydrofluoroalkanol of structure RfCFXCHROH or a hydrofluoroalkoxide of structure RfCFXCHROMX, wherein M is a reactive metal in the +2 oxidation state, with a carboxylic acid anhydride and a reactive metal in a reaction solvent to form a hydrofluoroalkene, and optionally, isolating the hydrofluoroalkene. In this embodiment, the hydrofluoroalkanol of structure RfCFXCHROH or a hydrofluoroalkoxide of structure RfCFXCHROMX, wherein M is a reactive metal in the +2 oxidation state, react first with the carboxylic acid anhydride to form an ester as described below. This ester then reacts with the reactive metal to form a hydrofluoroalkene. In this process Rf is selected from the group consisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, perfluoro-n-butyl and perfluoro-i-butyl, X is selected from Cl, Br, and I, and R is selected from the group consisting of H, CH3, C2H5, n-CsH/, and i- C3H7, and in particular Rf is CF3, X is Cl and R is H. In this process the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, and formic anhydride. The reactive metal powder is as described above. In some embodiments of this process, the reductive dehydroxyhalogenation can be done without neutralizing the product mixture from the reaction of a halofluorocarbon with a reactive metal and an aldehyde. In other embodiments, the reductive dehydroxyhalogenation is done after first isolating the hydrofluoroalkanol, and then reacting it with a carboxylic acid anhydride and a reactive metal. In some embodiments, the reductive dehydroxyhalogenation is done without isolating the ester. In other embodiments, the reductive dehydroxyhalogenation is done with the ester being isolated from the solvent and metal salts, and then reacted with the reactive metal.
In some embodiments, the product of the reductive dehydroxyhalogenation further comprises a substituted cyclobutane of the formula cyclo-(-CF(Rf)CHRCF(Rf)CHR-), wherein Rf is a perfluoroalkyl group having from one to four carbon atoms and R is CH3, CH3CH2, CH3CH2CH2, (CH3)2CH or H. In one particular embodiment, Rf is CF3 and R is H.
In one embodiment, the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, and formic anhydride. In another embodiment, the carboxylic acid anhydride is acetic anhydride. In one embodiment, the mole ratio of carboxylic acid anhydride to hydrofluoroalkanol is from about 1 :1 to about 2:1. In another embodiment, the mole ratio of carboxylic acid anhydride to hydrofluoroalkanol is from about 1.4:1 to about 1.8:1. In one embodiment, the mole ratio of reactive metal to hydrofluoroalkanol is about 1 :1. In another embodiment, the mole ratio of reactive metal to hydrofluoroalkanol is about 2:1. In yet another embodiment, the mole ratio of reactive metal to hydrofluoroalkanol is about 2.5:1. The reaction between the metal hydrofluoroalkoxide and the carboxylic acid anhydride produces an ester of the formula RfCFXCHROC(=O)R where Rf is as described above, R is as described above, X is as described above, and R' is the residue from the carboxylic acid anhydrides described above, and is selected from the group consisting Of -CH3, -C2H5, -CH2CH2CH3, CH2CH2CO2H, CH2CH2CH2CO2H, CH2CH2CH2CH2CO2H, and H. In one embodiment, Rf is CF3, R is H, X is Cl, and R' is CH3.
In one embodiment, the reductive dehydroxyhalogenation is conducted in a reaction solvent which is the same solvent in which the reaction of a halofluorocarbon with reactive metal and an aldehyde is conducted in. In another embodiment, the reductive dehydroxyhalogenation is conducted in a reaction solvent which is a different solvent than the reaction of a halofluorocarbon with reactive metal and an aldehyde is conducted in. In yet another embodiment, the reductive dehydroxyhalogenation is conducted in a mixture of pyridine or an alkyl-substituted pyridine, and dimethylformamide.
In one embodiment, the product of the estehfication of the hydrofluoroalkanol is a compound having the formula: RfCFXCHROC(=O)R' where Rf is a perfluoroalkyl group having from one to four carbon atoms, R is CH3, CH3CH2, CH3CH2CH2, (CH3)2CH or H, X is selected from Cl, Br, and I, and R' is selected from the group consisting of -CH3, -C2H5, -CH2CH2CH3, CH2CH2CO2H, CH2CH2CH2CO2H, CH2CH2CH2CH2CO2H and H.
As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
Also, use of "a" or "an" are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
Group numbers corresponding to columns within the Periodic Table of the elements use the "New Notation" convention as seen in the CRC Handbook of Chemistry and Physics, 81st Edition (2000-2001 ).
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is
cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
EXAMPLES
The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.
Example 1
Example 1 demonstrates the preparation of 2-chloro-3,3,3- trifluoropropanol from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane.
A 400 ml Hastelloy C shaker tube was charged with 32.8 g (0.5 mol) of activated Zinc powder, 12g (0.5 mol) of paraformaldehyde and 180 ml anhydrous DMF under N2. The tube was cooled down to -15° C and 64.4 g (0.2 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 50 0C for 6 hours. The results of gas chromatography analysis of the reaction are summarized in Table 1. After the reaction mixture cooled down to room temperature, it was poured into a 200 ml mixture of ice, 10% aqueous HCI and 200 ml diethyl ether with stirring. After another 30 min stirring, the organic layer was separated and washed with 100 ml_ of 2% aqueous HCI and then 100 ml_ brine. After it was dried with MgSO4, diethyl either was removed by vacuum to afford 13.36 of product (yield 8%).
Table 1
Example 2
Example 2 demonstrates the conversion of 2-chloro-2, 3,3,3- tetrafluoropropanol to 2,3,3,3- tetrafluoroi -propene.
A 400 ml Hastelloy C shaker tube was charged with 26g (0.4 mol) of activated Zinc powder, 33.3g (0.2 mol) of 2-chloro-2,3,3,3- tetrafluoropropanol, 30.6g (0.3 mol) of acetic anhydride and 180 ml anhydrous DMF under N2. Then the reaction mixture was stirred at 50 0C for 6 hours. After the reaction mixture cooled down to room temperature, the product was collected in a cold trap chilled by dry ice to produce 18.1 g of 2,3,3, 3-tetrafluoropropene.
Example 3
Example 3 demonstrates the synthesis of 2,3,3,3- tetrafluoro-1 - propene from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane. A 400 ml Hastelloy C shaker tube was charged with 20 g (0.315 mol) of activated Zinc powder, 7.5g (0.25 mol) of paraformaldehyde and 130 ml anhydrous DMF under N2. The tube was cooled down to -15 0C and 43 g (0.25 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 60 0C for 6 hours. After the reaction mixture cooled down to room temperature, 3Og (0.46 mol) of activated Zinc powder and 50 g (0.5 mol) of acetic anhydride were added into the reactor. The reaction mixture was stirred at 50 0C for 6 hr and then cooled down to room temp. The gas phase and the liquid phase were analyzed by GC-MS. Results are summarized in Table 2. Table 2
Example 4
Example 4 demonstrates the synthesis of 2-chloro-2, 3,3,3- tetrafluoropropanol (CF3CCIFCH2OH) in pyridine.
A 80 ml Fisher Porter tube was charged with 2.24 g (0.034 mol) of activated Zinc powder, 1.24g (0.041 mol) of paraformaldehyde and 30 ml anhydrous pyridine under N2. The tube was cooled down to -15 0C and 5 g (0.029 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 50 0C for 8 hours. The pressure of the reactor dropped to 8 psig at end of reaction from 25 psig. After the reaction mixture was cooled down to room temperature, it was analyzed by GC-MS. For GC-MS analysis, a portion of the reaction mixture was acidified with a 10% solution of HCI in acetone. The data is reported by area percent of GC-MS in table 3.
Table 3
Example 5
Example 5 demonstrates the synthesis of 2-chloro-2, 3,3,3- tetrafluoropropanol CF3CCIFCH2OH in dimethylacetamide.
A 80 ml Fisher Porter tube was charged with 2.23 g (0.034 mol) of activated Zinc powder, 1.21 g (0.040 mol) of paraformaldehyde and 30 ml anhydrous dimethylacetamide under N2. The tube was cooled down to -15 0C and 5.2 g (0.030 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 60 0C for 4.5 hours. The pressure of the reactor dropped to 9 psig at end of reaction from 30 psig. After the reaction mixture was cooled down to room temperature, it was analyzed by GC-MS. For GC-MS analysis, a portion of the reaction mixture was acidified with a 10% solution of HCI in acetone. The data is reported by area percent of GC-MS in table 4.
Table 4
Example 6
Example 6 demonstrates the synthesis of 2-chloro-2, 3,3,3- tetrafluoropropanol CF3CCIFCH2OH in pyridine, with pre-treatment of formaldehyde. A 80 ml Fisher Porter tube was charged with 1.82g (0.06 mol) of paraformaldehyde and 30 ml anhydrous pyridine under N2. The tube was heated up to 60 0C and stirred at 60 0C for 4hr. Then it was cooled down to room temp and 2.24 g (0.034 mol) of activated Zinc powder were added. After purging with N2 for 15 min, the tube was cooled down to -15 0C and 5 g (0.029 mol) of 1 ,1 -dichlorotetrafluoroethane were added.
Then the reaction mixture was stirred at 50 0C for 8 hours. The pressure
of the reactor dropped to 9 psig at end of reaction from 25 psig. After the reaction mixture was cooled down to room temperature, it was analyzed by GC-MS. For GC-MS analysis, a portion of the reaction mixture was acidified with a 10% solution of HCI in acetone. The data is reported by area percent of GC-MS in Table 5. The selectivity of 114a to
CF3CCIFCH2OZnCI (analyzed as CF3CCIFCH2OH) increased to 78.7%.
Table 5 (Liquid phase)
Example 7
Example 7 illustrates the esterification of 2,3,3, 3-tetrafluoro-2- chloropropanol with acetic anhydride to produce 2,3,3,3-tetrafluoro-2- chloropropyl acetate.
A 80 ml Fisher Porter tube was charged with 2g (0.012 mol) of CF3CCIFCH2OH (which contains -15% diethyl ether), 1.35g (0.0132) of acetic anhydride and 0.25g of concentrated sulfuric acid. The mixture was stirred at 60 0C for 6hr. After the reaction mixture was cooled down to room temperature, it was analyzed by GC-MS. The data is reported by area percent of GC-MS in Table 6. This result shows that more than 99% Of CF3CCIFCH2OH has been converted to CF3CCIFCH2OAC.
Table 6
Example 8
Example 8 illustrates the direct esterification of CF3CCIFCH2OZnCI to CF3CCIFCH2OAC. 10 ml of a pyridine solution containing about 14%
CF3CCIFCH2OZnCI was vacuum evaporated at room temp to remove the majority of the pyridine. Then 2.Og acetic anhydride and 1 ml DMF were added into the resultant solid. The mixture was stirred at 60 0C for 7hr.
After the reaction mixture was cooled down to room temperature, it was analyzed by GC-MS. The data is reported by area percent of GC-MS in
Table 7.
Table 7
Example 9 Example 9 illustrates the conversion of CF3CCIFCH2OAC to 2,3,3,3- tetrafluoropropene.
The reaction mixture from example 8, above, was stirred with 1g of Na2CO3 to remove the acid generated in esterification step. Then 3 mol of DMF and 1.3g of Zn were added. The reaction was run in 80ml Fisher Porter tube at 50 0C for 2hr and 60 0C for another 2 hr with stirring. The pressure of the reactor increased from 0 psig to 13 psig. After the reaction mixture was cooled down to room temperature, it was analyzed by GC- MS. The data is reported by area percent of GC-MS in Table 8. CF3CCIFCH2OAC became non-detectable in the liquid phase of the reactor. This result shows that CF3CCIFCH2OAC has been quantitatively converted to 2,3,3,3-tetrafluoropropene under the conditions above.
Table 8
Component (vapor phase) GC-MS area percent (%)
2,3,3,3-tetrafluoropropene 94.48
2,3,3,3-tetrafluoro-2-chloropropanol 0.115
Acetic anhydride 1.62
Methyl acetate 0.815
DMF 1.05
Pyridine 2.05
(Liquid phase)
2,3,3,3-tetrafluoropropene 1.61
Acetic anhydride 1.45
Methyl acetate 0.61
DMF 86.24
Pyridine 9.98
Example 10 Example 10 demonstrates the reaction of 1 ,1 - dichlorotetrafluoroethane with paraformaldehyde in a mixed solvent of dimethylformamide and pyridine to produce CF3CCIFCH2OZnCI.
A 80 ml Fisher Porter tube was charged with 2.2g Zn (0.037 mol), 0.3g Zinc acetate (0.0016mol), 2g (0.067 mol) of paraformaldehyde, 15g of anhydrous pyridine and 15g of dimethylformamide under N2. After N2 purge for 15 min, the tube was cooled down to -15 0C and 5 g (0.029 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 50 0C for 2 hours. The pressure of the reactor dropped to 5 psig at end of reaction from 25 psig. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. For GC-MS analysis, a portion of the reaction mixture was acidified with a 10% solution of HCI in acetone. Solvents DMF and pyridine are excluded from integration. The data is reported by area percent of GC-MS. The selectivity of 114a to CF3CCIFCH2OZnCI (analyzed as CF3CCIFCH2OH) is 83% based on GC-MS analysis.
Table 9 (Liquid phase)
Example 11
Example 11 illustrates esterification of CF3CCIFCH2OZnCI directly to CF3CCIFCH2OAC with acetic anhydride in a solvent mixture.
Excess Zn was filtrated off from the reaction mixture from example 10, then was charged into a 80 ml Fisher Porter tube. 4.4g of acetic
10 anhydride (0.043 mol) were also added into the reactor. The mixture was stirred at 60 0C for 6hr. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. The data is reported by area percent of GC-MS in Table 10. Solvents DMF, pyridine and acetic anhydride are excluded from integration. This result shows that more than
15 94% Of CF3CCIFCH2OZnCI has been converted to CF3CCIFCH2OAC at condition above.
Table 10 Liquid phase
20
Example 12
Example 12 illustrates the synthesis of 2,3,3,3- tetrafluoroi -propene from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane in 3:1 pyridine:DMF solvent.
A 80 ml Fisher Porter tube was charged with 2.1 g Zn (0.032), 0.3g
25 Zinc acetate (0.0016mol), 2g (0.067 mol) of paraformaldehyde, 3Og anhydrous pyridine under N2. After purging with N2 for 15 min, the tube was cooled down to -150C and 5 g (0.029 mol) of 1 ,1- dichlorotetrafluoroethane were added. Then the reaction mixture was
stirred at 500C for 3 hours. The pressure of the reactor dropped to 5.5 psig at end of reaction from 25 psig. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. For GC-MS analysis, a portion of the reaction mixture was acidified with a 10% solution of HCI in acetone. Solvent pyridine was excluded from integration. The data is reported in Table 11 by area percent of GC-MS. The selectivity of 1 ,1 -dichlorotetrafluoroethane to CF3CCIFCH2OZnCI (analyzed as CF3CCIFCH2OH) is 81 % based on GC-MS analysis.
Then the excess Zn was filtrated off from the reaction mix and it was charged into a 80 ml Fisher Porter tube. 10 ml Anhydrous DMF and 3.5g of acetic anhydride (0.034 mol) were also added into the reactor. The mixture was stirred at 60 0C for 4hrs. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. The data is reported in Table 12 by area percent of GC-MS. Solvents DMF and pyridine are excluded from integration. This result shows that more than 98% Of CF3CCIFCH2OZnCI has been converted, and selectivity to CF3CCIFCH2OAC and CF3CFCICH2OCH2OAC are 89%.
10 ml of reaction mix above was left in an 80 ml Fisher Porter tube, activated Zinc powder (1g, 0.015mol) was also added. The reaction was run in 80ml Fisher Porter tube at 600C for 4hr with stirring. The pressure of the reactor increased from 6 psig to 15.5 psig. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. The data is reported by area percent of GC-MS. The result of vapor phase was listed in Table 13 and the result of liquid phase was reported in Table 14 (solvent DMF and pyridine was excluded from integration).
CF3CCIFCH2OAC became non-detectable in liquid phase of reactor. Analysis shows that selectivity to 2,3,3,3-tetrafluoro-1 -propene is about 94%, and selectivity to 1 ,3-bis-trifluoromethyl-1 ,3-difluorocyclobutane (C6H4F8) is about 5%.
Table 11
Table 12
Table 13
Example 13
Example 13 illustrates the synthesis of 2,3,3,3- tetrafluoro-1- propene from 1 ,1 ,1 ,2-tetrafluoro-2,2-dichloroethane in 1 :1 pyridine:DMF solvent. A 80 ml Fisher Porter tube was charged with 2.1 g Zn (0.032), 0.3g
Zinc acetate (0.0016mol), 2g (0.067 mol) of paraformaldehyde, 0.2g Bis(hydrogenated alkyl) dimethyl ammonium acetate and 3Og anhydrous pyridine under N2. After purging with N2 for 15 min, the tube was cooled down to -15 0C and 5 g (0.029 mol) of 1 ,1 -dichlorotetrafluoroethane were added. Then the reaction mixture was stirred at 50 0C for 3 hours. The pressure of the reactor dropped to 5.5 psig at end of reaction from 23 psig. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. For GC-MS analysis, a portion of the reaction mixture was acidified with a 10% solution of HCI in acetone. Solvents DMF and pyridine are excluded from integration. The data is reported in Table 15 by area percent of GC-MS. The selectivity of 114a to CF3CCIFCH2OZnCI (analyzed as CF3CCIFCH2OH) is about 85% based on GC-MS analysis.
Then 10 ml reaction mix was filtrated and charged into an 80 ml Fisher Porter tube. 10 ml anhydrous DMF and 3.5g of acetic anhydride (0.034 mol) were also added into the reactor. The mixture was stirred at 60 0C for 4hrs. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. The data is reported in Table 16 by area percent of GC-MS. Solvents DMF and pyridine are excluded from integration. This result shows that more than 98% of CF3CCIFCH2OZnCI has been converted, and selectivity to CF3CCIFCH2OAC and CF3CFCICH2OCH2OAC are about 95%.
The reaction mix above was treated with 2g Na2CO3 in 80 ml Fisher Porter tube. After Na2CO3 was filtrated off, activated Zinc powder (1g, 0.015mol) was added. The reaction was run in an 80ml Fisher Porter tube at 60 0C for 4hr with stirring. The pressure of the reactor increased from 5 psig to 18 psig. After the reaction mixture cooled down to room temperature, it was analyzed by GC-MS. The data is reported by area percent of GC-MS. The result of vapor phase was listed in Table 17 and
the result of liquid phase was reported in Table 18 (solvent DMF and pyridine was excluded from integration). More than 99% CF3CCIFCH2OAC and more than 95% CF3CFCICH2OCH2OAC have been converted. Analysis shows that selectivity to 1234yf is about 98%, and selectivity to 1 ,3-bis-trifluoromethyl-1 ,3-difluorocyclobutane (C6H4F8) is about 0.1 %.
Table 14
Table 16
Example 14
Example 14 illustrates the synthesis of 2,3,3,4,4,4- hexafluoro-1 - butene from 1 ,1 ,1 ,2,2,3-hexafluoro-3,3-dichloropropane in 1 :1 pyhdine:DMF solvent.
A 80 ml Fisher Porter tube is charged with 2.1 g Zn (0.032), 0.3g Zinc acetate (0.0016mol), 2g (0.067 mol) of paraformaldehyde, 0.2g Bis(hydrogenated alkyl) dimethyl ammonium acetate and 3Og anhydrous pyridine under N2. After purging with N2 for 15 min, the tube is cooled down to -15 0C and 6.4 g (0.029 mol) of 1 ,1 ,1 , 2,2,3-hexafluoro-3,3- dichloropropane was added. Then the reaction mixture is stirred at 50 0C
for 3 hours. The pressure of the reactor drops to 5.5 psig at end of reaction from 23 psig. After the reaction mixture cooled down to room temperature, it is analyzed by GC-MS. For GC-MS analysis, a portion of the reaction mixture is acidified with a 10% solution of HCI in acetone. Solvents DMF and pyridine are excluded from integration. The data is reported in Table 18 by area percent of GC-MS. The selectivity of 216cb to CF3CF2CCIFCH2OZnCI (analyzed as CF3CF2CCIFCH2OH) is about 85% based on GC-MS analysis.
Then 10 ml reaction mix is filtrated and charged into an 80 ml Fisher Porter tube. 10 ml anhydrous DMF and 3.5g of acetic anhydride (0.034 mol) are also added into the reactor. The mixture is stirred at 60 0C for 4hrs. After the reaction mixture cooled down to room temperature, it is analyzed by GC-MS. The data is reported in Table 19 by area percent of GC-MS. Solvents DMF and pyridine are excluded from integration. This result shows that more than 98% of CF3CF2CCIFCH2OZnCI is converted and selectivity to CF3CF2CCIFCH2OAC and CF3CF2CFCICH2OCH2OAC are about 95%.
The reaction mix above is then treated with 2g Na2CO3 in an 80 ml Fisher Porter tube. After Na2CO3 is filtrated off, activated Zinc powder (1g, 0.015mol) is added. The reaction is run in an 80ml Fisher Porter tube at 60 0C for 4hr with stirring. The pressure of the reactor increases from 5 psig to 18 psig. After the reaction mixture is cooled down to room temperature, it is analyzed by GC-MS. The data is reported by area percent of GC-MS. The result of vapor phase is listed in Table 20 and the result of liquid phase is reported in Table 21 (solvent DMF and pyridine was excluded from integration). More than 99% CF3CF2CCIFCH2OAC and more than 95% CF3CF2CFCICH2OCH2OAC are converted. Analysis shows that selectivity to 2,3,3,4,4,4- hexafluoro-1 -butene is about 98%, and selectivity to 1 ,3-bis-pentafluoroethyl-1 ,3-difluorocyclobutane (C8H4Fi2) is about 0.1 %.
Table 18
Compounds GC-MS area %
1 ,2,3,3,3-pentafluoro-1 -propene 0.9
1 ,1 ,1 ,2,2,3-hexafluoro-3-chloropropane 7.1
1 ,1 ,1 ,2,2,3-hexafluoro-3,3-dichloropropane 1.5
CF3CF2CFCICH2OH 84
CF3CF2CFCICH2OAC 0.3
Unknowns 0.9
Table 19
Compounds GC-MS area %
1 ,1 ,1 ,2,2,3-hexafluoro-3-chloropropane 2.5
CF3CF2CFCICH2OH 1.2
CF3CF2CFCICH2OAC 73
2-chloro-2,3,3,4,4,4-hexafluorobutoxy methyl 5.2 acetate
Unknowns 17
Table 20
Compounds GC-MS area %
1 ,2,3,3,3-pentafluoro-i -propene 0.5
2,3,3,4,4,4-hexafluoro-1 -butene 96.5
CsH4Fi2 0.1
Unknowns 0.1
Table 21
Compounds GC-MS area %
2,3,3,4,4,4-hexafluoro-1 -butene 35.26
3-chloro-1 ,1 ,1 ,2,2,3-hexafluoropropane 6.3
CsH4Fi2 0.6
2,3,3,4,4,4-hexafluoro-2-chloropropanol 0.8
2,3,4,4,4-pentafluoro-2-propen-1 -ol acetate 1.4
Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed. In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.
Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.
It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges include each and every value within that range.
Claims
1. A process for the manufacture of hydrofluoroalkanols of the structure RfCFXCHROH, comprising reacting a halofluorocarbon of the structure RfCFX2, wherein each X is independently selected from Cl, Br, and I, with an aldehyde and a reactive metal in a reaction solvent to generate a reaction product comprising a metal hydrofluoroalkoxide, and neutralizing said metal hydrofluoroalkoxide to produce a hydrofluoroalkanol.
2. The process of claim 1 , further comprising, recovering said hydrofluoroalkanol.
3. The process of claim 1 wherein Rf is a perfluoroalkyl group having from one to four carbon atoms.
4. The process of claim 3 wherein Rf is selected from the group consisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, perfluoro-n-butyl and perfluoro-i-butyl.
5. The process of claim 3 wherein Rf is perfluoromethyl.
6. The process of claim 1 wherein the aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.
7. The process of claim 1 wherein the aldehyde is formaldehyde.
8. The process of claim 1 wherein the reactive metal is selected from the group consisting of magnesium turnings, activated zinc powder, aluminum, and a powder of any of the following metals: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc indium, and combinations thereof.
9. The process of claim 1 wherein the process further comprises adding a zinc salt in addition to the said reactive metal.
10. The process of claim 9 wherein the zinc salt is zinc acetate.
11. The process of claim 7, wherein the process further comprises adding a quaternary ammonium salt in the reaction of a halofluorocarbon with an aldehyde and a reactive metal.
12. The process of claim 1 , wherein the reaction solvent is selected from the group consisting of alkyl, dialkyl, and thalkyl linear or cylic amines, N-methylpyrrolidine, N-methylpiperidine, pyridine, alkyl- substituted pyridines, dimethylformamide, pyrazine or pyrimidine, and mixtures thereof.
13. The process of claim 12 wherein the reaction solvent is pyridine, alkyl-substituted pyridines, or mixtures thereof.
14. The process of claim 1 wherein the said halofluorocarbon is prepared by halogenating the corresponding hydrofluorocarbon RfCFH2.
15. A process for the manufacture of hydrofluoroalkenes of the structure RfCF=CHR, comprising reacting a halofluorocarbon of the structure RfCFX2, wherein each X is independently selected from Cl, Br, and I, with an aldehyde and a reactive metal in a reaction solvent to generate a reaction product comprising a metal hydrofluoroalkoxide, and reductively dehydroxyhalogenating said metal hydrofluoroalkoxide in a second step to produce a hydrofluoroalkene.
16. The process of claim 15, further comprising isolating said hydrofluoroalkene product.
17. The process of claim 15 wherein the aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.
18. The process of claim 15 wherein the reactive metal is selected from the group consisting of magnesium turnings, activated zinc powder, aluminum, and a powder of any of the following metals: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc indium, and combinations thereof.
19. The process of claim 15 further comprising adding a zinc salt in addition to said reactive metal.
20. The process of claim 19 wherein the zinc salt is zinc acetate.
21. The process of claim 17, when the aldehyde is formaldehyde, further comprising adding a quaternary ammonium salt in the reaction of a halofluorocarbon with an aldehyde and a reactive metal.
22. The process of step 15 wherein the reductive dehydroxyhalogenation comprises reacting the metal hydrofluoroalkoxide, with a carboxylic acid anhydride and a reactive metal, said reactive metal being the same as the reactive metal in claim 15, or different.
23. The process of claim 22 wherein the reactive metal is selected from the group consisting of magnesium turnings, activated zinc powder, aluminum, and a powder of any of the following metals: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc indium, and combinations thereof.
24. The process of claim 22 wherein the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, and formic anhydride.
25. The process of claim 15 wherein the R group of the hydrofluoroalkene is selected from the group consisting of H, CH3 and C2H5.
26. The process of claim 15 wherein Rf is a perfluoroalkyl group having from one to four carbon atoms.
27. The process of claim 26 wherein Rf is CF3.
28. The process of claim 15 wherein Rf is CF3 and R is H.
29. The process of claim 15 wherein the said halofluorocarbon is prepared by halogenating the corresponding hydrofluorocarbon RfCFH2.
30. The process of claim 15 wherein the reductive dehydroxyhalogenation comprises neutralizing the metal hydrofluoroalkoxide, to produce a hydrofluoroalkanol; mixing a dehydrating agent with the said hydrofluoroalkanol, thereby forming a gaseous mixture; and contacting a catalyst with said gaseous mixture, thereby forming the hydrofluoroalkene.
31. The process of claim 30 wherein said dehydrating agent is at least one gas selected from the group consisting of methane, ethane, propane, butane, natural gas, alcohols, aldehydes and carbon monoxide.
32. The process of claim 30 wherein said catalyst is a transition metal.
33. The process of claim 32 wherein said transition metal is at least one metal selected from the group consisting of nickel, palladium and platinum.
34. The process of claim 30 wherein said catalyst is a supported catalyst.
35. The process of claim 34 wherein said supported catalyst comprises a transition metal and a support material.
36. The process of claim 35 wherein said support material is at least one selected from the group consisting of activated carbon and γ- alumina.
37. A compound having the formula:
RfCFXCHROC(=O)R' where Rf is a perfluoroalkyl group having from one to four carbon atoms, R is CH3, CH3CH2, CH3CH2CH2, (CH3)2CH or H, X is selected from Cl, Br and I, and R' is selected from the group consisting Of -CH3, -C2H5, -CH2CH2CH3, CH2CH2CO2H, CH2CH2CH2CO2H, CH2CH2CH2CH2CO2H and H.
38. The compound of claim 37 wherein Rf is selected from CF3-, CF3CF2-, CF3CF2CF2-, (CF3)2CF-, CF3CF2CF2CF2- and CF3
CF(CF3)CF2-.
39. The compound of claim 37 wherein Rf is CF3, X is Cl, and R' is CH3.
40. A process for the manufacture of hydrofluoroalkenes of the structure RfCF=CHR, comprising reacting a hydrofluoroalkanol of structure RfCFXCHROH or a hydrofluoroalkoxide of structure
RfCFXCHROMX, wherein M is a reactive metal in the +2 oxidation state, with a carboxylic acid anhydride and a reactive metal in a reaction solvent to form a hydrofluoroalkene.
41. The process of claim 40, further comprising the step of isolating said hydrofluoroalkene.
42. The process of claim 40 wherein Rf is selected from the group consisting of perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, perfluoro-n-butyl and perfluoro-i-butyl, X is selected Cl, Br and I, and R is selected from the group consisting of H, CH3, C2H5, n-C3H7, and 1-C3H7.
43. The process of claim 42 wherein Rf is CF3 and R is H.
44. The process of claim 40 wherein the carboxylic acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, adipic anhydride and formic anhydride.
45. The process of claim 40 wherein the reactive metal is selected from the group consisting of magnesium turnings, activated zinc powder, aluminum, and a powder of any of the following metals: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc indium, and combinations thereof.
46. A compound having the formula:
RfCFCICHRO-Zn-CI where Rf is a perfluoroalkyl group having from one to four carbon atoms and R is CH3, CH3CH2, CH3CH2CH2, (CH3)2CH or H.
47. The compound of claim 46 wherein Rf is selected from the group consisting of CF3-, CF3CF2-, CF3CF2CF2-, (CF3)2CF-, CF3CF2CF2CF2- and CF3 CF(CF3)CF2-.
48. The compound of claim 46 wherein Rf is CF3 and R is H.
49. A compound having the formula: cyclo-(-CF(Rf)CHRCF(Rf)CHR-), where Rf is a perfluoroalkyl group having from one to four carbon atoms and R is CH3, CH3CH2, CH3CH2CH2, (CH3)2CH or H.
50. The compound of claim 49 wherein Rf is CF3 and R is H.
51. A process for the manufacture of hydrofluoroesters comprising reacting a halofluorocarbon of the structure RfCFX2, wherein each X is independently selected from Cl, Br, and I, with an aldehyde and a reactive metal in a reaction solvent to generate a reaction product comprising a metal hydrofluoroalkoxide, further reacting said metal hydrofluoroalkoxide with a carboxylic acid anhydride to provide an ester of the formula RfCFXCHROC(=O)R where Rf is a perfluoroalkyl group having from one to four carbon atoms, R is H, CH3 or C2H5, and R' is selected from the group consisting of -CH3, - C2H5, -CH2CH2CH3, CH2CH2CO2H, CH2CH2CH2CO2H, CH2CH2CH2CH2CO2H and H.
52. The process of claim 51 wherein Rf is CF3, R is H, and R' is CH3
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CA2736216A1 (en) | 2008-10-10 | 2010-04-15 | E. I. Du Pont De Nemours And Company | Compositions comprising 2,3,3,3-tetrafluoropropene, 2-chloro-2,3,3,3-tetrafluoropropanol, 2-chloro-2,3,3,3-tetrafluoro-propyl acetate or zinc (2-chloro-2,3,3,3-tetrafluoropropoxy)chloride |
JP6022770B2 (en) | 2008-10-13 | 2016-11-09 | ブルー キューブ アイピー エルエルシー | Method for producing chlorinated and / or fluorinated propene |
CN101851146B (en) * | 2009-04-02 | 2013-09-25 | 中化蓝天集团有限公司 | Method for preparing trifluoroethylene |
CN102686544B (en) | 2009-10-09 | 2017-02-15 | 蓝立方知识产权公司 | Processes for the production of chlorinated and/or fluorinated propenes and higher alkenes |
US8581011B2 (en) | 2009-10-09 | 2013-11-12 | Dow Global Technologies, Llc | Process for the production of chlorinated and/or fluorinated propenes |
JP5782038B2 (en) | 2009-10-09 | 2015-09-24 | ダウ グローバル テクノロジーズ エルエルシー | Isothermal multitubular reactor and process incorporating the reactor |
RU2009149445A (en) * | 2009-12-29 | 2011-07-10 | Е.И.Дюпон де Немур энд Компани (US) | Synthesis of Fluorinated Olefins from Fluorinated Alcohols |
ES2936125T3 (en) | 2010-11-25 | 2023-03-14 | Arkema France | Use of chloro-trifluoropropene and hexafluorobutene compositions |
CA2836493A1 (en) | 2011-05-31 | 2012-12-06 | Max Markus Tirtowidjojo | Process for the production of chlorinated propenes |
WO2012166394A1 (en) | 2011-05-31 | 2012-12-06 | Dow Global Technologies, Llc | Process for the production of chlorinated propenes |
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IN2015DN03949A (en) | 2012-10-26 | 2015-10-02 | Dow Global Technologies Llc | |
CN104870411B (en) | 2012-12-18 | 2018-10-02 | 蓝立方知识产权有限责任公司 | Method for producing propylene dichloride |
JP6251286B2 (en) | 2012-12-19 | 2017-12-20 | ブルー キューブ アイピー エルエルシー | Method for the production of chlorinated propene |
JP2016507590A (en) | 2013-02-27 | 2016-03-10 | ブルー キューブ アイピー エルエルシー | Method for producing chlorinated propene |
JP5755388B2 (en) * | 2013-03-06 | 2015-07-29 | ユニマテック株式会社 | Fluorine-containing calcium composite particles, process for producing the same, and surface treatment agent containing the same as an active ingredient |
EP2964597B1 (en) | 2013-03-09 | 2017-10-04 | Blue Cube IP LLC | Process for the production of chlorinated alkanes |
MY178665A (en) * | 2014-02-20 | 2020-10-20 | Asahi Glass Co Ltd | Composition for heat cycle system, and heat cycle system |
CN106029823B (en) * | 2014-02-20 | 2020-11-06 | Agc株式会社 | Working medium for heat cycle |
EP3121243A4 (en) * | 2014-03-17 | 2017-11-08 | Asahi Glass Company, Limited | Working medium for heat cycles, composition for heat-cycle systems, and heat-cycle system |
WO2016059698A1 (en) * | 2014-10-16 | 2016-04-21 | 三菱電機株式会社 | Refrigeration cycle device |
CN107076466B (en) * | 2014-10-16 | 2020-02-07 | 三菱电机株式会社 | Refrigeration cycle device |
CN105037401B (en) * | 2015-07-23 | 2018-12-14 | 暨南大学 | A kind of processing method of grignard reaction magnesium chips |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1496633A (en) * | 1966-02-07 | 1967-09-29 | Ici Ltd | Process for manufacturing oxygenated fluorinated organic compounds |
US7951982B2 (en) * | 2004-04-29 | 2011-05-31 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
US7026520B1 (en) * | 2004-12-09 | 2006-04-11 | Honeywell International Inc. | Catalytic conversion of hydrofluoroalkanol to hydrofluoroalkene |
-
2008
- 2008-11-20 KR KR1020107013445A patent/KR20100099182A/en not_active Application Discontinuation
- 2008-11-20 WO PCT/US2008/084107 patent/WO2009067571A1/en active Application Filing
- 2008-11-20 CN CN2008801165517A patent/CN101861322B/en not_active Expired - Fee Related
- 2008-11-20 JP JP2010535049A patent/JP2011522772A/en not_active Abandoned
- 2008-11-20 EP EP08851477A patent/EP2215097A1/en not_active Withdrawn
- 2008-11-20 BR BRPI0818958A patent/BRPI0818958A2/en not_active IP Right Cessation
- 2008-11-20 RU RU2010125261/04A patent/RU2010125261A/en not_active Application Discontinuation
Non-Patent Citations (2)
Title |
---|
I HEMER, J. FLUOR. CHEM., vol. 26, 1 January 1984 (1984-01-01), pages 467 - 479, XP055013618 * |
See also references of WO2009067571A1 * |
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RU2010125261A (en) | 2011-12-27 |
CN101861322A (en) | 2010-10-13 |
CN101861322B (en) | 2013-08-07 |
WO2009067571A1 (en) | 2009-05-28 |
BRPI0818958A2 (en) | 2017-12-12 |
KR20100099182A (en) | 2010-09-10 |
JP2011522772A (en) | 2011-08-04 |
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