TWI796452B - 苯胺衍生物之製造方法 - Google Patents
苯胺衍生物之製造方法 Download PDFInfo
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- TWI796452B TWI796452B TW108108885A TW108108885A TWI796452B TW I796452 B TWI796452 B TW I796452B TW 108108885 A TW108108885 A TW 108108885A TW 108108885 A TW108108885 A TW 108108885A TW I796452 B TWI796452 B TW I796452B
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- carbons
- aniline derivatives
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title 1
- -1 amine compound Chemical class 0.000 claims abstract description 61
- 150000001448 anilines Chemical class 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 238000010511 deprotection reaction Methods 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical group [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 16
- 238000005859 coupling reaction Methods 0.000 claims description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 125000002577 pseudohalo group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 239000002585 base Substances 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- XOJNEFQLMRCOMS-UHFFFAOYSA-N ditert-butyl(phenyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)C1=CC=CC=C1 XOJNEFQLMRCOMS-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000008542 feiji Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000002523 gelfiltration Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- WWGXHTXOZKVJDN-UHFFFAOYSA-M sodium;n,n-diethylcarbamodithioate;trihydrate Chemical compound O.O.O.[Na+].CCN(CC)C([S-])=S WWGXHTXOZKVJDN-UHFFFAOYSA-M 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- GSSDEYFPBMSLEL-UHFFFAOYSA-N 1,2-dichlorobenzene;1,2-xylene Chemical compound CC1=CC=CC=C1C.ClC1=CC=CC=C1Cl GSSDEYFPBMSLEL-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- IQTHEAQKKVAXGV-UHFFFAOYSA-N 4-ditert-butylphosphanyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(P(C(C)(C)C)C(C)(C)C)C=C1 IQTHEAQKKVAXGV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910014299 N-Si Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 101150083367 TRI3 gene Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 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
- 150000003519 bicyclobutyls Chemical group 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000004202 carbamide Chemical class 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000006165 cyclic alkyl 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
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical group C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-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
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([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
- 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
- NLUNLVTVUDIHFE-UHFFFAOYSA-N cyclooctylcyclooctane Chemical group C1CCCCCCC1C1CCCCCCC1 NLUNLVTVUDIHFE-UHFFFAOYSA-N 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
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 description 1
- 238000005828 desilylation reaction Methods 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- KYOBUEXQQCIAJH-UHFFFAOYSA-N diethylcarbamodithioic acid trihydrate Chemical compound O.O.O.CCN(CC)C(S)=S KYOBUEXQQCIAJH-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 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
- 125000003136 n-heptyl 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])* 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
- 150000002825 nitriles Chemical class 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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- B01J23/44—Palladium
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Abstract
Description
本發明為關於苯胺衍生物之製造方法。
有機電致發光(以下稱為有機EL)元件中,作為發光層或電荷注入層可使用由有機化合物所成的電荷輸送性薄膜。尤其,電洞注入層係擔當陽極與電洞輸送層或發光層之電荷之交換,為了達成有機EL元件之低電壓驅動及高亮度而展現重要之功能。
電洞注入層之形成方法係大致區別為蒸鍍法所代表之乾式製程,與旋轉塗佈法所代表之濕式製程,若比較該等之各個製程時,濕式製程可有效率地製造大面積且高平坦性之薄膜。因此,在有機EL顯示器發展大面積化的現在,期望能以濕式製程形成之電洞注入層。
鑑於此種情況,本發明者等已開發可適用於各種濕式製程,並且在適用於有機EL元件之電洞注入層時提供可實現優異EL元件特性的薄膜之苯胺衍生物,或對於其所使用的有機溶劑之溶解性為良好之苯胺衍生物(例如參照專利文獻1)。
上述專利文獻1中,作為這種苯胺衍生物之製造方法中的一種,例如揭示有如下述流程(scheme)所示般,在觸媒存在下,使胺化合物(A)與以苄基保護NH基之鹵化咔唑化合物(B)進行偶合後,將苄基脫保護的手段。
然而,使用上述以苄基保護之咔唑化合物時,於脫保護的步驟需要大量過剩的鹼與氧,而產生不適合作為工業製法的問題。
[先前技術文獻]
[專利文獻]
專利文獻1:國際公開2015/050253號
[發明欲解決之課題]
本發明係鑑於上述情況而完成者,其目的為提供一種在脫保護的過程中不需要大量過剩的鹼及氧,適用於有效率且為工業製法之苯胺衍生物之製造方法。
[用以解決課題之手段]
本發明者為了達成上述目的而精心研討之結果,發現使胺化合物與以特定的矽基(silyl group)保護NH基之咔唑化合物進行偶合反應後,藉由去矽基化,而不需要大量過剩的鹼或氧,而可有效率地製造苯胺衍生物,進而完成本發明。
亦即,本發明提供:
1、一種苯胺衍生物之製造方法,其係使式(1)
[式中,R1
~R5
相互獨立地表示氫原子或式(2)
(式中,Ar1
及Ar2
相互獨立地表示碳數6~20的芳基,Ar3
表示碳數6~20的伸芳基,但Ar1
~Ar3
的任2個可鍵結並與氮原子一起形成環。)
表示的基,但R1
~R5
的至少一個為氫原子。]
表示的胺化合物,在觸媒及鹼存在下,與式(3)
(式中,X表示鹵素原子或擬鹵素基,R6
~R8
表示可被Z1
取代之碳數1~20的烷基或碳數6~20的芳基,Z1
表示碳數1~20的烷氧基、鹵素原子、硝基或氰基。)
表示的咔唑化合物進行偶合反應後,將矽基脫保護之作為特徵的式(4)
[式中,R1’
~R5’
相互獨立地表示氫原子、式(2)表示的基或式(5)表示的基,但R1’
~R5’
的至少一個為式(5)表示的基。
(式中,Ar1
~Ar3
表示與前述相同意義。)]
表示的苯胺衍生物之製造方法;
2、如1之苯胺衍生物之製造方法,其中前述R6
~R8
為碳數1~10的烷基或碳數6~10的芳基;
3、如2之苯胺衍生物之製造方法,其中前述R6
~R8
的2個為甲基,其餘1個為第三丁基;
4、如1~3中任一項苯胺衍生物之製造方法,其中前述鹼為第三丁氧基鈉;
5、如1~4中任一項苯胺衍生物之製造方法,其中前述觸媒為鈀觸媒;
6、如1~5中任一項苯胺衍生物之製造方法,其中前述偶合反應係於40~100℃進行;
7、如1~6中任一項苯胺衍生物之製造方法,其中前述脫保護係使用氟化物離子進行;
8、如1~7中任一項苯胺衍生物之製造方法,其中前述R1
~R5
皆為氫原子。
[發明的效果]
本發明的苯胺衍生物之製造方法由於使用以矽基保護咔唑化合物的NH基之原料,故於脫保護的過程不需要大量過剩的鹼及氧,可有效率的製造作為目的之苯胺衍生物。
以下對於本發明進行更詳細的說明。
本發明的苯胺衍生物之製造方法的特徵在於:使式(1)表示的胺化合物在觸媒及鹼的存在下,與式(3)表示的咔唑化合物進行偶合反應後,脫保護咔唑部位的氮原子上的矽基。
上述式(1)中,R1
~R5
相互獨立地表示氫原子或式(2)表示的基,但為了與式(3)表示的咔唑化合物進行偶合反應, R1
~R5
的至少一個有必要為氫原子。
式(2)中,Ar1
及Ar2
相互獨立地表示碳數6~20的芳基,Ar3
表示碳數6~20的伸芳基,但Ar1
~Ar3
的任2個可鍵結並與氮原子一起形成環。
作為碳數6~20的芳基之具體例,可列舉苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等。
作為碳數6~20的伸芳基之具體例,可列舉苯-1,2-二基(鄰伸苯基)、苯-1,3-二基(間伸苯基)、苯-1,4-二基(對伸苯基)、萘-1,2-二基、萘-1,3-二基、萘-1,4-二基、萘-1,5-二基、萘-1,6-二基、萘-1,7-二基、萘-1,8-二基等。
又,作為Ar1
~Ar3
的任2個鍵結並與氮原子一起形成之環,可列舉咔唑環等。
該等之中,Ar1
及Ar2
較佳為苯基、1-萘基、2-萘基,更佳為苯基。
又,Ar3
較佳為苯-1,2-二基、苯-1,3-二基、苯-1,4-二基,更佳為苯-1,4-二基。
因此,式(2)表示的基較佳為式(2A)表示的基,更佳為式(2A-1)表示的基。
作為可合適地使用於本發明的製法之式(1)表示的化合物,可列舉上述R1
~R5
皆為氫原子之下述式(1A)所示的化合物、R2
及R4
為4-二苯基胺基苯基之下述式(1B)所示的化合物、R1
、R2
及R4
為4-二苯基胺基苯基之下述式(1C)所示的化合物等,但不限定於該等。
另一方面,式(3)中的X表示鹵素原子或擬鹵素基,R6
~R8
表示可被Z1
取代之碳數1~20的烷基或碳數6~20的芳基,Z1
表示碳數1~20的烷氧基、鹵素原子、硝基或氰基。
作為鹵素原子可列舉氟原子、氯原子、溴原子、碘原子等。
作為擬鹵素基可列舉甲烷磺醯氧基、三氟甲烷磺醯氧基、九氟丁烷磺醯氧基等之 (氟)烷基磺醯氧基;苯磺醯氧基、甲苯磺醯氧基等之芳香族磺醯氧基等。
於該等中,考量原料的取得性或反應性等,X較佳為鹵素原子,更佳為溴原子、碘原子。
又,X的取代位置,並無特別限定,但較佳相對於咔唑的氮原子為對位。
作為碳數1~20的烷基,可為直鏈狀、分支鏈狀、環狀之任意者,例如可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基等碳數1~20的直鏈或分支鏈狀烷基;環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、雙環丁基、雙環戊基、雙環己基、雙環庚基、雙環辛基、雙環壬基、雙環癸基等之碳數3~20的環狀烷基等。
作為碳數6~20的芳基,可列舉與上述相同者。
作為碳數1~20的烷氧基,其中烷基可為直鏈狀、分支鏈狀、環狀的任意者,例如可列舉甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第三丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、正壬氧基、正癸氧基等之碳數1~20的直鏈或分支鏈狀的烷氧基、環戊氧基、環己氧基等之碳數3~20的環狀烷氧基等。
於該等中,R6
~R8
較佳為碳數1~10的烷基、碳數6~10的芳基,更佳為碳數1~5的烷基。
更具體而言,較佳為R6
~R8
之2個為甲基且其餘1個為第三丁基的組合、R6
~R8
之2個為苯基且其餘1個為第三丁基的組合、R6
~R8
皆為異丙基者,更佳為R6
~R8
之2個為甲基且其餘1個為第三丁基的組合。
作為可合適地使用於本發明的製法之式(3)所示的化合物,可列舉下述式(3A)表示的化合物,尤其是式(3A-1)所示的化合物等,但不限定於該等。
再者,式(3)表示的化合物可使對應的咔唑在NaH等的鹼存在下,與三烷基氯矽烷等之三有機鹵化物(triorganohalide)進行反應,藉由公知的手段而獲得。
上述式(1)表示的胺化合物與式(3)表示的咔唑化合物之偶合反應中,式(1)表示的胺化合物與式(3)表示的咔唑化合物之進料比,以物質量(mol)比計,相對於將使胺化合物進行反應作為目的之NH基1,較佳為咔唑化合物1~5左右,更佳為1.1~2左右。
作為上述反應所使用之觸媒,例如可列舉氯化銅、溴化銅、碘化銅等之銅觸媒;Pd(PPh3
)4
(肆(三苯基膦)鈀)、Pd(PPh3
)2
Cl2
(雙(三苯基膦)二氯鈀)、Pd(dba)2
(雙(二亞苄基丙酮)鈀)、Pd2
(dba)3
(參(二亞苄基丙酮)二鈀)、Pd(P-t-Bu3
)2
(雙(三(第三丁基膦))鈀)、Pd(OAc)2
(乙酸鈀)等之鈀觸媒等。該等之觸媒,可單獨使用,亦可組合2種以上使用。
又,該等觸媒亦可與公知之適當的配位子一起使用。
作為此種配位子,可列舉三苯基膦、三-鄰甲苯基膦、二苯基甲基膦、苯基二甲基膦、三甲基膦、三乙基膦、三丁基膦、三-第三丁基膦、二-第三丁基(苯基)膦、二-第三丁基(4-二甲基胺基苯基)膦、1,2-雙(二苯基膦基)乙烷、1,3-雙(二苯基膦基)丙烷、1,4-雙(二苯基膦基)丁烷、1,1’-雙(二苯基膦基)二茂鐵等之3級膦、三甲基亞磷酸酯、三乙基亞磷酸酯、三苯基亞磷酸酯等之3級亞磷酸酯等,但本發明可合適地使用二-第三丁基(苯基)膦。
觸媒的使用量,分別相對於將使式(1)表示的胺化合物進行反應作為目的之NH基1 mol,可設為0.1~100 mol%左右,但較佳為1~10 mol%左右,更佳為2~5 mol%左右,進而更佳為2 mol%左右。
又,使用配位子的情況下,其使用量可相對於所使用之金屬錯合物設為0.1~5當量,但適合為1~2當量。
又,作為鹼可列舉鋰、鈉、鉀、氫化鋰、氫化鈉、氫氧化鉀、第三丁氧基鋰(lithium t-butoxide)、第三丁氧基鈉、第三丁氧基鉀、氫氧化鋰、氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀等之鹼金屬單體、氫氧化鹼金屬、烷氧基鹼金屬、碳酸鹼金屬、碳酸氫鹼金屬;碳酸鈣等之碳酸鹼土類金屬等,但考量到使偶合反應有效率地進行,較佳為第三丁氧基鈉。
鹼的使用量,分別相對於將使式(1)表示的胺化合物進行反應作為目的之NH基,較佳為1~2當量左右,更佳為1.2~1.5當量左右。
從原料化合物全部為固體的情況或有效率地得到作為目的之偶合生成物的觀點而言,上述反應在溶劑進行。在使用溶劑時,其種類只要係不對反應產生不良影響者,則無特別限制。作為其具體例,可列舉脂肪族烴類(戊烷、正己烷、正辛烷、正癸烷、十氫萘等)、鹵化脂肪族烴類(氯仿、二氯甲烷、二氯乙烷、四氯化碳等)、芳香族烴類(苯、硝基苯、甲苯、鄰二甲苯、間二甲苯、對二甲苯、均三甲苯等)、鹵化芳香族烴類(氯苯、溴苯、鄰二氯苯、間二氯苯、對二氯苯等)、醚類(二乙基醚、二異丙基醚、第三丁基甲基醚、四氫呋喃、二噁烷、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷等)、酮類(丙酮、甲基乙基酮、甲基異丁基酮、二-正丁基酮、環己酮等)、醯胺類(N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等)、內醯胺及內酯類(N-甲基吡咯啶酮、γ-丁內酯等)、脲類(N,N-二甲基咪唑啉酮(dimethylimidazolidinone)、四甲基脲等)、亞碸類(二甲基亞碸、環丁碸等)、腈類(乙腈、丙腈、丁腈等)等,可單獨使用該等溶劑,亦可混合2種以上使用。
該等之中,尤其較佳為芳香族烴類,更佳為甲苯。
在從使用之溶劑的融點至沸點的範圍內適當設定反應溫度即可,尤其較佳為0~200℃左右,更佳為20~150℃左右,若考量更提升偶合生成物的產率,則進而更佳為40~100℃左右。
反應終了後,可依循常法進行後處理而獲得偶合生成物。
接著,脫保護所得到的偶合生成物中之咔唑部位的氮原子上之矽基。
可從公知的手段適當選擇來進行脫保護,但本發明較佳藉由氟化物離子進行脫保護。
作為成為氟化物離子源之去矽化劑(desilylation reagent),並無特別限定,可適當地選擇使用公知者。
作為其具體例,可列舉四丁基氟化銨(TBAF),四乙基氟化銨,四甲基氟化銨及該等之水合物,氟化氫吡啶錯合物(pyridine hydrofluoride complex)、氟化銫、氟化鉀、氟化氫鉀、氟化鈉、氟化鋰、氟化鈣等,但該等中適合為TBAF。
去矽化劑的使用量,相對於偶合生成物中全部的N-Si鍵結,可設為1~5當量左右,但較佳為1.2~2當量左右。
在此反應之際亦可使用溶劑,可使用之溶劑的具體例如同上述,但較佳為醚類,更佳為四氫呋喃。
反應溫度可能為溶劑的融點至沸點,但較佳為0~100℃左右,更佳為0~30℃左右,進而更佳為25℃左右的室溫。
反應終了後,可依循常法進行後處理,而獲得作為目的之下述式(4)表示的苯胺衍生物。
作為以本發明的製法獲得之適當的苯胺衍生物,可列舉下述式(4A)~(4D)所示者,但不被該等所限定。
以下,列舉實施例更具體地說明本發明,但本發明不被下述實施例所限定。
再者,1
H-NMR係使用Bruker BioSpin (股)製 核磁共振分光計AVANCE III HD 500MHz來進行測定。
高效液相層析(HPLC)係使用(股)島津製作所製Prominence藉以下所示的測定條件進行測定。
溶離液A:0.05體積%三氟乙酸水溶液
溶離液B:乙腈/四氫呋喃(1比1體積換算,添加0.05體積%三氟乙酸)
流速:0.5 mL/min
管柱:Poroshell 120 EC-C8 (2.7μm,3.0×50mm,安捷倫科技(股))
級配(gradation)條件:溶離液B:30%(0-0.01min)→30-100%(0.01-10min)→100%(10-30min)
於燒瓶內加入DADPA 4.78 g、TBSCZ-Br 47.6 g、Pd(dba)2
1.38 g及第三丁氧基鈉16.6 g後,將燒瓶內進行氮取代。接著添加甲苯240 mL、預先調配好的二-第三丁基(苯基)膦之甲苯溶液20 mL(濃度:55 g/L),於90℃進行攪拌。2.5小時後,將反應液冷卻至室溫,混合離子交換水240 mL進行分液處理。進而以離子交換水、飽和食鹽水分液洗淨有機層後,以硫酸鈉進行乾燥,並且濃縮。將所獲得的粗產物溶解於甲苯200 mL,加入白鷺P活性炭(大阪瓦斯化學(股)製)3.5 g,於室溫攪拌2小時後進行矽凝膠過濾,以甲苯進行濾餅洗淨。將濾液濃縮至240 g後,將濃縮液滴下於N,N-二乙基二硫代胺基甲酸鈉三水合物7.02 g、甲醇1.20 L、乙酸乙酯0.40 L的預混合溶液中,將獲得的漿料於室溫下進行攪拌。18小時後濾過漿料,以甲醇洗淨濾物後,進行乾燥獲得TBSCZ5(產量:36.3 g、產率:95%)。1
H-NMR的測定結果如下所示。
1
H-NMR(500MHz, THF-d8
)δ[ppm]:7.88-7.98(m, 10H),7.55-7.61(m, 10H),7.19-7.30(m, 10H),7.12(t, J=7.3Hz, 1H),7.05(t, J=7.3Hz, 4H),6.96-7.00(m, 8H),1.05(s, 36H),1.04(s, 9H),0.74(s, 30H)。
並且,下述式所示之TBSCZ-Br係依循Chemistry of Materials (2015), 27(19), 6535-6542.而合成(以下相同)。
於燒瓶內加入THF 178 mL、TBSCZ5 33.5 g後,一邊以冰浴冷卻一邊攪拌,滴下TBAF的THF溶液(濃度:1M)158 mL。滴下完了後去除冰浴,以室溫攪拌1.5小時後將反應液滴下於離子交換水670mL中終止(quench)。濾取所獲得的析出物後,溶於130g的THF溶液,藉由滴下於甲醇1 L中而再度析出。進而重覆2次此從濾取到晶析的操作後,濾取、乾燥析出物而獲得CZ5(產量:18.6g、產率:87%)。
將所獲得之CZ5的HPLC圖表示於圖1、2。
於燒瓶內加入TRI3 55.1 g、TBSCZ-Br 95.4 g、Pd(dba)2
2.77 g及第三丁氧基鈉32.4 g後,將燒瓶內進行氮取代。接著添加甲苯550mL、預先調配好的二-第三丁基(苯基)膦之甲苯溶液22mL(濃度:96g/L),於90℃進行攪拌。1.5小時,將反應液冷卻至室溫,混合離子交換水550mL並進行分液處理。於所獲得的有機層中加入白鷺P活性炭(大阪瓦斯化學(股)製)11.0 g,於室溫攪拌1小時後進行矽凝膠過濾,以甲苯進行濾餅洗淨。將濾液濃縮至660 g,將濃縮液滴下於N,N-二乙基二硫代胺基甲酸鈉三水合物22.0 g、甲醇3.30 L、乙酸乙酯1.10 L的預混合溶液中,將獲得的漿料於室溫下攪拌。1小時後,濾過漿料,以甲醇洗淨濾物後,進行乾燥獲得3TBSCZ-TRI3 (產量:112 g、產率:92%)。1
H-NMR的測定結果如下所示。
1
H-NMR(500MHz, THF-d8
)δ[ppm]:7.93-7.95(m, 3H),7.89(d, J=2.1Hz, 3H),7.57-7.62(m, 6H),7.26-7.30(m, 3H),7.15-7.21(m, 11H),7.06-7.13(m, 3H),6.96-7.03(m, 20H),6.88-6.94(m, 8H),1.05(s, 18H),1.04(s, 9H),0.75(s, 12H),0.74(s, 6H)。
於燒瓶內加入THF 315 mL、3TBSCZ-TRI3 105 g後,一邊以冰浴冷卻一邊攪拌,滴下TBAF的THF溶液(濃度:1M)310 mL。滴下完了後去除冰浴,於室溫攪拌3小時後將反應液以THF稀釋至成為735 g為止,將其滴下於甲醇1.57 L中終止。將所獲得的析出物於室溫下攪拌1小時後進行濾取,於甲醇進行濾餅洗淨後,進而以甲醇1.05 L進行2小時漿料洗淨。將其濾取再以甲醇進行濾餅洗淨後,乾燥而獲得3CZ-TRI3 (產量:75.4g、產率:93%)。
於燒瓶內加入DADPA 1.99 g、TBSCZ-Br 7.22 g、Pd(dba)2
233 mg及第三丁氧基鈉2.69 g後,將燒瓶內進行氮取代。接著添加甲苯100mL、預先調配好的二-第三丁基(苯基)膦之甲苯溶液3.7 mL(濃度:49 g/L),於90℃進行攪拌。2小時後,將反應液冷卻至室溫,混合離子交換水100mL後,將其過濾。以熱甲苯溶解所獲得的濾物,進行熱過濾(hot filtration),在室溫下攪拌濾液。18小時後,濾取析出物,將其以甲醇洗淨後,進行乾燥獲得TBSCZ3(產量:3.87g、產率:51%)。1
H-NMR的測定結果如下所示。
1
H-NMR(500MHz, DMSO-d6
)δ[ppm]:7.99(d, J=7.6Hz, 2H),7.68(d, J=2.1Hz, 2H),7.63(s, 2H),7.59(d, J=8.5Hz, 2H),7.52(d, J=8.9Hz, 2H),7.49(s, 1H),7.30-7.33(m, 2H),7.12-7.15(m, 2H),7.07(dd, J=8.9, 2.1Hz, 2H),6.94-7.02(m, 8H),0.98(s, 18H),0.73(s, 12H)。
於燒瓶內加入TBSCZ3 2.65 g、TPA-Br 3.74 g、Pd(dba)2
121 mg及第三丁氧基鈉1.42 g後,將燒瓶內進行氮取代。接著添加甲苯80 mL、預先調配好的二-第三丁基(苯基)膦之甲苯溶液1.6mL(濃度:60g/L),於90℃進行攪拌。4小時後,將反應液冷卻至室溫,混合離子交換水100 mL並進行分液處理。進而將有機層以5%N,N-二乙基二硫代胺基甲酸鈉三水合物的水溶液、離子交換水、飽和食鹽水洗淨後,添加白鷺P活性炭(大阪瓦斯化學(股))0.1 g,於室溫攪拌1小時後進行矽凝膠過濾,以甲苯進行濾餅洗淨。將濾液濃縮後,將所獲得的粗產物溶解於甲苯50mL,滴下於甲醇375mL、乙酸乙酯125mL的預混合液中,將獲得的漿料於室溫下攪拌。3天後,濾過漿料,乾燥濾物而獲得3TPA-TBSCZ3(產量:4.80g、產率:92%)。1
H-NMR的測定結果如下所示。
1
H-NMR(500MHz, THF-d8
)δ[ppm]:7.94(d, J=7.3Hz, 2H),7.89(d, J=1.8Hz, 2H),7.61(t, J=8.2Hz, 4H),7.29(t, J=7.3Hz, 2H),7.16-7.20(m, 14H),7.10(t, J=7.3Hz, 2H),6.98-7.04(m, 26H),6.89-6.94(m, 12H)。
於燒瓶內加入THF 22.5 mL、3TPA-TBSCZ3 3.72 g後,一邊攪拌一邊滴下TBAF的THF溶液(濃度:1 M)7.5 mL。滴下完了過1小時後,將反應液滴下於甲醇300mL中終止,濾取所獲得的析出物。將其加熱溶解於甲苯90 mL、1,4-二噁烷10mL的混合液中並進行熱過濾後,使其再結晶。進而以甲醇50 mL漿料洗淨此結晶,進行濾取後,藉由乾燥而獲得3TPA-CZ3 (產量:1.78g、產率:57%)。1
H-NMR的測定結果如下所示。
1
H-NMR(500MHz, DMSO-d6
)δ[ppm]:11.26(s, 2H),8.03(d, J=7.6Hz, 2H),7.95(d, J=1.5Hz, 2H),7.47(t, J=8.9Hz, 4H),7.36(t, J=7.6Hz, 2H),7.17-7.26(m, 14H),7.08(t, J=7.6Hz, 2H),6.88-6.97(m, 38H)。
[比較例1]
依循國際公開2015/050253號(專利文獻1)合成Cz5。將所獲得之CZ5的HPLC圖表表示於圖3、4。
如圖1~4所示般,將實施例1合成的Cz5(圖1、2)與比較例1合成的Cz5(圖3、4)進行比較,相對於實施例1合成的Cz5之HPLC面積百分率為99.9%,比較例1合成的Cz5為93.5%。
從所獲得的Cz5之HPLC面積百分率的差異,了解到本發明在提供適於大量製造且效率良好之苯胺衍生物的製法的同時,亦提供高純度的化合物。
圖1係表示於實施例1得到的CZ5之HPLC圖表的圖。
圖2係表示圖1中縱軸0~300mAU的範圍之擴大圖。
圖3係表示於比較例1得到的CZ5之HPLC圖表的圖。
圖4係表示圖3中縱軸0~300mAU的範圍之擴大圖。
Claims (8)
- 一種苯胺衍生物之製造方法,其係使式(1)表示的胺化合物在觸媒及鹼存在下,與式(3)表示的味唑化合物進行偶合反應後,將矽基(silyl group)脫保護之作為特徵的式(4)表示的苯胺衍生物之製造方法;
- 如請求項1之苯胺衍生物之製造方法,其中前述R6~R8為碳數1~10的烷基或碳數6~10的芳基。
- 如請求項2之苯胺衍生物之製造方法,其中前述R6~R8的2個為甲基,其餘1個為第三丁基。
- 如請求項1~3中任一項之苯胺衍生物之製造方法,其中前述鹼為第三丁氧基鈉。
- 如請求項1~3中任一項之苯胺衍生物之製造方法,其中前述觸媒為鈀觸媒。
- 如請求項1~3中任一項之苯胺衍生物之製造方法,其中前述偶合反應係於40~100℃進行。
- 如請求項1~3中任一項之苯胺衍生物之製造方法,其中前述脫保護係使用氟化物離子進行。
- 如請求項1~3中任一項之苯胺衍生物之製造方法,其中前述R1~R5皆為氫原子。
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