JP4505568B2 - 被覆型ヘテロ芳香環化合物 - Google Patents
被覆型ヘテロ芳香環化合物 Download PDFInfo
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- JP4505568B2 JP4505568B2 JP2005065947A JP2005065947A JP4505568B2 JP 4505568 B2 JP4505568 B2 JP 4505568B2 JP 2005065947 A JP2005065947 A JP 2005065947A JP 2005065947 A JP2005065947 A JP 2005065947A JP 4505568 B2 JP4505568 B2 JP 4505568B2
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- 150000001875 compounds Chemical class 0.000 title claims description 98
- 125000001072 heteroaryl group Chemical group 0.000 title description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- 150000003839 salts Chemical class 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- -1 9-anthryl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000012776 electronic material Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 6
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 6
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
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- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- RPRMRYNFKTZKJJ-UHFFFAOYSA-N CC(C)(C)[Si](C1=CC=CC=C1)(C1=CC=CC=C1)OC1SC=C2C1=CC=C2 Chemical compound CC(C)(C)[Si](C1=CC=CC=C1)(C1=CC=CC=C1)OC1SC=C2C1=CC=C2 RPRMRYNFKTZKJJ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- SYQJMTBKSDYIPD-UHFFFAOYSA-N OCC1SC=C2C1=CC=C2 Chemical compound OCC1SC=C2C1=CC=C2 SYQJMTBKSDYIPD-UHFFFAOYSA-N 0.000 description 7
- 238000004949 mass spectrometry Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 125000000037 tert-butyldiphenylsilyl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1[Si]([H])([*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000021615 conjugation Effects 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
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- 239000007787 solid Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- ROUYSJJWMBZBEC-UHFFFAOYSA-N CCOC(C1SC=C2C1=CC=C2)=O Chemical compound CCOC(C1SC=C2C1=CC=C2)=O ROUYSJJWMBZBEC-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 239000006227 byproduct 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
- 239000013078 crystal Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- XEBBXVCRIRGDIC-UHFFFAOYSA-N 1h-cyclopenta[c]thiophene Chemical compound C1=C[C]2[CH]SCC2=C1 XEBBXVCRIRGDIC-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000005442 molecular electronic Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- RWWPYYXKJBWFQE-UHFFFAOYSA-N 2,5-dibromo-3,4-bis(bromomethyl)thiophene Chemical compound BrCC1=C(Br)SC(Br)=C1CBr RWWPYYXKJBWFQE-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 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
- PXACTUVBBMDKRW-UHFFFAOYSA-N 4-bromobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Br)C=C1 PXACTUVBBMDKRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 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
- 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
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- MHYGQXWCZAYSLJ-UHFFFAOYSA-N tert-butyl-chloro-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C(C)(C)C)C1=CC=CC=C1 MHYGQXWCZAYSLJ-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 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
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- H—ELECTRICITY
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Description
Y1〜Y6は、それぞれ独立に、酸素原子であるか、または存在せず、
R1〜R6は、それぞれ独立に、水素原子、炭素数1〜18の直鎖もしくは分枝アルキル基、炭素数2〜18の直鎖もしくは分枝不飽和炭化水素基、フェニル基、1−ナフチル基、2−ナフチル基、1−アントリル基、2−アントリル基、または9−アントリル基であり、
Zは、下記式(i)〜(vii)のいずれかで表される原子または原子団であり、
X1およびX2は、それぞれ独立に、水素原子またはメルカプト基であり、
nは正の整数である。
共役鎖に対して垂直に配置されたtert−ブチルジフェニルシリル基(TBDPS基)により剛直性が保持されるため、有効共役長を損なわない。さらに、TBDPS基は立体的に嵩高いため、共役鎖を効果的に外界から被覆することが可能である。
Y1〜Y6、R1〜R6およびZは、それぞれ前記式(I)と同じであり、Hal1およびHal2は、それぞれ独立に、塩素、臭素またはヨウ素である。
核磁気共鳴(NMR)スペクトルは、JEOL(日本電子株式会社)製の商品名JMN-270(1H測定時270MHz)を用いて測定した。ケミカルシフトは百万分率(ppm)で表している。内部標準0ppmには、テトラメチルシラン(TMS)を用いた。結合定数(J)は、ヘルツで示しており、略号s、d、t、q、mおよびbrは、それぞれ、一重線(singlet)、二重線(doublet)、三重線(triplet)、四重線(quartet)、多重線(multiplet)および広幅線(broad)を表す。質量分析(MS)は、PerSeptive Biosystems社製Voyager Linear DE-H(商品名)を用い、MALDI−TOF法により測定した。紫外可視吸収スペクトル(UV-VIS)は、株式会社島津製作所製UV-3100PC(商品名)を用い、溶液法により測定した。測定値(波長)はnmで表している。赤外線吸収スペクトル(IR)はKBr法により測定した。測定値(波数)はcm-1で表している。サイクリックボルタンメトリーは、ビー・エー・エス株式会社製CV-50W(商品名)を用いて測定した。融点は、株式会社柳本製作所製の微量融点測定器を用いて測定した。カラムクロマトグラフィー分離におけるシリカゲルは、関東化学株式会社製の商品名Silica gel 60N(40〜50μm)を用いた。全ての化学物質は、試薬級であり、和光純薬工業株式会社、東京化成工業株式会社、関東化学株式会社、ナカライテスク株式会社、またはシグマアルドリッチジャパン株式会社より購入した。
まず、水素化ナトリウム60%含有オイル(9.5g, 0.238 mol)を含むトルエン(293mL)およびDMF(29mL)混合溶媒を調製した。次に、それを60℃に加熱し、マロン酸ジエチル(17.4g, 0.108mol)および2,5−ジブロモ−3,4−ビス(ブロモメチル)チオフェン(45.0g, 0.105mol)の無水トルエン(225mL)溶液を、窒素雰囲気下、30分間かけて滴下した。この混合物を、60℃でさらに30分間攪拌した後、室温まで冷却し、水(20mL)を注意深く加え、そして、不溶固形物をセライトによる濾過で除去した。得られた濾液から有機層を分離し、水層はジクロロメタン(200mL×3)で抽出した。前記有機層および抽出液を合わせ、飽和食塩水で洗浄し、MgSO4で乾燥した。さらに、溶媒を留去し、得られた残渣をカラムクロマトグラフィー(シリカゲル、ジクロロメタン:ヘキサン=1:1)で精製し、ヘキサンから再結晶し、1,3-ジブロモ−5,5-ビス(エトキシカルボニル)シクロペンタ[c]チオフェンの無色板状結晶を得た(収量25.5g、収率56%)。以下に、この化合物の機器分析データを示す。
融点82〜83℃; 1HNMR(270MHz, CDCl3) δ1.27 (t, 6H, J=7.3Hz, CH3), 3.28 (s, 4H, CH2), 4.22 (q, 4H, J=7.3Hz, CH2); 13CNMR(100MHz, CDCl3) δ13.9, 36.1, 62.0, 64.6, 101.8, 144.5, 170.3; IR(KBr) ν1730, 1252cm-1(COO), MS(DI)m/z 424, 426, 428(M+); 元素分析:C13H14O4Br2Sに基く計算値: C,36.64; H,3.31%. 実測値:C,36.67; H,3.32%
まず、水素化リチウムアルミニウム(2.85g, 75.1mmol)の無水THF(120mL)溶液を調製した。次に、これを氷浴で冷却し、窒素雰囲気下、1,3-ジブロモ−5,5-ビス(エトキシカルボニル)シクロペンタ[c]チオフェン(8.0g, 18.8mmol)の無水THF(30mL)溶液を緩やかに滴下した。この混合溶液を20時間還流させた後、氷浴で冷却しながら、酢酸エチル(30mL)、水(6mL)および1N(1mol/L)塩酸(6mL)を、この順番で連続的に加えた。そして、不溶固形物を濾過により除去し、さらにアセトン(100mL×3)で洗浄した。前記濾液および洗浄液を合わせ、減圧下で濃縮した。得られた固形物をカラムクロマトグラフィー(シリカゲル、酢酸エチル)で精製し、酢酸エチルとクロロホルムの1:4混合溶媒から再結晶し、5,5−ビス(ヒドロキシメチル)シクロペンタ[c]チオフェンの無色針状結晶を得た(収量3.07g, 収率89%)。以下に、この化合物の機器分析データを示す。
分解点139〜141℃;1HNMR(270MHz, CDCl3) δ2.23 (t, 2H, J=4.8Hz, OH), 2.62 (s, 4H, CH2), 3.77 (d, 4H, J=4.8Hz, CH2), 6,79 (s, 2H, ArH); 13CNMR(100MHz, CDCl3) δ32.8, 55.9, 69.5, 115.4, 145.9; IR(KBr) ν3000-3600cm-1(OH), MS(DI)m/z 184(M+); 元素分析:C9H12O2Sに基く計算値: C,58.67; H,6.56%. 実測値:C,58.55; H,6.74%
以下のようにして、出発原料5,5-ビス(ヒドロキシメチル)シクロペンタ[c] チオフェンから5,5-ビス(tert-ブチルジフェニルシリルオキシ)シクロペンタ[c] チオフェン(1T)を合成した。すなわち、まず、 5,5-ビス(ヒドロキシメチル)シクロペンタ[c] チオフェン(1.35g, 7.3mmol)とイミダゾール (2.01g, 29.6mmol)のジメチルホルムアミド溶液(25mL)を調製した。次に、これにtert-ブチルジフェニルシリルクロライド(5mL, 19.5mmol)を室温で滴下し、4時間撹拌した。このようにして得られた反応液に水を加え酢酸エチルで抽出した。そして、有機層を飽和食塩水で洗浄後、無水硫酸ナトリウムで乾燥した。これを濾過して不溶物を除いた後、溶媒を減圧留去した。得られた残渣をシリカゲルカラムクロマトグラフィ(ヘキサン/クロロホルム (3:1))で単離精製し、化合物 (1T)を無色固体として得た(収量4.69g, 収率97%)。以下に、この化合物(1T)の機器分析データを示す。
1HNMR(CDCl3-TMS) : δ 1.03 (s, 18H), 2.60 (s, 4H), 3.74 (s, 4H), 6.69 (s, 4H), 7.26-7.42 (m, 12H), 7.60-7.64 (m, 8H). 13CNMR(CDCl3): δ19.48, 26.94, 32.74, 57.95, 66.25, 114.67, 127.53, 129.44, 133.45, 135.50, 146.58.
まず、化合物(1T) (823 mg, 1.24mmol)のテトラヒドロフラン溶液(14mL)を調製した。次に、この溶液を0℃に冷却し、その温度でn−ブチルリチウム (1.9mL, 1.6Mヘキサン溶液)を滴下し、1時間撹拌した。さらに、鉄アセチルアセトナート(888 mg, 2.51mmol)を加え、80℃まで昇温させた後、一晩還流させた。反応終了後、得られた反応液を室温まで冷却し、水にあけ、クロロホルムで抽出した。有機層を飽和食塩水で洗浄後、無水硫酸ナトリウムで乾燥した。これを濾過して不溶物を除いた後、溶媒を減圧留去した。得られた残渣をシリカゲルカラム(ヘキサン/クロロホルム (2:1))で単離精製を行い、化合物(2T)を黄色固体として得た(収量700mg, 収率86%)。以下に、この化合物(2T)の機器分析データを示す。
1HNMR(CDCl3-TMS) : δ 1.03 (s, 36H), 2.60 (s, 4H), 2.73 (s, 4H), 3.76 (s, 8H), 6.59 (s, 2H), 7.21-7.36 (m, 24H), 7.60-7.65 (m, 16H). 13CNMR(CDCl3): δ19.48, 26.99, 33.06, 34.05, 57.98, 66.35, 113.13, 127,53, 127.56, 133.30, 133.43, 135.49, 135.51, 141.88, 146.85. MS (m/z) : 1326.1 (M+).
原料として、化合物(1T)に代えて(2T)を用いること、および、反応温度を0℃に代えて−78℃とすること以外は、化合物(2T)の合成と同様の方法で反応および精製を行ない、化合物(4T)を合成した。(収量737mg, 収率60%)。以下に、この化合物(4T)の機器分析データを示す。
1HNMR(CDCl3-TMS) : δ 0.89 (s, 36H), 0.90 (s, 36H), 2.47 (s, 4H), 2.59 (s, 4H), 2.64 (s, 8H), 3.67 (s, 8H), 3.73 (s, 8H), 6.48 (s, 2H), 7.03-7.25 (m, 24H), 7.46-7.57 (m, 16H). 13CNMR(CDCl3): δ19.41, 26.93, 26.97, 33.64, 34.09, 34.78, 57.88, 57.97, 66.16, 113.23, 125.99, 126.07, 127.49, 127.53, 127.56, 129,42, 133.04, 133.07, 133.38, 133.49, 135.46, 135.50, 141.36, 141.83, 142.56, 147.21. MS (m/z) : 2643.5 (M+).
1HNMR(CDCl3-TMS) : δ 0.89 (s, 36H), 0.93 (s, 36H), 1.00 (s, 36H), 2.53 (s, 4H), 2.63 (s, 12H), 2.66 (s, 4H), 2.68 (s, 4H), 3.72 (s, 8H), 3.78 (s, 16H), 6.55(s, 2H), 7.04-7.32 (m, 72H), 7.49-7.62 (m, 48H). MS (m/z) : 3963.3 (M+).
原料として、化合物(1T)に代えて(4T)を用いること、および、反応温度を0℃に代えて−78℃とすること以外は、化合物(2T)の合成と同様の方法で反応および精製を行ない、化合物(8T)を合成した。(収量176mg, 収率30%)。以下に、この化合物(8T)の機器分析データを示す。
1HNMR(CDCl3-TMS) : δ 0.87 (s, 72H), 0.93 (s, 36H), 0.95 (s, 36H), 2.54-2.66 (m, 32H), 3.63 (m, 32H), 6.56 (s, 2H), 7.03-7.25 (m), 7.46-7.57 (m). MS (m/z) : 5270.7 (M+).
1HNMR(CDCl3-TMS) : δ 0.84-0.94 (m), 2.59 (m), 3.76 (m), 6.56 (s), 7.06-7.33 (m), 7.51-7.59 (m). MS (m/z) : 7758.1 (M+).
上記の通り合成した本実施例の化合物について、分子構造および電気的性質を測定した。
Claims (15)
- 下記式(I)で表される化合物、その互変異性体もしくは立体異性体、またはそれらの塩。
Y1〜Y6は、それぞれ独立に、酸素原子であるか、または存在せず、
R1〜R6は、それぞれ独立に、水素原子、炭素数1〜18の直鎖もしくは分枝アルキル基、炭素数2〜18の直鎖もしくは分枝不飽和炭化水素基、フェニル基、1−ナフチル基、2−ナフチル基、1−アントリル基、2−アントリル基、または9−アントリル基であり、
Zは、下記式(i)〜(vii)のいずれかで表される原子または原子団であり、
X1およびX2は、それぞれ独立に、水素原子またはメルカプト基であり、
nは正の整数である。 - R1〜R6が、それぞれ独立に、水素原子、炭素数1〜6の直鎖もしくは分枝アルキル基、炭素数2〜6の直鎖もしくは分枝不飽和炭化水素基、フェニル基、1−ナフチル基、2−ナフチル基、1−アントリル基、2−アントリル基、または9−アントリル基である請求項1に記載の化合物、その互変異性体もしくは立体異性体、またはそれらの塩。
- R1〜R6が、それぞれ独立に、水素原子、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、フェニル基、1−ナフチル基、2−ナフチル基、1−アントリル基、2−アントリル基、または9−アントリル基であり、
R7が、水素原子またはメチル基である、
請求項1または2に記載の化合物、その互変異性体もしくは立体異性体、またはそれらの塩。 - nが1〜96である請求項1〜4のいずれかに記載の化合物、その互変異性体もしくは立体異性体、またはそれらの塩。
- nが2の倍数である請求項5に記載の化合物、その互変異性体もしくは立体異性体、またはそれらの塩。
- nが1、2、4、6、8、12または16である、請求項5に記載の化合物、その互変異性体もしくは立体異性体、またはそれらの塩。
- X1およびX2が水素原子であり、n=1である請求項1に記載の式(I)で表される化合物、その互変異性体もしくは立体異性体、またはそれらの塩を製造する方法であり、X1およびX2が水素原子であり、n=1である請求項1に記載の式(I)で表される化合物が下記式(VI)で表される化合物であり、下記式(III)〜(V)で表される化合物のカップリング反応により下記式(VI)で表される化合物を製造する工程を含む製造方法。
Y1〜Y6、R1〜R6およびZは、それぞれ請求項1に記載の前記式(I)におけるY 1 〜Y 6 、R 1 〜R 6 およびZと同じであり、Hal1およびHal2は、それぞれ独立に、塩素、臭素またはヨウ素である。 - 請求項8に記載の前記式(VI)で表される化合物を重合させる工程を含む、請求項1に記載の式(I)で表される化合物、その互変異性体もしくは立体異性体、またはそれらの塩を製造する方法。
- 前記重合工程により得られた生成物をさらに重合させる工程を含む、請求項9に記載の製造方法。
- 前記重合が、有機リチオ化剤を用いた酸化的重合である、請求項9または10に記載の製造方法。
- 請求項1〜7のいずれかに記載の化合物、その互変異性体もしくは立体異性体、またはそれらの塩からなる分子集合体であり、前記分子集合体中における前記化合物分子の重合度nが均一である分子集合体。
- 請求項1〜7のいずれかに記載の化合物、その互変異性体もしくは立体異性体、またはそれらの塩、または請求項13に記載の分子集合体を含む、電子材料。
- 請求項1〜7のいずれかに記載の化合物、その互変異性体もしくは立体異性体、またはそれらの塩、または請求項13に記載の分子集合体を含む、半導体。
Priority Applications (5)
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JP2005065947A JP4505568B2 (ja) | 2005-03-09 | 2005-03-09 | 被覆型ヘテロ芳香環化合物 |
CA002600183A CA2600183A1 (en) | 2005-03-09 | 2006-03-02 | Covered heteroaromatic ring compound |
EP06715077A EP1878736A4 (en) | 2005-03-09 | 2006-03-02 | CONNECTION WITH COATED HETEROAROMATIC RING |
US11/885,878 US20080293909A1 (en) | 2005-03-09 | 2006-03-02 | Covered Heteroaromatic Ring Compound |
PCT/JP2006/303968 WO2006095631A1 (ja) | 2005-03-09 | 2006-03-02 | 被覆型へテロ芳香環化合物 |
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JP2005065947A JP4505568B2 (ja) | 2005-03-09 | 2005-03-09 | 被覆型ヘテロ芳香環化合物 |
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EP (1) | EP1878736A4 (ja) |
JP (1) | JP4505568B2 (ja) |
CA (1) | CA2600183A1 (ja) |
WO (1) | WO2006095631A1 (ja) |
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DE10133927A1 (de) * | 2001-07-12 | 2003-01-23 | Bayer Ag | Benzodioxinothiophene, deren Herstellung und Verwendung |
DE10215706A1 (de) * | 2002-04-10 | 2003-11-06 | Bayer Ag | Alkylendioxythiophene und Poly(alkylendioxythiophen)e mit Urethangruppierungen enthaltenden Seitengruppen |
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DE10311561A1 (de) * | 2003-03-17 | 2004-10-07 | H.C. Starck Gmbh | 3,4-Alkylendioxythiophen-Diole, deren Herstellung und Verwendung in Kondensatoren |
DE10357571A1 (de) * | 2003-12-10 | 2005-07-28 | H.C. Starck Gmbh | Multifunktionelle 3,4-Alkylendioxythiophen-Derivate und diese enthaltende elektrisch leitfähige Polymere |
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2006
- 2006-03-02 WO PCT/JP2006/303968 patent/WO2006095631A1/ja active Application Filing
- 2006-03-02 US US11/885,878 patent/US20080293909A1/en not_active Abandoned
- 2006-03-02 EP EP06715077A patent/EP1878736A4/en not_active Withdrawn
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EP1878736A1 (en) | 2008-01-16 |
JP2006248945A (ja) | 2006-09-21 |
CA2600183A1 (en) | 2006-09-14 |
WO2006095631A1 (ja) | 2006-09-14 |
US20080293909A1 (en) | 2008-11-27 |
EP1878736A4 (en) | 2010-07-28 |
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