TW201429933A - 高純度原冰片烯烷醇及其衍生物之製備方法 - Google Patents
高純度原冰片烯烷醇及其衍生物之製備方法 Download PDFInfo
- Publication number
- TW201429933A TW201429933A TW102146343A TW102146343A TW201429933A TW 201429933 A TW201429933 A TW 201429933A TW 102146343 A TW102146343 A TW 102146343A TW 102146343 A TW102146343 A TW 102146343A TW 201429933 A TW201429933 A TW 201429933A
- Authority
- TW
- Taiwan
- Prior art keywords
- formula
- compound
- methanol
- alkyl
- purity
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 title claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 147
- 150000001875 compounds Chemical class 0.000 claims description 76
- 238000006243 chemical reaction Methods 0.000 claims description 44
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 37
- -1 cyclopentadiene compound Chemical class 0.000 claims description 33
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 claims description 29
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 claims description 28
- 229940116229 borneol Drugs 0.000 claims description 28
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 claims description 28
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 238000005809 transesterification reaction Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- YXNICIBZSREEPY-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl acetate Chemical compound C1CC2C(OC(=O)C)CC1C2 YXNICIBZSREEPY-UHFFFAOYSA-N 0.000 claims description 5
- UNKBZJDUQFAXKF-UHFFFAOYSA-N C12C(CC(C=C1)C2)COC(CCCC(CCCC)(C2=CC=CC=C2)C2=CC=CC=C2)C Chemical compound C12C(CC(C=C1)C2)COC(CCCC(CCCC)(C2=CC=CC=C2)C2=CC=CC=C2)C UNKBZJDUQFAXKF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 5
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical group [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- MQCJJXAARUDSNC-UHFFFAOYSA-N 2-phenylundecan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(CCCCCCCCC)C1=CC=CC=C1 MQCJJXAARUDSNC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 claims description 2
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 2
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 claims description 2
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 9
- NSTVHFOHEYKXRQ-UHFFFAOYSA-N 4-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1CC2C=CC1(CO)C2 NSTVHFOHEYKXRQ-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000636 poly(norbornene) polymer Polymers 0.000 abstract description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000002585 base Substances 0.000 description 23
- 230000014509 gene expression Effects 0.000 description 17
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 15
- 150000001336 alkenes Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 7
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 150000002085 enols Chemical class 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 125000006239 protecting group Chemical group 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- VLCYCQAOQCDTCN-UHFFFAOYSA-N eflornithine Chemical group NCCCC(N)(C(F)F)C(O)=O VLCYCQAOQCDTCN-UHFFFAOYSA-N 0.000 description 3
- 229960002759 eflornithine Drugs 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 238000006276 transfer reaction Methods 0.000 description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 2
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 description 2
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical class CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 2
- HUMMQDLHLVLHCE-UHFFFAOYSA-N 1-phenylundecylbenzene Chemical compound C=1C=CC=CC=1C(CCCCCCCCCC)C1=CC=CC=C1 HUMMQDLHLVLHCE-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229920001774 Perfluoroether Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical class [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- VSLJKXDXVIJAFZ-UHFFFAOYSA-N (2-chloro-1-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(CCl)C1=CC=CC=C1 VSLJKXDXVIJAFZ-UHFFFAOYSA-N 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 description 1
- 125000006663 (C1-C6) perfluoroalkyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- UWYVPFMHMJIBHE-OWOJBTEDSA-N (e)-2-hydroxybut-2-enedioic acid Chemical compound OC(=O)\C=C(\O)C(O)=O UWYVPFMHMJIBHE-OWOJBTEDSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NLWBEORDOPDUPM-UHFFFAOYSA-N 1,2,3,4-cyclopentanetetracarboxylic dianhydride Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C1C2 NLWBEORDOPDUPM-UHFFFAOYSA-N 0.000 description 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- HSTCJLDQVIIDKF-UHFFFAOYSA-N 1-phenyldecylbenzene Chemical compound C=1C=CC=CC=1C(CCCCCCCCC)C1=CC=CC=C1 HSTCJLDQVIIDKF-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- PKRSYEPBQPFNRB-UHFFFAOYSA-N 2-phenoxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC1=CC=CC=C1 PKRSYEPBQPFNRB-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- BNNMDMGPZUOOOE-UHFFFAOYSA-N 4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CC1=CC=C(S(O)(=O)=O)C=C1 BNNMDMGPZUOOOE-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- 125000006163 5-membered heteroaryl group Chemical group 0.000 description 1
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical class CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 238000006742 Retro-Diels-Alder reaction Methods 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000006620 amino-(C1-C6) alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003725 azepanyl group Chemical group 0.000 description 1
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 description 1
- BLCFCVYGFDLOSC-UHFFFAOYSA-N benzene;benzenesulfonic acid Chemical compound C1=CC=CC=C1.OS(=O)(=O)C1=CC=CC=C1 BLCFCVYGFDLOSC-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 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
- 125000002619 bicyclic group Chemical group 0.000 description 1
- ZDLCTRXVPGDKOG-UHFFFAOYSA-N bicyclo[2.2.1]heptane;methanol Chemical compound OC.C1CC2CCC1C2 ZDLCTRXVPGDKOG-UHFFFAOYSA-N 0.000 description 1
- 150000001602 bicycloalkyls Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- MUJRNJDKBBSXSE-UHFFFAOYSA-N calcium;butan-1-olate Chemical compound [Ca+2].CCCC[O-].CCCC[O-] MUJRNJDKBBSXSE-UHFFFAOYSA-N 0.000 description 1
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 1
- AMJQWGIYCROUQF-UHFFFAOYSA-N calcium;methanolate Chemical compound [Ca+2].[O-]C.[O-]C AMJQWGIYCROUQF-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XDPCFUNJJWMBFH-UHFFFAOYSA-N cesium;ethanolate Chemical compound [Cs+].CC[O-] XDPCFUNJJWMBFH-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 125000006254 cycloalkyl carbonyl group Chemical group 0.000 description 1
- 125000004367 cycloalkylaryl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- RSPWPAYFBOWLKA-UHFFFAOYSA-N cyclohexane;formic acid Chemical compound OC=O.C1CCCCC1 RSPWPAYFBOWLKA-UHFFFAOYSA-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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- JBDSSBMEKXHSJF-UHFFFAOYSA-M cyclopentanecarboxylate Chemical compound [O-]C(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-M 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 238000005661 deetherification reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 125000005959 diazepanyl group Chemical group 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical class CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000002757 morpholinyl group Chemical group 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 150000002847 norbornane derivatives Chemical class 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229940093956 potassium carbonate Drugs 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000010963 scalable process Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- DBDCNCCRPKTRSD-UHFFFAOYSA-N thieno[3,2-b]pyridine Chemical group C1=CC=C2SC=CC2=N1 DBDCNCCRPKTRSD-UHFFFAOYSA-N 0.000 description 1
- 125000004001 thioalkyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/44—Allylic alkylation, amination, alkoxylation or analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
- B01J2531/004—Ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/54—Ortho- or ortho- and peri-condensed systems containing more than five condensed rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
揭示且主張多種高純度原冰片烯烷醇單體及其衍生物之製備方法。特定言之,揭示且主張工業規模高純度原冰片烯甲醇及其矽烷基醚衍生物之製備方法。根據本發明方法製備之高純度單體可用於多種應用,包括(但不限於)製備在多種電子應用中以及各種其他應用中具有效用之高品質及高純度聚原冰片烯。
Description
本申請案主張於2012年12月19日申請之美國臨時申請案第61/739,119號之權益,該臨時申請案以全文引用的方式併入本文中。
本發明之具體實例係關於工業規模的原冰片烯烷醇及其衍生物之製備方法。更特定言之,該等具體實例係關於多種高純度原冰片烯烷醇及相應矽烷基醚衍生物的製備方法,該等原冰片烯烷醇及相應矽烷基醚衍生物可用於多種工業應用,包括作為製造電子/光電聚合材料之起始物質。
官能化原冰片烯單體廣泛用於製備特別是在電子工業中具有多種應用的聚合物。詳言之,各種電子材料利用聚原冰片烯之原因在於聚原冰片烯具有獨特成膜特性外加合乎需要之電子材料特性。該等應用尤其包括其用作介電質、光阻、保護層及液晶顯示層。然而,因為此等應用需要極高純度材料,所以尤其重要的是各種官能化原冰片烯單體不含任何可能使高分子量聚合物難以形成之雜質。
近來,對在諸如應用於液晶顯示器(liquid crystal display;
LCD)之延遲膜之電子應用中使用聚原冰片烯烷醇衍生物相當感興趣,參見例如PCT國際申請案第WO 2008/130186號。
美國專利第7,541,073號揭示用於LCD之配向膜,其由含有聚原冰片烯烷醇衍生物之光敏聚合物製成。然而,單體原冰片烯甲醇之報導產率較低從而使得其不適用於工業操作。此外,已知很難製備高純度原冰片烯烷醇,例如純度超過95%之原冰片烯甲醇。尤其難以在缺乏任何相應氫化型式(例如原冰片烷甲醇)下製備原冰片烯烷醇。尤其已經報導,原冰片烯甲醇容易進行氫化,形成原冰片烷甲醇,參見例如Gasanov,Russian Journal of Organic Chemistry,第39卷,第7期,2003,第947-951頁。
亦已報導某些原冰片烯烷醇苯甲酸酯可藉由二環戊二烯與相應烯醇苯甲酸酯反應來製備。然而,報導產率低且以工業規模使用苯甲酸酯可能不適於製備各種原冰片烯烷醇衍生物,參見Guseinov等人,Doklady Akademiya Nauk Azerbaidzhanskoi SSR,35(10),45-8;(1979)。
考慮到上述內容,需要開發工業上可行的方法來製備高純度原冰片烯烷醇單體。
本發明之其他目標及另外的範疇將自以下實施方式變得顯而易見。
如本文所用之術語具有以下含義:如本文所用,除非另外清楚且明確地限於一個指示物,否則冠詞「一(a/an)」及「該」包括複數個指示物。
如本文所用,「烴基」指僅含碳及氫之部分或基團,非限制
性實例為烷基、環烷基、芳基、芳烷基、烷芳基及烯基。術語「鹵烴基」指其中至少一個氫經鹵素置換之烴基。術語全鹵烴基指其中所有氫經鹵素置換之烴基。
如本文所用,表述「烷基」(諸如「(C1-C6)烷基」)包括甲基及乙基,以及直鏈或分支鏈丙基、丁基、戊基及己基。特定烷基為甲基、乙基、正丙基、異丙基、第三丁基等等。諸如「(C1-C6)烷氧基」、「(C1-C6)硫基烷基」、「(C1-C6)烷氧基(C1-C6)烷基」、「羥基(C1-C6)烷基、「(C1-C6)烷基羰基」、「(C1-C6)烷氧基羰基(C1-C6)烷基」、「(C1-C6)烷氧基羰基」、「胺基(C1-C6)烷基」、「(C1-C6)烷基胺基」、「(C1-C6)烷基胺甲醯基(C1-C6)烷基」、「(C1-C6)二烷基胺甲醯基(C1-C4)烷基」、「單-或二-(C1-C6)烷基胺基(C1-C6)烷基」、「胺基(C1-C6)烷基羰基」、「二苯基(C1-C6)烷基」、「苯基(C1-C6)烷基」、「苯基羰基(C1-C6)烷基」及「苯氧基(C1-C6)烷基」之衍生表述將作相應解釋。另外,如本文所用,「低碳烷基」應一般意指(C1-C6)烷基。
如本文所用,表述「環烷基」包括所有已知環狀基團。「環烷基」之代表性實例包括(但不限於)環丙基、環丁基、環戊基、環己基、環庚基、環辛基及其類似基團。諸如「環烷氧基」、「環烷基烷基」、「環烷基芳基」、「環烷基羰基」之衍生表述將作相應解釋。
如本文所用,表述「(C2-C6)烯基」包括乙烯基及直鏈或分支鏈丙烯基、丁烯基、戊烯基及己烯基。類似地,表述「(C2-C6)炔基」包括乙炔基及丙炔基以及直鏈或分支鏈丁炔基、戊炔基及己炔基。諸如「(C5-C12)環烯基」、「(C2-C6)烯醇」、「(C5-C12)環烯醇」之衍生表述將作相應解釋。
如本文所用,表述「(C1-C4)醯基」應具有與「(C1-C4)烷醯基」
相同之含義,其亦可在結構上表示為「R-CO-」,其中R為如本文所定義之(C1-C3)烷基。另外,「(C1-C3)烷基羰基」應具有與(C1-C4)醯基相同之含義。特定言之,「(C1-C4)醯基」應意指甲醯基、乙醯基(acetyl)或乙烷醯基(ethanoyl)、丙醯基、正丁醯基等。諸如「(C1-C4)醯氧基」及「(C1-C4)醯氧基烷基」之衍生表述將作相應解釋。
如本文所用,表述「(C1-C6)全氟烷基」意指該烷基中之所有氫原子經氟原子置換。說明性實例包括三氟甲基及五氟乙基以及直鏈或分支鏈七氟丙基、九氟丁基、十一氟戊基及十三氟己基。因此衍生表述「(C1-C6)全氟烷氧基」將作相應解釋。
如本文所用,表述「(C6-C10)芳基」意指經取代或未經取代之苯基或萘基。經取代之苯基或萘基之特定實例包括鄰甲苯基、對甲苯基、間甲苯基、1,2-二甲苯基、1,3-二甲苯基、1,4-二甲苯基、1-甲基萘基、2-甲基萘基等。「經取代之苯基」或「經取代之萘基」亦包括如本文中進一步定義之任何可能取代基,或此項技術中已知之取代基。衍生表述「(C6-C10)芳基磺醯基」將作相應解釋。
如本文所用,表述「(C6-C10)芳基(C1-C4)烷基」意指如本文所定義之(C6-C10)芳基進一步連接於如本文所定義之(C1-C4)烷基。代表性實例包括苯甲基、苯基乙基、2-苯基丙基、1-萘基甲基、2-萘基甲基及其類似基團。
如本文所用,表述「雜芳基」包括所有已知之含雜原子之芳族基。代表性5員雜芳基包括呋喃基、噻吩基(thienyl/thiophenyl)、吡咯基、異吡咯基、吡唑基、咪唑基、噁唑基、噻唑基、異噻唑基及其類似基團。代表性6員雜芳基包括吡啶基、嗒基、嘧啶基、吡基、三基及其類
似基團。雙環雜芳基之代表性實例包括苯并呋喃基、苯并噻吩基、吲哚基、喹啉基、異喹啉基、啉基、苯并咪唑基、吲唑基、吡啶并呋喃基、吡啶并噻吩基及其類似基團。
如本文所用,表述「雜環」包括所有已知之含還原雜原子之環狀基團。代表性5員雜環基包括四氫呋喃基、四氫噻吩基、吡咯啶基、2-噻唑啉基、四氫噻唑基、四氫噁唑基及其類似基團。代表性6員雜環基包括哌啶基、哌基、嗎啉基、硫代嗎啉基及其類似基團。各種其他雜環基包括(但不限於)氮雜環丙烷基、氮雜環庚烷基、二氮雜環庚烷基、二氮雜二環[2.2.1]庚-2-基及三氮雜環辛烷基以及其類似基團。
「鹵素」或「鹵基」意謂氯、氟、溴及碘。
在廣義上,術語「經取代」預期包括有機化合物之所有允許之取代基。在如本文所揭示之幾個特定具體實例中,術語「經取代」意指經一或多個獨立地選自由以下各物組成之群之取代基取代:C1-6烷基、C2-6烯基、C1-6全氟烷基、苯基、羥基、-CO2H、酯、醯胺、C1-C6烷氧基、C1-C6硫基烷基、C1-C6全氟烷氧基、-NH2、Cl、Br、I、F、-NH-低碳烷基及-N(低碳烷基)2。然而,熟習此項技術者已知之任何其他適合取代基亦可用於此等具體實例。
此外,除非另外指示,否則本文所用之關於成分之量、反應條件、溫度、壓力、時間及其類似物的所有數字、值及/或表述應理解為在所有情況下均由術語「約」修飾以考慮與測定該等值有關之不確定性。
此外,本文所揭示之任何數值範圍將理解為連續的,且包括在各範圍之最小值與最大值之間的每個值。除非另外清楚地指示,否則該
等數值範圍為反映在獲得該等值之過程中所遇到之各種量測不確定性的近似值。因此,除非另外指示,否則本文所揭示之所有範圍或比率均應理解為涵蓋其中所包含的任何及所有子範圍或子比率。舉例而言,「1至10」之指定範圍或比率應被視為包括在最小值1與最大值10之間(且包括端點在內)之任何及所有子範圍;亦即,所有以1或大於1之最小值開始且以10或小於10之最大值結束的子範圍或子比率,包括(但不限於)1至6.1、3.5至7.8及5.5至10。
將本發明之具體實例特性化之特徵在申請專利範圍中特別指出,申請專利範圍形成本發明之一部分。將自下文中該等具體實例之描述及隨後之實施例更全面地瞭解該等具體實例之此等及其他特徵、其操作優點及用途。
因此,根據本發明之實施,提供式(I)化合物之製備方法:
其中n為1至10之整數,包括端點在內,且其中一或多個CH2視情況經C1-C10烷基或C1-C10全氟烷基取代;m為0至2之整數,包括端點在內;R1、R2及R3相同或不同且彼此獨立地選自氫、鹵素及烴基,其中烴基選自甲基、乙基、直鏈或分支鏈C3-C12烷基、C3-C12環烷基、C6-C12二環烷基、
C7-C14三環烷基、C6-C10芳基、C6-C10芳基-C1-C3烷基、C5-C10雜芳基、C5-C10雜芳基-C1-C3烷基、C1-C12烷氧基、C3-C12環烷氧基、C6-C12二環烷氧基、C7-C14三環烷氧基、C6-C10芳氧基-C1-C3烷基、C5-C10雜芳氧基-C1-C3烷基、C6-C10芳氧基、C5-C10雜芳氧基及C1-C6醯氧基;其包含:使二環戊二烯與式(II)化合物:CR2R3=CR1-(CH2)n-R (II)
其中R為-OCOC1-C6烷基、-CHO、-CN、-OC1-C6烷基、-OCH2Ph、-OSO2R4,其中R4為C1-C4烷基或C6-C12芳基;在適合溫度及條件下反應,以形成式(III)化合物:;及使式(III)化合物進行適合轉變反應以形成式(I)化合物。
因此,根據本發明之實施,現已發現,如由式(II)化合物表示之各種經取代之烯烴衍生物現可與二環戊二烯(DCPD)反應,以形成式(III)化合物,其可進一步轉化為如由式(IA)化合物表示之原冰片烯烷醇,其中m=0,如流程I中概述。
如流程I中描繪,根據本發明之方法,由二聚體形式DCPD產生之環戊二烯(CPD)首先與如由式(II)化合物表示之經取代之烯烴衍生物反應。此反應可使用任何已知之反應條件進行,以便形成式(IIIA)化合物。該等適合反應條件包括(但不限於)周圍、超過周圍或低於周圍之反應溫度及壓力條件,持續足夠時間段。典型地,該等反應在密閉反應系統中在高溫下在自生壓力條件下進行。亦即,壓力藉由在密閉反應容器中加熱反應物自身產生。舉例而言,該等反應可在適合密閉壓力反應器系統中在約130℃至約260℃之溫度範圍下進行。在一些其他具體實例中,反應可在約200℃至約240℃之溫度範圍下進行;且在一些其他具體實例中,反應可在約180℃至約240℃之溫度範圍下進行;而在一些其他具體實例中,在約210℃至約230℃之溫度範圍下進行。在一些其他具體實例中,反應可在約220℃之溫度下進行。適合的反應器系統包括(但不限於)密閉管式反應器、壓力容器(諸如帕爾反應器(Parr reactor))或由玻璃、玻璃襯裡金屬(或其他適當加襯之金屬,包括石英或TEFLON®(聚四氟乙烯))或金屬
(包括(但不限於)不鏽鋼、HASTELLOY®(包含Ni 57.0%、Mo 16.0%、Cr 15.5%、Fe 5.5%及W 3.8%之合金)、INCONEL®(鎳鉻合金)及其類似物)構造之該等適合容器及/或反應器。
一般而言,DCPD與式(II)化合物之反應首先藉由DCPD分解成單體環戊二烯(CPD),接著與式(II)化合物反應進行。一般而言,現已發現相對於CPD採用莫耳過量之式(II)化合物產生較高產率之式(III)化合物。典型地,CPD:式(II)化合物之莫耳比可在約1:1至約1:8、約1:1至約1:5及約1:1至約1:4之範圍內。然而,亦可使用將引起反應之任何其他莫耳比,例如亦可使用約2:1至1:2之比率。
對於其中m=1或2之式(I)化合物,式(IIIA)化合物可進一步依序與額外量的CPD(或DCPD,其在加熱至約150℃之溫度時,進行逆狄爾斯-阿德爾反應(retro Diels-Alder reaction),形成CPD)反應,獲得其中m≡1或2之式(I)化合物。
一般而言,反應純淨地,亦即無任何溶劑及/或其他試劑(諸如催化劑)及其類似物下進行。然而,視所採用的式(II)之經取代之烯烴衍生物的類型而定,在一些情況下亦可使用適合的溶劑。例示性溶劑包括(但不限於)烴溶劑,諸如己烷、庚烷、石油醚、苯、甲苯、二甲苯及其類似物;鹵化烴溶劑,諸如二氯甲烷、1,1-二氯乙烷、氯仿、四氯化碳及其類似物。其他適合的溶劑尤其包括二甲亞碸(DMSO)、二甲基甲醯胺(DMF)、二甲基乙醯胺(DMAc)、丙酮、甲基乙基酮(MEK)。
一般而言,反應進程可藉由自反應器移除等分試樣且用適合方法(諸如薄層層析法(TLC)、氣相層析法(GC)、液相層析法(LC)或
高效液相層析法(HPLC)或GC/質譜分析(MS)之組合、LC/MS之組合以及其他已知之技術)分析來監測。
有利地,現已發現藉由本發明之實施,現可獲得極高純度之式(I)化合物。如本文所用,「高純度」意指產物與其他雜質無關,尤其在原冰片烯部分氫化為原冰片烷的情況下。亦即,式(I)化合物基本上不含相應原冰片烷衍生物。在一個具體實例中,自本發明方法獲得之式(I)化合物具有至少99%純度。在另一具體實例中,自本發明方法獲得之式(I)化合物具有至少99.4%純度。在另一具體實例中,自本發明方法獲得之式(I)化合物具有至少99.8%純度。
應進一步指出,如下文由特定實施例進一步例示之任何先前技術方法藉由CPD與任何相應烯醇直接反應,產生低純度之式(I)化合物。如所指出,此反應不僅導致純度低,而且亦使得產率極低,因此不適於任何工業操作。一般而言,已發現推動氫轉移之任何官能基均產生不合乎需要之副產物。舉例而言,如本文中由比較實施例所顯示,使用烯醇作為共反應物及/或使用醇溶劑與CPD產生不合乎需要之副產物,可能是由氫轉移反應引起。另一方面,亦如本文中顯示,本發明之方法意外地產生極高純度之式(III)化合物,如下文進一步討論,其可非常容易地轉化為式(I)化合物。
任何已知的式(II)之經取代之烯烴衍生物可用於製備式(III)化合物。如所指出,該等式(II)之經取代之烯烴衍生物包括(但不限於)任何脂族酸酯。例示性脂族酸酯包括(但不限於)乙酸酯、丙酸酯、正丁酸酯、異丁酸酯、正戊酸酯及其類似物。亦可採用其他脂族酸酯,諸
如環脂族酸酯,諸如環戊烷甲酸酯、環己烷甲酸酯等。其他經取代之烯烴衍生物包括相應醛(-CHO)或腈(-CN),如流程I中所表示,其可在與CPD進行加成反應後轉化為醇官能基。其他經取代之烯烴衍生物包括各種醚,包括與各種C1-C6烷醇形成之醚,形成相應-OC1-C6烷基醚。可用於形成相應醚之例示性烷醇尤其包括甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三丁醇、戊醇或己醇之所有異構體形式及其類似物。最終,其他式(II)之經取代之烯烴衍生物亦可包括式-OSO2R4之各種磺酸酯,其中R4為C1-C4烷基、C1-C4全氟烷基或C6-C12芳基。例示性磺酸酯包括(但不限於)甲烷磺酸酯或甲磺酸酯、三氟甲烷磺酸酯或三氟甲磺酸酯、乙烷磺酸酯、苯磺酸酯(benzenesulfonate)(苯磺酸酯(besylate))、對甲苯磺酸酯(甲苯磺酸酯)及其類似物。應進一步指出,如本文所述之各種烯烴衍生物藉由相應醇用適合保護基保護而形成。對於各種該等保護基之實例,包括本文所述之保護基,可見於Greene,T.W.;Wuts,P.G.M."Protective Groups in Organic Synthesis"第4版(2007)中。
許多以上提及的式(II)之經取代之烯烴衍生物可購得或者可容易地藉由熟習此項技術者已知之任何程序合成。舉例而言,許多式(II)之烯醇酯可購得及/或可容易地藉由相應醇與酸之酯化反應來製備。類似地,烯醇醚及磺酸酯亦可藉由採用適合起始物質來製備。相應醛或腈化合物,亦即其中R=CHO或CN,亦可以適當起始物質為起始物且藉由採用任何已知之文獻程序類似地製備。
在本發明方法之一個具體實例中,所採用的式(II)之經取代之烯烴衍生物為乙酸烯丙酯,亦即其中n為1,R為CH3C(O)O且R1、R2
及R3中之每一者為氫的式(II)化合物。由此形成之式(IIIA)化合物,在此狀況下為酯,確切為乙酸酯,可在催化劑存在下經受適合的轉酯化劑,形成式(IA)化合物,其中n=1且m=0。
泛言之,為將式(III)之酯化合物轉化為式(I)化合物的轉酯化反應可使用此項技術中已知之任何程序進行。舉例而言,該等轉酯化反應可在適合溫度下在適合的酸或鹼催化劑存在下在適合溶劑及適合轉酯化劑中進行。適合轉酯化劑為醇,諸如甲醇、乙醇、異丙醇、正丁醇、異丁醇及其類似物。亦可採用各種其他醇。在本發明之一個具體實例中,所用醇為甲醇。各種其他溶劑亦可與以上提及之醇溶劑組合使用。特定實例包括石油醚、二氯甲烷、乙酸甲酯、乙酸乙酯、甲苯及其類似物。
適合鹼催化劑包括(但不限於)鹼性鹼,例如鋰、鈉、鉀或銫之氫氧化物、烷醇鹽、碳酸鹽、碳酸氫鹽及其類似物;鹼土金屬鹼,例如鈣或鎂之氫氧化物、烷醇鹽、碳酸鹽、碳酸氫鹽及其類似物;及適合的無機或有機鹼,例如氨、三烷胺、咪唑及其類似物。特定鹼性鹼包括(但不限於)氫氧化鋰、甲醇鋰、乙醇鋰、第三丁醇鋰、碳酸鋰、碳酸氫鋰、氫氧化鈉、甲醇鈉、乙醇鈉、第三丁醇鈉、碳酸鈉、碳酸氫鈉、氫氧化鉀、甲醇鉀、乙醇鉀、第三丁醇鉀、碳酸鉀、碳酸氫鉀、氫氧化銫、甲醇銫、乙醇銫、第三丁醇銫、碳酸銫、碳酸氫銫、氫氧化鈣、甲醇鈣、乙醇鈣、第三丁醇鈣、碳酸鈣、碳酸氫鈣、氫氧化鎂、甲醇鎂、乙醇鎂、第三丁醇鎂、碳酸鎂、碳酸氫鎂、氨、三甲胺、三乙胺、咪唑及其混合物之任何組合。
適合酸催化劑包括(但不限於)任何已知之布朗斯特酸
(Bronsted acid),諸如鹽酸、氫溴酸、氫氟酸、硫酸、甲烷磺酸、三氟甲烷磺酸、2-羥基乙烷磺酸、對甲苯磺酸、反丁烯二酸、順丁烯二酸、羥基順丁烯二酸、蘋果酸、抗壞血酸、丁二酸、戊二酸、乙酸、水楊酸、肉桂酸、2-苯氧基苯甲酸、羥基苯甲酸、苯乙酸、苯甲酸、乙二酸、檸檬酸、酒石酸、乙醇酸、乳酸、丙酮酸、丙二酸、碳酸或磷酸及其類似物。亦可採用任何已知之路易斯酸(Lewis acid),單獨或者與以上提及之布朗斯特酸組合。路易斯酸之特定實例包括(但不限於)三氟化硼、三氯化硼、氯化鋁、五氟化銻及其類似物。因此,在本發明之一個具體實例中,轉酯化劑為醇,諸如甲醇,且所用催化劑為酸,例如硫酸或磺酸,諸如甲烷磺酸(MsOH)或對甲苯磺酸(p-TsOH)。
一般而言,一或多種以上提及之酸或鹼催化劑可以催化量用於轉酯化反應中。舉例而言,與式(III)化合物相比,所用酸或鹼之催化量可在約0.1莫耳百分比至約50莫耳百分比之間變化。一般而言,與酸催化劑相比,使用略微較大莫耳百分比之鹼催化劑。亦即在酸用作催化劑時,所用酸之量可低至0.1莫耳百分比。然而,在鹼用作催化劑時,量可在約1莫耳百分比至約50莫耳百分比之範圍內。在一些具體實例中,所用催化劑為鹼催化劑,且用量為約4莫耳百分比至約20莫耳百分比,且在一些其他具體實例中為約5莫耳百分比至約10莫耳百分比。因此,在本發明之一個具體實例中,所用溶劑為甲醇且所用鹼為甲醇鈉,與式(III)化合物相比,量為約8莫耳百分比。
一般而言,轉酯化反應可在寬溫度範圍下進行,該寬溫度範圍包括低於周圍、周圍及超過周圍溫度範圍,且視所用酯之類型而定。舉
例而言,在一些具體實例中,溫度範圍可為約0℃至100℃。在一些其他具體實例中,溫度範圍可為約20℃至80℃。在一些其他具體實例中,溫度範圍可為約40℃至60℃。然而,亦可採用任何其他適合之溫度範圍,視起始物質而定,熟習此項技術者將容易地瞭解該等修改。
類似地,若加成產物為磺酸酯,亦即其中R為-OSO2R4之式(III)化合物,則該等式(III)之磺酸酯亦可藉由經受如上所述之酸或鹼催化之任何轉酯化反應而轉化為式(I)化合物。
若所形成之加成產物為醚,亦即其中R為-OC1-C6烷基之式(III)化合物,則該等醚可藉由採用任何已知之文獻程序裂解成式(I)化合物。該等醚裂解反應包括酸催化反應以及任何已知之矽烷基試劑,其將使醚裂解形成各別醇。
如所指出,藉由實施本發明之方法,現可獲得極高純度之式(I)化合物。因此,在一個具體實例中形成之式(I)化合物為純度為至少99%之外-/內-原冰片烯甲醇。
在本發明方法之另一具體實例中,方法進一步包含:使式(I)化合物與式(IV)之矽烷:R5R6R7SiH (IV)
其中R5、R6及R7各自彼此獨立地為甲基、乙基或直鏈或分支鏈C3-C9烷基或經取代或未經取代之C6-C14芳基;及適合的催化劑反應,獲得式(V)化合物:
;且其中由此形成之式(V)化合物純度高。
有利地,現已發現,式(IV)化合物與式(I)化合物之反應可使用鹼作為催化劑進行,參見例如Weickgenannt等人,Chem.Asian J.2009,4,406-410。可用於此反應中之各種鹼催化劑包括用於轉酯化且如上文所列舉之所有鹼催化劑。特定言之,在一個具體實例中,現已發現適合的鹼催化劑為第三丁醇鉀。然而,如上所指出,如上列出之任何其他鹼催化劑亦可用於此步驟中。
在一個具體實例中,由此形成之式(V)化合物中:n為1,R1、R2及R3中之每一者為氫,R5為甲基且R6及R7中之每一者為苯基。在本發明之另一具體實例中,由此形成之式(V)化合物具有高純度。特定言之,式(V)化合物之純度為至少99%。在另一具體實例中,式(V)化合物之純度為至少99.5%。在另一具體實例中,式(V)化合物之純度為至少99.8%。更特定言之,由此形成之式(V)化合物為(雙環[2.2.1]庚-5-烯-2-基甲氧基)(甲基)二苯基矽烷且具有至少99%純度。在另一具體實例中,由此形成之式(V)化合物為(雙環[2.2.1]庚-5-烯-2-基甲氧基)(甲基)二苯基矽烷且具有至少99.8%純度。
在本發明之另一具體實例中,亦提供式(IB)之原冰片烯甲醇之製備方法:
在此具體實例中,方法包含:使二環戊二烯與乙酸烯丙酯在約200℃至約240℃之溫度下反應足夠時間段,以形成式(IIIB)之乙酸原冰片烯甲酯:
蒸餾由此形成之式(IIIB)之乙酸原冰片烯甲酯;及使該蒸餾之乙酸原冰片烯甲酯(IIIB)在甲醇及甲醇鈉存在下在約40℃至約50℃之溫度下進行轉酯化反應,以形成原冰片烯甲醇(IB),純度為至少99.8%。在此方法中,未產生氫化原冰片烯甲醇,亦即原冰片烷甲醇(NBaneCH2OH)。
在本發明之另一具體實例中,提供式(VB)之(雙環[2.2.1]庚-5-烯-2-基甲氧基)(甲基)二苯基矽烷的製備方法:
此具體實例涵蓋:使二環戊二烯與乙酸烯丙酯在約200℃至約240℃之溫度下反應足夠時間段,以形成式(IIIB)之乙酸原冰片烯甲酯:
使乙酸原冰片烯甲酯(IIIB)在甲醇及甲醇鈉存在下在約40℃至約50℃之溫度下進行轉酯化反應,形成原冰片烯甲醇(IB):;及使原冰片烯甲醇(IB)與甲基二苯基矽烷在適合溶劑及第三丁醇鉀存在下反應,獲得(雙環[2.2.1]庚-5-烯-2-基甲氧基)(甲基)二苯基矽烷(VB),純度為至少99.5%。
應指出,本發明之方法提供若干迄今難得到之優點。更重要地,應指出許多文獻程序需要使用各種試劑,該等試劑不可避免地將某些雜質引入最終產物中。舉例而言,藉由採用自由烯醇作為起始物質(亦即式(II)化合物中R=OH),且根據文獻程序,產生低純度之式(I)化合物。更重要地,如以下比較實施例所顯示,質子源之任何存在(諸如醇)均引起式(I)化合物氫化,其始終作為顯著的副產物形成且在大部分情況下難以分離。亦即,在式(I)化合物氫化時,引起具有非常類似物理特性(諸如沸點)之相應原冰片烷化合物形成。
此外,如本文所述之矽烷化程序亦提供一種製備極高純度之式(V)化合物的獨特方法。尤其應指出,許多文獻程序需要酸或鹼條件,此不可避免地產生某些污染物,該等污染物難以移除且尤其在電子應用中為不適合之雜質。舉例而言,文獻中熟知藉由醇與適合氯矽烷或適合矽烷
基胺反應來製備矽烷基醚化合物。舉例而言,流程II說明藉由式(IA)化合物與二苯基甲基氯矽烷或N,N,1-三甲基-1,1-二苯基矽烷胺反應來製備式(VA)化合物。在該兩種文獻方法中,氯化烷基銨作為副產物形成,其需要費力的純化過程來純化式(VA)化合物。另一方面,本發明之方法提供一種有效的工業上容易上規模化的方法來製備高純度式(V)之矽烷基醚化合物及尤其式(VA)化合物。
本發明藉由以下實施例進一步說明,該等實施例出於說明目的而提供且決不限制本發明之範疇。
將乙酸烯丙酯及二環戊二烯(DCPD)以基於環戊二烯單體4:1之莫耳比置放於適合高壓管式反應器中,且在維持在220℃下之熱油浴中加熱且維持在該溫度下4小時。在反應結束時,高壓管自浴中移除且在濕冰浴中驟冷。接著管用甲醇及二氯甲烷洗滌且稱重以驗證未發生洩漏。所得粗單體樣品藉由GC-MS分析,其展示約7.5%未反應乙酸烯丙酯、10%外-/內-原冰片烯甲醇、82%乙酸外-/內-原冰片烯甲酯及0.6%(1,2,3,4,4a,5,8,8a-
八氫-1,4:5,8-二甲橋萘-2-基)甲醇。粗混合物之分餾分離出純度超過99.6%之乙酸原冰片烯甲酯。
GC-MS分析在Altech EC-5管柱上進行,30m,0.25mm ID,0.25μm膜;入口-F:250,MS源:230℃,電子電離。所用GC條件如下:梯度:以10℃/min,45℃至120℃,接著以40℃/min加熱至300℃,在300℃下保持2分鐘。
將乙酸外-/內-原冰片烯甲酯(純度99.6%,4.8kg)與甲醇(11.2kg)之混合物置放於尺寸適當之夾套反應器中。反應器裝備有攪拌器、頂置式冷凝器、頂置式冷凝液接收槽及具有計量泵之進料槽。反應器溫度由專用油循環單元控制;反應器壓力由人工控制,添加氮氣以增加壓力且打開排氣口以降低壓力。
反應器用氮氣使用三個壓力/真空週期性交替來淨化以移除反應器頂部空間中之任何氧氣。此氮氣淨化過程後,反應器經由頂置式冷凝器及接收器系統呈充分排氣模式,接著加熱至初始反應溫度(45℃)。將由含甲醇鈉之甲醇(25wt%,0.125kg)組成之催化劑溶液添加至玻璃進料槽中接著經15分鐘時間計量入反應器中(添加速率8.33g/min),同時維持反應器溫度(45℃)。催化劑計量添加結束後,反應器維持在溫度(45℃)下額外的1.75小時。
在反應過程結束後,反應器以排氣模式加熱至溶劑汽提溫度(60-68℃),且在塔頂閃蒸出甲醇/乙酸甲酯之混合物(4kg),且收集於頂置
式接收槽中。將額外的甲醇(4kg)轉移至反應器中,且進行第二溶劑汽提操作以移除甲醇/乙酸甲酯之混合物(4kg)。最終,進行第三溶劑汽提操作以移除甲醇/乙酸甲酯之混合物(6kg)。此溶劑汽提方法結束後,將乙酸(0.04kg)添加至反應濃縮物中,接著將其自反應器轉移出且經由GC分析以證實轉酯化反應完成。反應濃縮物之組成如下:原冰片烯甲醇83%,乙酸原冰片烯甲酯痕量,甲醇17%及MeOAc痕量。
接著將原冰片烯甲醇反應濃縮物(6kg)饋入適當裝備之真空蒸餾系統中,該系統由具有電加熱套之蒸餾釜、具有不鏽鋼規整填料之蒸餾塔(理論塔板數為4)、回流分流器、水冷式冷凝器、頂置式冷凝液接受器及真空泵組成。蒸餾釜溫度藉由調節加熱套上之熱輸入來控制,且系統真空藉由調節頂置式接收器處之真空壓力來控制。蒸餾釜最初以充分排氣模式加熱,直至在蒸餾塔中建立回流條件。接著回流分流器以所需回流比開始且分級蒸餾藉由自頂置式接收器週期性地移除液體餾份進行。使用GC分析來測定塔頂餾份之組成。按需要調節蒸餾釜溫度、頂置式接收器真空及回流比,以影響塔頂流之組成。初始塔頂餾份主要含有甲醇以及痕量乙酸甲酯。移除此等溶劑後,接著在以下條件下在塔頂蒸餾出高純度原冰片烯甲醇:塔頂溫度(70-75℃)、真空(4-5mmHg)及回流比(2:1)。一旦大部分產物已自蒸餾釜移除,即終止蒸餾過程。起始混合物中所含之原冰片烯甲醇的約90%作為高純度(99.8%分析)產物回收,具有痕量乙酸原冰片烯甲酯(<0.1%)及不可偵測含量之原冰片烷甲醇(NBAMeOH)。
GC分析在Ultra 1(交聯甲基矽氧烷)管柱上進行,25m,0.2mm ID,0.33μm膜。初始條件:70℃,保持1.0分鐘;梯度條件:以
10℃/min,70℃至240℃;最終條件:240℃,保持10.0分鐘。注射器:200℃。偵測器:250℃(FID)。GC滯留時間:NBMeOH 7.1-7.3min,NBAMeOH 7.5-7.6min,及NBMeOAc 8.8-8.9min。
將原冰片烯甲醇(NBMeOH,99g,0.797mol)置放於裝備有機械攪拌器、加料漏斗、氮氣入口及熱電偶套管之適當尺寸之燒瓶中。將無水THF(300mL)注射入燒瓶中,接著開始攪拌。添加第三丁醇鉀(3.3g,0.029mol)。當第三丁醇鉀均溶解得到黃色溶液時,在反應燒瓶下設置水浴。逐滴添加二苯基甲基矽烷(150.3g,0.756mol)。約十分鐘後,開始放出氫氣且反應溫度自23℃增加至25℃。以平穩滴落速率添加二苯基甲基矽烷以維持緩緩放出氫氣。在約50分鐘後完成添加。反應溫度上升至30℃。一分鐘內,突然停止放出氫氣且反應溫度迅速下降至26℃。GC分析展示2.3% NBMeOH及97.1% NBMeOSiPh2Me。未偵測到二苯基甲基矽烷。反應混合物在25℃下再攪拌15分鐘後,添加80ml飽和氯化銨水溶液。澈底混合且用甲基第三丁基醚(MTBE)沖洗後,分離各相。水相得到pH=8。有機部分用2×80ml鹽水洗滌以得到pH 10。有機部分再次用80ml飽和氯化銨水溶液洗滌至pH 8,接著用80ml鹽水洗滌,得到介於7與8之間的pH值。有機部分經硫酸鈉脫水,過濾,且旋轉蒸發,得到248.5g混濁的無色液體。GC分析展示2.9% NBMeOH、1.0% Ph2MeSiOH及1.0% Ph2MeSiO-t-Bu、95.7% NBMeOSiPh2Me及0.1% Ph2MeSiOSiMePh2。
物質在不使用分餾塔下真空蒸餾。首批20.8g在46-136℃之
間在0.27-0.42托(Torr)下收集,得到加權平均之30% NBMeOH、14.3% Ph2MeSiOH/Ph2MeSiO-t-Bu及48.5% NBMeOSiPh2Me。接下來71.1g在132-139℃(0.17-0.29托)下收集,得到加權平均之2.1% Ph2MeSiOH/Ph2MeSiO-t-Bu及97.6% NBMeOSiPh2Me。接下來7.8g在137-134℃(0.16-0.22托)下收集,得到99.8% NBMeOSiPh2Me。停止蒸餾且將含有99.4% NBMeOSiPh2Me之釜轉移至庫格爾若蒸餾器(Kugelrohr still)。在173-176℃(0.33-0.37托)下蒸餾得到142.1g清澈的無色液體,產率59%。GC分析展示99.6% NBMeOSiPh2Me。
GC分析在DB5-MS管柱上進行,25m,0.32mm ID,0.52μm膜。梯度:以15℃/min,75℃至200℃,接著以40℃/min加熱至300℃(保持3分鐘);注射器:200℃。偵測器:350℃(FID)。滯留時間:10.615分鐘。
此等比較實施例1-5顯示烯醇與CPD反應顯著形成如表1中概述之副產物。最值得注意地,在比較實施例1-5每一者中均形成氫化產物原冰片烷烷醇。
將如表1中概述之作為共反應物之各種烯醇及二環戊二烯(DCPD)以基於CPD單體4:1之莫耳比置放於適合高壓管式反應器中,且在維持在220℃下之熱油浴中加熱。分批高壓管反應進行4小時。在反應結束時,高壓管自浴中移除且在濕冰浴中驟冷。接著管用甲醇及二氯甲烷洗滌且稱重以驗證未發生洩漏。所得粗產物樣品藉由GC-MS分析。結果概述於表1中。
GC-MS分析在Altech EC-5管柱上進行,30m,0.25mm ID,0.25μm膜;入口-F:250,MS源:230℃,電子電離。所用GC條件為以下兩種條件中之一者:
a)梯度:以10℃/min,45℃至120℃,接著以40℃/min加熱至300℃,在300℃下保持2分鐘。-比較實施例2至5中使用此加熱型態。
b)梯度:在40℃下保持5分鐘,接著以40℃/min加熱至300℃,在300℃
下保持5分鐘。-比較實施例1中使用此加熱型態。
此等比較實施例6-7顯示諸如甲醇及異丙醇之醇與CPD的反應亦引起氫化反應,可能經由氫轉移反應。結果概述於表2中。
將如表2中概述之作為共反應物之各種醇及二環戊二烯(DCPD)以基於CPD單體4:1之莫耳比置放於適合高壓管式反應器中,且在維持在220℃下之熱油浴中加熱。分批高壓管反應進行4小時。在反應結束時,高壓管自浴中移除且在濕冰浴中驟冷。接著管用甲醇及二氯甲烷洗滌且稱重以驗證未發生洩漏。甲醇與DCPD之反應亦產生一些不溶固體。此等固體用二氯甲烷(DCM)萃取。接著DCM萃取物藉由GC-MS分析。所得產物樣品藉由GC-MS分析。結果概述於表2中。
GC-MS分析在Altech EC-5管柱上進行,30m,0.25mm ID,0.25μm膜;入口-F:250,MS源:230℃,電子電離。所用GC條件如下:梯度:在40℃下保持5分鐘,接著以40℃/min加熱至300℃,在300℃下保持5分鐘。
此等比較實施例8-10顯示諸如甲醇及異丙醇之醇與原冰片
烯或原冰片二烯的反應亦引起氫化反應,可能經由氫轉移反應。
將各種醇及烯烴(原冰片烯或原冰片二烯)以基於烯烴4:1之莫耳比置放於適合高壓管式反應器中,且在維持在220℃下之熱油浴中加熱。分批高壓管反應進行4小時。在反應結束時,高壓管自浴中移除且在濕冰浴中驟冷。接著管用甲醇及二氯甲烷洗滌且稱重以驗證未發生洩漏。所得產物樣品藉由GC-MS分析。結果概述於表3中。
GC-MS分析在Altech EC-5管柱上進行,30m,0.25mm ID,0.25μm膜;入口-F:250,MS源:230℃,電子電離。GC條件使用以下兩種條件中之一者:
a)梯度:以10℃/min,45℃至120℃,接著以40℃/min加熱至300℃,在300℃下保持2分鐘。-比較實施例8及9中使用此加熱型態。
b)梯度:在40℃下保持5分鐘,接著以40℃/min加熱至300℃,在300℃下保持5分鐘。-比較實施例10中使用此加熱型態。
雖然本發明已藉由某些前述實施例說明,但不應理解為受其限制;而實際上,本發明涵蓋如上文所揭示之通用領域。在不偏離本發明之精神及範疇下可進行各種修改及具體實例。
Claims (20)
- 一種用於製備式(I)化合物之方法,
- 如申請專利範圍第1項之方法,其中該式(I)化合物具有高純度。
- 如申請專利範圍第2項之方法,其中該式(I)化合物具有至少99%純度。
- 如申請專利範圍第2項之方法,其中該式(I)化合物具有至少99.8%純度。
- 如申請專利範圍第1項之方法,其中n為1,R為CH3C(O)O且R1、R2及R3中之每一者為氫。
- 如申請專利範圍第5項之方法,其中該式(I)化合物為至少99%純度之外-/內-原冰片烯甲醇。
- 如申請專利範圍第1項之方法,其中R為-OCOC1-C6烷基之該式(III)化合物在催化劑存在下經受適合轉酯化劑。
- 如申請專利範圍第7項之方法,其中該轉酯化劑為醇且該催化劑為鹼。
- 如申請專利範圍第8項之方法,其中該醇為甲醇且該鹼為甲醇鈉。
- 如申請專利範圍第7項之方法,其中該轉酯化劑為醇且該催化劑為酸。
- 如申請專利範圍第10項之方法,其中該醇為甲醇且該酸為硫酸或烷磺酸。
- 如申請專利範圍第1項之方法,其進一步包含: 使式(1)化合物與式(IV)之矽烷:R5R6R7SiH (IV)其中R5、R6及R7各自彼此獨立地為甲基、乙基或直鏈或分支鏈C3-C9烷基或經取代或未經取代之C6-C14芳基;及適合催化劑反應,以獲得式(V)化合物:;且其中該式(V)化合物具有高純度。
- 如申請專利範圍第12項之方法,其中n為1,R1、R2及R3中之每一者為氫,R5為甲基,且R6及R7中之每一者為苯基。
- 如申請專利範圍第12項之方法,其中該催化劑為鹼。
- 如申請專利範圍第14項之方法,其中該鹼催化劑為第三丁醇鉀。
- 如申請專利範圍第12項之方法,其中該式(V)化合物具有至少99%純度。
- 如申請專利範圍第12項之方法,其中該式(V)化合物具有至少99.5%純度。
- 如申請專利範圍第12項之方法,其中該式(V)化合物為(二環[2.2.1]庚-5-烯-2-基甲氧基)(甲基)二苯基矽烷且具有至少99.8%純度。
- 一種用於製備式(IB)之原冰片烯甲醇的方法,
- 一種用於製備式(VB)之(二環[2.2.1]庚-5-烯-2-基甲氧基)(甲基)-二苯基矽烷的方法,
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261739119P | 2012-12-19 | 2012-12-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201429933A true TW201429933A (zh) | 2014-08-01 |
TWI570100B TWI570100B (zh) | 2017-02-11 |
Family
ID=49885439
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW102146343A TWI570100B (zh) | 2012-12-19 | 2013-12-16 | 高純度原冰片烯烷醇及其衍生物之製備方法 |
Country Status (4)
Country | Link |
---|---|
US (2) | US9382271B2 (zh) |
JP (1) | JP5878270B2 (zh) |
TW (1) | TWI570100B (zh) |
WO (1) | WO2014099546A1 (zh) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6618682B2 (ja) | 2011-06-22 | 2019-12-11 | アペリス・ファーマシューティカルズ・インコーポレイテッドApellis Pharmaceuticals,Inc. | 補体阻害剤による慢性障害の治療方法 |
TWI675059B (zh) * | 2015-09-01 | 2019-10-21 | 日商住友電木股份有限公司 | 作爲光學材料的聚環烯烴聚合物組成物 |
ES2899411T3 (es) * | 2016-10-12 | 2022-03-11 | Basf Se | Procedimiento de preparación de ésteres de ácidos hidroxialquilcarboxílicos |
KR20200070355A (ko) | 2017-10-26 | 2020-06-17 | 알렉시온 파마슈티칼스, 인코포레이티드 | 발작성 야간 혈색소뇨 (pnh) 및 비정형 용혈성 요독 증후군 (ahus)의 치료를 위한 항-c5 항체의 투여량 및 투여 |
WO2020058759A1 (en) | 2018-09-17 | 2020-03-26 | Kyoto University | Administration of an anti-c5 agent for treatment of hepatic injury or failure |
US20200095307A1 (en) | 2018-09-21 | 2020-03-26 | Alexion Pharmaceuticals, Inc. | Compositions and methods for the treatment of neuromyelitis optica |
WO2020092546A1 (en) | 2018-10-30 | 2020-05-07 | Alexion Pharmaceuticals, Inc. | Co-administration of a hyaluronidase and anti-c5 antibody for treatment of complement-associated conditions |
AU2019370295A1 (en) | 2018-10-30 | 2021-06-03 | Alexion Pharmaceuticals, Inc. | Subcutaneous dosage and administration of anti-C5 antibodies for treatment of Paroxysmal Nocturnal Hemoglobinuria (PNH) |
WO2020154626A1 (en) | 2019-01-25 | 2020-07-30 | Alexion Pharmaceuticals, Inc. | Dosage and administration of anti-c5 antibodies for treatment of atypical hemolytic uremic syndrome (ahus) |
WO2020242849A1 (en) | 2019-05-24 | 2020-12-03 | Alexion Pharmaceuticals, Inc. | Methods of treating vitiligo using an anti-c5 antibody |
JP2023507852A (ja) | 2019-12-23 | 2023-02-27 | アレクシオン ファーマシューティカルズ, インコーポレイテッド | 抗c5抗体を使用して妊娠関連非典型溶血性尿毒症症候群を治療する方法 |
AU2021270867A1 (en) | 2020-05-12 | 2022-12-08 | Alexion Pharmaceuticals, Inc. | Use of complement factor D inhibitors alone or in combination with anti-C5 antibodies for treatment of paroxysmal nocturnal hemoglobinuria |
CN116194478A (zh) | 2020-06-24 | 2023-05-30 | 阿雷克森制药公司 | 皮下(sc)施用抗c5抗体治疗补体相关病症 |
EP4281472A1 (en) | 2021-01-22 | 2023-11-29 | Alexion Pharmaceuticals, Inc. | Methods of treating complement mediated thrombotic microangiopathy using an anti-c5 antibody |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6272630A (ja) * | 1985-09-25 | 1987-04-03 | Asahi Kagaku Kogyo Kk | アルキル化する方法 |
JP2865708B2 (ja) * | 1989-06-26 | 1999-03-08 | 株式会社クラレ | 縮合環含有化合物 |
JP2003055284A (ja) * | 2001-08-17 | 2003-02-26 | Nippon Petrochemicals Co Ltd | 縮合環含有化合物の製造法 |
JP2003055280A (ja) * | 2001-08-17 | 2003-02-26 | Nippon Petrochemicals Co Ltd | 縮合環含有化合物の製法 |
WO2004007587A1 (en) * | 2002-07-10 | 2004-01-22 | Lg Chem, Ltd. | Nobonene-ester based addition polymer and method for preparing the same |
WO2006078129A1 (en) | 2005-01-20 | 2006-07-27 | Lg Chem. Ltd. | Alignment film for lcd using photoreactive polymer and lcd comprising the same |
JP2008031304A (ja) * | 2006-07-28 | 2008-02-14 | Fujifilm Corp | ノルボルネン系共重合体を用いたフィルム、偏光板、液晶表示装置、ノルボルネン系共重合体 |
JP2010507831A (ja) | 2007-04-23 | 2010-03-11 | エルジー・ケム・リミテッド | 位相差フィルム、その製造方法及び位相差フィルムを含む偏光板 |
US7662996B2 (en) | 2007-11-05 | 2010-02-16 | Promerus, Llc | Generation of endo- and/or exo-norbornenecarboxaldehyde as an intermediate to functionalized norbornenes |
JP5332883B2 (ja) * | 2009-04-30 | 2013-11-06 | 住友ベークライト株式会社 | 感光性組成物、光導波路、光配線、光電気混載基板、電子機器、および光導波路の形成方法 |
JP2011073974A (ja) * | 2009-09-29 | 2011-04-14 | Sumitomo Bakelite Co Ltd | ノルボルネン誘導体およびその製造方法 |
-
2013
- 2013-12-11 WO PCT/US2013/074397 patent/WO2014099546A1/en active Application Filing
- 2013-12-11 JP JP2015549481A patent/JP5878270B2/ja active Active
- 2013-12-11 US US14/439,182 patent/US9382271B2/en active Active
- 2013-12-16 TW TW102146343A patent/TWI570100B/zh active
-
2016
- 2016-05-24 US US15/162,805 patent/US9505688B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
WO2014099546A1 (en) | 2014-06-26 |
US9382271B2 (en) | 2016-07-05 |
US20150291634A1 (en) | 2015-10-15 |
TWI570100B (zh) | 2017-02-11 |
US9505688B2 (en) | 2016-11-29 |
JP2016501276A (ja) | 2016-01-18 |
JP5878270B2 (ja) | 2016-03-08 |
US20160264498A1 (en) | 2016-09-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI570100B (zh) | 高純度原冰片烯烷醇及其衍生物之製備方法 | |
KR102608490B1 (ko) | 1-아릴-1-트리플루오로메틸시클로프로판의 신규 합성 방법 | |
KR102067651B1 (ko) | 신규 지환식 디카르본산에스테르 화합물, 및 그의 제조방법 | |
JP5359052B2 (ja) | 含フッ素モノマーの製造方法 | |
JP2022116175A (ja) | 含フッ素シラン化合物 | |
CN110437093A (zh) | 一种(s)-5-氟-3-甲基异苯并呋喃-3-酮的乙酰化中间体的制备方法 | |
JP6102548B2 (ja) | 新規エチルアダマンタンジカルボン酸エステル化合物、およびその製造方法 | |
US8993810B2 (en) | Preparation method of lycopene intermediate 3-methyl-4,4-dialkoxy-1-butaldehyde | |
JP2007261980A (ja) | エキソ体ノルボルネンモノカルボン酸エステルの製造方法 | |
JP6528947B2 (ja) | ノルボルナン骨格を有するジカルボン酸エステルの製造方法 | |
CN112159336B (zh) | 一种高纯度的芳炔取代的腈类化合物的制备方法 | |
IL305608A (en) | Process for preparing alkyl-4-oxotetrahydrofuran-2-carboxylate | |
CN108358780B (zh) | 合成高非对映选择性的α-酰氧化环酮类化合物的方法 | |
JP4022413B2 (ja) | パーフルオロアルキルアクリル酸多量体および多量体組成物ならびにそれらの製造方法 | |
JP2015044754A (ja) | 3−エトキシ−2−tert−ブチルプロピオン酸アルキルの製造方法 | |
JP2017071556A (ja) | オキソバナジウム錯体を用いたカルボン酸プレニル類及びプレノール類の製造方法 | |
US7399879B2 (en) | Process for preparing alkylidene-substituted-1,4-dions derivatives | |
JP2024509535A (ja) | 4-オキソテトラヒドロフラン-2-カルボン酸アルキルの調製方法 | |
EP1527039A1 (en) | Process for preparing alkylidene-substituted-1,4-dions derivatives | |
JP5498753B2 (ja) | 脂環構造と芳香環構造とを併せもつビニルエーテル | |
JP5413611B2 (ja) | 硫黄原子を有するノルボルネン化合物およびその製造方法 | |
JP2020536974A (ja) | 新しい方法 | |
JPH05148195A (ja) | アミノビニルエーテルの製法 | |
WO2013157388A1 (ja) | 2-エテニルオキシメチル-2-ヒドロキシメチルアダマンタン及び2,2-ビス(エテニルオキシメチル)アダマンタン並びにその製造方法 | |
JP2007246515A (ja) | 重合性アルキルジアマンチルエステル化合物の製造方法 |