FI115461B - Menetelmä 2,2-difluoriketeenisilyyliasetaalien ja alfa, alfa-difluori- beta-silyylioksi-1,3-dioksolaani-4-propaanihappoestereiden valmistamiseksi - Google Patents
Menetelmä 2,2-difluoriketeenisilyyliasetaalien ja alfa, alfa-difluori- beta-silyylioksi-1,3-dioksolaani-4-propaanihappoestereiden valmistamiseksi Download PDFInfo
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- FI115461B FI115461B FI945626A FI945626A FI115461B FI 115461 B FI115461 B FI 115461B FI 945626 A FI945626 A FI 945626A FI 945626 A FI945626 A FI 945626A FI 115461 B FI115461 B FI 115461B
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- Prior art keywords
- formula
- difluoro
- mixture
- reaction
- defined above
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- 150000001241 acetals Chemical class 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 33
- 230000008569 process Effects 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title claims description 18
- YLDGTYXTMNSOOA-UHFFFAOYSA-N 3-(1,3-dioxolan-4-yl)-2,2-difluoro-3-silyloxypropanoic acid Chemical class OC(=O)C(F)(F)C(O[SiH3])C1COCO1 YLDGTYXTMNSOOA-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims description 62
- -1 chlorine difluoroacetate Chemical compound 0.000 claims description 33
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 9
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical class OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 claims description 4
- 125000002015 acyclic group Chemical group 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- OAWAZQITIZDJRB-UHFFFAOYSA-M 2-chloro-2,2-difluoroacetate Chemical compound [O-]C(=O)C(F)(F)Cl OAWAZQITIZDJRB-UHFFFAOYSA-M 0.000 claims description 2
- WBNUVPGJLHTDTD-UHFFFAOYSA-N 4-ethyl-5-methylimidazolidin-2-one Chemical compound CCC1NC(=O)NC1C WBNUVPGJLHTDTD-UHFFFAOYSA-N 0.000 claims description 2
- RMELAEHDVILFLC-UHFFFAOYSA-N C[SiH](C)C(c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound C[SiH](C)C(c1ccccc1)(c1ccccc1)c1ccccc1 RMELAEHDVILFLC-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 2
- KMUIVDDMCZNNEJ-UHFFFAOYSA-N dimethyl(propan-2-yl)silicon Chemical compound CC(C)[Si](C)C KMUIVDDMCZNNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- TYZIDFVXYCLNGN-UHFFFAOYSA-N methyl-di(propan-2-yl)silane Chemical compound CC(C)[SiH](C)C(C)C TYZIDFVXYCLNGN-UHFFFAOYSA-N 0.000 claims description 2
- KTQKOGBTMNDCFG-UHFFFAOYSA-N tert-butyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C(C)(C)C)C1=CC=CC=C1 KTQKOGBTMNDCFG-UHFFFAOYSA-N 0.000 claims description 2
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 2
- 229910052794 bromium Chemical group 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- OCMIJJAEIFPHAG-UHFFFAOYSA-N ditert-butyl(methyl)silane Chemical compound CC(C)(C)[SiH](C)C(C)(C)C OCMIJJAEIFPHAG-UHFFFAOYSA-N 0.000 claims 1
- YYVGYULIMDRZMJ-UHFFFAOYSA-N propan-2-ylsilane Chemical compound CC(C)[SiH3] YYVGYULIMDRZMJ-UHFFFAOYSA-N 0.000 claims 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical compound C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 37
- 150000001875 compounds Chemical class 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000004293 19F NMR spectroscopy Methods 0.000 description 13
- 150000001299 aldehydes Chemical class 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VQUJCBMSUVZFGA-UHFFFAOYSA-N chloromethane 2,2-difluoroacetic acid Chemical compound FC(C(=O)O)F.CCl VQUJCBMSUVZFGA-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002024 ethyl acetate extract Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- YSGPYVWACGYQDJ-YFKPBYRVSA-N (4r)-2,2-dimethyl-1,3-dioxolane-4-carbaldehyde Chemical compound CC1(C)OC[C@H](C=O)O1 YSGPYVWACGYQDJ-YFKPBYRVSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003965 capillary gas chromatography Methods 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical class OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 150000003151 propanoic acid esters Chemical class 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UAWABSHMGXMCRK-UHFFFAOYSA-L samarium(ii) iodide Chemical compound I[Sm]I UAWABSHMGXMCRK-UHFFFAOYSA-L 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- QRKKTXWUDLJYCV-UHFFFAOYSA-N 1,3-dichloro-1,1,3,3-tetrafluoropropan-2-one Chemical compound FC(F)(Cl)C(=O)C(F)(F)Cl QRKKTXWUDLJYCV-UHFFFAOYSA-N 0.000 description 1
- SMWUDAKKCDQTPV-UHFFFAOYSA-N 1,3-dimethylimidazolidine Chemical compound CN1CCN(C)C1 SMWUDAKKCDQTPV-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RHMXAMDVHXEDGU-UHFFFAOYSA-N 2,2-difluoro-2-iodoacetic acid Chemical compound OC(=O)C(F)(F)I RHMXAMDVHXEDGU-UHFFFAOYSA-N 0.000 description 1
- SPHNGHPPFNDZLV-UHFFFAOYSA-N 2,2-difluoroacetic acid hydrobromide Chemical class OC(C(F)F)=O.Br SPHNGHPPFNDZLV-UHFFFAOYSA-N 0.000 description 1
- LZCMQBRCQWOSHZ-UHFFFAOYSA-N 2-bromo-2,2-difluoroacetic acid Chemical compound OC(=O)C(F)(F)Br LZCMQBRCQWOSHZ-UHFFFAOYSA-N 0.000 description 1
- OAWAZQITIZDJRB-UHFFFAOYSA-N 2-chloro-2,2-difluoroacetic acid Chemical class OC(=O)C(F)(F)Cl OAWAZQITIZDJRB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
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- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011732 Cyst Diseases 0.000 description 1
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- IUHDSPFIADNHQV-UHFFFAOYSA-N FC(C(=O)O)F.C(C)Cl Chemical compound FC(C(=O)O)F.C(C)Cl IUHDSPFIADNHQV-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Chemical class OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical class OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical class NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004472 Lysine Chemical class 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Chemical class NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 240000003429 Pupalia lappacea Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000015055 Talinum crassifolium Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- 230000004913 activation Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- PWAPCRSSMCLZHG-UHFFFAOYSA-N cyclopentylidene Chemical group [C]1CCCC1 PWAPCRSSMCLZHG-UHFFFAOYSA-N 0.000 description 1
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- 239000007857 degradation product Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
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- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000004220 glutamic acid Chemical class 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 102000006495 integrins Human genes 0.000 description 1
- 108010044426 integrins Proteins 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- AWUPLMYXZJKHEG-UHFFFAOYSA-N methyl 2-chloro-2,2-difluoroacetate Chemical compound COC(=O)C(F)(F)Cl AWUPLMYXZJKHEG-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002777 nucleoside Substances 0.000 description 1
- 125000003835 nucleoside group Chemical group 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- MQRWPMGRGIILKQ-UHFFFAOYSA-N sodium telluride Chemical compound [Na][Te][Na] MQRWPMGRGIILKQ-UHFFFAOYSA-N 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 description 1
- QXZGXRIXJAVMTI-UHFFFAOYSA-N tribenzylsilicon Chemical compound C=1C=CC=CC=1C[Si](CC=1C=CC=CC=1)CC1=CC=CC=C1 QXZGXRIXJAVMTI-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16054993A | 1993-11-30 | 1993-11-30 | |
| US16054993 | 1993-11-30 | ||
| US30712294A | 1994-09-16 | 1994-09-16 | |
| US30712294 | 1994-09-16 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| FI945626A0 FI945626A0 (fi) | 1994-11-29 |
| FI945626L FI945626L (fi) | 1995-05-31 |
| FI115461B true FI115461B (fi) | 2005-05-13 |
Family
ID=26856978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FI945626A FI115461B (fi) | 1993-11-30 | 1994-11-29 | Menetelmä 2,2-difluoriketeenisilyyliasetaalien ja alfa, alfa-difluori- beta-silyylioksi-1,3-dioksolaani-4-propaanihappoestereiden valmistamiseksi |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US5618951A (de) |
| EP (1) | EP0655454B1 (de) |
| JP (1) | JP3615253B2 (de) |
| KR (2) | KR100344363B1 (de) |
| AT (1) | ATE204283T1 (de) |
| BR (1) | BR9404776A (de) |
| CA (1) | CA2136788C (de) |
| DE (1) | DE69427955T2 (de) |
| DK (1) | DK0655454T3 (de) |
| ES (1) | ES2159296T3 (de) |
| FI (1) | FI115461B (de) |
| HU (2) | HU219466B (de) |
| IL (1) | IL111793A (de) |
| PT (1) | PT655454E (de) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756775A (en) * | 1995-12-13 | 1998-05-26 | Eli Lilly And Company | Process to make α,α-difluoro-β-hydroxyl thiol esters |
| US6001994A (en) * | 1995-12-13 | 1999-12-14 | Eli Lilly And Company | Process for making gemcitabine hydrochloride |
| AU1289697A (en) | 1995-12-13 | 1997-07-03 | Eli Lilly And Company | Alpha, alpha-difluoro-beta-hydroxy thiol esters and their synthesis |
| US7067600B2 (en) * | 2001-08-16 | 2006-06-27 | The Goodyear Tire & Rubber Company | Modified silane compounds |
| KR100578616B1 (ko) * | 2004-07-23 | 2006-05-10 | 한미약품 주식회사 | Ｄ-에리트로-2,2-다이플루오로-2-데옥시-1-옥소라이보스화합물의 제조방법 |
| EA017900B1 (ru) * | 2006-11-03 | 2013-04-30 | Басф Се | Способ получения дифторметилпиразолилкарбоксилатов |
| KR20090107506A (ko) * | 2006-12-21 | 2009-10-13 | 바스프 에스이 | 플루오로메틸-치환된 헤테로시클릭 화합물의 제조 방법 |
| AR072447A1 (es) | 2008-02-29 | 2010-09-01 | Basf Se | Proceso para preparar 2- alcoximetilen-4,4-difluoro-3-oxobutiratos de alquilo |
| BRPI0911898A2 (pt) | 2008-05-02 | 2015-10-13 | Basf Se | processo para preparar compostos, e, composto. |
| EP2297111B1 (de) * | 2008-05-02 | 2012-06-20 | Basf Se | Verfahren zur herstellung halogensubstituierter 2-(aminomethyliden)-3-oxobuttersäureester |
| EP2288597B1 (de) * | 2008-05-05 | 2014-10-29 | Basf Se | Verfahren zur herstellung von 1,3,4-substituierten pyrazolverbindungen |
| AU2009245791B2 (en) | 2008-05-08 | 2013-05-16 | Basf Se | Method for manufacturing aryl carboxamides |
| JP5558467B2 (ja) * | 2008-07-21 | 2014-07-23 | ビーエーエスエフ ソシエタス・ヨーロピア | １，３−二置換ピラゾールカルボン酸エステルの調製方法 |
| JP5540776B2 (ja) * | 2010-03-05 | 2014-07-02 | セントラル硝子株式会社 | ジフルオロ酢酸エステルの製造方法 |
| CN113603669A (zh) * | 2021-08-06 | 2021-11-05 | 江苏八巨药业有限公司 | 一种吉西他滨关键中间体的制备方法 |
| CN117843519A (zh) * | 2024-01-02 | 2024-04-09 | 南京工业大学 | 一种二氟烯酮的制备及其转化为二氟乙酸酯及酰胺的方法 |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508880A (en) * | 1981-06-30 | 1985-04-02 | E. I. Du Pont De Nemours And Company | "Living" polymers and process for their preparation |
| US4417034A (en) * | 1981-06-30 | 1983-11-22 | E. I. Du Pont De Nemours & Co. | Living polymers and process for their preparation |
| US4414372A (en) * | 1982-06-17 | 1983-11-08 | E. I. Du Pont De Nemours & Co. | Process for preparing living polymers |
| US4482729A (en) * | 1984-03-04 | 1984-11-13 | Daikin Kogyo Co., Ltd. | Fluoroalkyl silyl ketene acetals and a process for preparing the same |
| US4780554A (en) * | 1984-11-20 | 1988-10-25 | Union Carbide Corporation | O-silylated ketene acetals and enol ethers and method of preparation |
| US4754046A (en) * | 1987-06-25 | 1988-06-28 | Dow Corning Corporation | Stabilized silyl ketene acetals |
| US4824981A (en) * | 1987-07-06 | 1989-04-25 | Dow Corning Corporation | Process to produce silyl ketene acetals |
| US4746750A (en) * | 1987-08-31 | 1988-05-24 | Dow Corning Corporation | Synthesis of silyl ketene acetal from allyl 2-organoacrylates |
| JP2594605B2 (ja) * | 1988-03-12 | 1997-03-26 | 鹿島石油株式会社 | 光学活性なα，α−ジフルオロ−β−ヒドロキシカルボニル化合物 |
| US4824980A (en) * | 1988-09-02 | 1989-04-25 | Dow Corning Corporation | Process to produce O-silyl O,N-ketene acetals |
| JPH0267250A (ja) * | 1988-09-02 | 1990-03-07 | Asahi Glass Co Ltd | ２，２‐ジフルオロ‐３‐ヒドロキシカルボン酸誘導体の製造法 |
| KR900012940A (ko) * | 1989-02-14 | 1990-09-03 | 사와무라 하루오 | 유기규소 화합물의 제조방법 |
| JPH02270841A (ja) * | 1989-04-12 | 1990-11-05 | Asahi Glass Co Ltd | ２，２―ジフルオロ―３，４，５―トリヒドロキシカルボン酸誘導体の製造法 |
-
1994
- 1994-11-28 CA CA002136788A patent/CA2136788C/en not_active Expired - Fee Related
- 1994-11-28 KR KR1019940031485A patent/KR100344363B1/ko not_active Expired - Fee Related
- 1994-11-28 IL IL11179394A patent/IL111793A/en not_active IP Right Cessation
- 1994-11-29 HU HU9403423A patent/HU219466B/hu not_active IP Right Cessation
- 1994-11-29 AT AT94308806T patent/ATE204283T1/de active
- 1994-11-29 JP JP29448094A patent/JP3615253B2/ja not_active Expired - Fee Related
- 1994-11-29 PT PT94308806T patent/PT655454E/pt unknown
- 1994-11-29 BR BR9404776A patent/BR9404776A/pt not_active Application Discontinuation
- 1994-11-29 ES ES94308806T patent/ES2159296T3/es not_active Expired - Lifetime
- 1994-11-29 FI FI945626A patent/FI115461B/fi not_active IP Right Cessation
- 1994-11-29 DK DK94308806T patent/DK0655454T3/da active
- 1994-11-29 HU HU9904356A patent/HU224710B1/hu not_active IP Right Cessation
- 1994-11-29 DE DE69427955T patent/DE69427955T2/de not_active Expired - Lifetime
- 1994-11-29 EP EP94308806A patent/EP0655454B1/de not_active Expired - Lifetime
-
1995
- 1995-05-26 US US08/451,284 patent/US5618951A/en not_active Expired - Lifetime
-
2001
- 2001-11-22 KR KR1020010072944A patent/KR100332322B1/ko not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| HU9403423D0 (en) | 1995-02-28 |
| DK0655454T3 (da) | 2001-10-08 |
| US5618951A (en) | 1997-04-08 |
| PT655454E (pt) | 2001-12-28 |
| IL111793A0 (en) | 1995-01-24 |
| EP0655454A1 (de) | 1995-05-31 |
| ATE204283T1 (de) | 2001-09-15 |
| HU224710B1 (en) | 2006-01-30 |
| IL111793A (en) | 1998-12-06 |
| KR100332322B1 (ko) | 2002-04-13 |
| CA2136788C (en) | 2005-01-25 |
| DE69427955D1 (de) | 2001-09-20 |
| EP0655454B1 (de) | 2001-08-16 |
| BR9404776A (pt) | 1995-11-21 |
| JP3615253B2 (ja) | 2005-02-02 |
| KR100344363B1 (ko) | 2002-11-30 |
| FI945626L (fi) | 1995-05-31 |
| DE69427955T2 (de) | 2002-04-18 |
| KR950014125A (ko) | 1995-06-15 |
| ES2159296T3 (es) | 2001-10-01 |
| JPH07188260A (ja) | 1995-07-25 |
| HUT70178A (en) | 1995-09-28 |
| CA2136788A1 (en) | 1995-05-31 |
| FI945626A0 (fi) | 1994-11-29 |
| HU219466B (hu) | 2001-04-28 |
| HU9904356D0 (en) | 2000-02-28 |
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