JPWO2011087130A1 - Acetylene compound and organic semiconductor material containing the same - Google Patents
Acetylene compound and organic semiconductor material containing the same Download PDFInfo
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- JPWO2011087130A1 JPWO2011087130A1 JP2011550038A JP2011550038A JPWO2011087130A1 JP WO2011087130 A1 JPWO2011087130 A1 JP WO2011087130A1 JP 2011550038 A JP2011550038 A JP 2011550038A JP 2011550038 A JP2011550038 A JP 2011550038A JP WO2011087130 A1 JPWO2011087130 A1 JP WO2011087130A1
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- -1 Acetylene compound Chemical class 0.000 title claims abstract description 102
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000004065 semiconductor Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 23
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 13
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 12
- 238000013461 design Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 67
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 59
- 238000006243 chemical reaction Methods 0.000 description 48
- 125000000217 alkyl group Chemical group 0.000 description 43
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- 238000005481 NMR spectroscopy Methods 0.000 description 27
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 26
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 16
- 239000012044 organic layer Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000010898 silica gel chromatography Methods 0.000 description 14
- 235000019270 ammonium chloride Nutrition 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 13
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 description 12
- 235000011152 sodium sulphate Nutrition 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 10
- OKJKNBJRPCJTQY-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-[2-(2,3,4,5,6-pentafluorophenyl)ethynyl]benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C#CC1=C(F)C(F)=C(F)C(F)=C1F OKJKNBJRPCJTQY-UHFFFAOYSA-N 0.000 description 9
- 230000002194 synthesizing effect Effects 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 229940043279 diisopropylamine Drugs 0.000 description 8
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- OHIRKWPMCLVZHL-UHFFFAOYSA-N trimethyl-[2-(2,3,4,5,6-pentafluorophenyl)ethynyl]silane Chemical compound C[Si](C)(C)C#CC1=C(F)C(F)=C(F)C(F)=C1F OHIRKWPMCLVZHL-UHFFFAOYSA-N 0.000 description 7
- KMLBFBMEAWTLLH-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3-iodo-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(C(F)(F)F)=C(F)C(F)=C1I KMLBFBMEAWTLLH-UHFFFAOYSA-N 0.000 description 6
- CWOBVQLDUWEOEM-UHFFFAOYSA-N C[Si](C)(C)C#CC1=C(C(=C(C(=C1F)F)C(F)(F)F)F)F Chemical compound C[Si](C)(C)C#CC1=C(C(=C(C(=C1F)F)C(F)(F)F)F)F CWOBVQLDUWEOEM-UHFFFAOYSA-N 0.000 description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ATTBNAHYWGFEGX-UHFFFAOYSA-N CCCCC1=C(C(=C(C(=C1F)F)C#C[Si](C)(C)C)F)F Chemical compound CCCCC1=C(C(=C(C(=C1F)F)C#C[Si](C)(C)C)F)F ATTBNAHYWGFEGX-UHFFFAOYSA-N 0.000 description 5
- DDZDAOROKANPDT-UHFFFAOYSA-N C[Si](C)(C)C#CC1=C(C(=C(C(=C1F)F)CCC(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F Chemical compound C[Si](C)(C)C#CC1=C(C(=C(C(=C1F)F)CCC(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F DDZDAOROKANPDT-UHFFFAOYSA-N 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000000304 alkynyl group Chemical group 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- OPYHNLNYCRZOGY-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-iodobenzene Chemical compound FC1=C(F)C(F)=C(I)C(F)=C1F OPYHNLNYCRZOGY-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 3
- 150000001343 alkyl silanes Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000002523 gelfiltration Methods 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEKTVXADUPBFOA-UHFFFAOYSA-N 1-bromo-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(Br)C(F)=C1F XEKTVXADUPBFOA-UHFFFAOYSA-N 0.000 description 2
- SXKNFEQEZLZAQR-UHFFFAOYSA-N 4-[2-(4-amino-2,3,5,6-tetrafluorophenyl)ethynyl]-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(C(=C(C(=C1F)N)F)F)C#CC1=C(C(=C(C(=C1F)F)N)F)F SXKNFEQEZLZAQR-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000005428 anthryl 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 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 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 2
- 125000004113 cyclononanyl 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 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 2
- 238000011161 development Methods 0.000 description 2
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 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 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000000752 ionisation method Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 2
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 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 2
- 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 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [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
- 150000002964 pentacenes Chemical class 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 0 *c(c(*)c1*)c(*)c(*)c1C#Cc(c(*)c1*)c(*)c(*)c1C#Cc(c(*)c1*)c(*)c(*)c1C#Cc1c(*)c(*)c(*)c(*)c1* Chemical compound *c(c(*)c1*)c(*)c(*)c1C#Cc(c(*)c1*)c(*)c(*)c1C#Cc(c(*)c1*)c(*)c(*)c1C#Cc1c(*)c(*)c(*)c(*)c1* 0.000 description 1
- NVVZEKTVIXIUKW-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCI NVVZEKTVIXIUKW-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WAUKYPQSFIENDE-UHFFFAOYSA-N 1-ethynyl-4-(2-phenylethynyl)benzene Chemical group C1=CC(C#C)=CC=C1C#CC1=CC=CC=C1 WAUKYPQSFIENDE-UHFFFAOYSA-N 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
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SOEAFKHLOCOBTO-UHFFFAOYSA-N C(#CC1=C(C(=C(C(=C1F)F)I)F)F)C2=C(C(=C(C(=C2F)F)I)F)F Chemical group C(#CC1=C(C(=C(C(=C1F)F)I)F)F)C2=C(C(=C(C(=C2F)F)I)F)F SOEAFKHLOCOBTO-UHFFFAOYSA-N 0.000 description 1
- HGJXPBNRCBHNAR-UHFFFAOYSA-N C[Si](C)(C)C#CC(C(C(F)=C1C(F)(F)F)F)C(F)=C1F Chemical compound C[Si](C)(C)C#CC(C(C(F)=C1C(F)(F)F)F)C(F)=C1F HGJXPBNRCBHNAR-UHFFFAOYSA-N 0.000 description 1
- JBZHWNXMZYBXDQ-UHFFFAOYSA-N Cc(c(F)c(c(C(F)(F)F)c1F)F)c1F Chemical compound Cc(c(F)c(c(C(F)(F)F)c1F)F)c1F JBZHWNXMZYBXDQ-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-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
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical group CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000005135 aryl sulfinyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000005446 heptyloxy 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])O* 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002642 lithium compounds Chemical class 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
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000005029 naphthylthio group Chemical group C1(=CC=CC2=CC=CC=C12)S* 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000006611 nonyloxy group Chemical group 0.000 description 1
- 125000005447 octyloxy 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])O* 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-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
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
Abstract
π電子が広く非局在化できる平面性や対称性を有する分子設計がされており、電子移動がスムーズで強いＮ型特性を示す有機半導体材料となるアセチレン化合物およびそれを含有しているＮ型有機半導体材料を提供する。アセチレン化合物は、下記化学式（Ｉ）【化１】（式中、Ｒ１〜Ｒ１６、Ｘ１およびＸ２のうち、少なくとも４つが、相互に同一または異なり、直鎖状、分岐鎖状および／または環状で炭素数１〜２０のパーフルオロアルキル基またはフッ素原子であり、残余が、相互に同一または異なり、直鎖状、分岐鎖状および／または環状で炭素数１〜２０の炭化水素基または水素原子である）で表されるものである。An acetylene compound as an organic semiconductor material that has a flat and symmetrical molecular design that allows π electrons to be widely delocalized and has symmetry, and has a smooth and strong N-type characteristic, and an N-type containing the same Provide organic semiconductor materials. The acetylene compound has the following chemical formula (I): wherein at least four of R1 to R16, X1 and X2 are the same or different from each other, and are linear, branched and / or cyclic and carbon. A perfluoroalkyl group having 1 to 20 carbon atoms or a fluorine atom, and the remainder is the same or different from each other, and is a linear, branched and / or cyclic hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. ).
Description
本発明は、有機エレクトロニクスデバイスのＮ型特性を示す半導体材料として有用であるアセチレン化合物およびそれを含有しているＮ型有機半導体材料に関する。 The present invention relates to an acetylene compound that is useful as a semiconductor material exhibiting N-type characteristics of an organic electronic device, and an N-type organic semiconductor material containing the acetylene compound.
π共役性有機化合物は一般的に半導体的な特性を有しており、有機半導体と呼ばれている。近年、有機薄膜トランジスタ、有機エレクトロルミネセンス、プリンタブル回路、有機キャパシタ、および有機太陽電池等の有機エレクトロニクスデバイスが注目されており、有機半導体材料の開発に多くの研究がなされている。 A π-conjugated organic compound generally has semiconducting properties and is called an organic semiconductor. In recent years, organic electronic devices such as organic thin film transistors, organic electroluminescence, printable circuits, organic capacitors, and organic solar cells have attracted attention, and much research has been conducted on the development of organic semiconductor materials.
例えば、特許文献１に、有機電界発光素子用の正孔輸送材料や発光材として有用なアリール基含有トリアミン系化合物およびその製造方法が開示されている。また、特許文献２に、正孔輸送層にトリアジン骨格を有する芳香族アミン化合物を含有する有機電界発光素子が開示されている。 For example, Patent Document 1 discloses an aryl group-containing triamine compound useful as a hole transport material or a light-emitting material for an organic electroluminescence device, and a method for producing the same. Patent Document 2 discloses an organic electroluminescent device containing an aromatic amine compound having a triazine skeleton in a hole transport layer.
有機半導体材料は、正孔注入または正孔輸送に関連しているＰ型半導体と電子注入または電子輸送に関連しているＮ型半導体とに大別される。現状では、低分子および高分子を問わず、Ｐ型有機半導体材料は多数報告されているが、Ｎ型有機半導体材料は報告例自体が少ない。これは一般に、Ｎ型有機半導体が、外部から電子を容易に吸引できる特性を持ち、空気中の酸素により酸化され易く、本来のＮ型特性を容易に喪失し安定に存在し難いという問題を有しているためである。特に、電子吸引能が強くなるほど、その酸化される傾向が増すため、強いＮ型有機半導体特性を有する素材の開発は、Ｐ型のものに比べて相対的に難しいと言われていた。 Organic semiconductor materials are roughly classified into P-type semiconductors related to hole injection or hole transport and N-type semiconductors related to electron injection or electron transport. At present, a large number of P-type organic semiconductor materials have been reported regardless of whether they are small molecules or polymers, but N-type organic semiconductor materials are rarely reported. This generally has the problem that an N-type organic semiconductor has a characteristic of easily attracting electrons from the outside, is easily oxidized by oxygen in the air, easily loses its original N-type characteristic, and does not exist stably. It is because it is doing. In particular, the stronger the electron withdrawing ability, the greater the tendency to oxidize, so it has been said that the development of materials having strong N-type organic semiconductor characteristics is relatively difficult compared to P-type materials.
報告されているＮ型有機半導体として、ペンタセン類（非特許文献１）、オリゴチオフェン（非特許文献２）、および銅フタロシアニン化合物（非特許文献３）であるπ共役系化合物のフッ素置換や、フラーレン誘導体（非特許文献４）が挙げられる。これらのＮ型有機半導体や、ペンタセン類等は、π電子を広く非局在化できるが、それだけではデバイスの電極および有機半導体における電子の移動、また有機半導体同士における電子の移動が、不十分なものである。フラーレン誘導体は代表的なＮ型有機半導体であるが、フラーレン骨格はアーク放電やプラズマ分解等の特殊な製造方法を必要とするため、高価であり工業的に好適な材料とは言い難い。このようにＮ型の有機半導体の提案は精力的に行われているが、各種デバイスの性能向上のためには新規な有機半導体化合物の更なる提案が必要不可欠である。 Examples of reported N-type organic semiconductors include fluorine substitution of π-conjugated compounds such as pentacenes (Non-Patent Document 1), oligothiophenes (Non-Patent Document 2), and copper phthalocyanine compounds (Non-Patent Document 3), and fullerenes. A derivative (nonpatent literature 4) is mentioned. These N-type organic semiconductors, pentacenes, and the like can delocalize π electrons widely, but by themselves, the movement of electrons in device electrodes and organic semiconductors, and the movement of electrons between organic semiconductors are insufficient. Is. A fullerene derivative is a typical N-type organic semiconductor, but a fullerene skeleton requires a special manufacturing method such as arc discharge or plasma decomposition, and is therefore expensive and difficult to say as an industrially suitable material. As described above, proposals for N-type organic semiconductors have been made energetically, but further proposals for new organic semiconductor compounds are indispensable for improving the performance of various devices.
一方、本発明者らはこれまでに、非特許文献５に示されるように、アリーレンエチニレン誘導体を報告しているが、これらの誘導体はすべてＰ型半導体の性質を有しており、Ｎ型の性質を示す化合物は知られていない。 On the other hand, as shown in Non-Patent Document 5, the present inventors have reported arylene ethynylene derivatives, all of which have the properties of P-type semiconductors and N-type. The compound which shows the property is not known.
本発明は上記課題を解決するためになされたものであり、π電子が広く非局在化できるような平面性や対称性を有する分子設計がされており、電子移動がスムーズで強いＮ型特性を示す有機半導体材料となるアセチレン化合物およびそれを含有しているＮ型有機半導体材料を提供することを目的とするものである。 The present invention has been made in order to solve the above problems, and has a molecular design having planarity and symmetry so that π electrons can be widely delocalized. It aims at providing the acetylene compound used as the organic-semiconductor material which shows, and the N type organic-semiconductor material containing it.
前記の目的を達成するためになされた、請求の範囲の請求項１に記載されたアセチレン化合物は、下記化学式（Ｉ） The acetylene compound according to claim 1, which has been made to achieve the above object, has the following chemical formula (I):
請求項２に記載のアセチレン化合物は、請求項１に記載されたものであって、前記Ｘ１およびＸ２は、相互に同一または異なる前記パーフルオロアルキル基であり、前記Ｒ１〜Ｒ１６は、その内の少なくとも４つがフッ素原子であることを特徴とする。The acetylene compound according to claim 2 is the acetylene compound according to claim 1, wherein X 1 and X 2 are the same or different perfluoroalkyl groups from each other, and R 1 to R 16 are , At least four of which are fluorine atoms.
請求項３に記載のＮ型有機半導体材料は、請求項１に記載のアセチレン化合物を含有していることを特徴とする。 The N-type organic semiconductor material according to claim 3 contains the acetylene compound according to claim 1.
本発明のアセチレン化合物は、平面的なアリーレンエチニレン骨格にフッ素原子やパーフルオロアルキル基が導入されており、強いＮ型特性を示す有機半導体材料となることができる。 The acetylene compound of the present invention has a fluorine atom or a perfluoroalkyl group introduced into a planar arylene ethynylene skeleton, and can be an organic semiconductor material exhibiting strong N-type characteristics.
本発明のＮ型有機半導体材料は、デバイスの電極と有機半導体との間における効率的な電子の移動、および有機半導体分子間におけるスムーズな電子の移動を実現することができる。 The N-type organic semiconductor material of the present invention can realize efficient electron transfer between a device electrode and an organic semiconductor and smooth electron transfer between organic semiconductor molecules.
以下、本発明を実施するための好ましい形態について詳細に説明するが、本発明の範囲はこれらの形態に限定されるものではない。 Hereinafter, although the preferable form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.
本発明のアセチレン化合物は、前記化学式（Ｉ）で表されるものであって、アリーレンエチニレン骨格にフッ素原子やパーフルオロアルキル基が導入されているものである。また、このアセチレン化合物は、π電子が広く非局在化できる平面性や対称性を有する分子設計がされており、有機半導体材料として用いた際に、その最低空軌道（ＬＵＭＯ）準位とデバイスの電極における仕事関数とにおいて、良いバランスを示すものである。 The acetylene compound of the present invention is represented by the chemical formula (I), and has a fluorine atom or a perfluoroalkyl group introduced into the arylene ethynylene skeleton. In addition, this acetylene compound has a molecular design with planarity and symmetry that allows π electrons to be widely delocalized, and when used as an organic semiconductor material, its lowest unoccupied orbital (LUMO) level and device This shows a good balance with the work function of the electrode.
前記化学式（Ｉ）中において、Ｒ１〜Ｒ１６、Ｘ１およびＸ２が表す置換基を有してもよい炭素数１〜２０の炭化水素基は、例えば、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基等が挙げられる。In the chemical formula (I), the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent represented by R 1 to R 16 , X 1 and X 2 may have, for example, a substituent. Examples thereof include an alkyl group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and an aryl group which may have a substituent.
アルキル基は、直鎖状や分岐鎖状のアルキル基であってもよいし、環状のアルキル基であってもよい。例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ヘキシル基、イソヘキシル基、２−エチルヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基等の直鎖や分岐鎖のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプタニル基、シクロオクタニル基、シクロノナニル基、シクロデカニル基、シクロウンデカニル基、シクロドデカニル基等のシクロアルキル基が挙げられる。 The alkyl group may be a linear or branched alkyl group or a cyclic alkyl group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and other linear or branched alkyl groups; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group And cycloalkyl groups such as cyclononanyl group, cyclodecanyl group, cycloundecanyl group, and cyclododecanyl group.
前記アルキル基は置換基を有していてもよく、かかる置換基としては、例えば、フェニル基、ナフチル基、アントリル基、フェナントリル基等のアリール基；ピリジル基、チエニル基、フリル基、ピロリル基、イミダゾリル基、ピラジニル基、オキサゾリル基、チアゾリル基、ピラゾリル基、ベンゾチアゾリル基、ベンゾイミダゾリル基等の複素芳香環基；メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ペンチルオキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、ヘキシルオキシ基、シクロヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、ノニルオキシ基、デシルオキシ基、ドデシルオキシ基等のアルコキシ基；メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基等のアルキルチオ基；フェニルチオ基、ナフチルチオ基等のアリールチオ基；ｔｅｒｔ−ブチルジメチルシリルオキシ基、ｔｅｒｔ−ブチルジフェニルシリルオキシ基等の三置換シリルオキシ基；メチルスルフィニル基、エチルスルフィニル基等のアルキルスルフィニル基；フェニルスルフィニル基等のアリールスルフィニル基；メチルスルフォニルオキシ基、エチルスルフォニルオキシ基、フェニルスルフォニルオキシ基、メトキシスルフォニル基、エトキシスルフォニル基、フェニルオキシスルフォニル基等のスルフォン酸エステル基；シアノ基；ニトロ基；等が挙げられる。 The alkyl group may have a substituent. Examples of the substituent include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; a pyridyl group, a thienyl group, a furyl group, a pyrrolyl group, Heteroaromatic groups such as imidazolyl group, pyrazinyl group, oxazolyl group, thiazolyl group, pyrazolyl group, benzothiazolyl group, benzimidazolyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group , Alkoxy groups such as tert-butoxy group, pentyloxy group, isopentyloxy group, neopentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group; Methylthio group, Alkylthio groups such as tilthio group, propylthio group and butylthio group; arylthio groups such as phenylthio group and naphthylthio group; trisubstituted silyloxy groups such as tert-butyldimethylsilyloxy group and tert-butyldiphenylsilyloxy group; methylsulfinyl group and ethyl Alkylsulfinyl groups such as sulfinyl groups; arylsulfinyl groups such as phenylsulfinyl groups; sulfonic acid ester groups such as methylsulfonyloxy groups, ethylsulfonyloxy groups, phenylsulfonyloxy groups, methoxysulfonyl groups, ethoxysulfonyl groups, and phenyloxysulfonyl groups Cyano group; nitro group; and the like.
アルケニル基は、直鎖状であってもよく、分岐鎖状や環状であってもよい。アルケニル基としては、例えば、ビニル基、アリル基、メチルビニル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、シクロプロペニル基、シクロブテニル基、シクロペンテニル基、シクロヘキセニル基等が挙げられる。 The alkenyl group may be linear, branched or cyclic. Examples of the alkenyl group include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
アルキニル基は、直鎖状であっても分岐鎖状であってもよい。アルキニル基としては、例えば、エチニル基、プロピニル基、プロパルギル基、ブチニル基、ペンチニル基、ヘキシニル基、フェニルエチニル基等が挙げられる。 The alkynyl group may be linear or branched. Examples of the alkynyl group include ethynyl group, propynyl group, propargyl group, butynyl group, pentynyl group, hexynyl group, and phenylethynyl group.
これらのアルケニル基やアルキニル基は、置換基を有していてもよく、かかる置換基として、アルキル基で例示したものと同様の置換基を用いることができる。 These alkenyl groups and alkynyl groups may have a substituent, and as such a substituent, the same substituents as those exemplified for the alkyl group can be used.
アリール基は、例えば、フェニル基、ナフチル基、アントリル基、フェナントリル基等が挙げられる。これらアリール基は置換基を有していてもよく、かかる置換基としては、アルキル基で例示したアリール基以外の置換基や、前記のアルキル基、アルケニル基、アルキニル基等を用いることができる。 Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. These aryl groups may have a substituent, and as such a substituent, a substituent other than the aryl group exemplified for the alkyl group, the above-described alkyl group, alkenyl group, alkynyl group, and the like can be used.
前記化学式（Ｉ）中において、Ｒ１〜Ｒ１６、Ｘ１およびＸ２が表すパーフルオロアルキル基とは、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ヘキシル基、イソヘキシル基、２−エチルヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基等の直鎖や分岐鎖のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプタニル基、シクロオクタニル基、シクロノナニル基、シクロデカニル基、シクロウンデカニル基、シクロドデカニル基等のシクロアルキル基；等の直鎖状や分岐鎖状や環状で炭素数１〜２０のアルキル基の水素原子のうち、８０〜１００％がフッ素原子で置換されたものである。本発明におけるパーフルオロアルキル基とは、フッ素原子がアルキル基の水素原子数の８０％以上１００％未満であるパーシャルフルオロアルキル基をも含むものである。In the chemical formula (I), the perfluoroalkyl group represented by R 1 to R 16 , X 1 and X 2 is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec- A butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc. Chain or branched chain alkyl groups; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group, cyclononanyl group, cyclodecanyl group, cycloundecanyl group, cyclododecanyl group, etc. Straight chain, branched chain, or cyclic, and having 1 to 20 carbon atoms Of the hydrogen atoms of the kill group, in which 80 to 100 percent are substituted with fluorine atoms. The perfluoroalkyl group in the present invention includes a partial fluoroalkyl group in which the fluorine atom is 80% or more and less than 100% of the number of hydrogen atoms of the alkyl group.
本発明のアセチレン化合物は、Ｒ１〜Ｒ１６、Ｘ１およびＸ２のうち、少なくとも４つはパーフルオロアルキル基またはフッ素原子であり、例えば下記化合物（１）〜（１４）が挙げられる。これらの中でも、パーフルオロアルキル基またはフッ素原子が８つ以上のものがより好ましい。また、これらのＲ１〜Ｒ１６、Ｘ１およびＸ２は、夫々同一であってもよく、異なっていてもよい。In the acetylene compound of the present invention, at least four of R 1 to R 16 , X 1 and X 2 are perfluoroalkyl groups or fluorine atoms, and examples thereof include the following compounds (1) to (14). Among these, a perfluoroalkyl group or a group having 8 or more fluorine atoms is more preferable. Further, these R 1 to R 16 , X 1 and X 2 may be the same or different.
これらのアセチレン化合物は、該当するフェニルハライド化合物とフェニルアセチレン化合物とのいわゆる薗頭（そのがしら）クロスカップリング反応による方法や、芳香族フッ素化合物にフェニルアセチリド化合物を反応させる方法、またはそれらを組み合わせた方法で合成することができる。 These acetylene compounds can be obtained by a method based on the so-called Sonogashira cross-coupling reaction between the corresponding phenyl halide compound and the phenylacetylene compound, a method of reacting an aromatic fluorine compound with a phenylacetylide compound, or a combination thereof. Can be synthesized by different methods.
本発明のアセチレン化合物の一合成例を以下に示す。 One synthesis example of the acetylene compound of the present invention is shown below.
前記化学式（Ｉ）において、Ｒ５〜Ｒ１２がすべてフッ素原子であり、Ｒ１３〜Ｒ１６がＲ１〜Ｒ４と夫々同様であって、Ｘ２がＸ１と同様であるアセチレン化合物の合成例を下記化学反応式（II）に示す。Synthesis of an acetylene compound in which R 5 to R 12 are all fluorine atoms, R 13 to R 16 are the same as R 1 to R 4, and X 2 is the same as X 1 in the chemical formula (I) An example is shown in chemical reaction formula (II) below.
前記化学反応式（II）において、フェニルハライド化合物と反応させる末端アルキン化合物のＺは、水素原子またはアルキルシラン（−ＳｉＲ’３）である。アルキルシラン（−ＳｉＲ’３）は、そのＲ’がメチルやエチルのような低級アルキルであると好ましい。In the chemical reaction formula (II), Z of the terminal alkyne compound to be reacted with the phenyl halide compound is a hydrogen atom or an alkylsilane (—SiR ′ 3 ). The alkylsilane (—SiR ′ 3 ) is preferably such that R ′ is a lower alkyl such as methyl or ethyl.
前記化学反応式（II）の工程（Ａ）において、フェニルハライド化合物と末端アルキン化合物（Ｚ−Ｃ≡Ｃ−Ｈ）との薗頭クロスカップリング反応により、アセチレン化合物の一部分を構成するフェニルアセチレン化合物を得る。続いて、工程（Ａ）で得られた、アセチレン化合物（Ｉ）の一部分を構成するフェニルアセチレン化合物を塩基の作用によりＺを脱離させアセチリド化（Ｂ−１）してフェニルアセチリドアニオンとし、さらにそれを芳香族フッ素化合物であるパーフルオロジフェニルアセチレンと反応（Ｂ−２）させることで、目的とするアセチレン化合物を合成する。 A phenylacetylene compound constituting a part of the acetylene compound by the Sonogashira cross-coupling reaction between the phenyl halide compound and the terminal alkyne compound (Z—C≡C—H) in the step (A) of the chemical reaction formula (II) Get. Subsequently, the phenylacetylene compound constituting part of the acetylene compound (I) obtained in the step (A) is desorbed by the action of a base to be acetylated (B-1) to obtain a phenylacetylide anion. By reacting (B-2) with perfluorodiphenylacetylene, which is an aromatic fluorine compound, a target acetylene compound is synthesized.
また、フェニルハライド化合物のハロゲン置換基がヨウ素原子である例を示したが、そのハロゲン置換基は、臭素原子であってもよく、また塩素原子であってもよい。 Moreover, although the example in which the halogen substituent of the phenyl halide compound is an iodine atom has been shown, the halogen substituent may be a bromine atom or a chlorine atom.
前記化学反応式（II）において、工程（Ａ）の薗頭クロスカップリング反応は、パラジウム触媒、銅触媒および塩基存在下でおこなわれると好ましい。 In the chemical reaction formula (II), the Sonogashira cross-coupling reaction in the step (A) is preferably performed in the presence of a palladium catalyst, a copper catalyst and a base.
また、工程（Ａ）で得られたフェニルアセチリド化合物に芳香族フッ素化合物を反応させる工程（Ｂ）において、アセチリド化（Ｂ−１）は、溶媒および塩基存在下でおこなわれると好ましい。さらに、アセチレン化合物の一部分を構成するフェニルアセチレン化合物とパーフルオロジフェニルアセチレンとの反応（Ｂ−２）は、溶媒存在下でおこなわれると好ましい。 In the step (B) of reacting the phenylacetylide compound obtained in the step (A) with an aromatic fluorine compound, the acetylation (B-1) is preferably performed in the presence of a solvent and a base. Furthermore, the reaction (B-2) of the phenylacetylene compound and perfluorodiphenylacetylene constituting a part of the acetylene compound is preferably carried out in the presence of a solvent.
用いられる塩基としては、例えば、Ｚが水素原子の場合、ｎ−ブチルリチウム、ｓ−ブチルリチウム、ｔ−ブチルリチウムなどの有機リチウム化合物；水素化ナトリウム、水素化カリウムなどの金属水素化物；水酸化ナトリウム、水酸化カリウムなどの金属水酸化物；メチルマグネシウムブロミド、エチルマグネシウムクロリド、フェニルマグネシウムクロリドなどのグリニヤール化合物などが挙げられ、Ｚがアルキルシラン（−ＳｉＲ’３）の場合、テトラエチルアンモニウムフロリド、テトラブチルアンモニウムフロリド、などのアンモニウムフロリドが挙げられる。Examples of the base used include, when Z is a hydrogen atom, organic lithium compounds such as n-butyllithium, s-butyllithium and t-butyllithium; metal hydrides such as sodium hydride and potassium hydride; sodium, metal hydroxides such as potassium hydroxide; methyl magnesium bromide, ethyl magnesium chloride, is like Grignard compounds such as phenyl magnesium chloride, if Z is an alkyl silane (-SiR '3), tetraethyl ammonium fluoride, Examples thereof include ammonium fluoride such as tetrabutylammonium fluoride.
用いられる溶媒としては、原料となる夫々の化合物が反応速度に支障をきたさない程度に溶解し、かつ塩基存在下でも使用可能な溶媒であることが好ましい。かかる溶媒としては、例えば、テトラヒドロフラン、ジエチルエーテル、ｎ−ヘキサン、シクロヘキサン、ｎ−ヘプタンなどが挙げられる。 The solvent used is preferably a solvent which can be used even in the presence of a base, in which each compound as a raw material is dissolved to such an extent that the reaction rate is not hindered. Examples of such a solvent include tetrahydrofuran, diethyl ether, n-hexane, cyclohexane, n-heptane and the like.
このようにして得られたアセチレン化合物は、有機化合物の単離・精製において通常行われる方法により単離・精製することができる。例えば、反応混合液を分液漏斗を用いて有機層と水層とに分離し、水層をジエチルエーテル、酢酸エチル、トルエン、塩化メチレン、１，２−ジクロロエタン等の溶媒で抽出し、抽出液および有機層を合わせて無水硫酸ナトリウム等で乾燥後、濃縮して得られた粗生成物を、必要に応じて昇華、再結晶、蒸留、シリカゲルカラムクロマトグラフィー等で精製することで、純度の高いアセチレン化合物を得ることができる。 The acetylene compound thus obtained can be isolated and purified by a method usually performed in the isolation and purification of organic compounds. For example, the reaction mixture is separated into an organic layer and an aqueous layer using a separatory funnel, and the aqueous layer is extracted with a solvent such as diethyl ether, ethyl acetate, toluene, methylene chloride, 1,2-dichloroethane, and the extract. The organic layer is combined, dried over anhydrous sodium sulfate, etc., and then concentrated, and the crude product obtained by concentration is purified by sublimation, recrystallization, distillation, silica gel column chromatography, etc. An acetylene compound can be obtained.
本発明を適用するアセチレン化合物の合成を実施例１〜５に示す。 Examples 1 to 5 show the synthesis of acetylene compounds to which the present invention is applied.
（実施例１）
アセチレン化合物を合成する中間化合物となる２，３，４，５，６−ペンタフルオロジフェニルアセチレン（ａ）を得る化学反応式（III）を以下に示す。Example 1
A chemical reaction formula (III) for obtaining 2,3,4,5,6-pentafluorodiphenylacetylene (a) as an intermediate compound for synthesizing the acetylene compound is shown below.
窒素で置換した反応器に、テトラキス（トリフェニルホスフィン）パラジウム（Ｐｄ（ＰＰｈ３）４）（０．１０ｍｍｏｌ，０．１２ｇ）、ヨウ化銅（Ｉ）（０．１０ｍｍｏｌ，１９ｍｇ）、ペンタフルオロヨードベンゼン（２．０ｍｍｏｌ，０．５９ｇ）を加え、トルエン（１０ｍｌ）、ジイソプロピルアミン（１ｍｌ）に溶解させた。フェニルアセチレン（２．４ｍｍｏｌ，０．２６ｍｌ）を加えた後、室温で１５時間撹拌した。反応混合物を飽和塩化アンモニウム水溶液で３回洗浄した後、酢酸エチルで３回抽出した。得られた有機層を飽和食塩水で洗浄し、硫酸ナトリウムで乾燥させ、濃縮、減圧乾燥した。その後、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）で精製することにより、中間化合物（ａ）を白色固体として得た（収量：４５６ｍｇ，収率：８５％）。To a reactor substituted with nitrogen, tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) (0.10 mmol, 0.12 g), copper (I) iodide (0.10 mmol, 19 mg), pentafluoroiodo Benzene (2.0 mmol, 0.59 g) was added and dissolved in toluene (10 ml) and diisopropylamine (1 ml). After phenylacetylene (2.4 mmol, 0.26 ml) was added, the mixture was stirred at room temperature for 15 hours. The reaction mixture was washed 3 times with a saturated aqueous ammonium chloride solution and then extracted 3 times with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, concentrated and dried under reduced pressure. Then, the intermediate compound (a) was obtained as a white solid by purifying with silica gel column chromatography (developing solvent: hexane) (yield: 456 mg, yield: 85%).
中間化合物（ａ）の１Ｈおよび１９Ｆ核磁気共鳴（ＮＭＲ）スペクトルデータを以下に示す。Ａｒはアリールを示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：７．３６〜７．４３（ｍ，３Ｈ，Ａｒ），７．５７〜７．６１（ｍ，２Ｈ，Ａｒ）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１６２．４５〜−１６２．２７（ｍ，２Ｆ，Ａｒ），−１５３．２８（ｔ，Ｊ＝２０．６Ｈｚ，１Ｆ，Ａｒ），−１３６．６２〜−１３６．５２（ｍ，２Ｆ，Ａｒ）
これらの分析データは、前記化学反応式（III）で示される中間化合物（ａ）の構造であることを支持する。 1 H and 19 F nuclear magnetic resonance (NMR) spectrum data of the intermediate compound (a) are shown below. Ar represents aryl.
1 H-NMR (300 MHz, CDCl 3 ) δ: 7.36 to 7.43 (m, 3H, Ar), 7.57 to 7.61 (m, 2H, Ar)
19 F-NMR (282 MHz, CDCl 3 ) δ: −162.5 to −162.27 (m, 2F, Ar), −153.28 (t, J = 20.6 Hz, 1F, Ar), −136. 62-136.52 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (a) represented by the chemical reaction formula (III).
得られた中間化合物（ａ）を用いて４，４’−ビス（フェニルエチニル）−２，３，５，６−テトラフルオロジフェニルアセチレン（１）を合成する化学反応式（IV）を以下に示す。 A chemical reaction formula (IV) for synthesizing 4,4′-bis (phenylethynyl) -2,3,5,6-tetrafluorodiphenylacetylene (1) using the obtained intermediate compound (a) is shown below. .
窒素で置換した反応器に、４−（フェニルエチニル）フェニルアセチレン（０．８２ｍｍｏｌ，０．１７ｍｇ）を加えてテトラヒドロフラン（ＴＨＦ）（５ｍｌ）を加えた。この混合液を−７８℃に冷却し、ｎ−ブチルリチウム（ｎ−ＢｕＬｉ）（１．３７５７Ｍのヘキサン溶液，０．８７ｍｌ）を加えて、−７８℃で１５分撹拌した。次いで、前記合成で得られた２，３，４，５，６−ペンタフルオロジフェニルアセチレン（ａ）（０．６８ｍｍｏｌ，０．１８ｇ）のＴＨＦ（４ｍｌ）溶液を加え、室温に昇温し１８時間撹拌した。この反応液に飽和塩化アンモニウム水溶液（２０ｍｌ）を加え、ジクロロメタン（２０ｍｌ）で３回抽出した。有機層を硫酸ナトリウムで乾燥後、溶媒を減圧留去して得られた残渣を、トルエンとＴＨＦとの混合溶媒を用いて再結晶により精製し、目的物（１）を黄色固体として得た（収量：１８０ｍｇ、収率：５９％）。 4- (Phenylethynyl) phenylacetylene (0.82 mmol, 0.17 mg) was added to the reactor purged with nitrogen, and tetrahydrofuran (THF) (5 ml) was added. The mixture was cooled to −78 ° C., n-butyllithium (n-BuLi) (1.3757 M in hexane, 0.87 ml) was added, and the mixture was stirred at −78 ° C. for 15 minutes. Next, a solution of 2,3,4,5,6-pentafluorodiphenylacetylene (a) (0.68 mmol, 0.18 g) obtained in the above synthesis was added in THF (4 ml), and the mixture was warmed to room temperature and heated for 18 hours. Stir. Saturated aqueous ammonium chloride solution (20 ml) was added to the reaction mixture, and the mixture was extracted 3 times with dichloromethane (20 ml). After drying the organic layer with sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by recrystallization using a mixed solvent of toluene and THF to obtain the desired product (1) as a yellow solid ( Yield: 180 mg, yield: 59%).
目的物である４，４’−ビス（フェニルエチニル）−２，３，５，６−テトラフルオロジフェニルアセチレン（１）の１Ｈ−ＮＭＲ，１９Ｆ−ＮＭＲ，精密質量分析（Ｈｉｇｈ−Ｒｅｓｏｌｕｔｉｏｎ Ｍａｓｓ Ｓｐｅｃｔｒａ（ＨＲＭＳ））の結果を以下に示す。 1 H-NMR, 19 F-NMR, accurate mass spectrometry (High-Resolution Mass Spectra) of 4,4′-bis (phenylethynyl) -2,3,5,6-tetrafluorodiphenylacetylene (1) which is the target product The results of (HRMS)) are shown below.
ＨＲＭＳは、高性能二重収束質量分析計 ＪＥＯＬ−ＪＭＳ７００（日本電子株式会社製）を用い、加速電圧：８ｋＶ、イオン化方法：電子イオン化法、イオン化エネルギー：７０ｅＶ、検出器電圧：１．５ｋＶの条件により測定した。また、目的物の推定組成に対して、１０ｐｐｍ以下の誤差範囲であることを確認した。 HRMS uses a high performance double-focusing mass spectrometer JEOL-JMS700 (manufactured by JEOL Ltd.), acceleration voltage: 8 kV, ionization method: electron ionization method, ionization energy: 70 eV, detector voltage: 1.5 kV It was measured by. Moreover, it confirmed that it was an error range of 10 ppm or less with respect to the estimated composition of a target object.
１Ｈ−ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３）δ：７．２５〜７．４４（ｍ，６Ｈ），７．５４〜７．６１（ｍ，８Ｈ）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１３７．６２（ｓ，４Ｆ）
ＨＲＭＳ 実測値：４５０．０９９８ （計算値：４５０．１０３２）
これらの分析データは、前記化学反応式（IV）で示されるアセチレン化合物（１）の構造であることを支持する。 1 H-NMR (500 MHz, CDCl 3 ) δ: 7.25 to 7.44 (m, 6H), 7.54 to 7.61 (m, 8H)
19 F-NMR (282 MHz, CDCl 3 ) δ: −137.62 (s, 4F)
HRMS measured value: 450.0998 (calculated value: 450.1032)
These analytical data support the structure of the acetylene compound (1) represented by the chemical reaction formula (IV).
（実施例２）
アセチレン化合物を合成するための中間化合物となるトリメチルシリルエチニルペンタフルオロベンゼン（ｂ）を得る化学反応式（Ｖ）を以下に示す。式中、ＴＭＳはトリメチルシリル基（-Ｓｉ(ＣＨ３)３）の略である。
無色の液体の１Ｈ−ＮＭＲおよび１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：０．３０（ｓ，９Ｈ，ＴＭＳ）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１６２．２９〜−１６２．４８（ｍ，２Ｆ，Ａｒ），−１５２．８６（ｔ，Ｊ＝２０．６Ｈｚ，１Ｆ,Ａｒ），−１３６．２４〜−１３６．３６（ｍ，２Ｆ，Ａｒ）
これらの分析データは、前記化学反応式（Ｖ）で示される中間化合物（ｂ）の構造であることを支持する。(Example 2)
A chemical reaction formula (V) for obtaining trimethylsilylethynylpentafluorobenzene (b) as an intermediate compound for synthesizing the acetylene compound is shown below. In the formula, TMS is an abbreviation for trimethylsilyl group (—Si (CH 3 ) 3 ).
1 H-NMR and 19 F-NMR spectrum data of the colorless liquid are shown below.
1 H-NMR (300 MHz, CDCl 3 ) δ: 0.30 (s, 9H, TMS)
19 F-NMR (282 MHz, CDCl 3 ) δ: −162.29 to −162.48 (m, 2F, Ar), −152.86 (t, J = 20.6 Hz, 1F, Ar), −136. 24 to -136.36 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (b) represented by the chemical reaction formula (V).
得られた中間化合物（ｂ）より、さらに中間化合物となるパーフルオロジフェニルアセチレン（ｃ）を得る化学反応式（VI）を以下に示す。 A chemical reaction formula (VI) for obtaining perfluorodiphenylacetylene (c) as an intermediate compound from the obtained intermediate compound (b) is shown below.
窒素で置換した反応器に、Ｐｄ（ＰＰｈ３）４（０．１０ｍｍｏｌ，０．１２ｇ）、ヨウ化銅（Ｉ）（２．４ｍｍｏｌ，０．２４ｇ）、ペンタフルオロヨードベンゼン（２．０ｍｍｏｌ，０．４９ｇ）を加え、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）（４ｍｌ）、ジイソプロピルアミン（０．４０ｍｌ）に溶解させた後、前記合成で得られたトリメチルシリルエチニルペンタフルオロベンゼン（ｂ）（２．４ｍｍｏｌ，０．６３ｍｇ）を加え、８０℃で１５時間加熱撹拌した。反応液を冷却し酢酸エチル２０ｍｌを加えた後、有機層を飽和塩化アンモニウム水溶液で３回洗浄した。水層を酢酸エチルで３回再抽出し、先の有機層と混合し、硫酸ナトリウムで乾燥した。この溶液を減圧下濃縮して留去し、得られた残渣を、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）、次いでヘキサンによる再結晶精製を行い、中間化合物（ｃ）を白色固体として得た（収量：３５０ｍｇ、収率：４９％）。A reactor purged with nitrogen was charged with Pd (PPh 3 ) 4 (0.10 mmol, 0.12 g), copper (I) iodide (2.4 mmol, 0.24 g), pentafluoroiodobenzene (2.0 mmol, 0 .49 g) was added and dissolved in N, N-dimethylformamide (DMF) (4 ml) and diisopropylamine (0.40 ml), and then trimethylsilylethynylpentafluorobenzene (b) (2.4 mmol) obtained in the above synthesis was obtained. , 0.63 mg) was added and the mixture was heated and stirred at 80 ° C. for 15 hours. After cooling the reaction solution and adding 20 ml of ethyl acetate, the organic layer was washed three times with a saturated aqueous ammonium chloride solution. The aqueous layer was re-extracted 3 times with ethyl acetate, mixed with the previous organic layer, and dried over sodium sulfate. This solution was concentrated and evaporated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (developing solvent: hexane) and then recrystallized and purified with hexane to obtain intermediate compound (c) as a white solid ( Yield: 350 mg, yield: 49%).
中間化合物（ｃ）の１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１６１．０８〜−１６１．２８（ｍ，２Ｆ，Ａｒ），−１４９．８９（ｔ，Ｊ＝２０．６Ｈｚ，２Ｆ，Ａｒ），−１３４．８４〜−１３４．９４（ｍ，２Ｆ，Ａｒ）
これらの分析データは、前記化学反応式（VI）で示される中間化合物（ｃ）の構造であることを支持する。The 19 F-NMR spectrum data of the intermediate compound (c) is shown below.
19 F-NMR (282 MHz, CDCl 3 ) δ: −161.08 to −161.28 (m, 2F, Ar), −149.89 (t, J = 20.6 Hz, 2F, Ar), −134. 84 to -134.94 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (c) represented by the chemical reaction formula (VI).
得られた中間化合物（ｃ）を用いて４，４’−ビス（フェニルエチニル）−パーフルオロジフェニルアセチレン（７）を合成する化学反応式（VII）を以下に示す。 A chemical reaction formula (VII) for synthesizing 4,4′-bis (phenylethynyl) -perfluorodiphenylacetylene (7) using the obtained intermediate compound (c) is shown below.
窒素で置換した反応器に、フェニルアセチレン（０．６２ｍｍｏｌ，６３ｍｇ）およびＴＨＦ（１ｍｌ）を加えた後、−７８℃に冷却して、２．１当量のｎ−ＢｕＬｉ（１．３７５７Ｍのヘキサン溶液，０．４３ｍｌ）を加えて３０分撹拌した。この混合液に、前記合成で得られたパーフルオロジフェニルアセチレン（ｃ）（０．２８ｍｍｏｌ，０．１０ｇ）のＴＨＦ（２．０ｍｌ）溶液を添加し、室温に昇温して１５時間撹拌した。この反応液に飽和塩化アンモニウム水溶液（２０ｍｌ）を添加した後、ジクロロメタン（２０ｍｌ）で３回抽出した。有機層を無水硫酸ナトリウムにより乾燥した後、溶媒を減圧留去し、得られた残渣をトルエン溶媒を用いてゲルろ過した後、ＴＨＦを用いて再結晶を行うことにより、目的物（７）を黄色固体として得た（収量：８７．８ｍｇ，収率：６０％）。 To a reactor purged with nitrogen, phenylacetylene (0.62 mmol, 63 mg) and THF (1 ml) were added, then cooled to −78 ° C., and 2.1 equivalents of n-BuLi (1.3757 M in hexane solution). , 0.43 ml) was added and stirred for 30 minutes. To this mixture was added a THF (2.0 ml) solution of perfluorodiphenylacetylene (c) (0.28 mmol, 0.10 g) obtained in the above synthesis, and the mixture was warmed to room temperature and stirred for 15 hours. A saturated aqueous ammonium chloride solution (20 ml) was added to the reaction solution, and then extracted three times with dichloromethane (20 ml). The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, the obtained residue was subjected to gel filtration using a toluene solvent, and then recrystallized using THF to obtain the desired product (7). Obtained as a yellow solid (yield: 87.8 mg, yield: 60%).
目的物である４，４’−ビス（フェニルエチニル）−パーフルオロジフェニルアセチレン（７）の１Ｈ−ＮＭＲ，１９Ｆ−ＮＭＲ，ＨＲＭＳの分析結果を以下に示す。ＨＲＭＳは、実施例１と同条件で測定し、目的物の推定組成に対して、１０ｐｐｍ以下の誤差範囲であることを確認した。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：７．４１〜７．４３（ｍ，３Ｈ，Ａｒ），７．６１〜７．６３（ｍ，２Ｈ，Ａｒ）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１３６．８６〜−１３６．７１（ｍ，２Ｆ，Ａｒ），−１３６．２５〜−１３６．１１（ｍ，２Ｆ，Ａｒ）
ＨＲＭＳ 実測値：５２２．０７０２ （計算値：５２２．０６５５）
これらの分析データは、前記化学反応式（VII）で示されるアセチレン化合物（７）の構造であることを支持する。The results of 1 H-NMR, 19 F-NMR, and HRMS analysis of 4,4′-bis (phenylethynyl) -perfluorodiphenylacetylene (7), which is the target product, are shown below. HRMS was measured under the same conditions as in Example 1, and it was confirmed that the error range was 10 ppm or less with respect to the estimated composition of the target product.
1 H-NMR (300 MHz, CDCl 3 ) δ: 7.41 to 7.43 (m, 3H, Ar), 7.61 to 7.63 (m, 2H, Ar)
19 F-NMR (282 MHz, CDCl 3 ) δ: −136.86 to −136.71 (m, 2F, Ar), −136.225 to −136.11 (m, 2F, Ar)
HRMS measured value: 522.0702 (calculated value: 522.0655)
These analytical data support the structure of the acetylene compound (7) represented by the chemical reaction formula (VII).
（実施例３）
アセチレン化合物を合成するための中間化合物となる４−ヨード−２，３，５，６−テトラフルオロベンゾトリフルオリド（ｄ）を得る化学反応式（VIII）を以下に示す。(Example 3)
A chemical reaction formula (VIII) for obtaining 4-iodo-2,3,5,6-tetrafluorobenzotrifluoride (d) as an intermediate compound for synthesizing the acetylene compound is shown below.
窒素で置換した反応器に、ヨウ素（１．０ｍｍｏｌ，０．２５ｇ）、テトラフルオロベンゾトリフルオリド（１．０ｍｍｏｌ，０．２２ｇ）、リン酸三カリウム（２．０ｍｍｏｌ，０．４３ｇ）およびＴＨＦを加え、１３０℃にて２時間加熱撹拌した。反応液を冷却後、飽和亜硫酸水素ナトリウム水溶液（２０ｍｌ）で１回洗浄した後、水層をジエチルエーテル（２０ｍｌ）で３回再抽出し、先の有機層と混合した。この有機層を飽和食塩水（２０ｍｌ）で洗浄した後、無水硫酸ナトリウムで乾燥し、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ー（展開溶媒：ヘキサン）により精製し、中間化合物（ｄ）を得た（収量：１５８ｍｇ，収率：４６％）。 A reactor purged with nitrogen was charged with iodine (1.0 mmol, 0.25 g), tetrafluorobenzotrifluoride (1.0 mmol, 0.22 g), tripotassium phosphate (2.0 mmol, 0.43 g) and THF. In addition, the mixture was stirred with heating at 130 ° C. for 2 hours. The reaction solution was cooled, washed once with a saturated aqueous sodium hydrogen sulfite solution (20 ml), the aqueous layer was re-extracted three times with diethyl ether (20 ml), and mixed with the previous organic layer. The organic layer was washed with saturated brine (20 ml) and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane) to obtain an intermediate compound (d) (yield: 158 mg, yield: 46%).
中間化合物（ｄ）の１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤ２Ｃｌ２）δ：−１３８．２７〜−１３７．８８（ｍ，２Ｆ，Ａｒ），−１１６．８５〜−１１６．６９（ｍ，２Ｆ，Ａｒ），−５５．７０（ｔ，Ｊ＝２０．６Ｈｚ，３Ｆ，Ｆ３Ｃ）
これらの分析データは、前記化学反応式（VIII）で示される中間化合物（ｄ）の構造であることを支持する。The 19 F-NMR spectrum data of the intermediate compound (d) is shown below.
19 F-NMR (282 MHz, CD 2 Cl 2 ) δ: −138.27 to −137.88 (m, 2F, Ar), −116.85 to −116.69 (m, 2F, Ar), −55 .70 (t, J = 20.6 Hz, 3F, F 3 C)
These analytical data support the structure of the intermediate compound (d) represented by the chemical reaction formula (VIII).
得られた中間化合物（ｄ）より、さらに中間化合物となる４−トリメチルシリルエチニル−２，３，５，６−テトラフルオロベンゾトリフルオリド（ｅ）を得る化学反応式（IX）を以下に示す。 A chemical reaction formula (IX) for obtaining 4-trimethylsilylethynyl-2,3,5,6-tetrafluorobenzotrifluoride (e) as an intermediate compound from the obtained intermediate compound (d) is shown below.
窒素で置換した反応器に、Ｐｄ（ＰＰｈ３）４（０．０４２ｍｍｏｌ，４８ｍｇ）、ヨウ化銅（Ｉ）（０．０４２ｍｍｏｌ，８ｍｇ）、前記合成で得られた４−ヨード−２，３，５，６−テトラフルオロベンゾトリフルオリド（ｄ）（０．７３ｍｍｏｌ，２５１ｍｇ）、トルエン（４ｍｌ）およびジイソプロピルアミン（０．４ｍｌ）を加えた。この混合液に、トリメチルシリルアセチレン（０．８３ｍｍｏｌ，０．１１ｍｌ）を加え、８０℃で２０時間加熱撹拌した。反応液を冷却後、飽和塩化アンモニウム水溶液（２０ｍｌ）で３回洗浄した後、水層を酢酸エチル（２０ｍｌ）で３回抽出した。得られた有機層を飽和食塩水（２０ｍｌ）で洗浄し、無水硫酸ナトリウムで乾燥した後、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ー（展開溶媒：ヘキサン）により精製し、無色液体の中間化合物（ｅ）を得た（収量：１９７ｍｇ，収率：８６％）。In a reactor substituted with nitrogen, Pd (PPh 3 ) 4 (0.042 mmol, 48 mg), copper (I) iodide (0.042 mmol, 8 mg), 4-iodo-2,3, obtained in the above synthesis, were added. 5,6-Tetrafluorobenzotrifluoride (d) (0.73 mmol, 251 mg), toluene (4 ml) and diisopropylamine (0.4 ml) were added. Trimethylsilylacetylene (0.83 mmol, 0.11 ml) was added to the mixture, and the mixture was stirred with heating at 80 ° C. for 20 hours. The reaction mixture was cooled, washed with saturated aqueous ammonium chloride solution (20 ml) three times, and the aqueous layer was extracted three times with ethyl acetate (20 ml). The obtained organic layer was washed with saturated brine (20 ml) and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane) to obtain a colorless liquid intermediate compound (e) (yield: 197 mg, yield: 86%).
中間化合物（ｅ）の１Ｈ−ＮＭＲおよび１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：０．３０（ｓ，９Ｈ，ＴＭＳ）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１４１．５９〜−１４１．２２（ｍ，２Ｆ，Ａｒ），−１３４．９０〜−１３４．７６（ｍ，２Ｆ，Ａｒ），−５６．７８（ｔ，Ｊ＝２１．０Ｈｚ，３Ｆ，Ｆ３Ｃ）
これらの分析データは、前記化学反応式（IX）で示される中間化合物（ｅ）の構造であることを支持する。The 1 H-NMR and 19 F-NMR spectrum data of the intermediate compound (e) are shown below.
1 H-NMR (300 MHz, CDCl 3 ) δ: 0.30 (s, 9H, TMS)
19 F-NMR (282 MHz, CDCl 3 ) δ: −141.59 to −141.22 (m, 2F, Ar), −134.90 to −134.76 (m, 2F, Ar), −56.78 (T, J = 21.0Hz, 3F, F 3 C)
These analytical data support the structure of the intermediate compound (e) represented by the chemical reaction formula (IX).
得られた中間化合物（ｅ）および実施例２で得られた中間化合物（ｃ）を用いて、４，４’−ビス（２，３，５，６−テトラフルオロ−４−トリフルオロメチルフェニルエチニル）−パーフルオロジフェニルアセチレン（１４）を合成する化学反応式（Ｘ）を以下に示す。 Using the obtained intermediate compound (e) and the intermediate compound (c) obtained in Example 2, 4,4′-bis (2,3,5,6-tetrafluoro-4-trifluoromethylphenylethynyl) Chemical reaction formula (X) for synthesizing) -perfluorodiphenylacetylene (14) is shown below.
窒素で置換した反応器に、実施例２で得られたパーフルオロジフェニルアセチレン（ｃ）（０．２８ｍｍｏｌ，０．１０ｇ）、前記合成で得られた４−トリメチルシリルエチニル−２，３，５，６−テトラフルオロベンゾトリフルオリド（ｅ）（０．６７ｍｍｏｌ，０．２１ｇ）およびＴＨＦ（４ｍｌ）を加え、０℃に冷却した。この混合液に、テトラブチルアンモニウムフロリド（ＴＢＡＦ）（１．０Ｍテトラヒドロフラン溶液，０．２８ｍｍｏｌ，０．０２８ｍｌ）を加えて室温で１２時間撹拌した。この反応液に、飽和塩化アンモニウム水溶液（２０ｍｌ）を添加した後、ジクロロメタン（２０ｍｌ）で３回再抽出した。有機層の溶媒を減圧留去して、トルエンを用いてゲルろ過を行った後、トルエンにより再結晶精製することにより、白色固体の目的物（１４）を得た（収量：１５０ｍｇ、収率：６７％）。 In a reactor substituted with nitrogen, perfluorodiphenylacetylene (c) (0.28 mmol, 0.10 g) obtained in Example 2 and 4-trimethylsilylethynyl-2,3,5,6 obtained in the above synthesis were used. -Tetrafluorobenzotrifluoride (e) (0.67 mmol, 0.21 g) and THF (4 ml) were added and cooled to 0 ° C. Tetrabutylammonium fluoride (TBAF) (1.0 M tetrahydrofuran solution, 0.28 mmol, 0.028 ml) was added to the mixture and stirred at room temperature for 12 hours. A saturated aqueous ammonium chloride solution (20 ml) was added to the reaction solution, and then re-extracted three times with dichloromethane (20 ml). The solvent of the organic layer was distilled off under reduced pressure, gel filtration was performed using toluene, and then recrystallization purification was performed with toluene to obtain the target product (14) as a white solid (yield: 150 mg, yield: 67%).
目的物である４，４’−ビス（２，３，５，６−テトラフルオロ−４−トリフルオロメチルフェニルエチニル）−パーフルオロジフェニルアセチレン（１４）の１９Ｆ−ＮＭＲおよびＨＲＭＳの分析結果を以下に示す。ＨＲＭＳは、実施例１と同条件で測定し、目的物の推定組成に対して、１０ｐｐｍ以下の誤差範囲であることを確認した。
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，Ｃ６Ｄ５ＣＤ３）δ：−１４０．９０〜−１４０．６４（ｍ，２Ｆ，Ａｒ），−１３５．６０〜−１３５．３４（ｍ，２Ｆ，Ａｒ），−１３４．０４〜−１３３．９４（ｍ，２Ｆ，Ａｒ），−５７．０８（ｔ，Ｊ＝２３．１Ｈｚ，３Ｆ，Ｆ３Ｃ）
ＨＲＭＳ 実測値：８０１．９６４８ （計算値：８０１．９６４８）
これらの分析データは、前記化学反応式（Ｘ）で示されるアセチレン化合物（１４）の構造であることを支持する。The analysis results of 19 F-NMR and HRMS of 4,4′-bis (2,3,5,6-tetrafluoro-4-trifluoromethylphenylethynyl) -perfluorodiphenylacetylene (14), which is the object, are shown below. Shown in HRMS was measured under the same conditions as in Example 1, and it was confirmed that the error range was 10 ppm or less with respect to the estimated composition of the target product.
19 F-NMR (282 MHz, C 6 D 5 CD 3 ) δ: −140.90 to −140.64 (m, 2F, Ar), −135.60 to −135.34 (m, 2F, Ar), −134.04 to −133.94 (m, 2F, Ar), −57.08 (t, J = 23.1 Hz, 3F, F 3 C)
HRMS measured value: 801.9648 (calculated value: 801.9648)
These analytical data support the structure of the acetylene compound (14) represented by the chemical reaction formula (X).
（実施例４）
アセチレン化合物を合成するための中間化合物となるパーフルオロジフェニルアセチレン（ｃ）を実施例２で得られた中間化合物（ｂ）を用いて得る化学反応式（VI）を以下に示す。Example 4
A chemical reaction formula (VI) for obtaining perfluorodiphenylacetylene (c), which is an intermediate compound for synthesizing the acetylene compound, using the intermediate compound (b) obtained in Example 2 is shown below.
窒素で置換した反応器に、Ｐｄ（ＰＰｈ３）４（０．１０ｍｍｏｌ，０．１２ｇ）、ＣｕＣｌ（２．４ｍｍｏｌ，０．２４ｇ）、ペンタフルオロヨードベンゼン（２．０ｍｍｏｌ，０．４９ｇ）を加え、乾燥ＤＭＦ（４ｍｌ）、ジイソプロピルアミン(０．４０ｍｌ)に溶解させた。実施例２で得られたトリメチルシリルエチニルペンタフルオロベンゼン（ｂ）（２．４ｍｍｏｌ，０．６３ｍｇ）を加え、８０℃で１５時間撹拌した。反応液を飽和塩化アンモニウム水溶液で３回洗浄した後、酢酸エチルで３回抽出した。硫酸ナトリウムで乾燥させ、ろ紙でろ過した後、濃縮、減圧乾燥した。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン，Ｒｆ＝０．４３）で精製した。次いでヘキサンによる再結晶精製を行い、中間化合物（ｃ）を白色固体として得た（収率４９％）。Pd (PPh 3 ) 4 (0.10 mmol, 0.12 g), CuCl (2.4 mmol, 0.24 g), pentafluoroiodobenzene (2.0 mmol, 0.49 g) were added to the reactor substituted with nitrogen. , Dissolved in dry DMF (4 ml), diisopropylamine (0.40 ml). Trimethylsilylethynylpentafluorobenzene (b) (2.4 mmol, 0.63 mg) obtained in Example 2 was added, and the mixture was stirred at 80 ° C. for 15 hours. The reaction solution was washed 3 times with a saturated aqueous ammonium chloride solution and then extracted 3 times with ethyl acetate. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. The product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.43). Subsequently, recrystallization purification with hexane was performed to obtain the intermediate compound (c) as a white solid (yield 49%).
中間化合物（ｃ）の１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１６１．０８〜−１６１．２８（ｍ，２Ｆ，Ａｒ），−１４９．８９（ｔ，Ｊ＝２０．６Ｈｚ，２Ｆ，Ａｒ），−１３４．８４〜−１３４．９４（ｍ，２Ｆ，Ａｒ）
これらの分析データは、前記化学反応式（VI）で示される中間化合物（ｃ）の構造であることを支持する。The 19 F-NMR spectrum data of the intermediate compound (c) is shown below.
19 F-NMR (282 MHz, CDCl 3 ) δ: −161.08 to −161.28 (m, 2F, Ar), −149.89 (t, J = 20.6 Hz, 2F, Ar), −134. 84 to -134.94 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (c) represented by the chemical reaction formula (VI).
得られた中間化合物（ｃ）より、さらに中間化合物となるビス（２，３，５，６−テトラフルオロ−４−アミノフェニル）アセチレン（ｆ）を得る化学反応式（XI）を以下に示す。 A chemical reaction formula (XI) for obtaining bis (2,3,5,6-tetrafluoro-4-aminophenyl) acetylene (f) as an intermediate compound from the obtained intermediate compound (c) is shown below.
窒素で置換した反応器に、前記合成で得られたパーフルオロジフェニルアセチレン（ｃ）（２．０ｍｍｏｌ，０．７２ｇ）を加えてＴＨＦ（８ｍｌ）に溶解させた。０℃に冷やしてリチウムヘキサメチルジシラジド（ＬｉＨＭＤＳ）（１．０Ｍテトラヒドロフラン溶液，８．０ｍｍｏｌ，８．０ｍｌ）を加えた後、室温まで昇温して１８時間撹拌する。塩化アンモニウム水溶液を加えてクエンチした後、酢酸エチルで３回抽出する。減圧濃縮を行い、中間体の粗生成物を得る。その粗生成物を窒素置換した反応器に加えてＴＨＦ（５ｍｌ）で溶解させる。０℃に冷やして、ＴＢＡＦ（１．０Ｍテトラヒドロフラン溶液，９．６ｍｍｏｌ，９．６ｍｌ）を加えた後、室温で１５時間撹拌した。撹拌後、水を加えてクエンチを行った後、酢酸エチルで３回抽出した。硫酸ナトリウムで乾燥させ、ろ紙でろ過した後、濃縮、減圧乾燥した。シリカゲルカラムクロマトグラフィー（展開溶媒：酢酸エチル／ヘキサン:３０，Ｒｆ＝０．２６）で精製し、中間化合物（ｆ）を白色固体として得た（収率６８％）。 The perfluorodiphenylacetylene (c) (2.0 mmol, 0.72 g) obtained in the above synthesis was added to the reactor substituted with nitrogen and dissolved in THF (8 ml). After cooling to 0 ° C. and adding lithium hexamethyldisilazide (LiHMDS) (1.0 M tetrahydrofuran solution, 8.0 mmol, 8.0 ml), the mixture is warmed to room temperature and stirred for 18 hours. After quenching by adding aqueous ammonium chloride, extract three times with ethyl acetate. Concentration under reduced pressure yields an intermediate crude product. The crude product is added to a nitrogen purged reactor and dissolved with THF (5 ml). After cooling to 0 ° C. and adding TBAF (1.0 M tetrahydrofuran solution, 9.6 mmol, 9.6 ml), the mixture was stirred at room temperature for 15 hours. After stirring, water was added for quenching, followed by extraction with ethyl acetate three times. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. Purification by silica gel column chromatography (developing solvent: ethyl acetate / hexane: 30, Rf = 0.26) gave the intermediate compound (f) as a white solid (yield 68%).
中間化合物（ｆ）の１Ｈ−ＮＭＲおよび１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：４．２４（ｓ，４Ｈ，ＮＨ２）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１６２．４６〜−１６２．６４（ｍ，４Ｆ，Ａｒ），−１３８．８９〜−１３９．０４（ｍ，４Ｆ，Ａｒ）
これらの分析データは、前記化学反応式（XI）で示される中間化合物（ｆ）の構造であることを支持する。The 1 H-NMR and 19 F-NMR spectral data of the intermediate compound (f) are shown below.
1 H-NMR (300 MHz, CDCl 3 ) δ: 4.24 (s, 4H, NH 2 )
19 F-NMR (282 MHz, CDCl 3 ) δ: -162.46 to -162.64 (m, 4F, Ar), -138.89 to -139.04 (m, 4F, Ar)
These analytical data support the structure of the intermediate compound (f) represented by the chemical reaction formula (XI).
中間化合物（ｆ）より、さらに中間化合物となるビス（２，３，５，６−テトラフルオロ−４−ヨードフェニル）アセチレン（ｇ）を得る化学反応式（XII）を以下に示す。 A chemical reaction formula (XII) for obtaining bis (2,3,5,6-tetrafluoro-4-iodophenyl) acetylene (g) as an intermediate compound from the intermediate compound (f) is shown below.
窒素で置換した反応器に、前記合成で得られたビス（２，３，５，６−テトラフルオロ−４−アミノフェニル）アセチレン（ｆ）（２．０ｍｍｏｌ，０．７０ｇ）、Ｉ２（１２ｍｍｏｌ，３．０ｇ）を加えてＣＨ３ＣＮ（７．０ｍｌ）で溶解させた。３０℃で亜硝酸ｔ−ブチル（ｔ−ＢｕＯＮＯ）（８．０ｍｍｏｌ，０．９５ｍｌ）を滴下し、４時間撹拌した。撹拌終了後、Ｎａ２ＳＯ３水溶液で１回洗浄した後、ジクロメタンで３回抽出した。硫酸ナトリウムで乾燥させ、ろ紙でろ過した後、濃縮、減圧乾燥した。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン，Ｒｆ＝０．３０）で精製した。次いでヘキサンによる再結晶精製を行い、中間化合物（ｇ）を白色固体として得た（収率７０％）。Into a reactor substituted with nitrogen, bis (2,3,5,6-tetrafluoro-4-aminophenyl) acetylene (f) (2.0 mmol, 0.70 g) obtained in the above synthesis, I 2 (12 mmol) , 3.0 g) was added and dissolved with CH 3 CN (7.0 ml). At 30 ° C., t-butyl nitrite (t-BuONO) (8.0 mmol, 0.95 ml) was added dropwise and stirred for 4 hours. After completion of stirring, the mixture was washed once with an aqueous Na 2 SO 3 solution and then extracted three times with dichloromethane. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. The product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.30). Subsequently, recrystallization purification with hexane was performed to obtain the intermediate compound (g) as a white solid (yield 70%).
中間化合物（ｇ）の１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１３３．８０〜−１３３．９９（ｍ，４Ｆ，Ａｒ），−１１９．５８〜−１１９．７７（ｍ，４Ｆ，Ａｒ）
これらの分析データは、前記化学反応式（VII）で示される中間化合物（ｇ）の構造であることを支持する。The 19 F-NMR spectrum data of the intermediate compound (g) is shown below.
19 F-NMR (282 MHz, CDCl 3 ) δ: −133.80 to −133.99 (m, 4F, Ar), −119.58 to −119.77 (m, 4F, Ar)
These analytical data support the structure of the intermediate compound (g) represented by the chemical reaction formula (VII).
アセチレン化合物を合成するための中間化合物となる１−（４−トリメチルシリルエチニル−２，３，５，６−テトラフルオロフェニル）−３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタン（ｈ）を得る化学反応式（XIII）を以下に示す。 1- (4-trimethylsilylethynyl-2,3,5,6-tetrafluorophenyl) -3,3,4,4,5,5,6,6,7, which is an intermediate compound for synthesizing the acetylene compound A chemical reaction formula (XIII) for obtaining 7,8,8,8-tridecafluorooctane (h) is shown below.
窒素で置換した反応器に、ジエチルエーテル（２０ｍｌ）で溶解させた２−（トリデカフルオロヘキシル）エチルヨージド（１．２ｍｍｏｌ，０．５７ｇ）を加えて−７８℃に冷却した。そこにt−ＢｕＬｉ（１．５９Ｍ ｎ−ペンタン溶液，１．２ｍｍｏｌ，０．７５ｍｌ）を滴下し、３０分撹拌した。ジエチルエーテル（６．０ｍｌ）で溶解させたトリメチルシリルエチニルペンタフルオロベンゼン（ｂ）（１．０ｍｍｏｌ，０．２６ｇ）を滴下した後、室温まで昇温し１４時間撹拌した。その後、ＮＨ４Ｃｌ水溶液でクエンチを行い、酢酸エチルで３回抽出した。硫酸ナトリウムで乾燥させ、ろ紙でろ過した後、濃縮、減圧乾燥した。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン,Ｒｆ＝０．５３）で精製し、中間化合物（ｈ）を白色固体として得た（収率５９％）。To the reactor purged with nitrogen, 2- (tridecafluorohexyl) ethyl iodide (1.2 mmol, 0.57 g) dissolved in diethyl ether (20 ml) was added and cooled to -78 ° C. T-BuLi (1.59M n-pentane solution, 1.2 mmol, 0.75 ml) was added dropwise thereto and stirred for 30 minutes. Trimethylsilylethynylpentafluorobenzene (b) (1.0 mmol, 0.26 g) dissolved in diethyl ether (6.0 ml) was added dropwise, and the mixture was warmed to room temperature and stirred for 14 hours. Thereafter, quenched with aqueous NH 4 Cl and extracted 3 times with ethyl acetate. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. The product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.53) to obtain the intermediate compound (h) as a white solid (yield 59%).
中間化合物（ｈ）の１Ｈ−ＮＭＲおよび１９Ｆ−ＮＭＲスペクトルデータを以下に示す。を以下に示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：２．３０−２．４７（ｍ，２Ｈ，alkyl)，δ：３．０６（ｔ，Ｊ＝７．６８Ｈｚ，２Ｈ，alkyl）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１４５．０６〜−１４５．２４（ｍ，２Ｆ，Ａｒ），−１３７．０７〜−１３７．２５（ｍ，２Ｆ，Ａｒ），−１２６．６１〜−１２６．７８（ｍ，２Ｆ，alkyl），−１２４．０４（ｓ，２Ｆ，alkyl），−１２３．４４（ｓ，２Ｆ，alkyl），−１２２．４８（ｓ，２Ｆ，alkyl），−１１５．６５〜−１１５．９０（ｍ，２Ｆ，alkyl），−８１．３４（ｔ，Ｊ＝９．５９Ｈｚ，３Ｆ，alkyl）
これらの分析データは、前記化学反応式（VIII）で示される中間化合物（ｈ）の構造であることを支持する。 1 H-NMR and 19 F-NMR spectral data of the intermediate compound (h) are shown below. Is shown below.
1 H-NMR (300 MHz, CDCl 3 ) δ: 2.30-2.47 (m, 2H, alkyl), δ: 3.06 (t, J = 7.68 Hz, 2H, alkyl)
19 F-NMR (282 MHz, CDCl 3 ) δ: −145.06 to −145.24 (m, 2F, Ar), −137.007 to −137.25 (m, 2F, Ar), −126.61 ~ -126.78 (m, 2F, alkyl), -124.04 (s, 2F, alkyl), -123.44 (s, 2F, alkyl), -122.48 (s, 2F, alkyl),- 115.65 to −115.90 (m, 2F, alkyl), −81.34 (t, J = 9.59 Hz, 3F, alkyl)
These analytical data support the structure of the intermediate compound (h) represented by the chemical reaction formula (VIII).
中間化合物（ｈ）より、さらに中間化合物となる１−（２，３，５，６−テトラフルオロフェニル−４−エチニル）−３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタン（ｉ）を得る化学反応式（VI）を以下に示す。 From the intermediate compound (h), 1- (2,3,5,6-tetrafluorophenyl-4-ethynyl) -3,3,4,4,5,5,6,6,7, which is an intermediate compound. The chemical reaction formula (VI) for obtaining 7,8,8,8-tridecafluorooctane (i) is shown below.
ナスフラスコに１−（４−トリメチルシリルエチニル−２，３，５，６−テトラフルオロフェニル）−３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタン（ｈ）（１．３２ｍｍｏｌ，０．７８ｇ）を加えてＣＨ２Ｃｌ２（４．０ｍｌ）、メタノール（４．０ｍｌ）を加えて溶解させる。Ｋ２ＣＯ３（１３．２ｍｍｏｌ，１．８２ｇ）を加え懸濁状態で、０℃で３０分撹拌した。水を加えてＫ２ＣＯ３を溶かし、ＣＨ２Ｃｌ２で３回抽出した。硫酸ナトリウムで乾燥させ、ろ紙でろ過した後、濃縮、減圧乾燥する。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン，Ｒｆ＝０．４２）で精製し、中間化合物（ｉ）を白色固体として得た（収率９２％）。In an eggplant flask, 1- (4-trimethylsilylethynyl-2,3,5,6-tetrafluorophenyl) -3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluorooctane (h) (1.32 mmol, 0.78 g) is added, and CH 2 Cl 2 (4.0 ml) and methanol (4.0 ml) are added and dissolved. K 2 CO 3 (13.2 mmol, 1.82 g) was added, and the mixture was stirred for 30 minutes at 0 ° C. in a suspended state. Water was added to dissolve the K 2 CO 3 and extracted 3 times with CH 2 Cl 2 . Dry with sodium sulfate, filter with filter paper, concentrate and dry under reduced pressure. Purification by silica gel column chromatography (developing solvent: hexane, Rf = 0.42) gave intermediate compound (i) as a white solid (yield 92%).
中間化合物（ｉ）の１Ｈ−ＮＭＲおよび１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：２．３１−２．４８（ｍ，２Ｈ，alkyl），３．０８（ｔ，Ｊ＝８．０４Ｈｚ，２Ｈ，alkyl），３．６３（ｓ，１Ｈ，alkyne）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１４４．４４〜−１４４．６２（ｍ，２Ｆ，Ａｒ），−１３６．９３〜−１３７．１１（ｍ，２Ｆ，Ａｒ），−１２６．５９〜−１２６．７５（ｍ，２Ｆ，alkyl），−１２３．９９（ｓ，２Ｆ，alkyl），−１２３．４０（ｓ，２Ｆ，alkyl），−１２２．４２（ｓ，２Ｆ，alkyl），−１１５．６３〜−１１５．８４（ｍ，２Ｆ，alkyl），−８１．２８（ｔ，Ｊ＝１１．００Ｈｚ，３Ｆ，alkyl）
これらの分析データは、前記化学反応式（XIV）で示される中間化合物（ｉ）の構造であることを支持する。The 1 H-NMR and 19 F-NMR spectrum data of the intermediate compound (i) are shown below.
1 H-NMR (300 MHz, CDCl 3 ) δ: 2.31-2.48 (m, 2H, alkyl), 3.08 (t, J = 8.04 Hz, 2H, alkyl), 3.63 (s, 1H, alkyne)
19 F-NMR (282 MHz, CDCl 3 ) δ: −144.44 to −144.62 (m, 2F, Ar), −136.93 to −137.11 (m, 2F, Ar), −126.59 ~ -126.75 (m, 2F, alkyl), -123.99 (s, 2F, alkyl), -123.40 (s, 2F, alkyl), -122.42 (s, 2F, alkyl),- 115.63 to −115.84 (m, 2F, alkyl), −81.28 (t, J = 11.00 Hz, 3F, alkyl)
These analytical data support the structure of the intermediate compound (i) represented by the chemical reaction formula (XIV).
得られた中間化合物（ｉ）および（ｇ）を用いて４，４’−ビス［２，３，５，６−テトラフルオロ−４−（２−パーフルオロヘキシルエチル）フェニルエチニル）−パーフルオロジフェニルアセチレン（１５）を得る化学反応式（XV）を以下に示す。 Using the obtained intermediate compounds (i) and (g), 4,4′-bis [2,3,5,6-tetrafluoro-4- (2-perfluorohexylethyl) phenylethynyl) -perfluorodiphenyl The chemical reaction formula (XV) for obtaining acetylene (15) is shown below.
窒素で置換した反応器に、末端アセチレンである（ｉ）（０．９ｍｍｏｌ，０．４７ｇ）、ジヨード体である（ｇ）（０．３０ｍｍｏｌ，０．１７ｇ）、Ｐｄ（ＰＰｈ３）４（０．０３ｍｍｏｌ，３５ｍｇ）、ＣｕＩ（０．０３ｍｍｏｌ，６ｍｇ）を加えてトルエン（８ｍｌ）、ジイソプロピルアミン（０．８ｍｌ）に溶解させて８０℃で１８時間撹拌した。撹拌後、飽和塩化アンモニウム水溶液でクエンチした後、ジクロロメタンで３回抽出した。懸濁状態の有機層を濃縮、減圧乾燥した。トルエンを溶媒に用いて再結晶精製することにより、白色固体の目的物（１５）を得た（収率７６％，融点２３９−２４２℃）。In a reactor substituted with nitrogen, terminal acetylene (i) (0.9 mmol, 0.47 g), diiodine (g) (0.30 mmol, 0.17 g), Pd (PPh 3 ) 4 (0 0.03 mmol, 35 mg) and CuI (0.03 mmol, 6 mg) were added and dissolved in toluene (8 ml) and diisopropylamine (0.8 ml) and stirred at 80 ° C. for 18 hours. After stirring, the reaction mixture was quenched with a saturated aqueous ammonium chloride solution and extracted three times with dichloromethane. The suspended organic layer was concentrated and dried under reduced pressure. Recrystallization and purification using toluene as a solvent gave the target product (15) as a white solid (yield 76%, melting point 239-242 ° C.).
目的物（１５）の１Ｈ−ＮＭＲ、１９Ｆ−ＮＭＲおよびＨＲＭＳの分析結果を以下に示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：１．２０〜１．２２（ｍ，２Ｈ，alkyl），２．６６（ｔ，Ｊ＝７．５０Ｈｚ，２Ｈ，alkyl）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，Ｃ６Ｄ５ＣＤ３，１１０℃）δ：−１４４．２３〜−１４４．３５（ｍ，４Ｆ，Ａｒ），−１３５．８０〜−１３６．２２（ｍ，１６Ｆ，Ａｒ），−１２６．１２〜−１２６．１７（ｍ，４Ｆ，alkyl），−１２３．２６〜−１２３．３０（ｍ,４Ｆ，alkyl）,−１２２．７５〜−１２２．８９（ｍ，４Ｆ，alkyl）,−１２１．８１〜−１２１．８４（ｍ，４Ｆ，alkyl)，−１１４．７０(ｓ,４Ｆ,alkyl),−８１．５１〜−８１．６２（ｍ，６Ｆ，alkyl)
ＨＲＭＳ（ＭＡＬＤＩ） 実測値（Ｍ+）：１３５７．９９３２ （計算値：１３５７．９９６１（Ｃ４６Ｈ８Ｆ４２））
これらの分析データは、前記化学反応式（XV）で示されるアセチレン化合物（１５）の構造であることを支持する。The analysis results of 1 H-NMR, 19 F-NMR and HRMS of the target product (15) are shown below.
1 H-NMR (300 MHz, CDCl 3 ) δ: 1.20 to 1.22 (m, 2H, alkyl), 2.66 (t, J = 7.50 Hz, 2H, alkyl)
19 F-NMR (282 MHz, C 6 D 5 CD 3 , 110 ° C.) δ: −144.23 to −144.35 (m, 4F, Ar), −135.80 to −136.22 (m, 16F, Ar), −126.12 to −126.17 (m, 4F, alkyl), −123.26 to −123.30 (m, 4F, alkyl), −122.75 to −122.89 (m, 4F) , Alkyl), −121.81 to −121.84 (m, 4F, alkyl), −114.70 (s, 4F, alkyl), −81.51 to −81.62 (m, 6F, alkyl)
HRMS (MALDI) Found (M +): 1357.9932 (calc: 1357.9961 (C 46 H 8 F 42))
These analytical data support the structure of the acetylene compound (15) represented by the chemical reaction formula (XV).
（実施例５）
アセチレン化合物を合成するための中間化合物となるトリメチルシリルエチニルペンタフルオロベンゼン（ｂ）を得る化学反応式（Ｖ）を以下に示す。(Example 5)
A chemical reaction formula (V) for obtaining trimethylsilylethynylpentafluorobenzene (b) as an intermediate compound for synthesizing the acetylene compound is shown below.
窒素で置換した反応器に、Ｐｄ（ＰＰｈ３）４（０．２５ｍｍｏｌ，０．２９ｇ）、ＣｕＩ（０．２５ｍｍｏｌ，４８ｍｇ）、ペンタフルオロブロモベンゼン（５．０ｍｍｏｌ，１．２３ｇ）を加え、トルエン（２０ｍｌ）、ジイソプロピルアミン（２ｍｌ）に溶解させた。トリメチルシリルアセチレン（５．５ｍｍｏｌ，０．７７ｍｌ）を加え、８０℃で１５時間撹拌した。飽和塩化アンモニウム水溶液で３回洗浄した後、酢酸エチルで３回抽出する。得られた有機層を飽和食塩水で洗浄し、硫酸ナトリウムで乾燥させ、ろ紙ろ過した後、濃縮、減圧乾燥した。その後、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン，Ｒｆ＝０．５０）で精製した。トリメチルシリルアセチレンのジイン体が８％混入している無色の液体を得た（収率８０％）。To a reactor purged with nitrogen, Pd (PPh 3 ) 4 (0.25 mmol, 0.29 g), CuI (0.25 mmol, 48 mg), pentafluorobromobenzene (5.0 mmol, 1.23 g) were added, and toluene was added. (20 ml) was dissolved in diisopropylamine (2 ml). Trimethylsilylacetylene (5.5 mmol, 0.77 ml) was added, and the mixture was stirred at 80 ° C. for 15 hours. Wash 3 times with saturated aqueous ammonium chloride and then extract 3 times with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. Thereafter, the product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.50). A colorless liquid in which 8% of a triynesilylacetylene diyne was mixed was obtained (yield 80%).
無色の液体の１Ｈ−ＮＭＲおよび１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：０．３０（ｓ，９Ｈ，ＴＭＳ）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１６２．２９〜−１６２．４８（ｍ，２Ｆ，Ａｒ），−１５２．８６（ｔ，Ｊ＝２０．６Ｈｚ，１Ｆ,Ａｒ），−１３６．２４〜−１３６．３６（ｍ，２Ｆ，Ａｒ）
これらの分析データは、前記化学反応式（Ｖ）で示される中間化合物（ｂ）の構造であることを支持する。 1 H-NMR and 19 F-NMR spectrum data of the colorless liquid are shown below.
1 H-NMR (300 MHz, CDCl 3 ) δ: 0.30 (s, 9H, TMS)
19 F-NMR (282 MHz, CDCl 3 ) δ: −162.29 to −162.48 (m, 2F, Ar), −152.86 (t, J = 20.6 Hz, 1F, Ar), −136. 24 to -136.36 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (b) represented by the chemical reaction formula (V).
中間化合物（ｂ）より、さらに中間化合物となる１−トリメチルシリルエチニル−２，３，５，６−テトラフルオロ−４−ブチルベンゼン（ｊ）を得る化学反応式（XVI）を以下に示す。式中、Ｂｕはブチル基の略である。 A chemical reaction formula (XVI) for obtaining 1-trimethylsilylethynyl-2,3,5,6-tetrafluoro-4-butylbenzene (j) as an intermediate compound from the intermediate compound (b) is shown below. In the formula, Bu is an abbreviation for butyl group.
窒素で置換した反応器に、ＴＨＦに溶解させたトリメチルシリルエチニルペンタフルオロベンゼン（ｂ）（３．０ｍｍｏｌ）を加えて０℃に冷やし、ｎ−ブチルマグネシウムクロライド（ｎ−ＢｕＭｇＣｌ）（２．０Ｍテトラヒドロフラン溶液，４．５ｍｌ，９ｍｍｏｌ）を滴下した。室温に戻して１５時間撹拌した。撹拌終了後、０℃に冷やして塩化アンモニウム水溶液を加えてクエンチを行い、酢酸エチルで３回洗浄した。得られた有機層を飽和食塩水で洗浄し、硫酸ナトリウムで乾燥させ、ろ紙でろ過した後、濃縮、減圧乾燥した。その後、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン，Ｒｆ＝０．５０）で精製した。末端アセチレン体が３％、トリメチルシリルアセチレンのジイン体が８％混入している無色の液体を得た（収率８３％）。 Trimethylsilylethynylpentafluorobenzene (b) (3.0 mmol) dissolved in THF was added to the reactor substituted with nitrogen, and cooled to 0 ° C., and n-butylmagnesium chloride (n-BuMgCl) (2.0 M tetrahydrofuran solution). , 4.5 ml, 9 mmol) was added dropwise. It returned to room temperature and stirred for 15 hours. After completion of stirring, the mixture was cooled to 0 ° C., quenched by adding an aqueous ammonium chloride solution, and washed three times with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. Thereafter, the product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.50). A colorless liquid containing 3% of terminal acetylene and 8% of diyne of trimethylsilylacetylene was obtained (yield 83%).
無色の液体の１Ｈ−ＮＭＲおよび１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）δ：０．２７（ｓ，９Ｈ，ＴＭＳ）,０．９３（ｔ，Ｊ＝７．１４Ｈｚ，３Ｈ，alkyl），１．２９〜１．４２（ｍ，２Ｈ，alkyl), １．５１〜１．６２（ｍ，２Ｈ，alkyl），２．７２（ｔ，Ｊ＝７．５０Ｈｚ，２Ｈ，alkyl）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１４５．５０〜−１４５．７２（ｍ，２Ｆ，Ａｒ），−１３８．２５〜−１３８．４８（ｍ，２Ｆ，Ａｒ)
これらの分析データは、前記化学反応式（XVI）で示される中間化合物（Ｊ）の構造であることを支持する。 1 H-NMR and 19 F-NMR spectrum data of the colorless liquid are shown below.
1 H-NMR (300 MHz, CDCl 3 ) δ: 0.27 (s, 9H, TMS), 0.93 (t, J = 7.14 Hz, 3H, alkyl), 1.29 to 1.42 (m, 2H, alkyl), 1.51-1.62 (m, 2H, alkyl), 2.72 (t, J = 7.50 Hz, 2H, alkyl)
19 F-NMR (282 MHz, CDCl 3 ) δ: −145.50 to −145.72 (m, 2F, Ar), −138.25 to −138.48 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (J) represented by the chemical reaction formula (XVI).
中間化合物（ｂ）より、さらに中間化合物となるパーフルオロジフェニルアセチレン（ｃ）を得る化学反応式（VI）を以下に示す。 A chemical reaction formula (VI) for obtaining perfluorodiphenylacetylene (c) as an intermediate compound from the intermediate compound (b) is shown below.
窒素で置換した反応器に、Ｐｄ（ＰＰｈ３）４（０．１０ｍｍｏｌ，０．１２ｇ）、ＣｕＣｌ（２．４ｍｍｏｌ，０．２４ｇ）、ペンタフルオロヨードベンゼン（２．０ｍｍｏｌ，０．４９ｇ）を加え、乾燥ＤＭＦ（４ｍｌ）、ジイソプロピルアミン（０．４０ｍｌ）に溶解させる。前記合成で得られたトリメチルシリルエチニルペンタフルオロベンゼン（ｂ）（２．４ｍｍｏｌ，０．６３ｍｇ）を加え、８０℃で１５時間撹拌した。飽和塩化アンモニウム水溶液で３回洗浄した後、酢酸エチルで３回抽出した。硫酸ナトリウムで乾燥させ、ろ紙でろ過した後、濃縮、減圧乾燥した。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン，Ｒｆ＝０．４３）で精製した。次いでヘキサンによる再結晶精製を行い、中間化合物（ｃ）を白色固体として得た（収率４９％）。Pd (PPh 3 ) 4 (0.10 mmol, 0.12 g), CuCl (2.4 mmol, 0.24 g), pentafluoroiodobenzene (2.0 mmol, 0.49 g) were added to the reactor substituted with nitrogen. Dissolve in dry DMF (4 ml), diisopropylamine (0.40 ml). Trimethylsilylethynylpentafluorobenzene (b) (2.4 mmol, 0.63 mg) obtained in the above synthesis was added and stirred at 80 ° C. for 15 hours. The extract was washed 3 times with a saturated aqueous ammonium chloride solution and then extracted 3 times with ethyl acetate. The extract was dried over sodium sulfate, filtered through filter paper, concentrated and dried under reduced pressure. The product was purified by silica gel column chromatography (developing solvent: hexane, Rf = 0.43). Subsequently, recrystallization purification with hexane was performed to obtain the intermediate compound (c) as a white solid (yield 49%).
中間化合物（ｃ）の１９Ｆ−ＮＭＲスペクトルデータを以下に示す。
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，ＣＤＣｌ３）δ：−１６１．０８〜−１６１．２８（ｍ，２Ｆ，Ａｒ），−１４９．８９（ｔ，Ｊ＝２０．６Ｈｚ，２Ｆ，Ａｒ)，−１３４．８４〜−１３４．９４（ｍ，２Ｆ，Ａｒ）
これらの分析データは、前記化学反応式（VI）で示される中間化合物（ｃ）の構造であることを支持する。The 19 F-NMR spectrum data of the intermediate compound (c) is shown below.
19 F-NMR (282 MHz, CDCl 3 ) δ: −161.08 to −161.28 (m, 2F, Ar), −149.89 (t, J = 20.6 Hz, 2F, Ar), −134. 84 to -134.94 (m, 2F, Ar)
These analytical data support the structure of the intermediate compound (c) represented by the chemical reaction formula (VI).
得られた中間化合物（ｊ）および（ｃ）を用いて４，４’−ビス（２，３，５，６−テトラフルオロ−４−ｎ−ブチルフェニルエチニル）−パーフルオロジフェニルアセチレン（１６）を得る化学反応式（XVII）を以下に示す。 Using the obtained intermediate compounds (j) and (c), 4,4′-bis (2,3,5,6-tetrafluoro-4-n-butylphenylethynyl) -perfluorodiphenylacetylene (16) is obtained. The chemical reaction formula (XVII) to be obtained is shown below.
窒素で置換した反応器に、１−トリメチルシリルエチニル−２，３，５，６−テトラフルオロ−４−ブチルベンゼン（ｊ）（１．５ｍｍｏｌ）、パーフルオロジフェニルアセチレン（ｃ）（０．５ｍｍｏｌ，０．１８ｇ）を加えてＴＨＦ(５ｍｌ)に溶解させた。０℃に冷やし、ＴＢＡＦ（１．０Ｍテトラヒドロフラン溶液，０．１０ｍｌ，０．１０ｍｍｏｌ）を滴下して１８時間撹拌した。撹拌後、水でクエンチした後、ジクロロメタンで３回抽出した。懸濁状態の有機層を濃縮、減圧乾燥した。得られた残渣をトルエン溶媒を用いてゲルろ過を行った後、ＴＨＦを溶媒に用いて再結晶精製を行うことにより、目的物（１６）を黄色固体として得た（収率４４％，融点２１５−２１７℃）。 To the reactor substituted with nitrogen, 1-trimethylsilylethynyl-2,3,5,6-tetrafluoro-4-butylbenzene (j) (1.5 mmol), perfluorodiphenylacetylene (c) (0.5 mmol, 0 .18 g) was added and dissolved in THF (5 ml). After cooling to 0 ° C., TBAF (1.0 M tetrahydrofuran solution, 0.10 ml, 0.10 mmol) was added dropwise and stirred for 18 hours. After stirring, the reaction mixture was quenched with water and extracted three times with dichloromethane. The suspended organic layer was concentrated and dried under reduced pressure. The obtained residue was subjected to gel filtration using a toluene solvent, and then recrystallized and purified using THF as a solvent to obtain the target product (16) as a yellow solid (yield 44%, melting point 215). -217 ° C).
目的物（１６）の１Ｈ−ＮＭＲ，１９Ｆ−ＮＭＲ，ＨＲＭＳの分析結果を以下に示す。
１Ｈ−ＮＭＲ（３００ＭＨｚ，Ｃ６Ｄ６，７５℃）δ：０．７８（ｔ，Ｊ＝７．１４Ｈｚ，３Ｈ，alkyl），１．１０〜１．１７（ｍ，２Ｈ，alkyl），１．３２〜１．３７（ｍ，２Ｈ，alkyl），２．４０（ｔ，Ｊ＝７．６８Ｈｚ，２Ｈ，alkyl）
１９Ｆ−ＮＭＲ（２８２ＭＨｚ，Ｃ６Ｄ６，７５℃）δ：−１４４．６０〜−１４４．７９（ｍ，４Ｆ，Ａｒ），−１３７．０８〜−１３７．２６（ｍ，４Ｆ，Ａｒ），−１３５．９２〜−１３６．０９（ｍ，８Ｆ，Ａｒ）
ＨＲＭＳ（ＥＩ） 実測値（Ｍ+）：７７８．１１５８ （計算値：７７８．１１５３（Ｃ３８Ｈ１８Ｆ１６））
これらの分析データは、前記化学反応式（XVII）で示されるアセチレン化合物（１６）の構造であることを支持する。The analysis results of 1 H-NMR, 19 F-NMR, and HRMS of the target product (16) are shown below.
1 H-NMR (300 MHz, C 6 D 6 , 75 ° C.) δ: 0.78 (t, J = 7.14 Hz, 3H, alkyl), 1.10 to 1.17 (m, 2H, alkyl), 1 .32 to 1.37 (m, 2H, alkyl), 2.40 (t, J = 7.68 Hz, 2H, alkyl)
19 F-NMR (282 MHz, C 6 D 6 , 75 ° C.) δ: −144.60 to −144.79 (m, 4F, Ar), −137.008 to −137.26 (m, 4F, Ar) , −135.92 to −136.09 (m, 8F, Ar)
HRMS (EI) Found (M +): 778.1158 (calculated value: 778.1153 (C 38 H 18 F 16 ))
These analytical data support the structure of the acetylene compound (16) represented by the chemical reaction formula (XVII).
（サイクリックボルタンメトリー（ＣＶ）測定）
グラッシーカーボンを作用電極、白金線を補助電極、銀／過塩素酸銀(０．１Ｍアセトニトリル溶液)を参照極として配置した電解槽に、０．１Ｍテトラブチルアンモニウム ヘキサフルオロホスフェート／テトラヒドロフラン溶液１０ｍＬを加え、実施例１〜５のアセチレン化合物を１ｍＭの濃度となるように添加した。この電解槽の各電極に、北斗電工（株）製ポテンショスタット／ガルバノスタットＨＡＢ−１５１を接続し、０．１Ｖ／秒の速度で掃印してサイックリックボルタンメトリー（ＣＶ）測定を行った。フェロセン電極で電位を補正した実施例１〜５で得られたアセチレン化合物（１），（７），（１４），（１５），（１６）の第一還元電位と、代表的なＮ型有機半導体の一つであるフェニルＣ６０酪酸メチル（ＰＣＢＭ）の第一還元電位（Ｏｒｇａｎｉｃ Ｌｅｔｔｅｒｓ，２００７，９巻，４号，５５１―５５４頁参照）を表１に示す。(Cyclic voltammetry (CV) measurement)
Add 10 mL of 0.1 M tetrabutylammonium hexafluorophosphate / tetrahydrofuran solution to an electrolytic cell with glassy carbon as the working electrode, platinum wire as the auxiliary electrode, and silver / silver perchlorate (0.1 M acetonitrile solution) as the reference electrode. The acetylene compounds of Examples 1 to 5 were added to a concentration of 1 mM. A potentiostat / galvanostat HAB-151 manufactured by Hokuto Denko Co., Ltd. was connected to each electrode of this electrolytic cell, and cyclic voltammetry (CV) measurement was performed by sweeping at a speed of 0.1 V / second. First reduction potentials of acetylene compounds (1), (7), (14), (15), and (16) obtained in Examples 1 to 5 with potentials corrected with ferrocene electrodes, and typical N-type organic compounds the first reduction potential of phenyl C 60 butyric acid methyl which is one of semiconductor (PCBM) (Organic Letters, 2007,9 Vol, No. 4, pp. 551-554) are shown in Table 1.
表１の結果から、実施例１〜５で得られた本発明のアセチレン化合物（１），（７），（１４），（１５），（１６）は、Ｎ型有機半導体の性質を有することが分かった。 From the results of Table 1, the acetylene compounds (1), (7), (14), (15) and (16) of the present invention obtained in Examples 1 to 5 have the properties of N-type organic semiconductors. I understood.
本発明のアセチレン化合物は、電界効果トランジスタ、有機エレクトロルミネセンス、プリンタブル回路、有機キャパシタ、および有機太陽電池の有機エレクトロニクスデバイスの半導体材料として有用であり、Ｎ型特性を示す有機半導体として用いられる。 The acetylene compound of the present invention is useful as a semiconductor material for organic electronic devices such as field effect transistors, organic electroluminescence, printable circuits, organic capacitors, and organic solar cells, and is used as an organic semiconductor exhibiting N-type characteristics.
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| JP2002193853A (en) * | 2000-12-19 | 2002-07-10 | Merck Patent Gmbh | Tetracyclic compound with negative dielectric constant anisotropy and liquid crystalline medium |
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