JP6654900B2 - Cycloparaphenylene compound, production method thereof and intermediate compound - Google Patents
Cycloparaphenylene compound, production method thereof and intermediate compound Download PDFInfo
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- JP6654900B2 JP6654900B2 JP2015559088A JP2015559088A JP6654900B2 JP 6654900 B2 JP6654900 B2 JP 6654900B2 JP 2015559088 A JP2015559088 A JP 2015559088A JP 2015559088 A JP2015559088 A JP 2015559088A JP 6654900 B2 JP6654900 B2 JP 6654900B2
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- 150000001875 compounds Chemical class 0.000 title claims description 237
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- -1 salt compounds Chemical class 0.000 claims description 120
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 125000004397 aminosulfonyl group Chemical class NS(=O)(=O)* 0.000 claims description 28
- 125000002252 acyl group Chemical group 0.000 claims description 20
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 18
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000000304 alkynyl group Chemical group 0.000 claims description 15
- 125000004442 acylamino group Chemical group 0.000 claims description 14
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 14
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 14
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 14
- 125000004656 alkyl sulfonylamino group Chemical class 0.000 claims description 14
- 125000005199 aryl carbonyloxy group Chemical group 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 14
- 125000005117 dialkylcarbamoyl group Chemical group 0.000 claims description 14
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 125000000623 heterocyclic group Chemical group 0.000 claims description 14
- 238000007363 ring formation reaction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical group C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 6
- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 6
- 238000007429 general method Methods 0.000 claims 1
- 238000006894 reductive elimination reaction Methods 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 164
- 239000000243 solution Substances 0.000 description 106
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 81
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 78
- 238000005481 NMR spectroscopy Methods 0.000 description 77
- 230000002829 reductive effect Effects 0.000 description 40
- 239000000203 mixture Substances 0.000 description 38
- 239000011734 sodium Substances 0.000 description 38
- 238000003756 stirring Methods 0.000 description 35
- 239000012043 crude product Substances 0.000 description 34
- 239000012044 organic layer Substances 0.000 description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 26
- 239000007787 solid Substances 0.000 description 26
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- 239000000706 filtrate Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 229920006395 saturated elastomer Polymers 0.000 description 18
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 17
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 13
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 8
- 125000006239 protecting group Chemical group 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 8
- 239000012267 brine Substances 0.000 description 7
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 7
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- OOBYFCASWIDCGY-UHFFFAOYSA-N IC1=CC=C(C=C1)C=1C(CC=C(C1)O)=O Chemical compound IC1=CC=C(C=C1)C=1C(CC=C(C1)O)=O OOBYFCASWIDCGY-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005899 aromatization reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 4
- 235000019798 tripotassium phosphate Nutrition 0.000 description 4
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 3
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 3
- MRWWWZLJWNIEEJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-propan-2-yloxy-1,3,2-dioxaborolane Chemical compound CC(C)OB1OC(C)(C)C(C)(C)O1 MRWWWZLJWNIEEJ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 238000010511 deprotection reaction Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(C)(C1=CC(C)(C)C=C(*(C)*C(C)C2(C)C)C=C1)[Al]C(C)C1(C*)C=CC2=CC1 Chemical compound CCC(C)(C1=CC(C)(C)C=C(*(C)*C(C)C2(C)C)C=C1)[Al]C(C)C1(C*)C=CC2=CC1 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005442 molecular electronic Methods 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 1
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 1
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical compound C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000005955 1H-indazolyl group Chemical group 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006032 3-methyl-3-butenyl group Chemical group 0.000 description 1
- ARUBXNBYMCVENE-UHFFFAOYSA-N 4-(4-bromophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(Br)C=C1 ARUBXNBYMCVENE-UHFFFAOYSA-N 0.000 description 1
- WJXIAMCDWSUSEI-UHFFFAOYSA-N 4-(4-iodophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(I)C=C1 WJXIAMCDWSUSEI-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- BUADUHVXMFJVLH-UHFFFAOYSA-N 7-chloro-3-imidazol-1-yl-2H-1,2,4-benzotriazin-1-ium 1-oxide Chemical compound N1[N+](=O)C2=CC(Cl)=CC=C2N=C1N1C=CN=C1 BUADUHVXMFJVLH-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NMCYOQIDPVHCGB-UHFFFAOYSA-N BrC1=CC=C(C=C1)C=1C(CC=C(C=1)O)=O Chemical compound BrC1=CC=C(C=C1)C=1C(CC=C(C=1)O)=O NMCYOQIDPVHCGB-UHFFFAOYSA-N 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound 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 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N CC1CCCC1 Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- DRUOYXQMVSLHAR-UHFFFAOYSA-N CCN1C(C)C1 Chemical compound CCN1C(C)C1 DRUOYXQMVSLHAR-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910008449 SnF 2 Inorganic materials 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- NTIMUJCWXCWLNK-UHFFFAOYSA-N [4-(4-bromophenyl)phenoxy]-tert-butyl-dimethylsilane Chemical group C1=CC(O[Si](C)(C)C(C)(C)C)=CC=C1C1=CC=C(Br)C=C1 NTIMUJCWXCWLNK-UHFFFAOYSA-N 0.000 description 1
- YVFUEIAJZMQFKM-UHFFFAOYSA-N [Li]C1=CC=C(C=C1)C1=CC=C(O[Si](C)(C)C(C)(C)C)C=C1 Chemical group [Li]C1=CC=C(C=C1)C1=CC=C(O[Si](C)(C)C(C)(C)C)C=C1 YVFUEIAJZMQFKM-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 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 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 125000003016 chromanyl group Chemical group O1C(CCC2=CC=CC=C12)* 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001245 hexylamino group Chemical group [H]N([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- 125000006635 hexyloxycarbonylamino group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005932 isopentyloxycarbonyl group Chemical group 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C07C35/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a non-condensed ring
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
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Description
本発明は、置換されていてもよいシクロパラフェニレン化合物およびその製造方法並びに中間体化合物に関する。 The present invention relates to an optionally substituted cycloparaphenylene compound, a method for producing the same, and an intermediate compound.
シクロパラフェニレン化合物は、モレキュラー・エレクトロニクスにおいて注目されている。
フェニレン基が６個以上パラ位で結合したシクロパラフェニレン化合物が知られているが（非特許文献１〜５）、５個のフェニレン基がパラ位で結合したシクロパラフェニレン化合物は報告されていない。Cycloparaphenylene compounds have attracted attention in molecular electronics.
Cycloparaphenylene compounds in which six or more phenylene groups are bonded at the para position are known (
本発明は、置換されていてもよいシクロパラフェニレン化合物の製造方法並びにその製造中間体とその製造方法を提供することを目的とする。 An object of the present invention is to provide a method for producing an optionally substituted cycloparaphenylene compound, an intermediate for producing the same, and a method for producing the same.
さらに本発明は、５個のパラフェニレン基が環状に連結されたシクロパラフェニレン化合物を提供することを目的とする。 Still another object of the present invention is to provide a cycloparaphenylene compound in which five paraphenylene groups are cyclically connected.
本発明者は、大きな歪みを有する５個のフェニレン基がパラ位で1,4-結合したシクロパラフェニレン化合物は、その前駆体として環状のテトラヒドロキシ化合物を還元することで穏和な条件下で高収率で得られることを見出した。
本発明は、以下のシクロパラフェニレン化合物もしくはその中間体の製造方法、シクロパラフェニレン化合物の製造中間体及びパラフェニレン基を５個含むシクロパラフェニレン化合物を提供するものである。
項１． 下記式（II）の化合物から１，３−シクロヘキサジエン環に結合した２，５位のＯＨ基を下記（１）〜（４）：
（１）Ｓｎ（ＩＩ）化合物、
（２）Ｆｅ（ＩＩ）化合物、
（３）Ｃｕ、ＣｕＣｌ、ＣｕＢｒ，Ｍｎ，ＴｉＣｌ３又はＣｒＣｌ３から選ばれる低原子価無機金属塩化合物、
（４）シクロヘキサジエン
のいずれかに記載の還元剤の存在下に還元的に脱離させてパラフェニレン環に導くことを特徴とする下記式（Ｉ）で表される化合物の製造法。The present inventor has found that a cycloparaphenylene compound in which five phenylene groups having large strains are 1,4-bonded at the para position is reduced under mild conditions by reducing a cyclic tetrahydroxy compound as a precursor thereof. It was found that it was obtained in yield.
The present invention provides the following method for producing a cycloparaphenylene compound or an intermediate thereof, an intermediate for producing a cycloparaphenylene compound, and a cycloparaphenylene compound containing five paraphenylene groups.
(1) a Sn (II) compound,
(2) Fe (II) compounds,
(3) a low-valent inorganic metal salt compound selected from Cu, CuCl, CuBr, Mn, TiCl 3 or CrCl 3 ;
(4) A method for producing a compound represented by the following formula (I), wherein the compound is reductively eliminated in the presence of a reducing agent described in any of cyclohexadiene to lead to a paraphenylene ring.
(式中、ｎは２〜５の整数を示す。ｌは１〜５の整数を示す。ｏは１，３，５又は７を示す。ｍは１，３，５又は７を示す。ｌ＋ｍ＋ｎ＋ｏ＝５〜２０の整数を示す。Ｒは水素原子、アルキル、シクロアルキル、アルコキシ、アルケニル、アルキニル、ハロゲン原子、ＯＨ、ＣＮ、ＮＯ２、ＣＯＯＨ、ＮＨ２、アリール、ヘテロシクリル、アラルキル、モノアルキルアミノ、ジアルキルアミノ、アシルアミノ、アシル、アルキルカルボニルオキシ、アリールカルボニルオキシ、アルコキシカルボニル、アルコキシカルボニルアミノ、フルオロアルキル、パーフルオロアルキル、モノアルキルカルバモイル、ジアルキルカルバモイル、モノアルキル置換スルファモイル、ジアルキル置換スルファモイル又はアルキルスルホニルアミノを示す。(In the formula, n represents an integer of 2 to 5, l represents an integer of 1 to 5, o represents 1, 3, 5, or 7. m represents 1, 3, 5, or 7. l + m + n + o = Represents an integer of 5 to 20. R represents a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, halogen atom, OH, CN, NO 2 , COOH, NH 2 , aryl, heterocyclyl, aralkyl, monoalkylamino, dialkyl Amino, acylamino, acyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, alkoxycarbonylamino, fluoroalkyl, perfluoroalkyl, monoalkylcarbamoyl, dialkylcarbamoyl, monoalkyl-substituted sulfamoyl, dialkyl-substituted sulfamoyl or alkylsulfonylamino.
Ａ１及びＡ２は、同一又は異なって、下記式A 1 and A 2 are the same or different and are represented by the following formula:
（Ｒは前記に定義されるとおりである。ｐは０〜３の整数を示す。）で表される２価の基を示す。）
但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。）
項２． 下記式（IIA）の化合物を環化触媒の存在下に環化させて一般式(IIB)の化合物を得る工程、一般式(IIB)の化合物の水酸基の保護基(Pro)を脱保護する工程を含むことを特徴とする一般式(II)で表される化合物の製造方法：(R is as defined above. P represents an integer of 0 to 3.) )
However, when l = n = 2, unless p in A 1 and A 2 are both 0. )
(式中、ｎ１は１〜４の整数、ｎ２は１〜４の整数、ｎ１＋ｎ２＝ｎであり、ｎは２〜５の整数を示す。ｌは１〜５の整数を示す。ｌ＋ｎ＋２ｐ＋２＝５〜２０の整数を示す。Ｘ１、Ｘ２は、一方、あるいは両方がＩ、Ｂｒ、Ｃｌ、ＯＳＯ２Ｒ１（Ｒ１はＦ，アルキル基、パーフルオロアルキル基、Ｒで表される１〜５個、好ましくは１〜３個、より好ましくは１〜２個の置換基で置換されていてもよいフェニル基を示す。）、Sn含有基、Si含有基又はB含有基を示す。(In the formula, n 1 is an integer of 1 to 4, n 2 is an integer of 1 to 4, n 1 + n 2 = n, and n represents an integer of 2 to 5. 1 represents an integer of 1 to 5. L + n + 2p + 2 = an integer of 5 to 20. One or both of X 1 and X 2 are I, Br, Cl, OSO 2 R 1 (R 1 is represented by F, an alkyl group, a perfluoroalkyl group, or R. Represents a phenyl group which may be substituted with 1 to 5, preferably 1 to 3, more preferably 1 to 2 substituents), a Sn-containing group, a Si-containing group or a B-containing group. Show.
Ｒは水素原子、アルキル、シクロアルキル、アルコキシ、アルケニル、アルキニル、ハロゲン原子、ＯＨ、ＣＮ、ＮＯ２、ＣＯＯＨ、ＮＨ２、アリール、ヘテロシクリル、アラルキル、モノアルキルアミノ、ジアルキルアミノ、アシルアミノ、アシル、アルキルカルボニルオキシ、アリールカルボニルオキシ、アルコキシカルボニル、アルコキシカルボニルアミノ、フルオロアルキル、パーフルオロアルキル、モノアルキルカルバモイル、ジアルキルカルバモイル、モノアルキル置換スルファモイル、ジアルキル置換スルファモイル又はアルキルスルホニルアミノを示す。R is a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, halogen atom, OH, CN, NO 2 , COOH, NH 2 , aryl, heterocyclyl, aralkyl, monoalkylamino, dialkylamino, acylamino, acyl, alkylcarbonyl Oxy, arylcarbonyloxy, alkoxycarbonyl, alkoxycarbonylamino, fluoroalkyl, perfluoroalkyl, monoalkylcarbamoyl, dialkylcarbamoyl, monoalkyl-substituted sulfamoyl, dialkyl-substituted sulfamoyl or alkylsulfonylamino.
Ａ１ａ及びＡ２ａは、同一又は異なって、下記式A 1a and A 2a are the same or different and have the following formula:
（Ｒは前記に定義されるとおりである。ｐは０〜３の整数を示す。）で表される２価の基を示す。Ｐｒｏはトリアルキルシリル基、アシル基、ベンジル基、アルコキシメチル基、テトラヒドロピラニル基、テトラヒドロフラニル基からなる群から選ばれる水酸基の保護基を示す。 (R is as defined above. P represents an integer of 0 to 3.) Pro represents a hydroxyl-protecting group selected from the group consisting of trialkylsilyl, acyl, benzyl, alkoxymethyl, tetrahydropyranyl, and tetrahydrofuranyl groups.
Ａ１及びＡ２は、同一又は異なって、下記式A 1 and A 2 are the same or different and are represented by the following formula:
（Ｒは前記に定義されるとおりである。ｐは０〜３の整数を示す。）で表される２価の基を示す。）
但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。）
項３． 下記式（IIC）と下記式（IID）の化合物を環化触媒の存在下に環化させて一般式(IIB)の化合物を得る工程、一般式(IIB)の化合物の水酸基の保護基(Pro)を脱保護する工程を含むことを特徴とする一般式(II)で表される化合物の製造方法：(R is as defined above. P represents an integer of 0 to 3.) )
However, when l = n = 2, unless p in A 1 and A 2 are both 0. )
(式中、ｎ１は１〜４の整数、ｎ２は１〜４の整数、ｎ１＋ｎ２＝ｎ、ｌ１は１〜４の整数、ｌ２は１〜４の整数、ｌ１＋ｌ２＝ｌであり、ｎは２〜５の整数を示し、ｌは２〜５の整数を示す。ｌ＋ｎ＋２ｐ＋２＝６〜２０の整数を示す。Ｘ１、Ｘ２は、一方がＩ、Ｂｒ又はＣｌを示し、他方がSn含有基、Si含有基又はB含有基を示す。Ｒは水素原子、アルキル、シクロアルキル、アルコキシ、アルケニル、アルキニル、ハロゲン原子、ＯＨ、ＣＮ、ＮＯ２、ＣＯＯＨ、ＮＨ２、アリール、ヘテロシクリル、アラルキル、モノアルキルアミノ、ジアルキルアミノ、アシルアミノ、アシル、アルキルカルボニルオキシ、アリールカルボニルオキシ、アルコキシカルボニル、アルコキシカルボニルアミノ、フルオロアルキル、パーフルオロアルキル、モノアルキルカルバモイル、ジアルキルカルバモイル、モノアルキル置換スルファモイル、ジアルキル置換スルファモイル又はアルキルスルホニルアミノを示す。(In the formula, n 1 is an integer of 1 to 4, n 2 is an integer of 1 to 4, n 1 + n 2 = n, l 1 is an integer of 1 to 4, l 2 is an integer of 1 to 4, l 1 + l 2 = 1, n represents an integer of 2 to 5, l represents an integer of 2 to 5, 1 + n + 2p + 2 = an integer of 6 to 20. One of X 1 and X 2 is I, Br or Cl. And the other represents a Sn-containing group, a Si-containing group or a B-containing group, R represents a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, halogen atom, OH, CN, NO 2 , COOH, NH 2 , Aryl, heterocyclyl, aralkyl, monoalkylamino, dialkylamino, acylamino, acyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, alkoxycarbonylamino, fluoroalkyl, perfluoro Represents loalkyl, monoalkylcarbamoyl, dialkylcarbamoyl, monoalkyl-substituted sulfamoyl, dialkyl-substituted sulfamoyl or alkylsulfonylamino.
Ａ１ａ及びＡ２ａは、同一又は異なって、下記式A 1a and A 2a are the same or different and have the following formula:
（Ｒは前記に定義されるとおりである。ｐは０〜３の整数を示す。）で表される２価の基を示す。Ｐｒｏはトリアルキルシリル基、アシル基、ベンジル基、アルコキシメチル基、テトラヒドロピラニル基、テトラヒドロフラニル基からなる群から選ばれる水酸基の保護基を示す。 (R is as defined above. P represents an integer of 0 to 3.) Pro represents a hydroxyl-protecting group selected from the group consisting of trialkylsilyl, acyl, benzyl, alkoxymethyl, tetrahydropyranyl, and tetrahydrofuranyl groups.
Ａ１及びＡ２は、同一又は異なって、下記式A 1 and A 2 are the same or different and are represented by the following formula:
（Ｒは前記に定義されるとおりである。ｐは０〜３の整数を示す。）で表される２価の基を示す。）
但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。）
項４． 環化触媒がPd(0)、Ni(cod)2又はPt(cod)2（codは1,5-シクロオクタジエンである）である、項２又は３に記載の一般式(II)で表される化合物の製造方法。
項５． 下記式（II）で表される化合物：(R is as defined above. P represents an integer of 0 to 3.) )
However, when l = n = 2, unless p in A 1 and A 2 are both 0. )
Item 4. The compound represented by the general formula (II) according to
(式中、ｎは２〜５の整数を示す。ｌは１〜５の整数を示す。ｌ＋ｎ＋２ｐ＋２＝５〜２０の整数を示す。Ｒは水素原子、アルキル、シクロアルキル、アルコキシ、アルケニル、アルキニル、ハロゲン原子、ＯＨ、ＣＮ、ＮＯ２、ＣＯＯＨ、ＮＨ２、アリール、ヘテロシクリル、アラルキル、モノアルキルアミノ、ジアルキルアミノ、アシルアミノ、アシル、アルキルカルボニルオキシ、アリールカルボニルオキシ、アルコキシカルボニル、アルコキシカルボニルアミノ、フルオロアルキル、パーフルオロアルキル、モノアルキルカルバモイル、ジアルキルカルバモイル、モノアルキル置換スルファモイル、ジアルキル置換スルファモイル又はアルキルスルホニルアミノを示す。(In the formula, n represents an integer of 2 to 5. l represents an integer of 1 to 5. l + n + 2p + 2 = an integer of 5 to 20. R represents a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, Halogen atom, OH, CN, NO 2 , COOH, NH 2 , aryl, heterocyclyl, aralkyl, monoalkylamino, dialkylamino, acylamino, acyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, alkoxycarbonylamino, fluoroalkyl, Represents perfluoroalkyl, monoalkylcarbamoyl, dialkylcarbamoyl, monoalkyl-substituted sulfamoyl, dialkyl-substituted sulfamoyl or alkylsulfonylamino.
Ａ１及びＡ２は、同一又は異なって、下記式A 1 and A 2 are the same or different and are represented by the following formula:
（Ｒは前記に定義されるとおりである。ｐは０〜３の整数を示す。）で表される２価の基を示す。）
但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。）
項６． 下記式（IIB）で表される化合物：(R is as defined above. P represents an integer of 0 to 3.) )
However, when l = n = 2, unless p in A 1 and A 2 are both 0. )
(式中、ｎは１〜５の整数を示す。ｌは１〜５の整数を示す。Ｒは水素原子、アルキル、シクロアルキル、アルコキシ、アルケニル、アルキニル、ハロゲン原子、ＯＨ、ＣＮ、ＮＯ２、ＣＯＯＨ、ＮＨ２、アリール、ヘテロシクリル、アラルキル、モノアルキルアミノ、ジアルキルアミノ、アシルアミノ、アシル、アルキルカルボニルオキシ、アリールカルボニルオキシ、アルコキシカルボニル、アルコキシカルボニルアミノ、フルオロアルキル、パーフルオロアルキル、モノアルキルカルバモイル、ジアルキルカルバモイル、モノアルキル置換スルファモイル、ジアルキル置換スルファモイル又はアルキルスルホニルアミノを示す。(In the formula, n represents an integer of 1 to 5. l represents an integer of 1 to 5. R represents a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, halogen atom, OH, CN, NO 2 , COOH, NH 2 , aryl, heterocyclyl, aralkyl, monoalkylamino, dialkylamino, acylamino, acyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, alkoxycarbonylamino, fluoroalkyl, perfluoroalkyl, monoalkylcarbamoyl, dialkylcarbamoyl , Monoalkyl-substituted sulfamoyl, dialkyl-substituted sulfamoyl or alkylsulfonylamino.
Ａ１ａ及びＡ２ａは、同一又は異なって、下記式A 1a and A 2a are the same or different and have the following formula:
（Ｒは前記に定義されるとおりである。ｐは０〜３の整数を示す。）で表される２価の基を示す。Ｐｒｏはトリアルキルシリル基、アシル基、ベンジル基、アルコキシメチル基、テトラヒドロピラニル基、テトラヒドロフラニル基からなる群から選ばれる水酸基の保護基を示す。 (R is as defined above. P represents an integer of 0 to 3.) Pro represents a hydroxyl-protecting group selected from the group consisting of trialkylsilyl, acyl, benzyl, alkoxymethyl, tetrahydropyranyl, and tetrahydrofuranyl groups.
但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。）
項７． 下記式（Ｉ‘）However, when l = n = 2, unless p in A 1 and A 2 are both 0. )
（式中、Ｒは水素原子、アルキル、シクロアルキル、アルコキシ、アルケニル、アルキニル、ハロゲン原子、ＯＨ、ＣＮ、ＮＯ２、ＣＯＯＨ、ＮＨ２、アリール、ヘテロシクリル、アラルキル、モノアルキルアミノ、ジアルキルアミノ、アシルアミノ、アシル、アルキルカルボニルオキシ、アリールカルボニルオキシ、アルコキシカルボニル、アルコキシカルボニルアミノ、フルオロアルキル、パーフルオロアルキル、モノアルキルカルバモイル、ジアルキルカルバモイル、モノアルキル置換スルファモイル、ジアルキル置換スルファモイル又はアルキルスルホニルアミノを示す。）
で表される環状パラフェニレン化合物。(Wherein R is a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, halogen atom, OH, CN, NO 2 , COOH, NH 2 , aryl, heterocyclyl, aralkyl, monoalkylamino, dialkylamino, acylamino, Acyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, alkoxycarbonylamino, fluoroalkyl, perfluoroalkyl, monoalkylcarbamoyl, dialkylcarbamoyl, monoalkyl-substituted sulfamoyl, dialkyl-substituted sulfamoyl or alkylsulfonylamino are shown.)
A cyclic paraphenylene compound represented by the formula:
本発明によれば、1,4-フェニレン基が環状に５〜２０個結合したシクロパラフェニレン化合物及びその製造中間体を得ることができる。特に1,4-フェニレン基が環状に５個結合したシクロパラフェニレン化合物（[5]CPP）は、大きなひずみエネルギーを有し(図４)、ＨＯＭＯ−ＬＵＭＯギャップが狭いことから(図３)、カーボンナノチューブ、Ｃ６０フラーレンと類似の電子状態を有し、優れた導電性を有することが期待され、モレキュラー・エレクトロニクスにおいて有用である。 According to the present invention, it is possible to obtain a cycloparaphenylene compound in which 5 to 20 1,4-phenylene groups are cyclically bonded, and a production intermediate thereof. In particular, a cycloparaphenylene compound ([5] CPP) in which five 1,4-phenylene groups are cyclically bonded has a large strain energy (FIG. 4) and a narrow HOMO-LUMO gap (FIG. 3). It has a similar electronic state to carbon nanotubes and C60 fullerene, and is expected to have excellent conductivity, and is useful in molecular electronics.
本発明の製造法は、穏和な条件で高収率で進行するため工業的に有利である。 The production method of the present invention is industrially advantageous because it proceeds at a high yield under mild conditions.
なお、式(II)の化合物のOH基がOCH3基であると還元的芳香族化反応は進行せず、OH基である中間体(II)は重要な化合物である。When the OH group of the compound of the formula (II) is an OCH 3 group, the reductive aromatization reaction does not proceed, and the intermediate (II), which is the OH group, is an important compound.
シクロパラフェニレン化合物は、５〜２０個の置換されていてもよいパラフェニレン基が1,4-結合で環状に結合した分子である。歪んだ共役構造を持ち、カーボンナノチューブの最小構成単位であることから、その合成や物性は大変興味が持たれている。本発明者は、穏和な条件下でシクロパラフェニレンを製造できる一般的な合成法を開発した。 A cycloparaphenylene compound is a molecule in which 5 to 20 optionally substituted paraphenylene groups are cyclically linked by a 1,4-bond. Since it has a distorted conjugated structure and is the smallest constituent unit of carbon nanotubes, its synthesis and physical properties are of great interest. The present inventors have developed a general synthetic method that can produce cycloparaphenylene under mild conditions.
５個の置換されていてもよいパラフェニレン基が1,4-結合で環状に結合した化合物は、本発明で初めて製造されたものである。 A compound in which five optionally substituted paraphenylene groups are cyclically linked by a 1,4-bond has been produced for the first time in the present invention.
本発明の化合物(I)は、還元剤を用いて２つの水酸基を1,3-シクロヘキサジエン環の2,5-位に有する原料化合物(II)（ｎ＝１）のシクロヘキサジエン環をベンゼン環に還元することにより製造できる。還元剤としては、
（１）Ｓｎ（ＩＩ）化合物、例えばＳｎＦ２、ＳｎＣｌ２、ＳｎＢｒ２，ＳｎＩ２、Ｓｎ（ＣＨ３ＣＯＣＨＣＯＣＨ３）２、Ｓｎ（ＮＯ３）２、Ｓｎ（ＯＨ）２、ＳｎＳＯ４、Ｓｎ（ＣＨ３ＣＯＯ）２、
（２）Ｆｅ（ＩＩ）化合物、例えばＦｅＣｌ2 、ＦｅＳＯ4 、
（３）Ｃｕ、ＣｕＣｌ、ＣｕＢｒ，Ｍｎ，ＴｉＣｌ３又はＣｒＣｌ３から選ばれる低原子価無機金属塩化合物、
（４）シクロヘキサジエンが挙げられる。The compound (I) of the present invention is obtained by converting a cyclohexadiene ring of a starting compound (II) (n = 1) having two hydroxyl groups at the 2,5-position of a 1,3-cyclohexadiene ring with a benzene ring using a reducing agent. It can be produced by reducing to As a reducing agent,
(1) Sn (II) compounds, for example, SnF 2 , SnCl 2 , SnBr 2 , SnI 2 , Sn (CH 3 COCHCOCH 3 ) 2 , Sn (NO 3 ) 2 , Sn (OH) 2 , SnSO 4 , Sn (CH) 3 COO) 2 ,
(2) Fe (II) compounds such as FeCl 2 , FeSO 4 ,
(3) a low-valent inorganic metal salt compound selected from Cu, CuCl, CuBr, Mn, TiCl 3 or CrCl 3 ;
(4) Cyclohexadiene.
フェニレン基の置換基（R）としては、アルキル、シクロアルキル、アルコキシ、アルケニル、アルキニル、ハロゲン原子、ＯＨ、ＣＮ、ＮＯ２、ＣＯＯＨ、ＮＨ２、アリール、ヘテロシクリル、アラルキル、モノアルキルアミノ、ジアルキルアミノ、アシルアミノ、アシル、アルキルカルボニルオキシ、アリールカルボニルオキシ、アルコキシカルボニル、アルコキシカルボニルアミノ、フルオロアルキル、パーフルオロアルキル、モノアルキルカルバモイル、ジアルキルカルバモイル、モノアルキル置換スルファモイル、ジアルキル置換スルファモイル、アルキルスルホニルアミノが挙げられ、１つのフェニレン環に１〜４個、好ましくは１〜３個、より好ましくは１〜２個の置換基を有し得る。Examples of the substituent (R) for the phenylene group include alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, halogen atom, OH, CN, NO 2 , COOH, NH 2 , aryl, heterocyclyl, aralkyl, monoalkylamino, dialkylamino, Acylamino, acyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, alkoxycarbonylamino, fluoroalkyl, perfluoroalkyl, monoalkylcarbamoyl, dialkylcarbamoyl, monoalkyl-substituted sulfamoyl, dialkyl-substituted sulfamoyl, and alkylsulfonylamino; One phenylene ring may have 1-4, preferably 1-3, more preferably 1-2 substituents.
アルキルとしては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、tert−ブチル、ｎ−ペンチル、イソペンチル、ヘキシルなどの直鎖状又は分枝鎖状のＣ１−１８アルキル、好ましくはＣ１−6アルキル、より好ましくはＣ１−４アルキルが挙げられる。As the alkyl, a linear or branched C 1-18 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and hexyl, preferably C 1-6 alkyl, more preferably C 1-4 alkyl.
シクロアルキルとしては、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル及びシクロヘプチルなどのＣ３−１０シクロアルキル、好ましくはＣ３−6シクロアルキルが挙げられる。Cycloalkyl includes C 3-10 cycloalkyl, preferably C 3-6 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
アルコキシとしては、メトキシ、エトキシ、ｎ−プロポキシ、イソプロポキシ、ｎ−ブトキシ、イソブトキシ、tert−ブトキシ、ｎ−ペンチルオキシ、イソペンチルオキシ、ヘキシルオキシ、ポリエチレングリコール誘導体などの直鎖状又は分枝鎖状のＣ１−１８アルコキシ、好ましくはＣ１−6アルコキシ、より好ましくはＣ１−４アルコキシが挙げられる。As the alkoxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isopentyloxy, hexyloxy, linear or branched such as polyethylene glycol derivatives C 1-18 alkoxy, preferably C 1-6 alkoxy, more preferably C 1-4 alkoxy.
アルケニルとしては、ビニル、１−プロペニル、２−メチル−２−プロペニル、イソプロペニル、１−、２−若しくは３−ブテニル、２−、３−若しくは４−ペンテニル、２−メチル−２−ブテニル、３−メチル−２−ブテニル、５−ヘキセニル、１−シクロペンテニル、１−シクロヘキセニル、３−メチル−３−ブテニルなどの直鎖状、分枝鎖状又は環状のＣ２−１８アルケニル、好ましくはＣ２−６アルケニル、より好ましくはＣ２−４アルケニルが挙げられる。Examples of alkenyl include vinyl, 1-propenyl, 2-methyl-2-propenyl, isopropenyl, 1-, 2- or 3-butenyl, 2-, 3- or 4-pentenyl, 2-methyl-2-butenyl, 3 Linear, branched or cyclic C 2-18 alkenyl such as -methyl-2-butenyl, 5-hexenyl, 1-cyclopentenyl, 1-cyclohexenyl, 3-methyl-3-butenyl, preferably C 2-6 alkenyl, more preferably C2-4 alkenyl is mentioned.
アルキニルとしては、三重結合を少なくとも１個有するものを意味し、例えばエチニル、１−若しくは２−プロピニル、１−、２−若しくは３−ブチニル、１−メチル−２−プロピニルなどの直鎖状、分枝鎖状又は環状のＣ２−６アルキニル、好ましくはＣ２−４アルキニルが挙げられる。Alkynyl means one having at least one triple bond. Branched or cyclic C 2-6 alkynyl, preferably C 2-4 alkynyl is mentioned.
ハロゲン原子としては、Ｆ，Ｃｌ，Ｂｒ，Ｉが挙げられる。
アリールとしては、５又は６員の芳香族炭化水素環からなる単環又は多環系の基を意味し、具体例としては、フェニル、ナフチル、トルイル、キシリル、フルオレニル、アントリル、ビフェニリル、テトラヒドロナフチル、クロマニル、２，３−ジヒドロ−１，４−ジオキサナフタレニル、インダニル及びフェナントリルが挙げられる。Examples of the halogen atom include F, Cl, Br, and I.
Aryl means a monocyclic or polycyclic group composed of a 5- or 6-membered aromatic hydrocarbon ring, and specific examples include phenyl, naphthyl, toluyl, xylyl, fluorenyl, anthryl, biphenylyl, tetrahydronaphthyl, Chromanyl, 2,3-dihydro-1,4-dioxanaphthalenyl, indanyl and phenanthryl.
ヘテロシクリルとしては、アクリジニル、ベンゾイミダゾリル、ベンゾジオキソラン、１，３−ベンゾジオキソール−５−イル、ベンゾフラニル、ベンゾチオフェニル、ベンゾオキサゾリル、ベンゾチアゾリル、カルバゾリル、シンノリニル、２，３−ジヒドロベンゾフラニル、ジオキサニル、モルホリノ、フラニル、イミダゾリジニル、イミダゾリニル、イミダゾリル、１Ｈ−インダゾリル、インドリニル、インドリル、３Ｈ−インドリル、イソインドリル、イソキノリニル、イソチアゾリル、イソオキサゾリル、モルホリニル、１，８−ナフチリジニル、オキサジアゾリル、１，３−オキサチオラニル、オキサゾリジニル、オキサゾリル、オキシラニル、パラチアジニル、フェナジニル、フェノチアジニル、フェノキサジニル、フタラジニル、ピペラジニル、ピペリジニル、プテリジニル、ピラニル、ピラジニル、ピラゾリジニル、ピラゾリニル、ピラゾロ［１，５−ｃ］トリアジニル、ピラゾリル、ピリダジニル、ピリジル、ピリミジニル、ピリミジル、ピロリル、ピロリジニル、プリニル、キナゾリニル、キノリニル、４Ｈ−キノリジニル、キノキサリニル、テトラゾリジニル、テトラゾリル、チアジアゾリル、チアゾリジニル、チアゾリル、チエニル、チオモルホリニル、トリアジニル、およびトリアゾリルが挙げられる。 Examples of heterocyclyl include acridinyl, benzimidazolyl, benzodioxolan, 1,3-benzodioxol-5-yl, benzofuranyl, benzothiophenyl, benzoxazolyl, benzothiazolyl, carbazolyl, cinnolinyl, 2,3-dihydrobenzofuranyl, Dioxanyl, morpholino, furanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolinyl, indolyl, 3H-indolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, morpholinyl, 1,8-naphthyridinyl, oxadiazolyl, 1,3-oxathiolanyl Oxazolyl, oxiranyl, parathiazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, phthalazi , Piperazinyl, piperidinyl, pteridinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolo [1,5-c] triazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrimidyl, pyrrolyl, pyrrolidinyl, purinyl, quinazolinyl, quinolinyl, 4H-quinolinyl Examples include quinoxalinyl, tetrazolidinyl, tetrazolyl, thiadiazolyl, thiazolidinyl, thiazolyl, thienyl, thiomorpholinyl, triazinyl, and triazolyl.
アラルキルとしては、ベンジル、フェネチル、ナフチルメチルなどが挙げられる。
モノアルキルアミノとしては、メチルアミノ、エチルアミノ、ｎ−プロピルアミノ、イソプロピルアミノ、ｎ−ブチルアミノ、イソブチルアミノ、tert−ブチルアミノ、ｎ−ペンチルアミノ、イソペンチルアミノ、ヘキシルアミノが挙げられる。Aralkyl includes benzyl, phenethyl, naphthylmethyl and the like.
Examples of the monoalkylamino include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, tert-butylamino, n-pentylamino, isopentylamino, and hexylamino.
ジアルキルアミノとしては、ジメチルアミノ、ジエチルアミノ、ジｎ−プロピルアミノ、ジイソプロピルアミノ、ジｎ−ブチルアミノ、ジイソブチルアミノ、ジtert−ブチルアミノ、ジｎ−ペンチルアミノ、ジイソペンチルアミノ、ジヘキシルアミノが挙げられる。 Examples of the dialkylamino include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, ditert-butylamino, di-n-pentylamino, diisopentylamino, and dihexylamino. .
アシルアミノとしては、アセチルアミノ、プロピオニルアミノ、ブチリルアミノ、イソブチリルアミノ、バレリルアミノ、ベンゾイルアミノなどが挙げられる。
アシルとしては、アセチル、プロピオニル、ブチリル、イソブチリル、バレリル、ベンゾイルが挙げられる。Acylamino includes acetylamino, propionylamino, butyrylamino, isobutyrylamino, valerylamino, benzoylamino and the like.
Acyl includes acetyl, propionyl, butyryl, isobutyryl, valeryl, benzoyl.
アルキルカルボニルオキシとしては、メチルカルボニルオキシ、エチルカルボニルオキシ、ｎ−プロピルカルボニルオキシ、イソプロピルカルボニルオキシ、ｎ−ブチルカルボニルオキシ、イソブチルカルボニルオキシ、tert−ブチルカルボニルオキシ、ｎ−ペンチルカルボニルオキシ、イソペンチルカルボニルオキシ、ヘキシルカルボニルオキシが挙げられる。 Examples of the alkylcarbonyloxy include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, tert-butylcarbonyloxy, n-pentylcarbonyloxy, isopentylcarbonyloxy , Hexylcarbonyloxy.
アリールカルボニルオキシとしては、フェニルカルボニルオキシ、ナフチルカルボニルオキシ、フルオレニルカルボニルオキシ、アントリルカルボニルオキシ、ビフェニリルカルボニルオキシ、テトラヒドロナフチルカルボニルオキシ、クロマニルカルボニルオキシ、２，３−ジヒドロ−１，４−ジオキサナフタレニルカルボニルオキシ、インダニルカルボニルオキシ及びフェナントリルカルボニルオキシが挙げられる。 As arylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, fluorenylcarbonyloxy, anthrylcarbonyloxy, biphenylylcarbonyloxy, tetrahydronaphthylcarbonyloxy, chromanylcarbonyloxy, 2,3-dihydro-1,4- Dioxanaphthalenylcarbonyloxy, indanylcarbonyloxy and phenanthrylcarbonyloxy.
アルコキシカルボニルとしては、メトキシカルボニル、エトキシカルボニル、プロポキシカルボニル、イソプロポキシカルボニル、ブトキシカルボニル、イソブトキシカルボニル、tert−ブトキシカルボニル、ペンチルオキシカルボニル、イソペンチルオキシカルボニル及びヘキシルオキシカルボニルが挙げられる。 Alkoxycarbonyl includes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl and hexyloxycarbonyl.
アルコキシカルボニルアミノとしては、メトキシカルボニルアミノ、エトキシカルボニルアミノ、プロポキシカルボニルアミノ、イソプロポキシカルボニルアミノ、ブトキシカルボニルアミノ、イソブトキシカルボニルアミノ、tert−ブトキシカルボニルアミノ、ペンチルオキシカルボニルアミノ、イソペンチルオキシカルボニルアミノ及びヘキシルオキシカルボニルアミノが挙げられる。 Examples of alkoxycarbonylamino include methoxycarbonylamino, ethoxycarbonylamino, propoxycarbonylamino, isopropoxycarbonylamino, butoxycarbonylamino, isobutoxycarbonylamino, tert-butoxycarbonylamino, pentyloxycarbonylamino, isopentyloxycarbonylamino, and hexyl Oxycarbonylamino is mentioned.
フルオロアルキルとしては、モノフルオロメチル、ジフルオロメチルが挙げられる。
パーフルオロアルキルとしては、ＣｎＦ２ｎ＋１（ｎは１〜６の整数）で表される直鎖または分岐鎖を有するパーフルオロアルキル、特にトリフルオロメチルが挙げられる。Examples of fluoroalkyl include monofluoromethyl and difluoromethyl.
The perfluoroalkyl, C n F 2n + 1 ( n is an integer from 1 to 6) perfluoroalkyl having straight or branched chain represented by include, in particular, trifluoromethyl.
モノアルキルカルバモイルとしては、メチルカルバモイル、エチルカルバモイル、ｎ−プロピルカルバモイル、イソプロピルカルバモイル、ｎ−ブチルカルバモイル、イソブチルカルバモイル、tert−ブチルカルバモイル、ｎ−ペンチルカルバモイル、イソペンチルカルバモイル、ヘキシルカルバモイルが挙げられる。 Examples of the monoalkylcarbamoyl include methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, isopropylcarbamoyl, n-butylcarbamoyl, isobutylcarbamoyl, tert-butylcarbamoyl, n-pentylcarbamoyl, isopentylcarbamoyl, and hexylcarbamoyl.
ジアルキルカルバモイルとしては、ジメチルカルバモイル、ジエチルカルバモイル、ジｎ−プロピルカルバモイル、ジイソプロピルカルバモイル、ジｎ−ブチルカルバモイル、ジイソブチルカルバモイル、ジtert−ブチルカルバモイル、ジｎ−ペンチルカルバモイル、ジイソペンチルカルバモイル、ジヘキシルカルバモイルが挙げられる。 Examples of the dialkylcarbamoyl include dimethylcarbamoyl, diethylcarbamoyl, di-n-propylcarbamoyl, diisopropylcarbamoyl, di-n-butylcarbamoyl, diisobutylcarbamoyl, ditert-butylcarbamoyl, din-pentylcarbamoyl, diisopentylcarbamoyl, and dihexylcarbamoyl. Can be
モノアルキル置換スルファモイルとしては、メチルスルファモイル、エチルスルファモイル、ｎ−プロピルスルファモイル、イソプロピルスルファモイル、ｎ−ブチルスルファモイル、イソブチルスルファモイル、tert−ブチルスルファモイル、ｎ−ペンチルスルファモイル、イソペンチルスルファモイル、ヘキシルスルファモイルが挙げられる。 Examples of the monoalkyl-substituted sulfamoyl include methylsulfamoyl, ethylsulfamoyl, n-propylsulfamoyl, isopropylsulfamoyl, n-butylsulfamoyl, isobutylsulfamoyl, tert-butylsulfamoyl, and n-sulfamoyl. Pentylsulfamoyl, isopentylsulfamoyl and hexylsulfamoyl.
ジアルキル置換スルファモイルとしては、ジメチルスルファモイル、ジエチルスルファモイル、ジｎ−プロピルスルファモイル、ジイソプロピルスルファモイル、ジｎ−ブチルスルファモイル、ジイソブチルスルファモイル、ジtert−ブチルスルファモイル、ジｎ−ペンチルスルファモイル、ジイソペンチルスルファモイル、ジヘキシルスルファモイルが挙げられる。 Examples of the dialkyl-substituted sulfamoyl include dimethylsulfamoyl, diethylsulfamoyl, di-n-propylsulfamoyl, diisopropylsulfamoyl, di-n-butylsulfamoyl, diisobutylsulfamoyl, ditert-butylsulfamoyl, Di-n-pentylsulfamoyl, diisopentylsulfamoyl and dihexylsulfamoyl.
アルキルスルホニルアミノとしては、メチルスルホニルアミノ、エチルスルホニルアミノ、ｎ−プロピルスルホニルアミノ、イソプロピルスルホニルアミノ、ｎ−ブチルスルホニルアミノ、イソブチルスルホニルアミノ、tert−ブチルスルホニルアミノ、ｎ−ペンチルスルホニルアミノ、イソペンチルスルホニルアミノ、ヘキシルスルホニルアミノが挙げられる。 Examples of the alkylsulfonylamino include methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, isopropylsulfonylamino, n-butylsulfonylamino, isobutylsulfonylamino, tert-butylsulfonylamino, n-pentylsulfonylamino, isopentylsulfonylamino , Hexylsulfonylamino.
式（ＩＩ）の化合物１モルに対し（１）〜（４）のいずれかの還元剤（reducing agent）を１当量〜過剰量使用し、室温〜溶媒の沸騰する温度下で１〜２４時間反応させることで式（Ｉ）の化合物を得ることができる(スキーム１)。 Using 1 equivalent to excess amount of the reducing agent of any of (1) to (4) per 1 mol of the compound of the formula (II), reacting at room temperature to a temperature at which the solvent boils for 1 to 24 hours. By doing so, a compound of formula (I) can be obtained (Scheme 1).
(式中、ｌ、ｍ、ｎ、ｏ、Ｒ、Ａ１及びＡ２は、前記に定義される通りである。)
スキーム１の反応において、Ａ１及びＡ２は、以下のスキーム２のように反応し、１つのシクロヘキサジエン環に結合した２つの水酸基（OH）は還元剤によって除かれ、シクロヘキサジエン環はベンゼン環に還元される。本明細書において、ｏ＝２ｐ＋１、ｍ＝２ｐ＋１である。(Wherein l, m, n, o, R, A 1 and A 2 are as defined above)
In the reaction of
(式中、ｐ、Ｒは、前記に定義される通りである。還元剤(reducing agent)は、前記の（１）〜（４）に記載のものである)
本発明において、下記スキーム３に従い、式（IIA）の化合物１モルに対し、環化触媒を触媒量から過剰量、必要に応じて塩基を触媒量から過剰量使用し、室温〜溶媒の沸騰する温度で１〜２４時間反応させることで環化させて一般式(IIB)の化合物を得、さらに、一般式(IIB)の化合物１モルに対し酸または塩基を触媒量から過剰量使用し、０〜１００℃程度の温度で１〜２４時間反応させることで水酸基の保護基を脱保護し、一般式（ＩＩ）の化合物を得ることができる。(Wherein p and R are as defined above. The reducing agent is as described in (1) to (4) above).
In the present invention, a cyclization catalyst is used in an excess amount from a catalytic amount, and if necessary, a base is used in an excess amount from a catalytic amount, and the solvent is boiled at room temperature to 1 mol of the compound of the formula (IIA) according to the following
(式中、ｎ１、ｎ２、ｎ、ｌ、Ｘ１、Ｘ２、Ｒ、Ａ１ａ、Ａ２ａ、Ａ１及びＡ２は、前記に定義される通りである。但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。）
環化触媒としては、Ｐｄ金属(Pd(0))，Ｐｄ化合物(例えばPdCl2、Pd（NO3)2、Pd（acac)2、Pd(OAc)2、Pd(dba)2、Pd2(dba)3、Pd(PPh3)4)、PdCl(C6H4CH2NH2)(Sphos)、Ni化合物(例えばNi(cod)2、NiCl2(cod)など)、Pt化合物（例えばPt(cod)2、PtCl2 、PtCl2(cod)など）が挙げられる。(Where n 1 , n 2 , n, l, X 1 , X 2 , R, A 1a , A 2a , A 1 and A 2 are as defined above, provided that 1 = n = When 2, p and A 2 in A 1 and A 2 are both 0.)
Examples of the cyclization catalyst include Pd metal (Pd (0)), Pd compounds (for example, PdCl 2 , Pd (NO 3 ) 2 , Pd (acac) 2 , Pd (OAc) 2 , Pd (dba) 2 , Pd 2 ( dba) 3 , Pd (PPh 3 ) 4 ), PdCl (C 6 H 4 CH 2 NH 2 ) (Sphos), Ni compound (eg, Ni (cod) 2 , NiCl 2 (cod), etc.), Pt compound (eg, Pt (cod) such as 2, PtCl 2, PtCl 2 ( cod)) can be mentioned.
塩基としては、ピリジン、ビピリジル、トリエチルアミン、ジメチルアミノピリジン、テトラブチルアンモニウムフルオライド、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩、アルカリ金属水酸化物などが挙げられる。 Examples of the base include pyridine, bipyridyl, triethylamine, dimethylaminopyridine, tetrabutylammonium fluoride, alkali metal carbonate, alkali metal bicarbonate, and alkali metal hydroxide.
Ｒ１が、Ｒで表される１〜５個の置換基で置換されていてもよいフェニル基の場合、置換基の数は１〜３個が好ましく、１〜２個がより好ましい。置換基としては、Ｒで表わされる置換基が例示され、好ましくはＦ，アルキル基、パーフルオロアルキル基が挙げられる。When R 1 is a phenyl group which may be substituted with 1 to 5 substituents represented by R, the number of substituents is preferably 1 to 3, and more preferably 1 to 2. Examples of the substituent include a substituent represented by R, and preferably include F, an alkyl group, and a perfluoroalkyl group.
Ｘ１、Ｘ２としては、Ｃｌ、Ｂｒ、Ｉ、ＯＴｆ，ＯＴｓ，ＯＭｓ、ＯＳＯ２Ｃ４Ｆ９、ＯＳＯ２Ｆなどが好ましい。
Sn含有基としては、Sn(Rb)3（Rbは同一または異なってアルキル基、アリール基又はアラルキル基を示し、好ましくはアルキル基を示す)が挙げられる。X 1 and X 2 are preferably Cl, Br, I, OTf, OTs, OMs, OSO 2 C 4 F 9 , OSO 2 F and the like.
Examples of the Sn-containing group include Sn (R b ) 3 (R b is the same or different and represents an alkyl group, an aryl group or an aralkyl group, and preferably represents an alkyl group).
Si含有基としては、Si(Rc)3（Rcは同一または異なってアルキル基、アリール基又はアラルキル基を示し、好ましくはアルキル基を示す)が挙げられる。Examples of the Si-containing group include Si (R c ) 3 (R c is the same or different and represents an alkyl group, an aryl group or an aralkyl group, and preferably represents an alkyl group).
B含有基としては、B(OH)2、B(Rd)2 (Rdは同一または異なってアルキル基、アルコキシ基、フッ素原子を示すか、2つのRd基がBと一緒になって環状の含ホウ素アルキル基を示す。）The B-containing group, B (OH) 2, B (R d) 2 (R d are the same or different alkyl group, an alkoxy group, or a fluorine atom, an annular two Rd groups are taken together with B Represents a boron-containing alkyl group.)
などが挙げられる。 And the like.
Sn、Si、B含有基の導入は、ハロゲンー金属交換反応、もしくは、ニッケル、パラジウム触媒、IrH(CO)(PPh3)3、Ir2(cod)2Cl2、Ir2(cod)2(MeO)2などのイリジウム触媒を用いて常法に従い行うことができる。The introduction of Sn, Si, and B-containing groups is performed by halogen-metal exchange reaction or nickel, palladium catalyst, IrH (CO) (PPh 3 ) 3 , Ir 2 (cod) 2 Cl 2 , Ir 2 (cod) 2 (MeO ) It can be carried out according to a conventional method using an iridium catalyst such as 2 .
脱保護のための酸としては、塩酸、硫酸、硝酸、リン酸、臭化水素酸、ヨウ化水素酸などの鉱酸、トリフルオロ酢酸、メタンスルホン酸、トルエンスルホン酸などの有機酸が挙げられる。塩基としては、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物、炭酸カリウム、炭酸ナトリウムなどのアルカリ金属炭酸塩、炭酸水素ナトリウム、炭酸水素カリウムなどのアルカリ金属炭酸水素塩、ナトリウムメトキシド、ナトリウムエトキシド、カリウム-ｔ-ブトキシドなどのアルカリ金属アルコキシドが挙げられる。 Examples of the acid for deprotection include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid, and hydroiodic acid, and organic acids such as trifluoroacetic acid, methanesulfonic acid, and toluenesulfonic acid. . As the base, sodium hydroxide, alkali metal hydroxides such as potassium hydroxide, potassium carbonate, alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, alkali metal hydrogen carbonate such as potassium hydrogen carbonate, sodium methoxide, Alkali metal alkoxides such as sodium ethoxide, potassium-t-butoxide and the like can be mentioned.
さらに、下記スキーム4に従い、一般式（IIC）の化合物1モルに対し下記式（IID）の化合物を１モル程度、環化触媒を触媒量から過剰量を使用し、室温〜溶媒の沸騰する温度で１〜２４時間反応させることで環化させて一般式(IIB)の化合物を得、さらに一般式(IIB)の化合物１モルに対し、酸または塩基を触媒量から過剰量使用し、０〜１００℃程度の温度で１〜２４時間反応させることで水酸基の保護基を脱保護し、一般式(II)で表される化合物を得ることができる。環化触媒、塩基、酸などは、上記のものを使用できる。 Further, according to the following scheme 4, about 1 mole of the compound of the following formula (IID) is used per mole of the compound of the general formula (IIC), and the cyclization catalyst is used in an excess amount from a catalytic amount. The compound of formula (IIB) is cyclized by reacting for 1 to 24 hours to obtain a compound of general formula (IIB). By reacting at a temperature of about 100 ° C. for 1 to 24 hours, the protecting group of the hydroxyl group is deprotected, and the compound represented by the general formula (II) can be obtained. As the cyclization catalyst, base, acid and the like, those described above can be used.
(式中、ｎ１、ｎ２、ｎ、ｌ１、ｌ２、ｌ、Ｘ１、Ｘ２、Ｒ、Ａ１ａ、Ａ２ａ、Ａ１、Ａ２は前記に定義される通りである。但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。）
スキーム３、４の環化反応は、檜山クロスカップリング(Hiyama Cross Coupling)、鈴木・宮浦クロスカップリング(Suzuki-Miyaura Cross Coupling)、右田・小杉・スティルクロスカップリング(Migita-Kosugi-Stille Cross Coupling)の通常の反応条件に従い行うことができる。例えば右田・小杉・スティルクロスカップリングでは、トリアルキルホスフィン、トリフェニルホスフィンなどのホスフィン化合物を使用することができる。(Wherein, n 1 , n 2 , n, l 1 , l 2 , l, X 1 , X 2 , R, A 1a , A 2a , A 1 , and A 2 are as defined above. , when l = n = 2, unless p in a 1 and a 2 are both 0.)
The cyclization reactions of
本発明の５個のフェニレン基がパラ位で1,4-結合したシクロパラフェニレン化合物は、以下のスキーム5に従い合成することができる。
The cycloparaphenylene compound of the present invention in which five phenylene groups are 1,4-bonded at the para position can be synthesized according to the following
（式中、Ｒは前記に定義されるとおりである。Ｒａは同一又は異なって、水酸基の保護基を示し、好ましくはトリエチルシリル基等のトリアルキルシリル基を示す。ｎ３は１以上の整数、ｎ４は１以上の整数、ｎ３＋ｎ４＝５〜２０の整数を示す。）
原料である一般式(V)の化合物は、文献(Xia, J.; Jasti, R. Angew. Chem. Int. Ed. 2012, 51, 2474.)に記載の方法に準じて得ることができる。(Wherein R is as defined above. Ra is the same or different and represents a hydroxyl-protecting group, preferably a trialkylsilyl group such as a triethylsilyl group. N3 is an integer of 1 or more. , N4 represents an integer of 1 or more, and n3 + n4 = an integer of 5 to 20.)
The compound of the general formula (V) as a starting material can be obtained according to the method described in the literature (Xia, J .; Jasti, R. Angew. Chem. Int. Ed. 2012, 51, 2474.).
一般式(IV)の化合物は、Pt化合物又はNi化合物と環化反応（Metal-mediated ring closure）させ、さらに脱保護(deprotection)することで、一般式(V)の環状化合物を得ることができる。Pt化合物としてはPt(cod)2が挙げられ、Ni化合物としてはNi(cod)2が挙げられる(codは1,5-シクロオクタジエンである)。環化反応は、溶媒中で、式（IV）の化合物1モルに対し、Pt化合物又はNi化合物を1モルから過剰量、好ましくは2〜3モル、2,2’-ビピリジル(bpy)等の塩基を1モルから過剰量、好ましくは2〜3モル使用し、室温から溶媒の沸騰する温度下に１〜24時間反応することで反応は有利に進行する。スキーム１〜５で使用される溶媒としては、テトラヒドロフラン、ジオキサン、アセトニトリル、ベンゼン、トルエン、クロロホルム、塩化メチレン、ジクロロエタン、酢酸エチル、ジメチルホルムアミド（DMF)、ジメチルスルホキシド(DMSO)、N-メチルピロリドンなどが挙げられる。The compound of the general formula (IV) can be subjected to a cyclization reaction (Metal-mediated ring closure) with a Pt compound or a Ni compound, and further deprotected to obtain a cyclic compound of the general formula (V). . Pt compounds include Pt (cod) 2 and Ni compounds include Ni (cod) 2 (cod is 1,5-cyclooctadiene). The cyclization reaction is carried out in a solvent in an amount of 1 mol to an excess of the Pt compound or the Ni compound, preferably 2 to 3 mol, 2,2′-bipyridyl (bpy) or the like relative to 1 mol of the compound of the formula (IV). The reaction proceeds advantageously when the base is used in an amount of 1 mol to an excess amount, preferably 2 to 3 mol, and the reaction is carried out at room temperature to a temperature at which the solvent boils for 1 to 24 hours. Examples of the solvent used in
得られた環化生成物は、保護基がトリエチルシリル基等のトリアルキルシリル基の場合、溶媒中でフッ化テトラ-n-ブチルアンモニウム(TBAF)により脱保護されてRa=Hの化合物(V)を得ることができる。環化生成物1モルに対し、TBAFを1モルから過剰量、好ましくは3〜6モル程度使用し、室温から溶媒の沸騰する温度下に１〜24時間反応することで反応は有利に進行する。溶媒は、上記の溶媒を使用できる。 When the obtained cyclized product is a compound in which the protecting group is a trialkylsilyl group such as a triethylsilyl group, the compound is deprotected by tetra-n-butylammonium fluoride (TBAF) in a solvent and Ra = H (V ) Can be obtained. The reaction proceeds advantageously by using TBAF from 1 mol to an excess amount, preferably about 3 to 6 mol, and reacting from room temperature to a temperature at which the solvent boils for 1 mol to 1 mol of the cyclized product. . As the solvent, the above-mentioned solvents can be used.
上記ではＲａで表される保護基がトリアルキルシリル基の場合を例に取り説明したが、他の水酸基の保護基の場合、その保護基に通常使用される脱保護条件を用いることで容易に脱保護できる。In the above description, the case where the protecting group represented by Ra is a trialkylsilyl group is described as an example. However, in the case of a protecting group for another hydroxyl group, the protecting group can be easily obtained by using deprotection conditions usually used for the protecting group. Can be deprotected.
化合物（V）1モルに対し、SnCl2又はその水和物などの還元剤を1当量から過剰量、好ましくは2当量から過剰量使用し、溶媒中で、室温から80℃程度の温度下に1~24時間反応させることにより還元芳香族化を行い、目的の化合物(I)を得ることができる。溶媒としては、上記の溶媒が挙げられ、好ましくはTHFが挙げられる。A reducing agent such as SnCl 2 or a hydrate thereof is used in an amount of 1 equivalent to an excess amount, preferably 2 equivalents to an excess amount, relative to 1 mol of the compound (V). The reaction is carried out for 1 to 24 hours to carry out reductive aromatization to obtain the desired compound (I). Examples of the solvent include the above-mentioned solvents, and preferably, THF.
本発明の製造方法において、6, 7, 8, 9, 10, 11, もしくは12個の１，４-フェニレン基が環状に連結された化合物（[6]-[12]CPP） は、下記のように製造できる。 In the production method of the present invention, a compound in which 6, 7, 8, 9, 10, 11, or 12 1,4-phenylene groups are cyclically connected ([6]-[12] CPP) is as follows: Can be manufactured as follows.
上記の二量化反応は、Pt化合物又はNi化合物を用い、スキーム1の化合物(IIA)から化合物(II)の反応と同様にして得ることができる。原料化合物は、低濃度で反応させることで分子内環化反応よりも分子間の環化反応の比率を高めることができる。得られた環化生成物は、スキーム１と同様の条件化に保護基(TES)を脱保護し、還元芳香族化反応を行うことで、目的とする環化生成物を得ることができる。
The above-mentioned dimerization reaction can be obtained using a Pt compound or a Ni compound in the same manner as in the reaction of compound (II) from compound (IIA) in
以下、本発明を実施例を用いてより詳細に説明するが、本発明がこれら実施例に限定されないことは言うまでもない。
実施例１：[5]CPPの合成
本実施例では、以下のスキーム6に従い、５つの1,4-フェニレン基が環状に結合した化合物（[5]CPP）を得た。Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.
Example 1 Synthesis of [5] CPP In this example, a compound ([5] CPP) in which five 1,4-phenylene groups were cyclically bonded was obtained according to the following
4-ブロモ-4'-ヒドロキシビフェニル(1)(50.5 g, 203 mmol)とイミダゾール(1.6 equiv)(22.1 g, 325mmol)のCH2Cl2溶液にクロロトリメチルシラン(1.3 equiv)(33.5 mL, 264 mmol)を0℃で30分かけて加えた。得られた混合物を室温まで温め、室温で18時間反応させた後、飽和NaHCO3水溶液でクエンチし、CH2Cl2で抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮し、中間化合物(2)を得た。4-bromo-4'-hydroxybiphenyl (1) (50.5 g, 203 mmol) and imidazole (1.6 equiv) (22.1 g, 325mmol)
THF/CH3CN/H2O (1000 mL/400 mL/500 mL)の混合溶液に、化合物(2)(64.7 g, 200 mmol)とヨードベンゼンジアセタート(1.2 equiv)(77.8 g, 240 mmol)をそれぞれ、固体のまま1時間かけて交互に室温で加えた。室温で11時間撹拌した後、飽和NaHCO3水溶液でクエンチし、CH2Cl2で抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗反応物をTHFで洗浄することで、4-ブロモフェニル-4-ヒドロキシシクロヘキサジエノン(3)を得た。化合物(1)から化合物(3)の2工程の収率は82%であった。In a mixed solution of THF / CH 3 CN / H 2 O (1000 mL / 400 mL / 500 mL), compound (2) (64.7 g, 200 mmol) and iodobenzene diacetate (1.2 equiv) (77.8 g, 240 mmol) were added at room temperature alternately over 1 hour while remaining solid. After stirring at room temperature for 11 hours, it was quenched with saturated aqueous NaHCO 3 and extracted with CH 2 Cl 2 . The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude reaction product was washed with THF to obtain 4-bromophenyl-4-hydroxycyclohexadienone (3). The yield in two steps from compound (1) to compound (3) was 82%.
化合物(3)(10.0 g, 37.7 mmol)のTHF (150 mL)溶液に、NaH(1.3 equiv)(1.96 g, 49.0 mmol,60% in mineral oil)のTHF(100mL)懸濁液を-78℃で加えた。-78℃で30分間撹拌した後、4-ブロモ-4’-(tert-ブチルジメチルシリルオキシ)ビフェニル(2.1 equiv)(28.8 g, 79.2 mmol)のTHF(220mL)溶液とブチルリチウムのヘキサン溶液(2.2 equiv)(56.0 mL, 1.49 M, 83.2 mmol)より調整した 4-リチオ-4’-(tert-ブチルジメチルシリルオキシ)ビフェニル(4)の溶液を-78℃で加えた。-78℃で2時間撹拌した後、飽和NH4Cl水溶液でクエンチし、酢酸エチルで抽出した。さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮し、中間化合物(5)を混合物として得た。To a solution of compound (3) (10.0 g, 37.7 mmol) in THF (150 mL) was added a suspension of NaH (1.3 equiv) (1.96 g, 49.0 mmol, 60% in mineral oil) in THF (100 mL) at -78 ° C. Added in. After stirring at −78 ° C. for 30 minutes, a solution of 4-bromo-4 ′-(tert-butyldimethylsilyloxy) biphenyl (2.1 equiv) (28.8 g, 79.2 mmol) in THF (220 mL) and a hexane solution of butyllithium ( A solution of 4-lithio-4 ′-(tert-butyldimethylsilyloxy) biphenyl (4) prepared from 2.2 equiv) (56.0 mL, 1.49 M, 83.2 mmol) was added at −78 ° C. After stirring at -78 ° C for 2 hours, it was quenched with a saturated aqueous solution of NH 4 Cl and extracted with ethyl acetate. Further, the organic layer was washed with a saturated saline solution, dried over Na 2 SO 4 , and concentrated under reduced pressure to obtain an intermediate compound (5) as a mixture.
化合物(5)を含む混合物とイミダゾール (4.0 equiv) (10.3 g, 151 mmol)のDMF(100 mL)溶液に、TESCl (3.0 equiv)(19.0 mL, 113 mmol)を、室温で加えた。室温から40 °Cで9時間撹拌した後、飽和NaHCO3水溶液でクエンチし、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮し、中間化合物(6)を混合物として得た。To a mixture of compound (5) and imidazole (4.0 equiv) (10.3 g, 151 mmol) in DMF (100 mL) was added TESCl (3.0 equiv) (19.0 mL, 113 mmol) at room temperature. After stirring at room temperature to 40 ° C. for 9 hours, the mixture was quenched with saturated aqueous NaHCO 3 and extracted with ethyl acetate. The organic layer was washed with a saturated saline solution, dried over Na 2 SO 4 and concentrated under reduced pressure to obtain an intermediate compound (6) as a mixture.
化合物(6)を含む混合物のDMF(70 mL)溶液に、LiOH・H2O (2.5 equiv)(8.30 g, 198 mmol)を固体のまま室温で加えた。室温で11 時間撹拌した後、反応溶液に酢酸エチルを加えた。有機層を水、さらに飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をカラムクロマトグラフィー（ヘキサン/酢酸エチル= 8/1）により精製することで、化合物(7)を得た。化合物(3)から化合物(7)の3工程の全収率は92%であった。To a solution of the mixture containing the compound (6) in DMF (70 mL) was added LiOH.H 2 O (2.5 equiv) (8.30 g, 198 mmol) as a solid at room temperature. After stirring at room temperature for 11 hours, ethyl acetate was added to the reaction solution. The organic layer was washed with water and saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by column chromatography (hexane / ethyl acetate = 8/1) to obtain compound (7). The overall yield of the three steps from compound (3) to compound (7) was 92%.
化合物(7) (10.0 g, 15.1 mmol)のTHF/CH3CN/H2O (80 mL/20 mL/25 mL)混合溶液に、ヨードベンゼンジアセタート(1.5 equiv) (7.30 g, 22.6 mmol)を固体のまま30分かけて室温で加えた。室温で2.5 時間反応させた後、飽和NaHCO3水溶液でクエンチし、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮し、中間化合物(8)を混合物として得た。Compound (7) (10.0 g, 15.1 mmol) in a THF / CH 3 CN / H 2 O (80 mL / 20 mL / 25 mL) mixed solution, iodobenzene diacetate (1.5 equiv) (7.30 g, 22.6 mmol ) Was added over 30 minutes at room temperature as a solid. After reacting at room temperature for 2.5 hours, the reaction was quenched with a saturated aqueous solution of NaHCO 3 and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over Na 2 SO 4 , and concentrated under reduced pressure to obtain an intermediate compound (8) as a mixture.
化合物(8)を含む混合物のTHF (50 mL)溶液に、NaH(1.3 equiv) (0.788 g, 19.6 mmol, 60% in mineral oil)のTHF(75 mL)懸濁液を-78℃で加えた。-78℃で1時間撹拌した後、1,4-ジブロモベンゼン(2.1 equiv) (7.50 g, 31.7 mmol)のTHF(100mL)溶液とブチルリチウムのヘキサン溶液(2.2 equiv)(21.0 mL, 1.55 M in hexane, 33.2 mmol)より調整した 4-ブロモフェニルリチウム(9)の溶液を-78℃で加えた。-78℃で2.5時間撹拌した後、飽和NH4Cl水溶液でクエンチし、酢酸エチルで抽出した。さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮し、中間化合物(10)を混合物として得た。To a solution of the mixture containing compound (8) in THF (50 mL) was added a suspension of NaH (1.3 equiv) (0.788 g, 19.6 mmol, 60% in mineral oil) in THF (75 mL) at -78 ° C. . After stirring at -78 ° C for 1 hour, a solution of 1,4-dibromobenzene (2.1 equiv) (7.50 g, 31.7 mmol) in THF (100 mL) and a hexane solution of butyllithium (2.2 equiv) (21.0 mL, 1.55 M in A solution of 4-bromophenyllithium (9) prepared from hexane (33.2 mmol) was added at -78 ° C. After stirring at −78 ° C. for 2.5 hours, it was quenched with a saturated aqueous solution of NH 4 Cl and extracted with ethyl acetate. Further, the organic layer was washed with a saturated saline solution, dried over Na 2 SO 4 and concentrated under reduced pressure to obtain an intermediate compound (10) as a mixture.
化合物(10)を含む混合物とイミダゾール (4.0 equiv) (4.10 g, 60.4 mmol)のDMF(50 mL)溶液に、TESCl (3.0 equiv) (7.60 mL, 45.3 mmol)を、室温で加えた。室温から40 °Cで10時間撹拌した後、飽和NaHCO3水溶液でクエンチし、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をカラムクロマトグラフィー（ヘキサン/酢酸エチル= 20/1）により精製することで、化合物(11)を得た。化合物(7)から化合物(11)の3工程の全収率は53%であった。To a mixture of the compound (10) and imidazole (4.0 equiv) (4.10 g, 60.4 mmol) in DMF (50 mL) was added TESCl (3.0 equiv) (7.60 mL, 45.3 mmol) at room temperature. After stirring at room temperature to 40 ° C for 10 hours, the mixture was quenched with saturated aqueous NaHCO 3 and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by column chromatography (hexane / ethyl acetate = 20/1) to obtain compound (11). The overall yield of the three steps from compound (7) to compound (11) was 53%.
Ni(cod)2(0.52 g, 1.88 mmol)と2,2’-ビピリジル (0.29 g, 1.88 mmol)のTHF（70 mL）溶液を50℃で30分撹拌した。得られた混合溶液を化合物(11) (1.00 g, 0.94 mmol)のTHF (400 mL)溶液に室温で加えた。加熱還流下、17時間撹拌した後、反応溶液をセライト濾過し、酢酸エチルで洗浄した。濾液を濃縮した後、分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(12a)を63%の収率で得た。A solution of Ni (cod) 2 (0.52 g, 1.88 mmol) and 2,2′-bipyridyl (0.29 g, 1.88 mmol) in THF (70 mL) was stirred at 50 ° C. for 30 minutes. The obtained mixed solution was added to a solution of compound (11) (1.00 g, 0.94 mmol) in THF (400 mL) at room temperature. After stirring under heating and refluxing for 17 hours, the reaction solution was filtered through celite and washed with ethyl acetate. The filtrate was concentrated and then purified by preparative gel permeation chromatography to obtain the compound (12a) in a yield of 63%.
化合物(12a) (0.50 g, 0.55 mmol)のTHF (5 mL)溶液にTBAFのTHF溶液(4.2 equiv)(2.30 mL, 1.00 M, 2.30 mmol)を室温で加えた。室温で2時間反応させた後、反応溶液に水を加えた。THFを留去した後、濾過し、濾過物の固体を水、クロロホルムで洗浄することで、化合物(12b)を94%の収率で得た。 To a solution of compound (12a) (0.50 g, 0.55 mmol) in THF (5 mL) was added a THF solution of TBAF (4.2 equiv) (2.30 mL, 1.00 M, 2.30 mmol) at room temperature. After reacting at room temperature for 2 hours, water was added to the reaction solution. After THF was distilled off, the residue was filtered, and the solid obtained by filtration was washed with water and chloroform to obtain a compound (12b) in a yield of 94%.
化合物(12b) (22.5 mg, 0.05 mmol)とSnCl2・2H2O (10 equiv)(112.8 mg, 0.50 mmol)のTHF溶液60℃で6時間撹拌した。その後、反応溶液に10％NaOH水溶液を加え、CH2Cl2で抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をCH2Cl2に溶解しショートシリカゲルパッド（ヘキサン/CH2Cl2= 1:1 to 1:2）に通した。濾液を濃縮した後、58%の収率で[5]CPPを濃紫色固体として得た。A THF solution of the compound (12b) (22.5 mg, 0.05 mmol) and SnCl 2 .2H 2 O (10 equiv) (112.8 mg, 0.50 mmol) was stirred at 60 ° C. for 6 hours. Thereafter, a 10% aqueous solution of NaOH was added to the reaction solution, extracted with CH 2 Cl 2 , and the organic layer was washed with saturated saline, dried over Na 2 SO 4 , and concentrated under reduced pressure. Short silica gel pad to dissolve the crude product in CH 2 Cl 2 (
[5]CPPは、空気中で比較的安定であり、トルエン、THF、CHCl3、CH2Cl2、アセトン等の汎用有機溶媒に溶解した。化合物(12b)から[5]CPPを得るSnCl2を用いた還元反応は、通常酸性溶媒中で実施するが、酸性溶媒中では化合物(I)（[5]CPP）は得られなかった。従って、この還元的芳香族化反応は中性条件で行うことが望ましい。 [5]CPPの構造は、NMRと質量分析により決定された。1H NMRスペクトルは、CDCl3中、25 °Cで測定し、7.85 ppmに１つのシングレットが観測された。これは[5]CPPが非常に対称な化合物であることを示すとともに、パラフェニレン単位はNMR測定時に室温で自由回転可能であることを示している。その化学シフト値は、[6]CPP及び[7]CPP (各々δ7.63及び7.48 ppm)と比較して0.22ppm及び0.37 ppm低磁場シフトしていた。13C NMRでは、126.61 ppmと131.97 ppmに２つのシグナルが観測された。MALDI-TOFマススペクトルでは、[5]CPP に由来する分子イオンピークがm/z = 380.1136で観測され、その同位体パターンは計算値とよい一致を示した。[5]CPPのクロロホルム溶液の紫外可視吸収スペクトルを図1に示す。[5]CPPのCHCl3溶液は暗紫色であった。335 nmに極大吸収を示すとともに（吸光係数(Ε)は6.82×104 M-1 cm-1）、600nm付近までブロードリングしたスペクトルが得られた。理論計算(TD-DFT計算)より、短波長側の強い吸収は縮退したHOMO-1、HOMO-2からLUMOおよびHOMOから縮退したLUMO+1、LUMO+2への遷移であり、長波長側のブロードな弱い吸収はHOMO-LUMO遷移であることが分かった。さらに、HOMO-LUMOギャップを見積もったところ、2.47 eVであった。また、電気化学測定（サイクリックボルタンメトリー測定）を行った（図2）。その結果、1,1,2,2-テトラクロロエタン中で、2つの可逆的な酸化波が 0.13、0.27 V (vs. Fe/Fc+)に観測された。同じ測定をTHF中で行うと、非可逆な酸化波が+0.10 V, +0.30 V (vs. Fe/Fc+) に、2つの擬可逆的な還元波が-1.59、-1.91 V (vs. Fe/Fc+)に観測された。[5] CPP was relatively stable in air and was dissolved in general-purpose organic solvents such as toluene, THF, CHCl 3 , CH 2 Cl 2 , and acetone. The reduction reaction using SnCl 2 to obtain [5] CPP from compound (12b) is usually performed in an acidic solvent, but compound (I) ([5] CPP) was not obtained in the acidic solvent. Therefore, this reductive aromatization reaction is desirably performed under neutral conditions. [5] The structure of CPP was determined by NMR and mass spectrometry. The 1 H NMR spectrum was measured in CDCl 3 at 25 ° C. and one singlet was observed at 7.85 ppm. This indicates that [5] CPP is a very symmetric compound, and that the paraphenylene unit can freely rotate at room temperature during NMR measurement. The chemical shift values were 0.22 ppm and 0.37 ppm downfield shifted compared to [6] CPP and [7] CPP (δ7.63 and 7.48 ppm, respectively). In 13 C NMR, two signals were observed at 126.61 ppm and 131.97 ppm. In the MALDI-TOF mass spectrum, a molecular ion peak derived from [5] CPP was observed at m / z = 380.1136, and its isotopic pattern showed good agreement with the calculated value. [5] FIG. 1 shows an ultraviolet-visible absorption spectrum of a chloroform solution of CPP. [5] The CPP CHCl 3 solution was dark purple. The spectrum showed a maximum absorption at 335 nm (the extinction coefficient (Ε) was 6.82 × 10 4 M −1 cm −1 ) and a spectrum broadened to around 600 nm was obtained. From the theoretical calculation (TD-DFT calculation), strong absorption on the short wavelength side is a transition from degenerated HOMO-1 and HOMO-2 to LUMO and LUMO + 1 and LUMO + 2 degenerated from HOMO, The broad weak absorption was found to be a HOMO-LUMO transition. Further, when the HOMO-LUMO gap was estimated, it was 2.47 eV. In addition, electrochemical measurement (cyclic voltammetry measurement) was performed (FIG. 2). As a result, two reversible oxidation waves were observed at 0.13 and 0.27 V (vs. Fe / Fc + ) in 1,1,2,2-tetrachloroethane. When the same measurement is performed in THF, irreversible oxidation waves are +0.10 V, +0.30 V (vs.Fe / Fc + ), and two quasi-reversible reduction waves are -1.59 and -1.91 V (vs. Fe / Fc + ).
実施例で得られた化合物の物性値を以下に示す。
化合物(6): 1H NMR (CDCl3, 400 MHz) 0.23 (s, 6H, -SiMe2t-Bu), 0.60 (q, 6H, J = 7.6 Hz, -SiEt3), 0.60 (q, 6H, J = 7.6 Hz, -SiEt3), 0.93 (t, 9H, J = 7.6 Hz, -SiEt3), 0.94 (t, 9H, J = 7.6 Hz, -SiEt3), 1.00 (s, 9H, -SiMe2t-Bu), 5.94 (d, 2H, J = 10.0 Hz, -CH=CH-), 6.04 (d, 2H, J = 10.0 Hz, -CH=CH-), 6.89 (d, 2H, J = 8.8 Hz, -Ar), 7.21 (d, 2H, J = 8.4 Hz, -Ar), 7.36 (d, 2H, J = 8.4 Hz, -Ar), 7.37 (d, 2H, J = 8.8 Hz, -Ar), 7.46 (m, 4H, -Ar); 13C NMR (CDCl3, 100 MHz) -4.38, 6.41, 6.45, 7.03, 18.24, 25.70, 71.23, 120.332, 121.12, 126.17, 126.41, 127.70, 127.96, 128.09, 131.01, 131.15, 131.50, 131.85, 133.73, 139.80, 144.14, 145.22, 155.30; HRMS (FAB-MS) m/z: Calcd for C42H61BrO3Si3(M)+, 776.3112, found 776.3102; IR (neat) 737, 823, 839, 914, 1074, 1263, 1472, 1493, 2876, 2955. The physical properties of the compounds obtained in the examples are shown below.
Compound (6): 1 H NMR (CDCl 3 , 400 MHz) 0.23 (s, 6H, -SiMe 2 t-Bu), 0.60 (q, 6H, J = 7.6 Hz, -SiEt 3 ), 0.60 (q, 6H , J = 7.6 Hz, -SiEt 3 ), 0.93 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 0.94 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 1.00 (s, 9H,- SiMe 2 t-Bu), 5.94 (d, 2H, J = 10.0 Hz, -CH = CH-), 6.04 (d, 2H, J = 10.0 Hz, -CH = CH-), 6.89 (d, 2H, J = 8.8 Hz, -Ar), 7.21 (d, 2H, J = 8.4 Hz, -Ar), 7.36 (d, 2H, J = 8.4 Hz, -Ar), 7.37 (d, 2H, J = 8.8 Hz,- Ar), 7.46 (m, 4H, -Ar); 13 C NMR (CDCl 3 , 100 MHz) -4.38, 6.41, 6.45, 7.03, 18.24, 25.70, 71.23, 120.332, 121.12, 126.17, 126.41, 127.70, 127.96, 128.09, 131.01, 131.15, 131.50, 131.85, 133.73, 139.80, 144.14, 145.22, 155.30; HRMS (FAB-MS) m / z: Calcd for C 42 H 61 BrO 3 Si 3 (M) + , 776.3112, found 776.3102; IR (neat) 737, 823, 839, 914, 1074, 1263, 1472, 1493, 2876, 2955.
化合物(7): 1H NMR (CDCl3, 400 MHz) 0.60 (q, 6H, J = 7.2 Hz, -SiEt3), 0.62 (q, 6H, J = 7.2 Hz, -SiEt3), 0.94 (t, 9H, J = 7.6 Hz, -SiEt3), 0.96 (t, 9H, J = 7.6 Hz, -SiEt3), 4.87 (s, 1H, -OH), 5.94 (d, 2H, J = 10.0 Hz, -CH=CH-), 6.04 (d, 2H, J = 10.4 Hz, -CH=CH-), 6.89 (d, 2H, J = 8.8 Hz, -Ar), 7.22 (d, 2H, J = 8.4 Hz, -Ar), 7.35 (d, 2H, J = 8.8 Hz, -Ar), 7.38 (d, 2H, J = 8.8 Hz, -Ar), 7.46 (m, 4H, -Ar); 13C NMR (CDCl3, 100 MHz) 5.76, 6.41, 6.44, 6.55, 7.03, 25.62, 71.22, 71.23, 115.64, 121.13, 126.20, 126.38, 127.70, 128.25, 131.02, 131.15, 131.84, 133.39, 139.67, 144.20, 145.21, 155.18; HRMS (FAB-MS) m/z: Calcd for C36H47BrO3Si2(M)+, 662.2247, found 662.2218; IR (neat) 729, 818, 909, 1005, 1435, 1238, 1263, 1479, 1495, 1605, 2876, 2955, 3251 (br).Compound (7): 1 H NMR (CDCl 3 , 400 MHz) 0.60 (q, 6H, J = 7.2 Hz, -SiEt 3 ), 0.62 (q, 6H, J = 7.2 Hz, -SiEt 3 ), 0.94 (t , 9H, J = 7.6 Hz, -SiEt 3 ), 0.96 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 4.87 (s, 1H, -OH), 5.94 (d, 2H, J = 10.0 Hz, -CH = CH-), 6.04 (d, 2H, J = 10.4 Hz, -CH = CH-), 6.89 (d, 2H, J = 8.8 Hz, -Ar), 7.22 (d, 2H, J = 8.4 Hz , -Ar), 7.35 (d, 2H, J = 8.8 Hz, -Ar), 7.38 (d, 2H, J = 8.8 Hz, -Ar), 7.46 (m, 4H, -Ar); 13 C NMR (CDCl (3 , 100 MHz) 5.76, 6.41, 6.44, 6.55, 7.03, 25.62, 71.22, 71.23, 115.64, 121.13, 126.20, 126.38, 127.70, 128.25, 131.02, 131.15, 131.84, 133.39, 139.67, 144.20, 145.21, 155.18; HRMS (FAB-MS) m / z: Calcd for C 36 H 47 BrO 3 Si 2 (M) + , 662.2247, found 662.2218; IR (neat) 729, 818, 909, 1005, 1435, 1238, 1263, 1479, 1495 , 1605, 2876, 2955, 3251 (br).
化合物(11): 1H NMR (CDCl3, 400 MHz) 0.56 (q, 12H, J = 8.0 Hz, -SiEt3), 0.62 (q, 12H, J = 8.0 Hz, -SiEt3), 0.91 (t, 18H, J = 7.6 Hz, -SiEt3), 0.94 (t, 9H, J = 7.6 Hz, -SiEt3), 5.90 (d, 4H, J = 10.0 Hz, -CH=CH-), 6.02 (d, 4H, J = 10.4 Hz, -CH=CH-), 7.16 (dd, 4H, J = 6.8, 2.0 Hz, -Ar), 7.24 (s, 2H, -Ar), 7.35 (dd, 4H, J = 6.8, 2.0 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.39, 6.45, 7.01, 7.03, 71.11, 71.23, 121.10, 125.74, 125.77, 127.60, 131.10, 131.69, 144.98, 145.17; HRMS (FAB-MS) m/z: Calcd for C54H80Br2O4Si4(M)+, 1064.3480, found 1064.3424; IR (neat) 540, 716, 733, 961, 1011, 1072, 1188, 1240, 1406, 1456, 1479, 2876, 2910, 2953. Compound (11): 1 H NMR (CDCl 3 , 400 MHz) 0.56 (q, 12H, J = 8.0 Hz, -SiEt 3 ), 0.62 (q, 12H, J = 8.0 Hz, -SiEt 3 ), 0.91 (t , 18H, J = 7.6 Hz, -SiEt 3 ), 0.94 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 5.90 (d, 4H, J = 10.0 Hz, -CH = CH-), 6.02 (d , 4H, J = 10.4 Hz, -CH = CH-), 7.16 (dd, 4H, J = 6.8, 2.0 Hz, -Ar), 7.24 (s, 2H, -Ar), 7.35 (dd, 4H, J = 6.8, 2.0 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.39, 6.45, 7.01, 7.03, 71.11, 71.23, 121.10, 125.74, 125.77, 127.60, 131.10, 131.69, 144.98, 145.17; HRMS (FAB -MS) m / z: Calcd for C 54 H 80 Br 2 O 4 Si 4 (M) + , 1064.3480, found 1064.3424; IR (neat) 540, 716, 733, 961, 1011, 1072, 1188, 1240, 1406 , 1456, 1479, 2876, 2910, 2953.
化合物(12a): 1H NMR (CDCl3, 400 MHz) 0.61 (q, 12H, J = 8.4 Hz, -SiEt3), 0.65 (q, 12H, J = 8.0 Hz, -SiEt3), 5.59 (d, 4H, J = 10.0 Hz, -CH=CH-), 5.87 (s, 4H, -Ar), 6.35 (d, 4H, J = 10.0 Hz, -CH=CH-), 7.43 (s, 8H, -Ar); 13C NMR (CDCl3, 100 MHz) 6.45, 6.46, 6.93, 7.02, 69.67, 71.91, 124.75, 127.41, 128.64, 132.37, 132.44, 139.85, 143.53, 144.46; HRMS (MALDI-TOF) m/z: Calcd for C54H80O4Si4Ag (M + Ag)+, 1011.4185, found 1011.4126; IR (neat) 741, 962, 1012, 1088, 1168, 1238, 1415, 2875, 2955.Compound (12a): 1 H NMR (CDCl 3 , 400 MHz) 0.61 (q, 12H, J = 8.4 Hz, -SiEt 3 ), 0.65 (q, 12H, J = 8.0 Hz, -SiEt 3 ), 5.59 (d , 4H, J = 10.0 Hz, -CH = CH-), 5.87 (s, 4H, -Ar), 6.35 (d, 4H, J = 10.0 Hz, -CH = CH-), 7.43 (s, 8H,- Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.45, 6.46, 6.93, 7.02, 69.67, 71.91, 124.75, 127.41, 128.64, 132.37, 132.44, 139.85, 143.53, 144.46; HRMS (MALDI-TOF) m / z : Calcd for C 54 H 80 O 4 Si 4 Ag (M + Ag) + , 1011.4185, found 1011.4126; IR (neat) 741, 962, 1012, 1088, 1168, 1238, 1415, 2875, 2955.
化合物(12b): 1H NMR (CDCl3, 400 MHz) 4.40 (s, 2H, -OH), 4.92 (s 2H, -OH), 5.60 (d, 4H, J = 10.0 Hz, -CH=CH-), 5.97 (s, 4H, -Ar), 6.45 (d, 4H, J = 10.0 Hz, -CH=CH-), 7.52 (t, 4H, J = 8.8 Hz, -Ar), 7.55 (t, 4H, J = 8.8 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 68.48, 70.28, 125.62, 127.80, 129.27, 133.50, 133.57, 140.00, 143.73, 145.81; HRMS (ESI-TOF) m/z: Calcd for C30H24O4Na (M + Na)+, 471.1572, found 471.1498; IR (KBr) 584, 770, 827, 951, 1032, 1192, 1398, 3325 (br); dp 273 oC.
[5]CPP: 1H NMR (CDCl3, 400 MHz) 7.85 (s, 20H, -Ar); 13C NMR (CDCl3, 100 MHz) 126.61, 131.97; HRMS (MALDI-TOF) m/z: calcd for C30H20 [M]+: 380.1560, found 380.1136.Compound (12b): 1 H NMR (CDCl 3 , 400 MHz) 4.40 (s, 2H, -OH), 4.92 (s 2H, -OH), 5.60 (d, 4H, J = 10.0 Hz, -CH = CH- ), 5.97 (s, 4H, -Ar), 6.45 (d, 4H, J = 10.0 Hz, -CH = CH-), 7.52 (t, 4H, J = 8.8 Hz, -Ar), 7.55 (t, 4H , J = 8.8 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 68.48, 70.28, 125.62, 127.80, 129.27, 133.50, 133.57, 140.00, 143.73, 145.81; HRMS (ESI-TOF) m / z: Calcd for C 30 H 24 O 4 Na (M + Na) + , 471.1572, found 471.1498; IR (KBr) 584, 770, 827, 951, 1032, 1192, 1398, 3325 (br); dp 273 o C.
[5] CPP: 1 H NMR (CDCl 3 , 400 MHz) 7.85 (s, 20H, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 126.61, 131.97; HRMS (MALDI-TOF) m / z: calcd for C 30 H 20 [M] + : 380.1560, found 380.1136.
実施例２：[5]CPPの合成
本実施例では、以下のスキーム7に従い、５つの1,4-フェニレン基が環状に結合した化合物（[5]CPP）を得た。Example 2: Synthesis of [5] CPP In this example, a compound in which five 1,4-phenylene groups were cyclically bonded ([5] CPP) was obtained according to
4-ヨード-4'-ヒドロキシビフェニル(13)(25.0 g, 84.4 mmol)とイミダゾール(2.0 equiv)(11.5 g, 168.9 mol)のCH2Cl2(150 mL)溶液にクロロトリメチルシラン(1.5 equiv) (16.1 mL, 126.6 mmol)を0℃で20分かけて加えた。得られた混合物を室温まで温め、室温で20時間反応させた後、飽和NaHCO3水溶液でクエンチし、CH2Cl2で抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮し、化合物(14)を得た。4-iodo-4'-hydroxybiphenyl (13) (25.0 g, 84.4 mmol) and imidazole (2.0 equiv) (11.5 g, 168.9 mol)
THF/CH3CN/H2O (500 mL/125 mL/200 mL)混合溶液に、化合物(14) (30.5 g, 82.8 mmol)とヨードベンゼンジアセタート(1.2 equiv) (32.0 g, 99.4 mmol)をそれぞれ、固体のまま1時間かけて交互に室温で加えた。室温で11時間撹拌した後、飽和NaHCO3水溶液でクエンチし、CH2Cl2で抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗反応物をTHFで洗浄することで、4-ヨードフェニル-4-ヒドロキシシクロヘキサジエノン(15)を得た。化合物(13)から化合物(15)の2工程の収率は79%であった。Compound (14) (30.5 g, 82.8 mmol) and iodobenzene diacetate (1.2 equiv) (32.0 g, 99.4 mmol) were added to a mixed solution of THF / CH 3 CN / H 2 O (500 mL / 125 mL / 200 mL). ) Were alternately added at room temperature over 1 hour while remaining solid. After stirring at room temperature for 11 hours, it was quenched with saturated aqueous NaHCO 3 and extracted with CH 2 Cl 2 . The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude reaction product was washed with THF to obtain 4-iodophenyl-4-hydroxycyclohexadienone (15). The yield in two steps from compound (13) to compound (15) was 79%.
4-ヨードフェニル-4-ヒドロキシシクロヘキサジエノン(15) (10.0 g, 32.0 mmol)のTHF (100 mL)溶液に、NaH(1.3 equiv)(1.00 g, 41.6 mmol, 60% in mineral oil) のTHF(100mL)懸濁液を-78℃で加えた。-78℃で1時間撹拌した後、1,4-ジブロモベンゼン(2.0 equiv) (15.1 g, 64.0 mmol)のTHF(100mL)溶液とブチルリチウムのヘキサン溶液(2.2 equiv) (45.2 mL, 1.56 M, 70.4 mmol)より調整した 4-ブロモフェニルリチウム(9)の溶液を-78℃で加えた。-78℃で2時間撹拌した後、TESCl (3.0 equiv)(16.0 mL, 96 mmol)のDMF(75 mL)溶液を-50 °Cで加えた。得られた混合物を室温まで温めた後、室温で11時間反応させた後、飽和NaHCO3水溶液でクエンチし、酢酸エチルで抽出し、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をカラムクロマトグラフィー（ヘキサン / 酢酸エチル= 100/1）により精製することで、化合物(16)を80%の収率で得た。To a solution of 4-iodophenyl-4-hydroxycyclohexadienone (15) (10.0 g, 32.0 mmol) in THF (100 mL) was added NaH (1.3 equiv) (1.00 g, 41.6 mmol, 60% in mineral oil) in THF. (100 mL) suspension was added at -78 ° C. After stirring at -78 ° C for 1 hour, a solution of 1,4-dibromobenzene (2.0 equiv) (15.1 g, 64.0 mmol) in THF (100 mL) and a hexane solution of butyllithium (2.2 equiv) (45.2 mL, 1.56 M, (70.4 mmol) was added at -78 ° C. After stirring at −78 ° C. for 2 hours, a solution of TESCl (3.0 equiv) (16.0 mL, 96 mmol) in DMF (75 mL) was added at −50 ° C. The resulting mixture was warmed to room temperature, reacted at room temperature for 11 hours, quenched with saturated aqueous NaHCO 3 , extracted with ethyl acetate, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by column chromatography (hexane / ethyl acetate = 100/1) to obtain compound (16) in a yield of 80%.
化合物(16)(3.47 g, 4.97 mmol)のTHF(70mL)溶液にブチルリチウムのヘキサン溶液(1.0 equiv)(3.20 mL, 1.57 M, 4.97 mmol)を-78°Cで加えた。-78°Cで1時間撹拌した後、化合物(3)(2.0 equiv)(2.64 g, 9.95 mmol)のTHF (50 mL)溶液に、NaH(2.6 equiv)(0.31 g, 12.9 mmol, 60% in mineral oil)のTHF(50mL)懸濁液を-78°Cで加えることで調整した脱プロトン化体(17)の溶液を-78°Cで加えた。-78°Cで4時間撹拌した後、飽和NH4Cl水溶液でクエンチし、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮し、中間ジオール化合物を混合物として得た。さらに、その混合物とイミダゾール (6.0 equiv)(2.03 g, 29.8 mmol)のDMF(50 mL)溶液に、TESCl (4.0 equiv)(3.30 mL, 19.9 mmol)を、室温で加えた。室温から40°Cで13時間撹拌した後、飽和NaHCO3水溶液でクエンチし、酢酸エチルで抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をカラムクロマトグラフィー（ヘキサン100%）により精製することで、化合物(11)を得た。化合物(16)から化合物(11)の2工程のトータルの収率は53%であった。To a solution of compound (16) (3.47 g, 4.97 mmol) in THF (70 mL) was added a hexane solution of butyllithium (1.0 equiv) (3.20 mL, 1.57 M, 4.97 mmol) at -78 ° C. After stirring at -78 ° C for 1 hour, a solution of compound (3) (2.0 equiv) (2.64 g, 9.95 mmol) in THF (50 mL) was added NaH (2.6 equiv) (0.31 g, 12.9 mmol, 60% in A solution of the deprotonated form (17) prepared by adding a suspension of THF (50 mL) of mineral oil) at -78 ° C was added at -78 ° C. After stirring at -78 ° C for 4 hours, the mixture was quenched with a saturated aqueous solution of NH 4 Cl and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over Na 2 SO 4 , and concentrated under reduced pressure to obtain an intermediate diol compound as a mixture. Further, to a solution of the mixture and imidazole (6.0 equiv) (2.03 g, 29.8 mmol) in DMF (50 mL), TESCl (4.0 equiv) (3.30 mL, 19.9 mmol) was added at room temperature. After stirring at room temperature to 40 ° C. for 13 hours, the mixture was quenched with a saturated aqueous solution of NaHCO 3 , extracted with ethyl acetate, and the organic layer was washed with brine, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by column chromatography (
Ni(cod)2(2.0 equiv)(1.04 g, 3.76 mmol)と2,2’-ビピリジル(2.0 equiv)(0.58 g, 3.76 mmol)のTHF (140 mL)溶液を50°Cで30分撹拌した。得られた混合溶液を11 (2.00 g, 1.88 mmol) の THF (800 mL)溶液に室温で加えた。加熱還流下、17 時間撹拌した後、反応溶液をセライト濾過し、酢酸エチルで洗浄した。濾液を濃縮した後、分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(12a)を73%の収率で得た。A solution of Ni (cod) 2 (2.0 equiv) (1.04 g, 3.76 mmol) and 2,2'-bipyridyl (2.0 equiv) (0.58 g, 3.76 mmol) in THF (140 mL) was stirred at 50 ° C for 30 minutes. . The obtained mixed solution was added to a solution of 11 (2.00 g, 1.88 mmol) in THF (800 mL) at room temperature. After stirring under heating and refluxing for 17 hours, the reaction solution was filtered through celite and washed with ethyl acetate. The filtrate was concentrated and then purified by preparative gel permeation chromatography to obtain the compound (12a) in a yield of 73%.
化合物(12a) (1.24 g, 1.37 mmol)のTHF (8 mL)溶液にTBAFのTHF溶液(4.2 equiv)(5.75 mL, 1.00 M in THF, 5.75 mmol)を室温で加えた。室温で2時間反応させた後、溶媒を留去した。粗生成物を水、CH2Cl2で洗浄することで、化合物(12b)を96%の収率で得た。To a THF (8 mL) solution of the compound (12a) (1.24 g, 1.37 mmol) was added a THF solution (4.2 equiv) of TBAF (5.75 mL, 1.00 M in THF, 5.75 mmol) at room temperature. After reacting at room temperature for 2 hours, the solvent was distilled off. The crude product was washed with water and CH 2 Cl 2 to give compound (12b) in a 96% yield.
SnCl2・2H2O (2.2 equiv) (0.65 g, 2.88 mmol)のTHF溶液に濃塩酸溶液(4.4 equiv)(0.48 mL, 12 N, 5.75 mmol)を室温で加えた。室温で30分間撹拌した後、化合物(12b) (0.54 g, 1.20 mmol)を固体で添加し、さらに室温で30分間撹拌した。反応溶液に10％NaOH水溶液を加え、CH2Cl2で抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をCH2Cl2に溶解しショートシリカゲルパッド（CH2Cl2100%）に通した。濾液を濃縮した後、72%の収率で[5]CPPを濃紫色固体として得た。 SnCl 2 · 2H 2 O (2.2 equiv) (0.65 g, 2.88 mmol) THF solution of concentrated hydrochloric acid solution (4.4 equiv) (0.48 mL, 12 N, 5.75 mmol) was added at room temperature. After stirring at room temperature for 30 minutes, compound (12b) (0.54 g, 1.20 mmol) was added as a solid, and the mixture was further stirred at room temperature for 30 minutes. A 10% aqueous NaOH solution was added to the reaction solution, extracted with CH 2 Cl 2 , and the organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was passed through a short silica gel pad was dissolved in CH 2 Cl 2 (CH 2 Cl 2 100%). After concentrating the filtrate, [5] CPP was obtained as a dark purple solid in 72% yield.
化合物(15): 1H NMR (CDCl3, 400 MHz) 2.35 (s, 1H, -OH), 6.24 (d, 2H, J = 10.0 Hz, -CH=CH-), 6.84 (d, 2H, J = 10.0 Hz, -CH=CH-), 7.22 (d, 2H, J = 8.8 Hz, -Ar), 7.71 (d, 2H, J = 8.4 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 70.78, 94.25, 127.21, 127.29, 138.01, 138.47, 150.03, 185.30; HRMS (EI-MS) m/z: Calcd for C12H9IO2 (M)+, 311.9647, found 311.9008; IR (KBr) 729, 821, 862, 942, 1003, 1071, 1356, 1396, 1475, 1612, 1662, 2873, 2951, 3392; mp 165.5 oC.Compound (15): 1 H NMR (CDCl 3 , 400 MHz) 2.35 (s, 1H, -OH), 6.24 (d, 2H, J = 10.0 Hz, -CH = CH-), 6.84 (d, 2H, J = 10.0 Hz, -CH = CH-), 7.22 (d, 2H, J = 8.8 Hz, -Ar), 7.71 (d, 2H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz ) 70.78, 94.25, 127.21, 127.29 , 138.01, 138.47, 150.03, 185.30; HRMS (EI-MS) m / z: Calcd for C 12 H 9 IO 2 (M) +, 311.9647, found 311.9008; IR (KBr) 729 , 821, 862, 942, 1003, 1071, 1356, 1396, 1475, 1612, 1662, 2873, 2951, 3392; mp 165.5 o C.
化合物(16): 1H NMR (CDCl3, 400 MHz) 0.59 (q, 6H, J = 8.0 Hz, -SiEt3), 0.59 (q, 6H, J = 7.6 Hz, -SiEt3), 0.92 (t, 9H, J = 8.0 Hz, -SiEt3), 0.92 (t, 9H, J = 7.6 Hz, -SiEt3), 5.94 (s, 4H, -CH=CH-), 7.04 (d, 2H, J= 8.4 Hz, -Ar), 7.17 (d, 2H, J = 8.4 Hz, -Ar), 7.39 (d, 2H, J = 8.8 Hz, -Ar), 7.58 (d, 2H, J = 8.4 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.39, 6.99, 71.07, 71.14, 92.97, 121.29, 127.60, 127.86, 131.25, 131.35, 131.39, 137.23, 144.95, 145.67; HRMS (FAB-MS) m/z: Calcd for C30H42BrIO2Si2, 696.0951, found 696.0962; IR (KBr) 729, 859, 958, 1003, 1074, 1145, 1317, 1355, 1397, 1457, 1607, 2872, 2849; mp 61.6 oC.Compound (16): 1 H NMR (CDCl 3 , 400 MHz) 0.59 (q, 6H, J = 8.0 Hz, -SiEt 3 ), 0.59 (q, 6H, J = 7.6 Hz, -SiEt 3 ), 0.92 (t , 9H, J = 8.0 Hz, -SiEt 3 ), 0.92 (t, 9H, J = 7.6 Hz, -SiEt 3 ), 5.94 (s, 4H, -CH = CH-), 7.04 (d, 2H, J = 8.4 Hz, -Ar), 7.17 (d, 2H, J = 8.4 Hz, -Ar), 7.39 (d, 2H, J = 8.8 Hz, -Ar), 7.58 (d, 2H, J = 8.4 Hz, -Ar ); 13 C NMR (CDCl 3 , 100 MHz) 6.39, 6.99, 71.07, 71.14, 92.97, 121.29, 127.60, 127.86, 131.25, 131.35, 131.39, 137.23, 144.95, 145.67; HRMS (FAB-MS) m / z: calcd for C 30 H 42 BrIO 2
実施例３：[6]CPPの合成
本実施例では、以下のスキーム8に従い、6つの1,4-フェニレン基が環状に結合した化合物（[6]CPP）を得た。Example 3: Synthesis of [6] CPP In this example, a compound in which six 1,4-phenylene groups were cyclically bonded ([6] CPP) was obtained according to
4-ブロモフェニル-4’-ヒドロキシシクロヘキサジエノン(3) (10.0 g, 37.7 mmol)のTHF (80 mL)溶液に、NaH(1.3 equiv)(1.18 g, 49.0 mmol, 60% in mineral oil)のTHF(100mL)懸濁液を-78°Cで加えた。-78°Cで1時間撹拌した後、1,4-ジブロモベンゼン(2.0 equiv)(18.7 g, 79.2 mmol)のTHF(220 mL)溶液とブチルリチウムのヘキサン溶液(2.2 equiv)(54.0 mL, 1.54 M, 83.0 mmol)より調整した 4-ブロモフェニルリチウム(9)の溶液を-78°Cで加えた。-78°Cで3時間撹拌した後、TESCl (3.0 equiv)(19.0 mL, 113.2 mmol)のDMF(100 mL)溶液を-50 °Cで作用させた。得られた混合物を室温まで温めた後、室温で12時間反応させた後、飽和NaHCO3水溶液でクエンチし、酢酸エチルで抽出した。有機層を水、飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物の固体をヘキサンで洗浄することで、化合物(18c)を得た。化合物(3)から化合物(18c)の2工程のトータルの収率は82%であった。To a solution of 4-bromophenyl-4'-hydroxycyclohexadienone (3) (10.0 g, 37.7 mmol) in THF (80 mL) was added NaH (1.3 equiv) (1.18 g, 49.0 mmol, 60% in mineral oil). A suspension of THF (100 mL) was added at -78 ° C. After stirring at -78 ° C for 1 hour, a THF (220 mL) solution of 1,4-dibromobenzene (2.0 equiv) (18.7 g, 79.2 mmol) and a butyllithium hexane solution (2.2 equiv) (54.0 mL, 1.54 M, 83.0 mmol) and a solution of 4-bromophenyllithium (9) was added at -78 ° C. After stirring at -78 ° C for 3 hours, a solution of TESCl (3.0 equiv) (19.0 mL, 113.2 mmol) in DMF (100 mL) was allowed to act at -50 ° C. The resulting mixture was warmed to room temperature, reacted at room temperature for 12 hours, quenched with saturated aqueous NaHCO 3 and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The solid of the crude product was washed with hexane to obtain a compound (18c). The total yield of the two steps from compound (3) to compound (18c) was 82%.
化合物(18c) (4.00 g, 6.15 mmol)のTHF (40 mL)溶液に、ブチルリチウムのヘキサン溶液(2.0 equiv)(8.30 mL, 1.49 M, 12.3 mmol)を-78°Cで加えた。-78°Cで1時間撹拌した後、トリメチルスズクロリド(2.0 equiv)(2.94 g, 14.8 mmol)のTHF(1mL)の溶液を-78°Cで加えた。得られた混合物を室温まで温めた後、室温で4時間反応させた後、飽和NH4Cl水溶液でクエンチし、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物を分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(18d)を89%の収率で得た。To a solution of compound (18c) (4.00 g, 6.15 mmol) in THF (40 mL) was added a hexane solution of butyllithium (2.0 equiv) (8.30 mL, 1.49 M, 12.3 mmol) at -78 ° C. After stirring at -78 ° C for 1 hour, a solution of trimethyltin chloride (2.0 equiv) (2.94 g, 14.8 mmol) in THF (1 mL) was added at -78 ° C. The resulting mixture was warmed to room temperature, reacted at room temperature for 4 hours, quenched with a saturated aqueous solution of NH 4 Cl, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by preparative gel permeation chromatography to give compound (18d) in 89% yield.
化合物(18d) (0.36 g, 0.97 mmol)とPt(cod)Cl2(1.0 equiv)(0.79 g, 0.97 mmol)のTHF (50 mL)溶液を60°Cで22時間撹拌した。その後、反応溶液に水を加えた後、CH2Cl2で抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物の固体をヘキサンで洗浄することで、化合物(19)を78%の収率で得た。A solution of compound (18d) (0.36 g, 0.97 mmol) and Pt (cod) Cl 2 (1.0 equiv) (0.79 g, 0.97 mmol) in THF (50 mL) was stirred at 60 ° C. for 22 hours. Thereafter, water was added to the reaction solution, and the mixture was extracted with CH 2 Cl 2 . The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The solid of the crude product was washed with hexane to obtain a compound (19) in a yield of 78%.
化合物(19) (0.57 g, 0.30 mmol)とPPh3(6.0 equiv)(0.47 g, 1.8 mmol)のトルエン(8 mL)溶液を90°Cで13時間撹拌した。反応懸濁液を濾過し、濾液を濃縮した後、粗生成物をカラムクロマトグラフィー（ヘキサン/CH2Cl2= 4:1 to 1:4）により精製することで、化合物(20a)を54%の収率で得た。A toluene (8 mL) solution of compound (19) (0.57 g, 0.30 mmol) and PPh 3 (6.0 equiv) (0.47 g, 1.8 mmol) was stirred at 90 ° C for 13 hours. The reaction suspension was filtered, the filtrate was concentrated, and the crude product was purified by column chromatography (hexane / CH 2 Cl 2 = 4: 1 to 1: 4) to give compound (20a) with 54% In a yield of
化合物(20a) (0.166 g, 0.17 mmol)のTHF (5 mL)溶液にTBAFのTHF溶液(4.2 equiv)(0.72 mL, 1.00 M in THF, 0.72 mmol)を室温で加えた。室温で2時間反応させた後、溶媒を留去した。粗生成物を水、クロロホルムで洗浄することで、化合物(20b)を96%の収率で得た。 To a solution of compound (20a) (0.166 g, 0.17 mmol) in THF (5 mL) was added a THF solution of TBAF (4.2 equiv) (0.72 mL, 1.00 M in THF, 0.72 mmol) at room temperature. After reacting at room temperature for 2 hours, the solvent was distilled off. By washing the crude product with water and chloroform, compound (20b) was obtained with a yield of 96%.
SnCl2・2H2O(2.2 equiv)(0.74 g, 3.3 mmol)のTHF溶液(3.3 mL)に濃塩酸水溶液(4.4 equiv)(0.55 mL, 12 N, 6.6 mmol)を室温で加えた。室温で30分間撹拌した後、反応溶液を化合物(20b) (0.79 g, 1.5 mmol)のTHF (6.0 mL)懸濁液に室温で加え、さらに室温で24時間撹拌した。反応溶液に10％NaOH水溶液を加え、CH2Cl2で抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をCH2Cl2に溶解しショートシリカゲルパッド（CH2Cl2100%）に通した。濾液を濃縮した後、74%の収率で[6]CPPを橙色固体として得た。To a THF solution (3.3 mL) of SnCl 2 .2H 2 O (2.2 equiv) (0.74 g, 3.3 mmol) was added a concentrated aqueous hydrochloric acid solution (4.4 equiv) (0.55 mL, 12 N, 6.6 mmol) at room temperature. After stirring at room temperature for 30 minutes, the reaction solution was added to a suspension of compound (20b) (0.79 g, 1.5 mmol) in THF (6.0 mL) at room temperature, and further stirred at room temperature for 24 hours. A 10% aqueous NaOH solution was added to the reaction solution, extracted with CH 2 Cl 2 , and the organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was passed through a short silica gel pad was dissolved in CH 2 Cl 2 (CH 2 Cl 2 100%). After concentration of the filtrate, [6] CPP was obtained as an orange solid in 74% yield.
化合物(18c): 1H NMR (CDCl3, 400 MHz) 0.59 (q, 12H, J = 8.0 Hz, -SiEt3), 0.92 (t, 18H, J = 8.0 Hz, -SiEt3), 5.95 (s, 4H, -CH=CH-), 7.17 (d, 4H, J = 8.4 Hz, -Ar), 7.38 (d, 4H, J = 8.8 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.41, 6.99, 71.09, 121.30, 127.60, 131.26, 131.39, 144.95; HRMS (FAB-MS) m/z: Calcd for C30H42Br2O2Si2(M)+, 648.1090, found 648.1201; IR (KBr) 728, 859, 959, 1009, 1073, 1239, 1355, 1399, 1457, 1481, 1607, 2872, 2951; mp 55.2 oC.Compound (18c): 1 H NMR (CDCl 3 , 400 MHz) 0.59 (q, 12H, J = 8.0 Hz, -SiEt 3 ), 0.92 (t, 18H, J = 8.0 Hz, -SiEt 3 ), 5.95 (s , 4H, -CH = CH-), 7.17 (d, 4H, J = 8.4 Hz, -Ar), 7.38 (d, 4H, J = 8.8 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.41, 6.99, 71.09, 121.30, 127.60, 131.26, 131.39, 144.95; HRMS (FAB-MS) m / z: Calcd for C 30 H 42 Br 2 O 2 Si 2 (M) + , 648.1090, found 648.1201; IR ( KBr) 728, 859, 959, 1009, 1073, 1239, 1355, 1399, 1457, 1481, 1607, 2872, 2951; mp 55.2 o C.
化合物(18d): 1H NMR (CDCl3, 400 MHz) 0.27 (s, 18H, JSn-H= 54.2 Hz, SnMe3), 0.60 (q, 18H, J = 8.0 Hz, SiEt3), 0.93 (t, 12H, J = 8.0 Hz, SiEt3), 5.96 (s, 4H, -CH=CH-), 7.32 (d, 4H, J = 8.0 Hz, -Ar), 7.39 (d, 4H, J = 8.0 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) -9.55, 6.43, 7.03, 71.39, 125.47, 131.48, 135.57, 140.86, 146.10; HRMS (FAB-MS) m/z: Calcd for C36H60O2Si2Sn2(M)+, 818.2170, found 817.9856; IR (KBr) 709, 738, 861, 958, 1004, 1058, 1179, 1238, 1400, 1457, 2875, 2956; mp 73.9-75.0 oC.Compound (18d): 1 H NMR (CDCl 3 , 400 MHz) 0.27 (s, 18H, J Sn-H = 54.2 Hz, SnMe 3 ), 0.60 (q, 18H, J = 8.0 Hz, SiEt 3 ), 0.93 ( t, 12H, J = 8.0 Hz, SiEt 3 ), 5.96 (s, 4H, -CH = CH-), 7.32 (d, 4H, J = 8.0 Hz, -Ar), 7.39 (d, 4H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) -9.55, 6.43, 7.03, 71.39, 125.47, 131.48, 135.57, 140.86, 146.10; HRMS (FAB-MS) m / z: Calcd for C 36 H 60 O 2 Si 2 Sn 2 (M) + , 818.2170, found 817.9856; IR (KBr) 709, 738, 861, 958, 1004, 1058, 1179, 1238, 1400, 1457, 2875, 2956; mp 73.9-75.0 o C.
化合物(19): 1H NMR (CDCl3, 400 MHz) 0.54 (q, 24H, J = 7.2 Hz, -SiEt3), 0.87 (t, 36H, J= 7.2 Hz, -SiEt3), 2.51 (brs, 16H, cod), 5.10 (brs, 8H, cod), 5.85 (s, 8H, -CH=CH-), 6.97 (d, 8H, J = 8.4 Hz, -Ar), 7.08 (d, 8H, J = 8.4 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.44, 7.06, 29.82, 71.28, 104.29, 125.03, 131.19, 134.32, 140.67, 153.43; IR (KBr) 739, 863, 957, 1004, 1057, 1238, 1414, 1458, 2875, 2957; dp > 200 oC.Compound (19): 1 H NMR (CDCl 3 , 400 MHz) 0.54 (q, 24H, J = 7.2 Hz, -SiEt 3 ), 0.87 (t, 36H, J = 7.2 Hz, -SiEt 3 ), 2.51 (brs , 16H, cod), 5.10 (brs, 8H, cod), 5.85 (s, 8H, -CH = CH-), 6.97 (d, 8H, J = 8.4 Hz, -Ar), 7.08 (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.44, 7.06, 29.82, 71.28, 104.29, 125.03, 131.19, 134.32, 140.67, 153.43; IR (KBr) 739, 863, 957, 1004, 1057, 1238, 1414, 1458, 2875, 2957; dp> 200 o C.
化合物(20a): 1H NMR (CDCl3, 400 MHz) 0.56 (q, 24H, J = 8.0 Hz, -SiEt3), 0.92 (t, 36H, J= 8.0 Hz, -SiEt3), 6.43 (s, 8H, -CH=CH-), 6.75 (d, 8H, J = 8.0 Hz, -Ar), 7.89 (d, 8H, J = 8.0 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.34, 6.98, 72.36, 126.19, 126.75, 134.56, 140.19, 141.60; IR (KBr) 713, 818, 860, 958, 1004, 1069, 1239, 1361, 1400, 1458, 1489, 2875, 2910; dp > 200 oC.Compound (20a): 1 H NMR (CDCl 3 , 400 MHz) 0.56 (q, 24H, J = 8.0 Hz, -SiEt 3 ), 0.92 (t, 36H, J = 8.0 Hz, -SiEt 3 ), 6.43 (s , 8H, -CH = CH-), 6.75 (d, 8H, J = 8.0 Hz, -Ar), 7.89 (d, 8H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.34, 6.98, 72.36, 126.19, 126.75, 134.56, 140.19, 141.60; IR (KBr) 713, 818, 860, 958, 1004, 1069, 1239, 1361, 1400, 1458, 1489, 2875, 2910; dp> 200 o C.
化合物(20b): 1H NMR (DMSO-d6, 400 MHz) 5.66 (s, 4H, -OH), 6.36 (s, 8H, -CH=CH-), 6.80 (d, 8H, J = 8.0 Hz, -Ar), 6.90 (d, 8H, J = 8.0 Hz, -Ar); 13C NMR (DMSO-d6, 100 MHz) 69.53, 125.41, 126.80, 134.50, 138.86, 142.19; HRMS (ESI-TOF) m/z: Calcd for C36H28O4(M + H)-, 525.2071, found 525.2159; IR (KBr) 732, 860, 958, 1005, 1068, 1187, 1239, 1361, 1400, 1457, 1489, 2876, 2594, 3318 (br); dp >300 oC.
[6]CPP: 1H NMR (CDCl3, 400 MHz) 7.63 (s, 24H, Ar-H); 13C NMR (CDCl3, 100 MHz) 127.03, 134.90; HRMS (MALDI-TOF) m/z: calcd for C36H24 [M]+: 456.1873, found 456.1908.Compound (20b): 1 H NMR (DMSO-d 6 , 400 MHz) 5.66 (s, 4H, -OH), 6.36 (s, 8H, -CH = CH-), 6.80 (d, 8H, J = 8.0 Hz , -Ar), 6.90 (d, 8H, J = 8.0 Hz, -Ar); 13 C NMR (DMSO-d 6 , 100 MHz) 69.53, 125.41, 126.80, 134.50, 138.86, 142.19; HRMS (ESI-TOF) m / z: Calcd for C 36 H 28 O 4 (M + H) - , 525.2071, found 525.2159; IR (KBr) 732, 860, 958, 1005, 1068, 1187, 1239, 1361, 1400, 1457, 1489, 2876, 2594, 3318 (br); dp> 300 o C.
[6] CPP: 1 H NMR (CDCl 3 , 400 MHz) 7.63 (s, 24H, Ar-H); 13 C NMR (CDCl 3 , 100 MHz) 127.03, 134.90; HRMS (MALDI-TOF) m / z: calcd for C 36 H 24 [M] + : 456.1873, found 456.1908.
実施例４：[7]CPPの合成
本実施例では、以下のスキーム9に従い、7つの1,4-フェニレン基が環状に結合した化合物（[7]CPP）を得た。Example 4: Synthesis of [7] CPP In this example, a compound in which seven 1,4-phenylene groups were cyclically bonded ([7] CPP) was obtained according to the following scheme 9.
化合物(18c)とTHF(70mL)溶液にTMEDAを加えた後、ブチルリチウムのヘキサン溶液(3.20 mL, 1.57 M in hexane, 4.97 mmol) を-78℃で加えた。-78℃で1時間撹拌した後、4-ブロモフェニル-4’-ヒドロキシシクロヘキサジエノン(3)(2.64 g, 9.95 mmol)のTHF (50 mL)溶液に、NaH(1.3 equiv)(0.31 g, 12.9 mmol, 60% in mineral oil)のTHF(50mL)懸濁液を-78℃で加えることで調整した脱プロトン化体(17)の溶液を-78℃で加えた。-78℃で2時間撹拌した後、TESCl (3.0 equiv)(5.8 mL, 34.3 mmol)のDMF(40 mL)溶液を-50 °Cで作用させた。得られた混合物を室温まで温めた後、室温で12時間反応させ、飽和NaHCO3水溶液でクエンチし、酢酸エチルで抽出した。有機層を水、飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をカラムクロマトグラフィー（ヘキサン/酢酸エチル = 100:1）により精製することで、化合物(21)を得た。化合物(12)から化合物(21)の3工程のトータルの収率は13%であった。After adding TMEDA to a solution of the compound (18c) and THF (70 mL), a hexane solution of butyllithium (3.20 mL, 1.57 M in hexane, 4.97 mmol) was added at -78 ° C. After stirring at -78 ° C for 1 hour, a solution of 4-bromophenyl-4'-hydroxycyclohexadienone (3) (2.64 g, 9.95 mmol) in THF (50 mL) was added with NaH (1.3 equiv) (0.31 g, A solution of the deprotonated product (17) prepared by adding a suspension of 12.9 mmol, 60% in mineral oil) in THF (50 mL) at -78 ° C was added at -78 ° C. After stirring at -78 ° C for 2 hours, a solution of TESCl (3.0 equiv) (5.8 mL, 34.3 mmol) in DMF (40 mL) was allowed to act at -50 ° C. After warming the resulting mixture to room temperature, it was allowed to react at room temperature for 12 hours, quenched with saturated aqueous NaHCO 3 and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by column chromatography (hexane / ethyl acetate = 100: 1) to obtain compound (21). The total yield of the three steps from compound (12) to compound (21) was 13%.
Ni(cod)2(0.33 g, 1.20 mmol)と2,2’-ビピリジル (0.19 g, 1.20 mmol)のTHF（50 mL）溶液を50℃で30分撹拌した。得られた混合溶液を化合物(21) (0.88 g, 0.59 mmol) の THF (250 mL)溶液に室温で加えた。 加熱還流下、13時間撹拌した後、反応溶液をセライト濾過し、酢酸エチルで洗浄した。濾液を濃縮した後、分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(22a)を73%の収率で得た。A solution of Ni (cod) 2 (0.33 g, 1.20 mmol) and 2,2′-bipyridyl (0.19 g, 1.20 mmol) in THF (50 mL) was stirred at 50 ° C. for 30 minutes. The obtained mixed solution was added to a solution of compound (21) (0.88 g, 0.59 mmol) in THF (250 mL) at room temperature. After stirring under reflux with heating for 13 hours, the reaction solution was filtered through celite and washed with ethyl acetate. The filtrate was concentrated and then purified by preparative gel permeation chromatography to obtain the compound (22a) in a yield of 73%.
化合物(22a)(0.35 g, 0.26 mmol)のTHF (6 mL)溶液にTBAF (6.3 equiv)(1.65 mL, 1.00 M in THF, 1.65 mmol)のTHF溶液を室温で加えた。室温で2時間反応させた後、溶媒を留去した。粗生成物を水、CH2Cl2で洗浄することで、化合物(22b)を98%の収率で得た。To a solution of compound (22a) (0.35 g, 0.26 mmol) in THF (6 mL) was added a THF solution of TBAF (6.3 equiv) (1.65 mL, 1.00 M in THF, 1.65 mmol) at room temperature. After reacting at room temperature for 2 hours, the solvent was distilled off. The crude product was washed with water and CH 2 Cl 2 to give compound (22b) in 98% yield.
SnCl2・2H2O (3.3 equiv)(165.0 mg, 0.73 mmol)のTHF溶液(6 mL)に濃塩酸水溶液(6.6 equiv)(0.12mL, 12 N, 1.45 mmol)を室温で加えた。室温で10分撹拌した後、化合物(22b) (139.6 mg, 0.22 mmol)を固体で添加し、さらに室温で3時間撹拌した。混合物を10％NaOH水溶液で処理し、CH2Cl2で抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をCH2Cl2に溶解しショートシリカゲルパッド（CH2Cl2 100%）に通した。濾液を濃縮した後、87%の収率で[7]CPPを淡黄色固体として得た。To a THF solution (6 mL) of SnCl 2 .2H 2 O (3.3 equiv) (165.0 mg, 0.73 mmol) was added a concentrated aqueous hydrochloric acid solution (6.6 equiv) (0.12 mL, 12 N, 1.45 mmol) at room temperature. After stirring at room temperature for 10 minutes, compound (22b) (139.6 mg, 0.22 mmol) was added as a solid, and the mixture was further stirred at room temperature for 3 hours. The mixture was treated with a 10% aqueous solution of NaOH, extracted with CH 2 Cl 2 , and the organic layer was washed with brine, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was passed through a short silica gel pad was dissolved in CH 2 Cl 2 (CH 2 Cl 2 100%). After concentrating the filtrate, [7] CPP was obtained as a pale yellow solid in 87% yield.
化合物(21): 1H NMR (CDCl3, 400 MHz) 0.54 (m, 12H, -SiEt3), 0.61 (m, 24H, -SiEt3), 0.87 (m, 18H, -SiEt3), 0.94 (m, 36H, -SiEt3), 5.88 (d, 4H, J= 9.6 Hz, -CH=CH-), 5.97 (s, 4H, -CH=CH-), 6.02 (d, 4H, J = 9.6 Hz, -CH=CH-), 7.14 (d, 4H, J = 8.4 Hz, -Ar), 7.23 (s, 8H, -Ar), 7.32 (d, 2H, J = 8.4 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.41, 6.44, 6.47, 6.98, 7.04, 7.06, 71.06, 71.29, 121.01, 125.66, 125.73, 127.61, 127.91, 131.07, 131.41, 131.73, 132.38, 144.71, 145.20, 145.28; HRMS (ESI-MS) m/z: Calcd for C78H118Br2O6Si6Na (M + Na)+, 1499.5808, found 1501.6121; IR (neat) 728, 860, 959, 1003, 1072, 1239, 1357, 1403, 1458, 1607, 2875, 2952; mp 39.2 oC.Compound (21): 1 H NMR (CDCl 3 , 400 MHz) 0.54 (m, 12H, -SiEt 3 ), 0.61 (m, 24H, -SiEt 3 ), 0.87 (m, 18H, -SiEt 3 ), 0.94 ( m, 36H, -SiEt 3 ), 5.88 (d, 4H, J = 9.6 Hz, -CH = CH-), 5.97 (s, 4H, -CH = CH-), 6.02 (d, 4H, J = 9.6 Hz , -CH = CH-), 7.14 (d, 4H, J = 8.4 Hz, -Ar), 7.23 (s, 8H, -Ar), 7.32 (d, 2H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.41, 6.44, 6.47, 6.98, 7.04, 7.06, 71.06, 71.29, 121.01, 125.66, 125.73, 127.61, 127.91, 131.07, 131.41, 131.73, 132.38, 144.71, 145.20, 145.28; HRMS ( ESI-MS) m / z: Calcd for C 78 H 118 Br 2 O 6 Si 6 Na (M + Na) + , 1499.5808, found 1501.6121; IR (neat) 728, 860, 959, 1003, 1072, 1239, 1357 , 1403, 1458, 1607, 2875, 2952; mp 39.2 o C.
化合物(22a): 1H NMR (CDCl3, 400 MHz) 0.54 (q, 12H, J= 8.0 Hz, -SiEt3), 0.58 (q, 12H, J= 8.0 Hz, -SiEt3), 0.67 (q, 12H, J= 8.0 Hz, -SiEt3), 0.90 (t, 18H, J= 7.6 Hz, -SiEt3), 0.93 (t, 18H, J= 8.0 Hz, -SiEt3), 0.99 (t, 18H, J= 8.0 Hz, -SiEt3), 5.98 (s, 4H, -CH=CH-), 6.01 (s, 4H, -CH=CH-), 6.02 (s, 4H, -CH=CH-), 6.15 (d, 4H, J = 10.0 Hz, -CH=CH-), 7.13 (m, 4H, -Ar), 7.24 (m, 12H, -Ar); 13C NMR (CDCl3, 100 MHz) 6.47, 6.47, 6.58, 7.01, 7.06, 7.12, 70.05, 71.68, 72.11, 125.32, 126.19, 126.26, 126.64, 131.28, 132.13, 132.32, 139.89, 143.99, 144.37, 146.00; HRMS (ESI-TOF) m/z: Calcd for C78H118O6Si6Cs (M + Cs)+, 1451.6598, found 1451.6485; IR (KBr) 726, 858, 1004, 1070, 1189, 1239, 1402, 1457, 1489, 1607, 2876, 2952; dp > 300 oC.Compound (22a): 1 H NMR (CDCl 3 , 400 MHz) 0.54 (q, 12H, J = 8.0 Hz, -SiEt 3 ), 0.58 (q, 12H, J = 8.0 Hz, -SiEt 3 ), 0.67 (q , 12H, J = 8.0 Hz, -SiEt 3 ), 0.90 (t, 18H, J = 7.6 Hz, -SiEt 3 ), 0.93 (t, 18H, J = 8.0 Hz, -SiEt 3 ), 0.99 (t, 18H , J = 8.0 Hz, -SiEt 3 ), 5.98 (s, 4H, -CH = CH-), 6.01 (s, 4H, -CH = CH-), 6.02 (s, 4H, -CH = CH-), 6.15 (d, 4H, J = 10.0 Hz, -CH = CH-), 7.13 (m, 4H, -Ar), 7.24 (m, 12H, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.47, 6.47, 6.58, 7.01, 7.06, 7.12, 70.05, 71.68, 72.11, 125.32, 126.19, 126.26, 126.64, 131.28, 132.13, 132.32, 139.89, 143.99, 144.37, 146.00; HRMS (ESI-TOF) m / z: Calcd for C 78 H 118 O 6 Si 6 Cs (M + Cs) + , 1451.6598, found 1451.6485; IR (KBr) 726, 858, 1004, 1070, 1189, 1239, 1402, 1457, 1489, 1607, 2876, 2952; dp > 300 o C.
化合物(22b): 1H NMR (acetone-d6, 400 MHz) 4.28 (s, 2H, -OH), 4.65 (s, 2H, -OH), 4.79 (s 2H, -OH), 5.85 (s, 4H, -CH=CH-), 5.95 (d, 4H, J= 10.0 Hz, -CH=CH-), 6.15 (d, 4H, J = 10.0 Hz, -CH=CH-), 7.15 (d, 4H, J = 8.4 Hz, -Ar), 7.28 (d, 4H, J = 8.4 Hz, -Ar), 7.28 (d, 4H, J = 8.4 Hz, -Ar), 7.55 (d, 4H, J = 8.0 Hz, -Ar); 13C NMR (acetone-d6, 100 MHz) 72.55, 74.46, 74.68, 129.96, 131.14, 131.19, 132.05, 136.82, 137.27, 138.13, 144.26, 148.79, 149.39, 149.67; HRMS (ESI-TOF) m/z: Calcd for C42H34ClO6(M + Cl)-, 669.2044, found 669.2180; IR (KBr) 765, 822, 946, 1004, 1067, 1181, 1391, 1490, 1687, 3348 (br); dp > 300 oC.
[7]CPP: 1H NMR (CDCl3, 400 MHz) 7.48 (s, 28H, -Ar); 13C NMR (CDCl3, 100 MHz) 127.42, 136.86; HRMS (MALDI-TOF) m/z: Calcd for C42H28 (M)+, 532.2186, found 532.1787.Compound (22b): 1 H NMR (acetone-d 6 , 400 MHz) 4.28 (s, 2H, -OH), 4.65 (s, 2H, -OH), 4.79 (s 2H, -OH), 5.85 (s, 4H, -CH = CH-), 5.95 (d, 4H, J = 10.0 Hz, -CH = CH-), 6.15 (d, 4H, J = 10.0 Hz, -CH = CH-), 7.15 (d, 4H , J = 8.4 Hz, -Ar), 7.28 (d, 4H, J = 8.4 Hz, -Ar), 7.28 (d, 4H, J = 8.4 Hz, -Ar), 7.55 (d, 4H, J = 8.0 Hz , -Ar); 13 C NMR (acetone-d 6 , 100 MHz) 72.55, 74.46, 74.68, 129.96, 131.14, 131.19, 132.05, 136.82, 137.27, 138.13, 144.26, 148.79, 149.39, 149.67, HRMS (ESI-TOF ) m / z: Calcd for C 42 H 34 ClO 6 (M + Cl) - , 669.2044, found 669.2180; IR (KBr) 765, 822, 946, 1004, 1067, 1181, 1391, 1490, 1687, 3348 (br ); dp> 300 o C.
[7] CPP: 1 H NMR (CDCl 3 , 400 MHz) 7.48 (s, 28H, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 127.42, 136.86; HRMS (MALDI-TOF) m / z: Calcd for C 42 H 28 (M) + , 532.2186, found 532.1787.
実施例５：[8]CPPの合成
本実施例では、以下のスキーム１０に従い、８つの1,4-フェニレン基が環状に結合した化合物（[８]CPP）を得た。Example 5: Synthesis of [8] CPP In this example, a compound in which eight 1,4-phenylene groups were cyclically bonded ([8] CPP) was obtained according to Scheme 10 below.
化合物(18)(4.00 g, 6.15 mmol)のTHF (55 mL)溶液に、ブチルリチウムのヘキサン溶液(2.20 equiv)(8.60 mL, 1.57 M in hexane, 13.5 mmol)を-78℃で加えた。-78℃で30分間撹拌した後、2-イソプロポキシ-4,4,5,5-テトラメチル-1,3,2-ジオキサボロラン(2.40 equiv)(3.00 mL, 14.8 mmol)を-78℃で加えた。得られた混合物を室温まで温めた後、室温で4時間反応させた後、飽和NH4Cl水溶液でクエンチし、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物の固体をヘキサンで洗浄することで、化合物(23)を96%の収率で得た。To a solution of compound (18) (4.00 g, 6.15 mmol) in THF (55 mL) was added a hexane solution of butyllithium (2.20 equiv) (8.60 mL, 1.57 M in hexane, 13.5 mmol) at -78 ° C. After stirring at -78 ° C for 30 minutes, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.40 equiv) (3.00 mL, 14.8 mmol) was added at -78 ° C. Was. The resulting mixture was warmed to room temperature, reacted at room temperature for 4 hours, quenched with a saturated aqueous solution of NH 4 Cl, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The solid of the crude product was washed with hexane to obtain the compound (23) in a yield of 96%.
化合物(23)(260.7 mg, 0.35 mmol)、実施例1もしくは2で得た化合物(11)（372.8 mg, 0.35 mmol）、PdCl(C6H4CH2NH2)(Sphos)（Sphosは2-ジシクロヘキシルホスフィノ-2′,6′-ジメトキシビフェニル）（46.1 mg, 0.07 mmol）、及びリン酸三カリウム（K3PO4）(594 mg, 2.8 mmol）のトルエン/水混合溶液（120 mL/12 mL）を100℃で24時間攪拌した。室温まで冷却後、反応溶液をセライト濾過し、濾液に水を加えた後、CH2Cl2で抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物を分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(24a)を37%の収率で得た。Compound (23) (260.7 mg, 0.35 mmol), compound (11) obtained in Example 1 or 2 (372.8 mg, 0.35 mmol), PdCl (C 6 H 4 CH 2 NH 2 ) (Sphos) (Sphos is 2 -Dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl) (46.1 mg, 0.07 mmol) and tripotassium phosphate (K 3 PO 4 ) (594 mg, 2.8 mmol) in a toluene / water mixed solution (120 mL / 12 mL) was stirred at 100 ° C. for 24 hours. After cooling to room temperature, the reaction solution was filtered through celite, water was added to the filtrate, and extracted with CH 2 Cl 2 . The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by preparative gel permeation chromatography to give compound (24a) in 37% yield.
化合物(24a)(166.2 mg, 0.12 mmol)のTHF (6 mL)溶液にTBAFのTHF溶液(6.3 equiv)(0.75 mL, 1.00 M in THF, 0.75 mmol)を室温で加えた。室温で2時間反応させた後、溶媒を留去した。粗生成物を水、CH2Cl2で洗浄することで、化合物(24b)を90%の収率で得た。To a THF (6 mL) solution of the compound (24a) (166.2 mg, 0.12 mmol) was added a THF solution of TBAF (6.3 equiv) (0.75 mL, 1.00 M in THF, 0.75 mmol) at room temperature. After reacting at room temperature for 2 hours, the solvent was distilled off. The crude product was washed with water and CH 2 Cl 2 to give compound (24b) in 90% yield.
SnCl2・2H2O (3.3 equiv)(223.3 mg, 0.99 mmol)のTHF溶液(30 mL)に濃塩酸水溶液(6.6 equiv)(0.17mL, 12 N, 1.98 mmol)を室温で加えた。室温で15分撹拌した後、化合物(24b) (213.2 mg, 0.30 mmol)を固体で添加し、さらに室温で12時間撹拌した。混合物を10％NaOH水溶液で処理し、CH2Cl2で抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をCH2Cl2に溶解しショートシリカゲルパッド（CH2Cl2 100%）に通した。濾液を濃縮した後、67%の収率で[8]CPPを淡黄色固体として得た。To a THF solution (30 mL) of SnCl 2 .2H 2 O (3.3 equiv) (223.3 mg, 0.99 mmol) was added a concentrated aqueous hydrochloric acid solution (6.6 equiv) (0.17 mL, 12 N, 1.98 mmol) at room temperature. After stirring at room temperature for 15 minutes, compound (24b) (213.2 mg, 0.30 mmol) was added as a solid, and the mixture was further stirred at room temperature for 12 hours. The mixture was treated with a 10% aqueous solution of NaOH, extracted with CH 2 Cl 2 , and the organic layer was washed with brine, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was passed through a short silica gel pad was dissolved in CH 2 Cl 2 (CH 2 Cl 2 100%). After concentrating the filtrate, [8] CPP was obtained as a pale yellow solid in 67% yield.
化合物(23): 1H NMR (CDCl3, 400 MHz) 0.59 (q, 12H, J= 8.0 Hz, SiEt3), 0.92 (t, 18H, J = 8.0 Hz, SiEt3), 5.96 (s, 4H, -CH=CH-), 7.34 (d, 4H, J = 8.4 Hz, -Ar), 7.70 (d, 4H, J = 8.4 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.44, 7.03, 24.88, 71.56, 83.72, 125.18, 131.41, 134.70, 149.08; HRMS (FAB-MS) m/z: Calcd for C42H66B2O6Si2(M)+, 744.4584, found 744.4721; IR (KBr) 734, 860, 959, 1075, 1089, 1145, 1318, 1357, 1390, 1457, 1607, 2873, 2951; mp 142.8 oC.Compound (23): 1 H NMR (CDCl 3 , 400 MHz) 0.59 (q, 12 H, J = 8.0 Hz, SiEt 3 ), 0.92 (t, 18 H, J = 8.0 Hz, SiEt 3 ), 5.96 (s, 4H , -CH = CH-), 7.34 (d, 4H, J = 8.4 Hz, -Ar), 7.70 (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.44, 7.03, 24.88, 71.56, 83.72, 125.18, 131.41, 134.70, 149.08; HRMS (FAB-MS) m / z: Calcd for C 42 H 66 B 2 O 6 Si 2 (M) + , 744.4584, found 744.4721; IR ( KBr) 734, 860, 959, 1075, 1089, 1145, 1318, 1357, 1390, 1457, 1607, 2873, 2951; mp 142.8 o C.
化合物(24a): 1H NMR (CDCl3, 400 MHz) 0.53 (q, 12H, J = 8.0 Hz, SiEt3), 0.66 (q, 12H, J= 8.0 Hz, SiEt3), 0.71 (q, 12H, J = 8.0 Hz, SiEt3), 0.93 (t, 18H, J = 8.0 Hz, SiEt3), 0.98 (t, 18H, J = 8.0 Hz, SiEt3), 0.98 (t, 18H, J = 8.0 Hz, SiEt3), 5.91 (t, 4H, J = 10.0 Hz, -CH=CH-), 6.06 (t, 4H, J = 10.0 Hz, -CH=CH-), 6.09 (s, 4H,-CH=CH-), 7.07 (d, 4H, J = 8.0 Hz, -Ar), 7.32 (d, 4H, J = 8.4 Hz, -Ar), 7.41 (d, 4H, J = 8.0 Hz, -Ar), 7.46 (d, 4H, J = 8.4 Hz, -Ar), 7.48 (s, 4H,-CH=CH-); 13C NMR (CDCl3, 100 MHz) 6.32, 6.43, 6.47, 7.06, 7.12, 7.12, 70.65, 71.15, 72.42, 125.87, 125.96, 126.26, 126.58, 126.86, 130.98, 131.85, 132.07, 139.37, 139.50, 143.08, 145.30, 145.90; HRMS (FAB-MS) m/z: Calcd for C84H122O6Si6(M)+, 1394.7857, found 1394.7684; IR (KBr) 720, 818, 862, 958, 1004, 1075, 1178, 1189, 1239, 1412, 1458, 1490, 2875, 2953; dp > 300 oC.Compound (24a): 1 H NMR (CDCl 3 , 400 MHz) 0.53 (q, 12H, J = 8.0 Hz, SiEt 3 ), 0.66 (q, 12H, J = 8.0 Hz, SiEt 3 ), 0.71 (q, 12H , J = 8.0 Hz, SiEt 3 ), 0.93 (t, 18H, J = 8.0 Hz, SiEt 3 ), 0.98 (t, 18H, J = 8.0 Hz, SiEt 3 ), 0.98 (t, 18H, J = 8.0 Hz , SiEt 3 ), 5.91 (t, 4H, J = 10.0 Hz, -CH = CH-), 6.06 (t, 4H, J = 10.0 Hz, -CH = CH-), 6.09 (s, 4H, -CH = CH-), 7.07 (d, 4H, J = 8.0 Hz, -Ar), 7.32 (d, 4H, J = 8.4 Hz, -Ar), 7.41 (d, 4H, J = 8.0 Hz, -Ar), 7.46 (d, 4H, J = 8.4 Hz, -Ar), 7.48 (s, 4H, -CH = CH-); 13 C NMR (CDCl 3 , 100 MHz) 6.32, 6.43, 6.47, 7.06, 7.12, 7.12, 70.65 , 71.15, 72.42, 125.87, 125.96 , 126.26, 126.58, 126.86, 130.98, 131.85, 132.07, 139.37, 139.50, 143.08, 145.30, 145.90; HRMS (FAB-MS) m / z: Calcd for C 84 H 122 O 6 Si 6 (M) + , 1394.7857, found 1394.7684; IR (KBr) 720, 818, 862, 958, 1004, 1075, 1178, 1189, 1239, 1412, 1458, 1490, 2875, 2953; dp> 300 o C.
化合物(24b): 1H NMR (DMSO-d6, 400 MHz) 5.61 (brs, 2H, -OH), 5.69 (brs 2H, -OH), 5.83 (s, 8H, -CH=CH-), 5.87 (brs, 2H, -OH), 6.04 (s, 4H, -CH=CH-), 7.12 (d, 4H, J = 8.0 Hz, -Ar), 7.41 (d, 4H, J = 8.0 Hz, -Ar), 7.42 (s, 4H, -Ar), 7.46 (d, 4H, J= 8.0 Hz, -Ar), 7.59 (d, 4H, J = 8.0 Hz, -Ar); 13C NMR (DMSO-d6, 150 MHz) 68.42, 68.63, 69.82, 125.79, 126.04, 126.25, 126.50, 126.82, 127.37, 131.65, 131.74, 132.48, 144.43, 145.69, 146.01; HRMS (ESI-TOF) m/z: Calcd for C48H39O6 (M-H)-, 711.2752, found 711.2598; IR (KBr) 773, 821, 935, 1004, 1186, 1392, 1491, 3332 (br); dp > 350 oC.
[8]CPP: 1H NMR (CDCl3, 400 MHz) 7.48 (s, 32H, -Ar); 13C NMR (CDCl3, 100 MHz) 127.61, 137.81; HRMS (MALDI-TOF) m/z: Calcd for C48H32(M)+, 608.2499, found 608.2485.Compound (24b): 1 H NMR (DMSO-d 6 , 400 MHz) 5.61 (brs, 2H, -OH), 5.69 (brs 2H, -OH), 5.83 (s, 8H, -CH = CH-), 5.87 (brs, 2H, -OH), 6.04 (s, 4H, -CH = CH-), 7.12 (d, 4H, J = 8.0 Hz, -Ar), 7.41 (d, 4H, J = 8.0 Hz, -Ar ), 7.42 (s, 4H, -Ar), 7.46 (d, 4H, J = 8.0 Hz, -Ar), 7.59 (d, 4H, J = 8.0 Hz, -Ar); 13 C NMR (DMSO-d 6 , 150 MHz) 68.42, 68.63, 69.82, 125.79, 126.04, 126.25, 126.50, 126.82, 127.37, 131.65, 131.74, 132.48, 144.43, 145.69, 146.01; HRMS (ESI-TOF) m / z: Calcd for C 48 H 39 O 6 (MH) - , 711.2752, found 711.2598; IR (KBr) 773, 821, 935, 1004, 1186, 1392, 1491, 3332 (br); dp> 350 o C.
[8] CPP: 1 H NMR (CDCl 3 , 400 MHz) 7.48 (s, 32H, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 127.61, 137.81; HRMS (MALDI-TOF) m / z: Calcd for C 48 H 32 (M) + , 608.2499, found 608.2485.
実施例６：[9]CPPの合成
本実施例では、以下のスキーム１１に従い、９つの1,4-フェニレン基が環状に結合した化合物（[９]CPP）を得た。Example 6: Synthesis of [9] CPP In this example, a compound in which nine 1,4-phenylene groups were cyclically bonded ([9] CPP) was obtained according to the following Scheme 11.
実施例2で得た化合物(16)(1.00 g, 1.43 mmol)のTHF (100 mL)溶液に、ブチルリチウムのヘキサン溶液(1.00 equiv)(0.95 mL, 1.51 M in hexane, 1.43 mmol)を-78℃で加えた。-78℃で30分間撹拌した後、2-イソプロポキシ-4,4,5,5-テトラメチル-1,3,2-ジオキサボロラン(1.20 equiv)(0.35 mL, 1.72 mmol)を-78℃で加えた。得られた混合物を室温まで温めた後、室温で4時間反応させた後、飽和NH4Cl水溶液でクエンチし、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物の固体をヘキサンで洗浄することで、化合物(26)を87%の収率で得た。To a THF (100 mL) solution of the compound (16) (1.00 g, 1.43 mmol) obtained in Example 2, a hexane solution of butyllithium (1.00 equiv) (0.95 mL, 1.51 M in hexane, 1.43 mmol) was -78. Added at ° C. After stirring at -78 ° C for 30 minutes, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.20 equiv) (0.35 mL, 1.72 mmol) was added at -78 ° C. Was. The resulting mixture was warmed to room temperature, reacted at room temperature for 4 hours, quenched with a saturated aqueous solution of NH 4 Cl, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The solid of the crude product was washed with hexane to obtain the compound (26) in a yield of 87%.
化合物(25)(1.00 g, 1.43 mmol)、実施例2で得た化合物(16)(1.00 equiv)(1.00 g, 1.43 mmol)、Pd(PPh3)4（5 mol%）(83.2 mg, 71.5 μmol）、及び炭酸カリウム(K2CO3)(10 equiv)(2.9 mL, 5 M in H2O, 14.3 mmol）のTHF溶液（14 mL）を加熱還流下で36時間攪拌した。室温まで冷却後、反応溶液をセライト濾過し、濾液に水を加えた後、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物を分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(26)を56%の収率で得た。Compound (25) (1.00 g, 1.43 mmol), compound (16) obtained in Example 2 (1.00 equiv) (1.00 g, 1.43 mmol), Pd (PPh 3 ) 4 (5 mol%) (83.2 mg, 71.5 μmol) and potassium carbonate (K 2 CO 3 ) (10 equiv) (2.9 mL, 5 M in H 2 O, 14.3 mmol) in THF (14 mL) were stirred under heating and reflux for 36 hours. After cooling to room temperature, the reaction solution was filtered through celite, water was added to the filtrate, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by preparative gel permeation chromatography to give compound (26) in 56% yield.
化合物(26) (150 mg, 0.13 mmol)、実施例5で得た化合物(23)(97.9 mg, 0.13 mmol）、PdCl(C6H4CH2NH2)(Sphos)（8.70 mg、13 μmol）、及びリン酸三カリウム（K3PO4）（276 mg, 1.3 mmol）のトルエン/水混合溶液（45 mL/4.5 mL）を100℃で18時間攪拌した。室温まで冷却後、反応溶液をセライト濾過し、濾液に水を加えた後、CH2Cl2で抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物を分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(27a)を44%の収率で得た。
化合物(27a)(140 mg, 0.095 mmol)のTHF (6 mL)溶液にTBAFのTHF溶液(6.3 equiv)(0.6 mL, 1.00 M in THF, 0.60 mmol)を室温で加えた。室温で2時間反応させた後、溶媒を留去した。粗生成物を水、CH2Cl2で洗浄することで、化合物(27b)を96%の収率で得た。Compound (26) (150 mg, 0.13 mmol), compound (23) obtained in Example 5 (97.9 mg, 0.13 mmol), PdCl (C 6 H 4 CH 2 NH 2 ) (Sphos) (8.70 mg, 13 μmol ) And a mixed solution of toluene / water (45 mL / 4.5 mL) of tripotassium phosphate (K 3 PO 4 ) (276 mg, 1.3 mmol) was stirred at 100 ° C. for 18 hours. After cooling to room temperature, the reaction solution was filtered through celite, water was added to the filtrate, and extracted with CH 2 Cl 2 . The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by preparative gel permeation chromatography to give compound (27a) in 44% yield.
To a solution of compound (27a) (140 mg, 0.095 mmol) in THF (6 mL) was added a THF solution of TBAF (6.3 equiv) (0.6 mL, 1.00 M in THF, 0.60 mmol) at room temperature. After reacting at room temperature for 2 hours, the solvent was distilled off. The crude product was washed with water and CH 2 Cl 2 to give compound (27b) in 96% yield.
SnCl2・2H2O (3.6 equiv) (62 mg, 0.274 mmol) のTHF溶液(8 mL)に濃塩酸水溶液 (7.2 equiv)(46 μL, 12 N, 0.55 mmol)を室温で加えた。室温で15分撹拌した後、化合物(27b) (60 mg, 0.076 mmol)を固体で添加し、さらに室温で1時間撹拌した。混合物を10％NaOH水溶液で処理し、CH2Cl2で抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をCH2Cl2に溶解しショートシリカゲルパッド（CH2Cl2 100%）に通した。濾液を濃縮した後、63%の収率で[9]CPPを淡黄色固体として得た。To a THF solution (8 mL) of SnCl 2 .2H 2 O (3.6 equiv) (62 mg, 0.274 mmol) was added a concentrated aqueous hydrochloric acid solution (7.2 equiv) (46 μL, 12 N, 0.55 mmol) at room temperature. After stirring at room temperature for 15 minutes, compound (27b) (60 mg, 0.076 mmol) was added as a solid, and the mixture was further stirred at room temperature for 1 hour. The mixture was treated with a 10% aqueous solution of NaOH, extracted with CH 2 Cl 2 , and the organic layer was washed with brine, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was passed through a short silica gel pad was dissolved in CH 2 Cl 2 (CH 2 Cl 2 100%). After concentrating the filtrate, [9] CPP was obtained as a pale yellow solid in 63% yield.
化合物(25): 1H NMR (CDCl3, 400 MHz) 0.61 (q, 6H, J = 8.0 Hz, SiEt3), 0.64 (q, 6H, J = 8.0 Hz, SiEt3), 0.94 (t, 9H, J = 8.0 Hz, SiEt3), 0.96 (t, 9H, J = 8.0 Hz, SiEt3), 5.94 (d, 2H, J = 10.0 Hz, -CH=CH-), 6.03 (d, 2H, J = 10.4 Hz, -CH=CH-), 7.21 (d, 2H, J= 8.4 Hz, -Ar), 7.28-7.65 (m, 4H, J = 8.4 Hz, -Ar), 7.75 (d, 2H, J = 8.0 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.35, 6.39, 6.46, 7.01, 24.84, 71.16, 71.39, 83.74, 121.09, 125.12, 127.60, 131.14, 131.58, 134.72, 137.12, 145.08, 145.08, 148.85; HRMS (FAB-MS) m/z: Calcd for C36H54BBrO4Si2(M)+, 696.2837, found 696.2781; IR (KBr) 657, 727, 859, 959, 1010, 1070, 1145, 1239, 1360, 1399, 1457, 1609, 2875, 2954; mp 45.6 oC.Compound (25): 1 H NMR (CDCl 3 , 400 MHz) 0.61 (q, 6H, J = 8.0 Hz, SiEt 3 ), 0.64 (q, 6H, J = 8.0 Hz, SiEt 3 ), 0.94 (t, 9H , J = 8.0 Hz, SiEt 3 ), 0.96 (t, 9H, J = 8.0 Hz, SiEt 3 ), 5.94 (d, 2H, J = 10.0 Hz, -CH = CH-), 6.03 (d, 2H, J = 10.4 Hz, -CH = CH-), 7.21 (d, 2H, J = 8.4 Hz, -Ar), 7.28-7.65 (m, 4H, J = 8.4 Hz, -Ar), 7.75 (d, 2H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.35, 6.39, 6.46, 7.01, 24.84, 71.16, 71.39, 83.74, 121.09, 125.12, 127.60, 131.14, 131.58, 134.72, 137.12, 145.08, 145.08, 148.85; HRMS (FAB-MS) m / z: Calcd for C 36 H 54 BBrO 4 Si 2 (M) + , 696.2837, found 696.2781; IR (KBr) 657, 727, 859, 959, 1010, 1070, 1145, 1239, 1360, 1399, 1457, 1609, 2875, 2954; mp 45.6 o C.
化合物(26): 1H NMR (CDCl3, 400 MHz) 0.61 (q, 12H, J = 8.0 Hz, SiEt3), 0.61 (q, 12H, J = 8.0 Hz, SiEt3), 0.94 (t, 18H, J = 8.0 Hz, SiEt3), 0.94 (t, 18H, J = 8.0 Hz, SiEt3), 5.95 (d, 4H, J = 10.4 Hz, -CH=CH-), 6.04 (d, 4H, J = 10.0 Hz, -CH=CH-), 7.22 (d, 4H, J = 8.4 Hz, -Ar), 7.37 (m, 8H, J = 8.4 Hz, -Ar), 7.51 (d, 4H, J = 8.4 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.42, 7.04, 71.22, 71.26, 121.18, 126.25, 126.78, 127.71, 131.10, 131.19, 131.81, 139.60, 144.89, 145.21; HRMS (FAB-MS) m/z: Calcd for C60H84Br2O4Si4(M)+, 1138.3813, found 1140.3028; IR (KBr) 727, 860, 859, 959, 1004, 1069, 1239, 1361, 1400, 1457, 1609, 2875, 2953; dp > 300 oC.Compound (26): 1 H NMR (CDCl 3 , 400 MHz) 0.61 (q, 12H, J = 8.0 Hz, SiEt 3 ), 0.61 (q, 12H, J = 8.0 Hz, SiEt 3 ), 0.94 (t, 18H , J = 8.0 Hz, SiEt 3 ), 0.94 (t, 18H, J = 8.0 Hz, SiEt 3 ), 5.95 (d, 4H, J = 10.4 Hz, -CH = CH-), 6.04 (d, 4H, J = 10.0 Hz, -CH = CH-), 7.22 (d, 4H, J = 8.4 Hz, -Ar), 7.37 (m, 8H, J = 8.4 Hz, -Ar), 7.51 (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.42, 7.04, 71.22, 71.26, 121.18, 126.25, 126.78, 127.71, 131.10, 131.19, 131.81, 139.60, 144.89, 145.21; HRMS (FAB-MS) m / z: Calcd for C 60 H 84 Br 2 O 4 Si 4 (M) + , 1138.3813, found 1140.3028; IR (KBr) 727, 860, 859, 959, 1004, 1069, 1239, 1361, 1400, 1457, 1609, 2875, 2953; dp> 300 o C.
化合物(27a): 1H NMR (CDCl3, 400 MHz) 0.64 (q, 36H, J = 8.0 Hz, SiEt3), 0.96 (t, 54H, J = 8.0 Hz, SiEt3), 6.02 (s, 12H, -CH=CH-), 7.43 (d, 12H, J = 7.6 Hz, -Ar), 7.57 (d, 12H, J = 8.8 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.50, 7.08, 71.48, 126.31, 126.53, 131.43, 139.19, 145.23; HRMS (MALDI-TOF) m/z: Calcd for C90H126AgO6Si6(M + Ag)+, 1577.7221, found 1577.6958; IR (KBr) 720, 818, 862, 958, 1004, 1073, 1178, 1189, 1239, 1412, 1458, 1490, 2875, 2953; dp > 300 oC.Compound (27a): 1 H NMR (CDCl 3 , 400 MHz) 0.64 (q, 36 H, J = 8.0 Hz, SiEt 3 ), 0.96 (t, 54H, J = 8.0 Hz, SiEt 3 ), 6.02 (s, 12H , -CH = CH-), 7.43 (d, 12H, J = 7.6 Hz, -Ar), 7.57 (d, 12H, J = 8.8 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.50, 7.08, 71.48, 126.31, 126.53, 131.43, 139.19, 145.23; HRMS (MALDI-TOF) m / z: Calcd for C 90 H 126 AgO 6 Si 6 (M + Ag) + , 1577.7221, found 1577.6958; IR (KBr) 720, 818, 862, 958, 1004, 1073, 1178, 1189, 1239, 1412, 1458, 1490, 2875, 2953; dp> 300 o C.
化合物(27b): 1H NMR (DMSO-d6, 600 MHz) 5.78 (s, 6H, -OH), 5.93 (s, 12H, -CH=CH-), 7.44 (d, 12H, J = 8.4 Hz, -CH=CH-), 7.65 (d, 12H, J = 9.0 Hz, -Ar); 13C NMR (DMSO-d6, 150 MHz) 68.98, 126.62, 126.71, 131.66, 138.56, 146.01; HRMS (ESI-TOF) m/z: Calcd for C54H43O6 (M + H)-, 787.3065, found 787.3213; IR (KBr) 724, 819, 863, 957, 1004, 1072, 1178, 1239, 1401, 1458, 1490, 2876, 2912, 2953; dp > 300 oC.
[9]CPP: 1H NMR (CDCl3, 400 MHz) 7.52 (s, 36H, -Ar); H); 13C NMR (100 MHz, CDCl3) 127.51, 138.02; HRMS (MALDI-TOF) m/z: Calcd for C54H36 (M)+, 684.2812, found 684.2825.Compound (27b): 1 H NMR (DMSO-d 6 , 600 MHz) 5.78 (s, 6H, -OH), 5.93 (s, 12H, -CH = CH-), 7.44 (d, 12H, J = 8.4 Hz , -CH = CH-), 7.65 (d, 12H, J = 9.0 Hz, -Ar); 13 C NMR (DMSO-d 6 , 150 MHz) 68.98, 126.62, 126.71, 131.66, 138.56, 146.01; HRMS (ESI -TOF) m / z: Calcd for C 54 H 43 O 6 (M + H) - , 787.3065, found 787.3213; IR (KBr) 724, 819, 863, 957, 1004, 1072, 1178, 1239, 1401, 1458 , 1490, 2876, 2912, 2953; dp> 300 o C.
[9] CPP: 1 H NMR (CDCl 3 , 400 MHz) 7.52 (s, 36H, -Ar); H); 13 C NMR (100 MHz, CDCl 3 ) 127.51, 138.02; HRMS (MALDI-TOF) m / z: Calcd for C 54 H 36 (M) + , 684.2812, found 684.2825.
実施例７：[10]CPPの合成
本実施例では、以下のスキーム１２に従い、10個の1,4-フェニレン基が環状に結合した化合物（[10]CPP）を得た。Example 7: Synthesis of [10] CPP In this example, a compound ([10] CPP) in which ten 1,4-phenylene groups were cyclically bonded was obtained according to the following Scheme 12.
化合物(11) (0.50 g, 0.47 mmol)のTHF (4.7 mL)溶液に、ブチルリチウムのヘキサン溶液(2.20 equiv)(0.70 mL, 1.49 M in hexane, 1.03 mmol)を-78℃で加えた。-78℃で1時間撹拌した後、2-イソプロポキシ-4,4,5,5-テトラメチル-1,3,2-ジオキサボロラン(2.40 equiv)(0.23 mL, 1.13 mmol)を-78℃で加えた。得られた混合物を室温まで温めた後、室温で4時間反応させた後、飽和NH4Cl水溶液でクエンチし、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物の固体をヘキサンで洗浄することで、化合物(28)を92%の収率で得た。To a solution of compound (11) (0.50 g, 0.47 mmol) in THF (4.7 mL) was added a hexane solution of butyllithium (2.20 equiv) (0.70 mL, 1.49 M in hexane, 1.03 mmol) at -78 ° C. After stirring at -78 ° C for 1 hour, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.40 equiv) (0.23 mL, 1.13 mmol) was added at -78 ° C. Was. The resulting mixture was warmed to room temperature, reacted at room temperature for 4 hours, quenched with a saturated aqueous solution of NH 4 Cl, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. By washing the solid of the crude product with hexane, compound (28) was obtained in a yield of 92%.
化合物(28) (0.41 g, 0.35 mmol)、実施例１もしくは2で得た化合物(11)（0.40 g, 0.35 mmol）、PdCl(C6H4CH2NH2)(Sphos)(20 mol%)(46 mg, 0.07 mmol）、及びリン酸三カリウム（K3PO4）(8 equiv)(0.30 g、1.40 mmol）のトルエン/水混合溶液（120 mL/12 mL）を100℃で40時間攪拌した。室温まで冷却後、反応溶液をセライト濾過し、濾液に水を加えた後、CH2Cl2で抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物を分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(29a)を37%の収率で得た。Compound (28) (0.41 g, 0.35 mmol), compound (11) obtained in Example 1 or 2 (0.40 g, 0.35 mmol), PdCl (C 6 H 4 CH 2 NH 2 ) (Sphos) (20 mol% ) (46 mg, 0.07 mmol) and a solution of tripotassium phosphate (K 3 PO 4 ) (8 equiv) (0.30 g, 1.40 mmol) in toluene / water (120 mL / 12 mL) at 100 ° C for 40 hours Stirred. After cooling to room temperature, the reaction solution was filtered through celite, water was added to the filtrate, and extracted with CH 2 Cl 2 . The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by preparative gel permeation chromatography to give compound (29a) in 37% yield.
化合物(29a)(0.20 g, 0.11 mmol)のTHF (6 mL)溶液にTBAFのTHF溶液(8.4 equiv)(0.92 mL, 1.00 M in THF, 0.92 mmol)を室温で加えた。室温で3時間反応させた後、溶媒を留去した。粗生成物を水、CH2Cl2で洗浄することで、化合物(29b)を91%の収率で得た。To a THF (6 mL) solution of the compound (29a) (0.20 g, 0.11 mmol) was added a THF solution of TBAF (8.4 equiv) (0.92 mL, 1.00 M in THF, 0.92 mmol) at room temperature. After reacting at room temperature for 3 hours, the solvent was distilled off. The crude product was washed with water and CH 2 Cl 2 to give compound (29b) in 91% yield.
SnCl2・2H2O (4.4 equiv) (99.3 mg, 0.44 mmol) のTHF溶液(5 mL)に濃塩酸水溶液 (8.8 equiv)(73.3 μL, 12 N, 0.88 mmol)を室温で加えた。室温で15分撹拌した後、化合物(29b) (90.1 mg, 0.10 mmol)を固体で添加し、さらに室温で12時間撹拌した。混合物を10％NaOH水溶液で処理し、CH2Cl2で抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をCH2Cl2に溶解しショートシリカゲルパッド（CH2Cl2 100%）に通した。濾液を濃縮した後、分取用ゲル浸透クロマトグラフィーにより精製することで、56%の収率で[10]CPPを淡黄色固体として得た。To a THF solution (5 mL) of SnCl 2 .2H 2 O (4.4 equiv) (99.3 mg, 0.44 mmol) was added a concentrated aqueous hydrochloric acid solution (8.8 equiv) (73.3 μL, 12 N, 0.88 mmol) at room temperature. After stirring at room temperature for 15 minutes, compound (29b) (90.1 mg, 0.10 mmol) was added as a solid, and the mixture was further stirred at room temperature for 12 hours. The mixture was treated with a 10% aqueous solution of NaOH, extracted with CH 2 Cl 2 , and the organic layer was washed with brine, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was passed through a short silica gel pad was dissolved in CH 2 Cl 2 (CH 2 Cl 2 100%). The filtrate was concentrated and then purified by preparative gel permeation chromatography to obtain [10] CPP as a pale yellow solid in a yield of 56%.
化合物(28): 1H NMR (CDCl3, 400 MHz) 0.59 (m, 24H, SiEt3), 0.92 (m, 36H, SiEt3), 1.32 (s, 24H, Bpin), 5.94 (d, 4H, J = 10.4 Hz, -CH=CH-), 5.98 (d, 4H, J = 10.4 Hz, -CH=CH-), 7.22 (s, 4H, -Ar), 7.32 (d, 4H, J = 8.4 Hz, -Ar), 7.69 (d, 4H, J = 8.4 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.45, 7.03, 24.86, 71.25, 71.59, 83.67, 125.15, 125.68, 131.22, 131.61, 134.65, 144.91, 149.16; HRMS (FAB-MS) m/z: Calcd for C66H104B2O8Si4(M)+, 1158.6994, found 1158.7027; IR (KBr) 734, 860, 959, 1075, 1089, 1145, 1318, 1357, 1390, 1457, 1607, 2873, 2951; dp > 350 oC.Compound (28): 1 H NMR (CDCl 3 , 400 MHz) 0.59 (m, 24H, SiEt 3 ), 0.92 (m, 36H, SiEt 3 ), 1.32 (s, 24H, Bpin), 5.94 (d, 4H, J = 10.4 Hz, -CH = CH-), 5.98 (d, 4H, J = 10.4 Hz, -CH = CH-), 7.22 (s, 4H, -Ar), 7.32 (d, 4H, J = 8.4 Hz , -Ar), 7.69 (d, 4H, J = 8.4 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.45, 7.03, 24.86, 71.25, 71.59, 83.67, 125.15, 125.68, 131.22, 131.61, 134.65, 144.91, 149.16; HRMS (FAB-MS) m / z: Calcd for C 66 H 104 B 2 O 8 Si 4 (M) + , 1158.6994, found 1158.7027; IR (KBr) 734, 860, 959, 1075, 1089, 1145, 1318, 1357, 1390, 1457, 1607, 2873, 2951; dp> 350 o C.
化合物(29a): 1H NMR (CDCl3, 400 MHz) 0.59 (q, 24H, J = 8.0 Hz, SiEt3), 0.64 (q, 12H, J = 8.0 Hz, SiEt3), 0.92 (t, 36H, J = 8.0 Hz, SiEt3), 0.95 (t, 36H, J = 8.0 Hz, SiEt3), 5.94 (s, 16H, -CH=CH-), 7.21 (s, 8H, -Ar), 7.31 (d, 8H, J = 8.0 Hz, -Ar), 7.41 (d, 8H, J = 8.0 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.46, 7.05, 71.35, 71.37, 125.60, 126.16, 126.59, 131.27, 131.51, 139.31, 144.97, 145.10; HRMS (MALDI-TOF) m/z: Calcd for C108H160AgO8Si8(M + Ag)+, 1915.9318, found 1916.3896; IR (KBr) 723, 862, 960, 1004, 1068, 1189, 1400, 1457, 1490, 2876, 2911; dp > 300 oC.Compound (29a): 1 H NMR (CDCl 3 , 400 MHz) 0.59 (q, 24H, J = 8.0 Hz, SiEt 3 ), 0.64 (q, 12H, J = 8.0 Hz, SiEt 3 ), 0.92 (t, 36H , J = 8.0 Hz, SiEt 3 ), 0.95 (t, 36H, J = 8.0 Hz, SiEt 3 ), 5.94 (s, 16H, -CH = CH-), 7.21 (s, 8H, -Ar), 7.31 ( d, 8H, J = 8.0 Hz, -Ar), 7.41 (d, 8H, J = 8.0 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.46, 7.05, 71.35, 71.37, 125.60, 126.16, 126.59, 131.27, 131.51, 139.31, 144.97, 145.10; HRMS (MALDI-TOF) m / z: Calcd for C 108 H 160 AgO 8 Si 8 (M + Ag) + , 1915.9318, found 1916.3896; IR (KBr) 723, 862, 960, 1004, 1068, 1189, 1400, 1457, 1490, 2876, 2911; dp> 300 o C.
化合物(29b): 1H NMR (DMSO-d6, 400 MHz) 5.59 (d, 8H, J = 8.8 Hz, -Ar), 5.85 (s, 8H, - CH=CH-), 5.86 (s, 8H, - CH=CH-), 7.28 (s, 8H, -OH), 7.39 (d, 8H, J = 8.4 Hz, -Ar), 7.52 (d, 8H, J = 8.4 Hz, -Ar); 13C NMR (DMSO-d6, 100 MHz) 68.00, 68.14, 125.25, 126.11, 126.43, 131.07, 131.54, 138.58, 144.82, 145.34; HRMS (ESI-TOF) m/z: Calcd for C60H49O8 (M + H)-, 897.3433, found 897.3465; IR (KBr) 723, 819, 960, 1004, 1033, 1055, 1189, 1239, 1361, 1400, 1456, 1489, 2876, 2953, 3326 (br); dp > 400 oC.
[10]CPP: 1H NMR (CDCl3, 400 MHz) 7.56 (s, 40H, Ar-H); 13C NMR (CDCl3, 100 MHz) 127.51, 138.29; HRMS (MALDI-TOF) m/z calcd for C60H40 [M]+: 760.3125, found 760.3077.Compound (29b): 1 H NMR (DMSO-d 6 , 400 MHz) 5.59 (d, 8H, J = 8.8 Hz, -Ar), 5.85 (s, 8H,-CH = CH-), 5.86 (s, 8H ,-CH = CH-), 7.28 (s, 8H, -OH), 7.39 (d, 8H, J = 8.4 Hz, -Ar), 7.52 (d, 8H, J = 8.4 Hz, -Ar); 13 C NMR (DMSO-d 6 , 100 MHz) 68.00, 68.14, 125.25, 126.11, 126.43, 131.07, 131.54, 138.58, 144.82, 145.34; HRMS (ESI-TOF) m / z: Calcd for C 60 H 49 O 8 (M + H) - , 897.3433, found 897.3465; IR (KBr) 723, 819, 960, 1004, 1033, 1055, 1189, 1239, 1361, 1400, 1456, 1489, 2876, 2953, 3326 (br); dp> 400 o C.
[10] CPP: 1 H NMR (CDCl 3 , 400 MHz) 7.56 (s, 40H, Ar-H); 13 C NMR (CDCl 3 , 100 MHz) 127.51, 138.29; HRMS (MALDI-TOF) m / z calcd for C 60 H 40 [M] + : 760.3125, found 760.3077.
実施例８：[11]CPPの合成
本実施例では、以下のスキーム１３に従い、11個の1,4-フェニレン基が環状に結合した化合物（[11]CPP）を得た。Example 8: Synthesis of [11] CPP In this example, a compound in which 11 1,4-phenylene groups were cyclically bonded ([11] CPP) was obtained according to the following Scheme 13.
実施例6で得た化合物(26) (0.49 g, 0.43 mmol)、実施例7で得た化合物28 (1.0 equiv)(0.50 g, 0.43 mmol）、PdCl(C6H4CH2NH2)(Sphos)(10 mol%)(28.4 mg, 0.043 mmol）、及びリン酸三カリウム（K3PO4）(4 equiv)(0.92 g, 1.40 mmol）のトルエン/水混合溶液（140 mL/14 mL）を100℃で40時間攪拌した。室温まで冷却後、反応溶液をセライト濾過し、濾液に水を加えた後、CH2Cl2で抽出した。有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物を分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(30a)を58%の収率で得た。Compound (26) (0.49 g, 0.43 mmol) obtained in Example 6, Compound 28 (1.0 equiv) (0.50 g, 0.43 mmol) obtained in Example 7, PdCl (C 6 H 4 CH 2 NH 2 ) ( Sphos) (10 mol%) (28.4 mg, 0.043 mmol) and tripotassium phosphate (K 3 PO 4 ) (4 equiv) (0.92 g, 1.40 mmol) in a toluene / water mixed solution (140 mL / 14 mL) Was stirred at 100 ° C. for 40 hours. After cooling to room temperature, the reaction solution was filtered through celite, water was added to the filtrate, and extracted with CH 2 Cl 2 . The organic layer was washed with saturated saline, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by preparative gel permeation chromatography to give compound (30a) in 58% yield.
化合物(30a)(0.40 g, 0.21 mmol)のTHF (10 mL)溶液にTBAFのTHF溶液(8.4 equiv)(1.80 mL, 1.00 M in THF, 1.78 mmol)を室温で加えた。室温で3時間反応させた後、溶媒を留去した。粗生成物を水、CH2Cl2で洗浄することで、化合物(30b)を98%の収率で得た。To a THF (10 mL) solution of the compound (30a) (0.40 g, 0.21 mmol) was added a THF solution of TBAF (8.4 equiv) (1.80 mL, 1.00 M in THF, 1.78 mmol) at room temperature. After reacting at room temperature for 3 hours, the solvent was distilled off. The crude product was washed with water and CH 2 Cl 2 to give compound (30b) in 98% yield.
SnCl2・2H2O (4.4 equiv) (203.1 mg, 0.90 mmol) のTHF溶液(5 mL)に濃塩酸水溶液 (8.8 equiv)(154 μL, 12 N, 1.85 mmol)を室温で加えた。室温で15分撹拌した後、化合物(30b) (200 mg, 0.21 mmol)を固体で添加し、さらに室温で12時間撹拌した。混合物を10％NaOH水溶液で処理し、CH2Cl2で抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をCH2Cl2に溶解しショートシリカゲルパッド（CH2Cl2 100%）に通した。濾液を濃縮した後、78%の収率で[11]CPPを淡黄色固体として得た。To a THF solution (5 mL) of SnCl 2 .2H 2 O (4.4 equiv) (203.1 mg, 0.90 mmol) was added a concentrated aqueous hydrochloric acid solution (8.8 equiv) (154 μL, 12 N, 1.85 mmol) at room temperature. After stirring at room temperature for 15 minutes, compound (30b) (200 mg, 0.21 mmol) was added as a solid, and the mixture was further stirred at room temperature for 12 hours. The mixture was treated with a 10% aqueous solution of NaOH, extracted with CH 2 Cl 2 , and the organic layer was washed with brine, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was passed through a short silica gel pad was dissolved in CH 2 Cl 2 (CH 2 Cl 2 100%). After concentration of the filtrate, [11] CPP was obtained as a pale yellow solid in 78% yield.
化合物(30a): 1H NMR (CDCl3, 400 MHz) 0.49-0.71 (m, 48H, SiEt3), 0.81-1.03 (m, 72H, SiEt3), 5.94 (d, 4H, J = 10.0 Hz, -CH=CH-), 6.00 (d, 4H, J = 10.0 Hz, -CH=CH-), 6.02 (s, 8H, -CH=CH-), 7.21-7.37 (m, 8H, -Ar), 7.37-7.47 (m, 8H, -Ar); 13C NMR (CDCl3, 100 MHz) 6.39, 6.42, 7.05, 7.05, 71.14, 71.29, 71.43, 71.62, 125.72, 126.09, 126.31, 126.51, 126.74, 131.29, 131.37, 131.43, 131.48, 131.58, 131.95, 139.37, 139.52, 139.73, 144.76, 144.98, 145.10, 145.35; HRMS (MALDI-TOF) m/z: Calcd for C114H164AgO8Si8(M + Ag)+, 1991.9631, found 1992.3016; IR (KBr) 720, 862, 960, 1004, 1074, 1189, 1238, 1412, 1458, 1490, 2875, 2909, 2953; dp > 300 oC.Compound (30a): 1 H NMR (CDCl 3 , 400 MHz) 0.49-0.71 (m, 48H, SiEt 3 ), 0.81-1.03 (m, 72H, SiEt 3 ), 5.94 (d, 4H, J = 10.0 Hz, -CH = CH-), 6.00 (d, 4H, J = 10.0 Hz, -CH = CH-), 6.02 (s, 8H, -CH = CH-), 7.21-7.37 (m, 8H, -Ar), 7.37-7.47 (m, 8H, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.39, 6.42, 7.05, 7.05, 71.14, 71.29, 71.43, 71.62, 125.72, 126.09, 126.31, 126.51, 126.74, 131.29, 131.37, 131.43, 131.48, 131.58, 131.95, 139.37, 139.52, 139.73, 144.76, 144.98, 145.10, 145.35; HRMS (MALDI-TOF) m / z: Calcd for C 114 H 164 AgO 8 Si 8 (M + Ag) + , 1991.9631, found 1992.3016; IR (KBr) 720, 862, 960, 1004, 1074, 1189, 1238, 1412, 1458, 1490, 2875, 2909, 2953; dp> 300 o C.
化合物(30b): 1H NMR (DMSO-d6, 400 MHz) 5.58 (brs, 4H, -OH), 5.62 (brs, 4H, -OH), 5.76 (brs, 4H, -OH), 5.82-6.06 (m, 16H, -CH=CH-), 7.28-7.47 (m, 16H, -Ar), 7.48-7.68 (m, 12H, -Ar); 13C NMR (DMSO-d6, 150 MHz) 67.54, 68.39, 68.52, 68.74, 68.99, 79.70, 125.92, 126.45, 126.65, 126.70, 126.95, 131.58, 131.72, 131.83, 131.88, 138.80, 139.10, 139.21, 145.65, 145.79; HRMS (ESI-TOF) m/z: Calcd for C66H53O8(M + H)-, 973.3746, found 973.3765; IR (KBr) 730, 737, 820, 934, 1003, 1178, 1407, 1492, 3339 (br); dp > 300 oC.
[11]CPP: 1H NMR (CDCl3, 400 MHz) 7.58 (s, 44H, -Ar); 13C NMR (100 MHz, CDCl3) 127.40, 138.49; HRMS (MALDI-TOF) m/z: Calcd for C66H44 (M)+, 836.3438, found 836.3215.Compound (30b): 1 H NMR (DMSO-d 6 , 400 MHz) 5.58 (brs, 4H, -OH), 5.62 (brs, 4H, -OH), 5.76 (brs, 4H, -OH), 5.82-6.06 (m, 16H, -CH = CH-), 7.28-7.47 (m, 16H, -Ar), 7.48-7.68 (m, 12H, -Ar); 13 C NMR (DMSO-d 6 , 150 MHz) 67.54, 68.39, 68.52, 68.74, 68.99, 79.70, 125.92, 126.45, 126.65, 126.70, 126.95, 131.58, 131.72, 131.83, 131.88, 138.80, 139.10, 139.21, 145.65, 145.79; HRMS (ESI-TOF) m / z: Calcd for C 66 H 53 O 8 (M + H) - , 973.3746, found 973.3765; IR (KBr) 730, 737, 820, 934, 1003, 1178, 1407, 1492, 3339 (br); dp> 300 o C.
[11] CPP: 1 H NMR (CDCl 3 , 400 MHz) 7.58 (s, 44H, -Ar); 13 C NMR (100 MHz, CDCl 3 ) 127.40, 138.49; HRMS (MALDI-TOF) m / z: Calcd for C 66 H 44 (M) + , 836.3438, found 836.3215.
実施例9：[12]CPPの合成
本実施例では、以下のスキーム14に従い、12個の1,4-フェニレン基が環状に結合した化合物（[12]CPP）を得た。Example 9: Synthesis of [12] CPP In this example, a compound in which 12 1,4-phenylene groups were cyclically bonded ([12] CPP) was obtained according to the following Scheme 14.
Ni(cod)2(57.8 mg, 0.21 mmol)と2,2’-ビピリジル (32.8 mg, 0.21 mmol)のTHF（10 mL）溶液を50℃で30分撹拌した。得られた混合溶液を26 (114.1 mg, 0.10 mmol) の THF (10 mL)溶液に室温で加えた。 加熱還流下、16時間撹拌した後、反応溶液をセライト濾過し、酢酸エチルで洗浄した。濾液を濃縮した後、分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(31a)を71%の収率で得た。A solution of Ni (cod) 2 (57.8 mg, 0.21 mmol) and 2,2′-bipyridyl (32.8 mg, 0.21 mmol) in THF (10 mL) was stirred at 50 ° C. for 30 minutes. The obtained mixed solution was added to a solution of 26 (114.1 mg, 0.10 mmol) in THF (10 mL) at room temperature. After stirring for 16 hours while heating under reflux, the reaction solution was filtered through celite, and washed with ethyl acetate. The filtrate was concentrated and then purified by preparative gel permeation chromatography to obtain the compound (31a) in a yield of 71%.
化合物(31a)(0.21 g, 0.10 mmol)のTHF (6 mL)溶液にTBAFのTHF溶液(8.8 equiv)(0.90 mL, 1.00 M in THF, 1.80 mmol)を室温で加えた。室温で3時間反応させた後、溶媒を留去した。粗生成物を水、CH2Cl2で洗浄することで、化合物(31b)を94%の収率で得た。To a THF (6 mL) solution of the compound (31a) (0.21 g, 0.10 mmol) was added a THF solution of TBAF (8.8 equiv) (0.90 mL, 1.00 M in THF, 1.80 mmol) at room temperature. After reacting at room temperature for 3 hours, the solvent was distilled off. The crude product was washed with water and CH 2 Cl 2 to give compound (31b) in 94% yield.
SnCl2・2H2O (4.4 equiv) (88.0 mg, 0.39 mmol) のTHF溶液(40 mL)に濃塩酸水溶液 (8.8 equiv)(65.0 μL, 12 N, 0.77 mmol)を室温で加えた。室温で15分撹拌した後、化合物(31b) (92.0 mg, 0.088 mmol)を固体で添加し、さらに室温で12時間撹拌した。混合物を10％NaOH水溶液で処理し、CH2Cl2で抽出し、さらに、有機層を飽和食塩水で洗浄後、Na2SO4で乾燥させ、減圧濃縮した。粗生成物をCH2Cl2に溶解しショートシリカゲルパッド（CH2Cl2 100%）に通した。濾液を濃縮した後、72%の収率で[12]CPPを淡黄色固体として得た。To a THF solution (40 mL) of SnCl 2 .2H 2 O (4.4 equiv) (88.0 mg, 0.39 mmol) was added a concentrated hydrochloric acid aqueous solution (8.8 equiv) (65.0 μL, 12 N, 0.77 mmol) at room temperature. After stirring at room temperature for 15 minutes, compound (31b) (92.0 mg, 0.088 mmol) was added as a solid, and the mixture was further stirred at room temperature for 12 hours. The mixture was treated with a 10% aqueous solution of NaOH, extracted with CH 2 Cl 2 , and the organic layer was washed with brine, dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was passed through a short silica gel pad was dissolved in CH 2 Cl 2 (CH 2 Cl 2 100%). After concentrating the filtrate, [12] CPP was obtained as a pale yellow solid in 72% yield.
化合物(31a): 1H NMR (CDCl3, 400 MHz) 0.61 (q, 48H, J = 8.0 Hz, SiEt3), 0.94 (t, 72H, J = 8.0 Hz, SiEt3), 6.01 (s, 16H, -CH=CH-), 7.36 (d, 16H, J = 7.2 Hz, -Ar), 7.43 (d, 16H, J = 6.8 Hz, -Ar); 13C NMR (CDCl3, 100 MHz) 6.42, 7.08, 71.35, 71.37, 126.27, 126.75, 131.47, 139.61, 144.96; HRMS (MALDI-TOF) m/z: Calcd for C120H168AgO8Si8(M + Ag)+, 2067.9944, found 2068.6758; IR (KBr) 722, 818, 860, 958, 1005, 1070, 1185, 1237, 1407, 1460, 2877, 2952; dp > 300 oC.Compound (31a): 1 H NMR (CDCl 3 , 400 MHz) 0.61 (q, 48H, J = 8.0 Hz, SiEt 3 ), 0.94 (t, 72H, J = 8.0 Hz, SiEt 3 ), 6.01 (s, 16H , -CH = CH-), 7.36 (d, 16H, J = 7.2 Hz, -Ar), 7.43 (d, 16H, J = 6.8 Hz, -Ar); 13 C NMR (CDCl 3 , 100 MHz) 6.42, 7.08, 71.35, 71.37, 126.27, 126.75, 131.47, 139.61, 144.96; HRMS (MALDI-TOF) m / z: Calcd for C 120 H 168 AgO 8 Si 8 (M + Ag) + , 2067.9944, found 2068.6758; IR ( KBr) 722, 818, 860, 958, 1005, 1070, 1185, 1237, 1407, 1460, 2877, 2952; dp> 300 o C.
化合物(31b): 1H NMR (DMSO-d6, 400 MHz) 5.71 (s, 8H, -OH), 5.93 (s, 16H, - CH=CH-), 7.41 (d, 16H, J = 7.6 Hz, -Ar), 7.56 (d, 16H, J = 7.6 Hz, -Ar); 13C NMR (DMSO-d6, 150 MHz) 68.68, 126.64, 126.89, 131.76, 139.05, 145.85; HRMS (ESI-TOF) m/z: Calcd for C72H57O8 (M + H)-, 1049.4059, found 1049.4132; IR (KBr) 730, 787, 822, 934, 1003, 1178, 1407, 1492, 3339 (br); dp > 300 oC.
[12]CPP: 1H NMR (CDCl3, 400 MHz) 7.61 (s, 48H, -Ar); 13C NMR (100 MHz, CDCl3) 127.33, 138.49; IR HRMS (MALDI-TOF) m/z: Calcd for C72H48 (M)+, 912.3756, found 912.3797.Compound (31b): 1 H NMR (DMSO-d 6 , 400 MHz) 5.71 (s, 8H, -OH), 5.93 (s, 16H,-CH = CH-), 7.41 (d, 16H, J = 7.6 Hz , -Ar), 7.56 (d, 16H, J = 7.6 Hz, -Ar); 13 C NMR (DMSO-d 6 , 150 MHz) 68.68, 126.64, 126.89, 131.76, 139.05, 145.85; HRMS (ESI-TOF) m / z: Calcd for C 72 H 57 O 8 (M + H) - , 1049.4059, found 1049.4132; IR (KBr) 730, 787, 822, 934, 1003, 1178, 1407, 1492, 3339 (br); dp > 300 o C.
[12] CPP: 1 H NMR (CDCl 3 , 400 MHz) 7.61 (s, 48H, -Ar); 13 C NMR (100 MHz, CDCl 3) 127.33, 138.49; IR HRMS (MALDI-TOF) m / z: Calcd for C 72 H 48 (M) + , 912.3756, found 912.3797.
実施例10：[6], [9], [12]CPP前駆体の合成
本実施例では、以下のスキーム15に従い、6, 9, 12個の1,4-フェニレン基が環状に結合した化合物（[6], [9], [12]CPP）の前駆体を得た。Example 10: Synthesis of [6], [9], [12] CPP precursor In this example, according to the following scheme 15, a compound in which 6, 9, 12 1,4-phenylene groups are cyclically bonded ([6], [9], [12] CPP) precursors were obtained.
Ni(cod)2(275.1 mg, 1.00 mmol)と2,2’-ビピリジル (156.2 mg, 1.00 mmol)のTHF（10 mL）溶液を50℃で30分撹拌した。得られた混合溶液を18 (325.3 mg, 0.50 mmol) の THF (90 mL)溶液に室温で加えた。 加熱還流下、20時間撹拌した後、反応溶液をセライト濾過し、酢酸エチルで洗浄した。濾液を濃縮した後、分取用ゲル浸透クロマトグラフィーにより精製することで、化合物(20a)、化合物(27a)、化合物(31a)を11、31、16%の収率で得た。化合物(20a)、化合物(27a)、化合物(31a)が得られたことは、上記の物性値と同じであることで確認した。A solution of Ni (cod) 2 (275.1 mg, 1.00 mmol) and 2,2′-bipyridyl (156.2 mg, 1.00 mmol) in THF (10 mL) was stirred at 50 ° C. for 30 minutes. The obtained mixed solution was added to a solution of 18 (325.3 mg, 0.50 mmol) in THF (90 mL) at room temperature. After stirring under reflux with heating for 20 hours, the reaction solution was filtered through celite and washed with ethyl acetate. The filtrate was concentrated and then purified by preparative gel permeation chromatography to obtain compound (20a), compound (27a) and compound (31a) in 11, 31, and 16% yields. It was confirmed that the compound (20a), the compound (27a), and the compound (31a) were obtained because they were the same as the above physical properties.
本発明の化合物(I)は狭いHOMO-LUMOギャップを持つことから、有機トランジスターや有機太陽電池材料などの有機エレクトロニクス材料の開発に対して新しい骨格を提供するものである。また、構造の明確なカーボンナノチューブ合成の種化合物としての利用が検討されている、光、電子材料などを初めとする様々なナノテク材料への応用も期待される。 Since the compound (I) of the present invention has a narrow HOMO-LUMO gap, it provides a new framework for the development of organic electronic materials such as organic transistors and organic solar cell materials. It is also expected to be applied to various nanotech materials such as optical and electronic materials, which are being considered for use as seed compounds for synthesizing carbon nanotubes having a clear structure.
Claims (9)
（１）Ｓｎ（ＩＩ）化合物、
（２）Ｆｅ（ＩＩ）化合物、
（３）Ｃｕ、ＣｕＣｌ、ＣｕＢｒ，Ｍｎ，ＴｉＣｌ３又はＣｒＣｌ３から選ばれる低原子価無機金属塩化合物
のいずれかに記載の還元剤の存在下に還元的に脱離させてパラフェニレン環に導くことを特徴とする下記式（Ｉ）で表される化合物の製造法。
Ａ１及びＡ２は、同一又は異なって、下記式
但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。） From the compound of the following formula (II), the OH group at the 2,5-position bonded to the 1,3-cyclohexadiene ring is represented by the following (1) to (3):
(1) a Sn (II) compound,
(2) Fe (II) compounds,
(3) Reductive elimination in the presence of a reducing agent described in any of low-valent inorganic metal salt compounds selected from Cu, CuCl, CuBr, Mn, TiCl 3 and CrCl 3 to lead to a paraphenylene ring. A method for producing a compound represented by the following formula (I):
A 1 and A 2 are the same or different and are represented by the following formula:
However, when l = n = 2, unless p in A 1 and A 2 are both 0. )
Ｒは水素原子、アルキル、シクロアルキル、アルコキシ、アルケニル、アルキニル、ハロゲン原子、ＯＨ、ＣＮ、ＮＯ２、ＣＯＯＨ、ＮＨ２、アリール、ヘテロシクリル、アラルキル、モノアルキルアミノ、ジアルキルアミノ、アシルアミノ、アシル、アルキルカルボニルオキシ、アリールカルボニルオキシ、アルコキシカルボニル、アルコキシカルボニルアミノ、フルオロアルキル、パーフルオロアルキル、モノアルキルカルバモイル、ジアルキルカルバモイル、モノアルキル置換スルファモイル、ジアルキル置換スルファモイル又はアルキルスルホニルアミノを示す。
Ａ１ａ及びＡ２ａは、同一又は異なって、下記式
Ａ１及びＡ２は、同一又は異なって、下記式
但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。） A step of cyclizing a compound of the following formula (IIA) in the presence of a cyclization catalyst to obtain a compound of the general formula (IIB), and a step of deprotecting the hydroxyl-protecting group (Pro) of the compound of the general formula (IIB) A method for producing a compound represented by the general formula (II), comprising:
R is a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, halogen atom, OH, CN, NO 2 , COOH, NH 2 , aryl, heterocyclyl, aralkyl, monoalkylamino, dialkylamino, acylamino, acyl, alkylcarbonyl Oxy, arylcarbonyloxy, alkoxycarbonyl, alkoxycarbonylamino, fluoroalkyl, perfluoroalkyl, monoalkylcarbamoyl, dialkylcarbamoyl, monoalkyl-substituted sulfamoyl, dialkyl-substituted sulfamoyl or alkylsulfonylamino.
A 1a and A 2a are the same or different and have the following formula:
A 1 and A 2 are the same or different and are represented by the following formula:
However, when l = n = 2, unless p in A 1 and A 2 are both 0. )
Ａ１ａ及びＡ２ａは、同一又は異なって、下記式
Ａ１及びＡ２は、同一又は異なって、下記式
但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。） A step of cyclizing a compound of the following formula (IIC) and a compound of the following formula (IID) in the presence of a cyclization catalyst to obtain a compound of the general formula (IIB); A method for producing a compound represented by the general formula (II), comprising a step of deprotecting:
A 1a and A 2a are the same or different and have the following formula:
A 1 and A 2 are the same or different and are represented by the following formula:
However, when l = n = 2, unless p in A 1 and A 2 are both 0. )
Ａ１及びＡ２は、同一又は異なって、下記式
但し、ｌ＝ｎ＝２のとき、Ａ１及びＡ２におけるｐがともに０である場合を除く。） Compound represented by the following formula (II):
A 1 and A 2 are the same or different and are represented by the following formula:
However, when l = n = 2, unless p in A 1 and A 2 are both 0. )
Ａ１ａ及びＡ２ａは、同一又は異なって、下記式
但し、ｌ＝ｎ＝２のとき、Ａ １ａ 及びＡ ２ａ におけるｐがともに０である場合を除く。） A compound represented by the following formula (IIB):
A 1a and A 2a are the same or different and have the following formula:
However, when l = n = 2, the case where p in A 1a and A 2a are both 0 is excluded. )
で表される環状パラフェニレン化合物。 The following formula (I ')
A cyclic paraphenylene compound represented by the formula:
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