JP2024049953A - Compound having diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton and method for producing same - Google Patents
Compound having diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton and method for producing same Download PDFInfo
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- JP2024049953A JP2024049953A JP2022156485A JP2022156485A JP2024049953A JP 2024049953 A JP2024049953 A JP 2024049953A JP 2022156485 A JP2022156485 A JP 2022156485A JP 2022156485 A JP2022156485 A JP 2022156485A JP 2024049953 A JP2024049953 A JP 2024049953A
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- Prior art keywords
- chrysene
- compound
- group
- pqr
- ghi
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 45
- 125000005578 chrysene group Chemical group 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 32
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 25
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 5
- 125000003003 spiro group Chemical group 0.000 claims abstract description 4
- -1 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene Chemical compound 0.000 claims description 37
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002841 Lewis acid Substances 0.000 claims description 7
- 150000007517 lewis acids Chemical class 0.000 claims description 7
- 230000002140 halogenating effect Effects 0.000 claims description 4
- GQDKQZAEQBGVBS-UHFFFAOYSA-N dibenzo[g,p]chrysene Chemical compound C1=CC=CC2=C3C4=CC=CC=C4C4=CC=CC=C4C3=C(C=CC=C3)C3=C21 GQDKQZAEQBGVBS-UHFFFAOYSA-N 0.000 abstract description 32
- 239000000463 material Substances 0.000 description 33
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000004896 high resolution mass spectrometry Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- 239000012043 crude product Substances 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 125000005011 alkyl ether group Chemical group 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 7
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 229940126142 compound 16 Drugs 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 4
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 4
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WREOTYWODABZMH-DTZQCDIJSA-N [[(2r,3s,4r,5r)-3,4-dihydroxy-5-[2-oxo-4-(2-phenylethoxyamino)pyrimidin-1-yl]oxolan-2-yl]methoxy-hydroxyphosphoryl] phosphono hydrogen phosphate Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)O[C@H]1N(C=C\1)C(=O)NC/1=N\OCCC1=CC=CC=C1 WREOTYWODABZMH-DTZQCDIJSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125773 compound 10 Drugs 0.000 description 4
- 229940125797 compound 12 Drugs 0.000 description 4
- 229940126543 compound 14 Drugs 0.000 description 4
- 229940125758 compound 15 Drugs 0.000 description 4
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 235000009518 sodium iodide Nutrition 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000007860 aryl ester derivatives Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 150000001846 chrysenes Chemical class 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 150000008376 fluorenones Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 3
- 238000011403 purification operation Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 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
- 239000010409 thin film Substances 0.000 description 3
- CHHASAIQKXOAOX-UHFFFAOYSA-N 1-(2,2-dimethylpropoxy)-2,2-dimethylpropane Chemical group CC(C)(C)COCC(C)(C)C CHHASAIQKXOAOX-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical group CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical group CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical group CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- BNBBKIZXDPOOLI-UHFFFAOYSA-N BrC=1C=C(C(C2=CC3=CC(=CC=C3C12)C(C)(C)C)=O)C(C)(C)C Chemical compound BrC=1C=C(C(C2=CC3=CC(=CC=C3C12)C(C)(C)C)=O)C(C)(C)C BNBBKIZXDPOOLI-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical group C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- VXRUJZQPKRBJKH-UHFFFAOYSA-N corannulene Chemical compound C1=CC(C2=C34)=CC=C3C=CC3=C4C4=C2C1=CC=C4C=C3 VXRUJZQPKRBJKH-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 230000000447 dimerizing effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002523 gelfiltration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000002074 nanoribbon Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WOYKPMSXBVTRKZ-UHFFFAOYSA-N sumanene Chemical compound C1=C(C2=C34)CC3=CC=C(C3)C4=C4C3=CC=C(C3)C4=C2C3=C1 WOYKPMSXBVTRKZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical group CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical group CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical group CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical group CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 description 1
- DKZRLCHWDNEKRH-UHFFFAOYSA-N 1-nonoxynonane Chemical group CCCCCCCCCOCCCCCCCCC DKZRLCHWDNEKRH-UHFFFAOYSA-N 0.000 description 1
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- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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Landscapes
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Abstract
【課題】ジベンゾ［ｇ，ｐ］クリセンの２つのベイ領域に五員環を導入したジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物とその製造方法を提供する。【解決手段】３位、６位、１１位、１４位に、水素原子、アルキル基、アルケニル基またはアルキニル基を有し、１位と１６位の炭素原子、および、８位と９位の炭素原子が、それぞれ１個のメチレン基、または、１，３－ジチアノ基がスピロ構造を保持して結合した炭素原子を介して５員環構造を形成したジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物に関する。【選択図】 なし[Problem] To provide a compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton in which five-membered rings are introduced into two bay regions of dibenzo[g,p]chrysene, and a method for producing the same. [Solution] To provide a compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton in which hydrogen atoms, alkyl groups, alkenyl groups or alkynyl groups are present at the 3rd, 6th, 11th and 14th positions, and the carbon atoms at the 1st and 16th positions and the carbon atoms at the 8th and 9th positions each have one methylene group or one 1,3-dithiano group bonded to them while maintaining a spiro structure, forming a five-membered ring structure via the carbon atom. [Selected Figure] None
Description
本発明は、ジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物とその製造方法に関する。 The present invention relates to a compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton and a method for producing the same.
ジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン、および、４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンは、以下の化学式に示すように、６個の六員環と２個の五員環を有しており、バックミンスターフラーレン（Ｃ６０）の部分構造に相当するバッキーボウル分子である。 Diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene and 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene have six hexagonal rings and two pentagonal rings, as shown in the chemical formula below, and are buckybowl molecules that correspond to the partial structure of buckminsterfullerene (C60).
ジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン、および、４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンは、典型的な非平面性のπ共役系構造を有する多環芳香族炭化水素（ＰＡＨｓ）として知られ、炭素数２８個の比較的小さな有機分子である。Ｃ６０の断片構造（フラグメント）であることから、Ｃ６０と似たような有機エレクトロニクス材料・有機半導体材料としての性質を持つのではないかと目されている。また、Ｃ６０の部分構造であることから様々な炭素材料としての可能性も有すると期待されている。しかしながら、これまでにこれらの実質的な合成に関する報告は皆無であり、誘導体さえ報告されていない。従来の技術、とりわけ過去の合成例においては、バッキーボウルと言えば１９６６年のコランニュレンと２００３年のスマネンの合成報告（たとえば特許文献１）が最もよく知られている。コランニュレンとスマネンと同じくらいの影響を学界や産業界に与えるようなバッキーボウルの報告はほとんど見当たらない。材料展開という視点において、それらの可能性は滞っている。 Diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene and 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene are known as polycyclic aromatic hydrocarbons (PAHs) with a typical nonplanar π-conjugated structure, and are relatively small organic molecules with 28 carbon atoms. Since they are fragments of C60, they are expected to have properties similar to those of C60 as organic electronic materials and organic semiconductor materials. In addition, since they are partial structures of C60, they are expected to have the potential to be used as various carbon materials. However, there have been no reports of their substantial synthesis, and even derivatives have not been reported. In terms of conventional technology, especially past synthesis examples, the most well-known reports on the synthesis of corannulene in 1966 and sumanene in 2003 (for example, Patent Document 1) are the most well-known reports on the synthesis of buckybowls. There are few reports of buckybowls that have had the same impact on academia and industry as corannulene and sumanene. From the perspective of material development, these possibilities are stalled.
非特許文献１には、一方のベイ領域が５員環構造となったインデノクリセン誘導体が開示されている。しかしながら、両方のベイ領域が５員環構造のクリセン誘導体は開示されていない。また、開示された方法では、両方のベイ領域に５員環構造を導入することは不可能である。 Non-Patent Document 1 discloses an indenochrysene derivative in which one of the bay regions has a five-membered ring structure. However, it does not disclose a chrysene derivative in which both bay regions have five-membered ring structures. In addition, the disclosed method does not allow the introduction of a five-membered ring structure into both bay regions.
ジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン誘導体、および、４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン誘導体は、下記化学式に示すように、ジベンゾ［ｇ，ｐ］クリセンのベイ領域と言われる箇所（１位・８位・９位・１６位の炭素原子周辺）に二つの五員環を形成することで得られる。この反応では、対称性良く二炭素を増炭することが鍵となる。 Diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene derivatives and 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene derivatives can be obtained by forming two five-membered rings in what is called the bay region of dibenzo[g,p]chrysene (around the 1st, 8th, 9th, and 16th carbon atoms), as shown in the chemical formula below. The key to this reaction is to increase the number of carbon atoms symmetrically.
しかしながら、ジベンゾ［ｇ，ｐ］クリセンは、フィヨルド領域と呼ばれる４位、５位、１２位、１３位の炭素原子に結合した水素原子が大きな立体反発を生むため、ベイ領域をメチレン架橋することは非常に困難である。実際、これまでに、２箇所のベイ領域に五員環を形成して架橋した報告は皆無である。 However, in dibenzo[g,p]chrysene, the hydrogen atoms bonded to the carbon atoms at positions 4, 5, 12, and 13, known as the fjord region, create a large steric repulsion, making it extremely difficult to bridge the bay region with methylene bridges. In fact, there have been no reports to date of forming five-membered rings to bridge two bay regions.
本発明は、ジベンゾ［ｇ，ｐ］クリセンの２つのベイ領域に五員環を導入したジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物とその製造方法を提供することを目的とする。 The objective of the present invention is to provide a compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton in which five-membered rings are introduced into the two bay regions of dibenzo[g,p]chrysene, and a method for producing the same.
本発明者らは、ジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物の合成方法について検討を進めたところ、ジベンゾ［ｇ，ｐ］クリセンのベイ領域をカルボニル基で架橋した化合物を前駆体として用い、カルボニル基を還元して、ジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物を合成することができることを見出し、本発明を完成した。また、ｔｅｒｔ－ブチル基は、ルイス酸等を用いて除去でき、４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンを液相合成できることも見出した。
すなわち、本発明は、３位、６位、１１位、１４位に、水素原子、アルキル基、アルケニル基またはアルキニル基を有し、１位と１６位の炭素原子、および、８位と９位の炭素原子が、それぞれ１個のメチレン基、または、１，３－ジチアノ基がスピロ構造を保って結合した炭素原子を介して５員環構造を形成したジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物に関する。 In other words, the present invention relates to a compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton in which the carbon atoms at the 1st and 16th positions, and the carbon atoms at the 8th and 9th positions each have a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group at the 3rd, 6th, 11th, and 14th positions, and in which the carbon atoms at the 1st and 16th positions, and the carbon atoms at the 8th and 9th positions each have one methylene group or one 1,3-dithiano group bonded to them in a spiro structure to form a five-membered ring structure.
前期化合物は、下記式
で表される化合物が好ましい。
The compound has the following formula:
Preferred is a compound represented by the following formula:
また、本発明は、
（ａ）３，６，１１，１４位に、アルキル基、アルケニル基またはアルキニル基から選ばれる置換基を有するジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン－４，１１－ジ－オンを還元する工程、および、
（ｂ）得られた３，６，１１，１４位に、アルキル基、アルケニル基またはアルキニル基を有する４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンを脱アルキル化、脱アルケニル化または脱アルキニル化する工程
を含む４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンの製造方法に関する。
The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of:
(a) reducing diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene-4,11-dione having substituents selected from an alkyl group, an alkenyl group, or an alkynyl group at the 3-, 6-, 11-, and 14-positions; and
(b) A method for producing 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene, which comprises a step of dealkylating, dealkenylating or dealkynylating the obtained 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene having alkyl groups, alkenyl groups or alkynyl groups at the 3-, 6-, 11- and 14-positions.
還元工程（ａ）において、３，６，１１，１４位に、アルキル基、アルケニル基またはアルキニル基から選ばれる置換基を有するジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン－４，１１－ジ－オンと、アルカンジチオールおよびルイス酸を反応させた後に、ハロシリル化剤およびハロゲン化剤を反応させることが好ましい。 In the reduction step (a), it is preferable to react diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene-4,11-dione having substituents selected from an alkyl group, an alkenyl group, or an alkynyl group at the 3-, 6-, 11-, and 14-positions with an alkanedithiol and a Lewis acid, and then react it with a halosilylating agent and a halogenating agent.
本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物は、新たなバッキーボウルであり、特に３位、６位、１１位、１４位に、水素原子、または、分岐構造または直鎖構造を有するアルキル基等の置換基を有している。特に、純粋な炭化水素である４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンは、初めて化学合成することに成功したものであり、優れた電子材料の簡便創製につながるだけでなく、グラフェン断片構造体など新材料の化学合成も期待することができる。 The compound having the diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton of the present invention is a new buckybowl, and has substituents such as hydrogen atoms or alkyl groups having a branched or linear structure, particularly at the 3rd, 6th, 11th, and 14th positions. In particular, 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene, which is a pure hydrocarbon, has been successfully chemically synthesized for the first time, and this is not only expected to lead to the easy creation of excellent electronic materials, but also to the chemical synthesis of new materials such as graphene fragment structures.
本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格の誘導体は、３位、６位、１１位、１４位に、水素原子、分岐構造または直鎖構造を有するアルキル基、アルケニル基、および、アルキニル基からなる群から選択される置換基を有し、１位と１６位の炭素原子、および、８位と９位の炭素原子が、それぞれ１個のメチレン基、または、１，３－ジチアノ基がスピロ構造を保持して結合した炭素原子を介して５員環構造を形成することを特徴とする。 The diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene derivative of the present invention has substituents selected from the group consisting of hydrogen atoms, alkyl groups having a branched or straight chain structure, alkenyl groups, and alkynyl groups at the 3rd, 6th, 11th, and 14th positions, and is characterized in that the carbon atoms at the 1st and 16th positions, and the carbon atoms at the 8th and 9th positions each form a 5-membered ring structure via a carbon atom to which one methylene group or 1,3-dithiano group is bonded while maintaining a spiro structure.
ジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンの骨格構造は、ジベンゾ［ｇ，ｐ］クリセンの１位と１６位の炭素原子、および、８位と９位の炭素原子が、それぞれ１個の炭素原子を介して５員環構造を形成した化合物である。ここで、ジベンゾ［ｇ，ｐ］クリセンは、下記化学式
本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物において、３位、６位、１１位、１４位に、アルキル基、アルケニル基、および、アルキニル基からなる群から選択される置換基を有すると、有機溶媒に対する溶解性が向上する。有機溶媒としては、－７８℃から１５０℃の温度範囲における溶解度の点で、トルエン、キシレン、塩化メチレン、メチルエチルケトン、アセトン、酢酸エチル、ジエチルエーテル、テトラヒドロフラン、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシドなどの溶媒を利用することが好ましい。 In the compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton of the present invention, when the compound has a substituent selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group at the 3rd, 6th, 11th, and 14th positions, the solubility in an organic solvent is improved. In terms of solubility in the temperature range of -78°C to 150°C, it is preferable to use a solvent such as toluene, xylene, methylene chloride, methyl ethyl ketone, acetone, ethyl acetate, diethyl ether, tetrahydrofuran, N,N-dimethylformamide, or dimethyl sulfoxide as the organic solvent.
アルキル基、アルケニル基およびアルキニル基の中では、幅広い種類の有機溶媒に対する溶解性の点で、アルキル基が好ましい。 Among the alkyl, alkenyl and alkynyl groups, the alkyl group is preferred in terms of solubility in a wide variety of organic solvents.
アルキル基、アルケニル基、アルキニル基の炭素数は３～１２が好ましく、３～８がより好ましい。例えば、ｉｓｏ－プロピル、ｎ－プロピル、ｉｓｏ－ブチル、ｎ－ブチル、ｔｅｒｔ－ブチル、ｎ－ブチル、２，２－ジメチルプロピル、ｎ－ペンチル、ｉｓｏ－ヘキシル、ｎ－ヘキシル、ｉｓｏ－ヘプチル、ｎ－ヘプチル、ｉｓｏ－オクチル、ｎ－オクチル、ｉｓｏ－ノニル、ｎ－ノニル、ｉｓｏ－デシル、ｎ－デシル、ｉｓｏ－ウンデシル、ｎ－ウンデシル、ｉｓｏ－ドデシル、ｎ－ドデシル等が挙げられる。なかでも、分岐構造を有するものが好ましく、ｉｓｏ－プロピル、ｉｓｏ－ブチル、ｔｅｒｔ－ブチルなどがより好ましい。アルケニル基は、前記アルキル基の内部または末端に二重結合を有する基であり、アルキニル基は、前記アルキル基の内部または末端に三重結合を有する基である。 The number of carbon atoms of the alkyl group, alkenyl group, and alkynyl group is preferably 3 to 12, and more preferably 3 to 8. Examples include iso-propyl, n-propyl, iso-butyl, n-butyl, tert-butyl, n-butyl, 2,2-dimethylpropyl, n-pentyl, iso-hexyl, n-hexyl, iso-heptyl, n-heptyl, iso-octyl, n-octyl, iso-nonyl, n-nonyl, iso-decyl, n-decyl, iso-undecyl, n-undecyl, iso-dodecyl, and n-dodecyl. Among these, those having a branched structure are preferred, and iso-propyl, iso-butyl, and tert-butyl are more preferred. The alkenyl group is a group having a double bond inside or at the end of the alkyl group, and the alkynyl group is a group having a triple bond inside or at the end of the alkyl group.
３位、６位、１１位、１４位に、水素原子、または、アルキル基等の置換基を有していれば、他の置換位置に置換基を有していても良い。他の置換基としては、アルキル基、アリル基、アリール基、アルケニル基、アルキニル基、ハロゲノ基、水酸基、アルキルエーテル基、ポリオキシアルキレン基、アミド基、および、アミノ基などが挙げられる。 As long as the 3rd, 6th, 11th and 14th positions have hydrogen atoms or substituents such as alkyl groups, the other positions may also have substituents. Examples of other substituents include alkyl groups, allyl groups, aryl groups, alkenyl groups, alkynyl groups, halogeno groups, hydroxyl groups, alkyl ether groups, polyoxyalkylene groups, amide groups and amino groups.
アリール基の炭素数は６～１４が好ましい。例えば、フェニル基、ナフチル基、アントリル（ａｎｔｈｒｙｌ）基などが挙げられる。 The number of carbon atoms in the aryl group is preferably 6 to 14. Examples include a phenyl group, a naphthyl group, and an anthryl group.
アルキルエーテル基としては、置換基を有していてもよい直鎖状又は分枝状のアルキルエーテル基が挙げられる。アルキルエーテル基の炭素数は１～１２が好ましく、１～８がより好ましい。例えば、メチルエーテル基、エチルエーテル基、ｎ－プロピルエーテル基、ｉｓｏ－プロピルエーテル基、ｎ－ブチルエーテル基、２―メチルプロピルエーテル基、ｎ－ペンチルエーテル基、２，２－ジメチルプロピルエーテル基、ｎ－ヘキシルエーテル基、ｎ－ヘプチルエーテル基、ｎ－オクチルエーテル基、ｎ－ノニルエーテル基、ｎ－デシルエーテル基、ｎ－ウンデシルエーテル基、ｎ－ドデシルエーテル基等が挙げられ、メチルエーテル基、エチルエーテル基、ｎ－プロピルエーテル基、ｎ－ブチルエーテル基、２―メチルプロピルエーテル基、ｎ－ペンチルエーテル基、２，２－ジメチルプロピルエーテル基、ｎ－ヘキシルエーテル基が好ましい。アルケニルエーテル基は、前記アルキルエーテル基の内部または末端に二重結合を有する基であり、アルキニルエーテル基は、前記アルキルエーテル基の内部または末端に三重結合を有する基である。 The alkyl ether group may be a linear or branched alkyl ether group which may have a substituent. The number of carbon atoms in the alkyl ether group is preferably 1 to 12, more preferably 1 to 8. For example, methyl ether group, ethyl ether group, n-propyl ether group, iso-propyl ether group, n-butyl ether group, 2-methylpropyl ether group, n-pentyl ether group, 2,2-dimethylpropyl ether group, n-hexyl ether group, n-heptyl ether group, n-octyl ether group, n-nonyl ether group, n-decyl ether group, n-undecyl ether group, n-dodecyl ether group, etc. are mentioned, and methyl ether group, ethyl ether group, n-propyl ether group, n-butyl ether group, 2-methylpropyl ether group, n-pentyl ether group, 2,2-dimethylpropyl ether group, and n-hexyl ether group are preferred. The alkenyl ether group is a group having a double bond inside or at the end of the alkyl ether group, and the alkynyl ether group is a group having a triple bond inside or at the end of the alkyl ether group.
ポリオキシアルキレン基としては、アルキレンジオールの単独重合体または共重合体の末端の水素を取った置換基である。このような置換基を導入することで、水または水溶性有機溶媒に溶解しやすくなる。ポリオキシアルキレンとしては、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン等が挙げられる。重合度は、ポリエチレングリコールの場合には４～４５０が好ましく、ポリエチレンオキシドの場合には４５０～１００００が好ましい。 A polyoxyalkylene group is a substituent in which a hydrogen atom at the end of an alkylene diol homopolymer or copolymer has been removed. The introduction of such a substituent makes the compound more soluble in water or a water-soluble organic solvent. Examples of polyoxyalkylene include polyoxyethylene, polyoxypropylene, and polyoxybutylene. The degree of polymerization is preferably 4 to 450 for polyethylene glycol and 450 to 10,000 for polyethylene oxide.
前記ジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物の中でも、下記式
、または、
で表される化合物が好ましい。これらのジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物は、たとえば以下に説明する本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物の製造方法により、合成することができる。
Among the compounds having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton, the compound represented by the following formula
,or,
These compounds having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton can be synthesized, for example, by the method for producing a compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton of the present invention described below.
本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物の製造方法は、
（ａ）３，６，１１，１４位に、アルキル基、アルケニル基またはアルキニル基から選ばれる置換基を有するジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン－４，１１－ジ－オンを還元する工程、および、
（ｂ）得られた３，６，１１，１４位に、アルキル基、アルケニル基またはアルキニル基を有する４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンを脱アルキル化、脱アルケニル化または脱アルキニル化する工程
を含むことを特徴とする。
The method for producing a compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton of the present invention comprises the steps of:
(a) reducing diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene-4,11-dione having substituents selected from an alkyl group, an alkenyl group, or an alkynyl group at the 3-, 6-, 11-, and 14-positions; and
(b) a step of dealkylating, dealkenylating or dealkynylating the obtained 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene having alkyl groups, alkenyl groups or alkynyl groups at the 3-, 6-, 11- and 14-positions.
［還元工程（ａ）］
３，６，１１，１４位に、アルキル基、アルケニル基またはアルキニル基から選ばれる置換基を有するジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン－４，１１－ジ－オンを還元する工程（ａ）において、還元方法は特に限定されない。たとえば三フッ化ホウ素ジエチルエーテル錯体、三塩化アルミニウムなどのルイス酸試薬と、１，３－プロパンジチオール、１,２―エタンジチオールなどのアルカンジチオールを反応させた後に、トリメチルシリルクロライド、トリメチルシリルブロマイド、トリメチルシリルヨージドなどのハロシリル化剤およびヨウ化ナトリウム、臭化ナトリウム、塩化ナトリウムなどのハロゲン化剤を組み合わせて反応させることにより還元する方法などが挙げられる。
[Reduction step (a)]
In the step (a) of reducing diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene-4,11-dione having substituents selected from an alkyl group, an alkenyl group, or an alkynyl group at the 3-, 6-, 11-, and 14-positions, the reduction method is not particularly limited. For example, a reduction method can be mentioned in which a Lewis acid reagent such as boron trifluoride diethyl ether complex or aluminum trichloride is reacted with an alkanedithiol such as 1,3-propanedithiol or 1,2-ethanedithiol, and then a halosilylating agent such as trimethylsilyl chloride, trimethylsilyl bromide, or trimethylsilyl iodide and a halogenating agent such as sodium iodide, sodium bromide, or sodium chloride are reacted in combination to reduce the reaction.
［脱アルキル化、脱アルケニル化または脱アルキニル化する工程（ｂ）］
工程（ａ）で得られた３，６，１１，１４位に、アルキル基、アルケニル基またはアルキニル基を有する４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンを脱アルキル化、脱アルケニル化または脱アルキニル化する方法は特に限定されない。たとえば、三塩化アルミニウム、二塩化アルキルアルミニウム、三臭化アルミニウム、三臭化ホウ素、三フッ化ホウ素などのルイス酸と反応させる方法などが挙げられる。
[Dealkylation, de-alkenylation or de-alkynylation step (b)]
The method for dealkylating, dealkenylating or dealkynylating the 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene having alkyl, alkenyl or alkynyl groups at the 3-, 6-, 11- and 14-positions obtained in step (a) is not particularly limited, and examples thereof include a method of reacting the chrysene with a Lewis acid such as aluminum trichloride, an alkylaluminum dichloride, aluminum tribromide, boron tribromide or boron trifluoride.
工程（ａ）で使用する３，６，１１，１４位に、アルキル基、アルケニル基またはアルキニル基から選ばれる置換基を有するジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン－４，１１－ジ－オンは、たとえば以下の方法により合成することができる。 The diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene-4,11-dione having substituents selected from an alkyl group, an alkenyl group, or an alkynyl group at the 3, 6, 11, and 14 positions used in step (a) can be synthesized, for example, by the following method.
（Ａ）３位、６位、１１位、１４位に、分岐構造または直鎖構造を有するアルキル基、アルケニル基、および、アルキニル基からなる群から選択される置換基を有し、８位または９位、１位または１６位に、それぞれハロゲノ基を有するジベンゾ［ｇ，ｐ］クリセン誘導体αと、ジアルキルカーボネート化合物を反応させて、ハロゲノ基をアルキルまたはアリールエステル基に変換させ、ジベンゾ［ｇ，ｐ］クリセン誘導体βを合成する工程
（Ｂ）ジベンゾ［ｇ，ｐ］クリセン誘導体βを加水分解し、アルキルまたはアリールエステル基をカルボキシル基に変換し、ジベンゾ［ｇ，ｐ］クリセン誘導体γを合成する工程
（Ｃ）ジベンゾ［ｇ，ｐ］クリセン誘導体γのカルボキシル基を酸ハライド基に変換し、ジベンゾ［ｇ，ｐ］クリセン誘導体δを合成する工程、および、
（Ｄ）ジベンゾ［ｇ，ｐ］クリセン誘導体δをルイス酸の存在下でフリーデルクラフツ反応を行い、環化する工程
(A) a step of reacting a dibenzo[g,p]chrysene derivative α having substituents selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group having a branched or linear structure at the 3-position, 6-position, 11-position, and 14-position, and a halogeno group at the 8-position or 9-position, and the 1-position or 16-position, with a dialkyl carbonate compound to convert the halogeno groups to alkyl or aryl ester groups, thereby synthesizing a dibenzo[g,p]chrysene derivative β; (B) a step of hydrolyzing the dibenzo[g,p]chrysene derivative β and converting the alkyl or aryl ester groups to carboxyl groups, thereby synthesizing a dibenzo[g,p]chrysene derivative γ; (C) a step of converting the carboxyl groups of the dibenzo[g,p]chrysene derivative γ to acid halide groups, thereby synthesizing a dibenzo[g,p]chrysene derivative δ; and
(D) A step of subjecting the dibenzo[g,p]chrysene derivative δ to a Friedel-Crafts reaction in the presence of a Lewis acid to cyclization.
工程（Ａ）
工程（Ａ）で使用する３位、６位、１１位、１４位に、分岐構造または直鎖構造を有するアルキル基、アルケニル基、および、アルキニル基からなる群から選択される置換基を有し、８位または９位、１位または１６位に、それぞれハロゲノ基を有するジベンゾ［ｇ，ｐ］クリセン誘導体αにおいて、ハロゲンとしては、フッ素、塩素、臭素、ヨウ素が挙げられる。なかでも、リチウム－ハロゲン交換反応が容易であることから臭素またはヨウ素が好ましい。他の置換位置に、アルキル基、アリル基、アリール基、アルケニル基、アルキニル基、ハロゲノ基、水酸基、アルキルエーテル基、ポリオキシアルキレン基、アミド基、および、アミノ基などの置換基を有していても良い。具体的なジベンゾ［ｇ，ｐ］クリセン誘導体としては、たとえば
などが挙げられる。
Step (A)
In the dibenzo[g,p]chrysene derivative α used in step (A) having substituents selected from the group consisting of alkyl groups, alkenyl groups, and alkynyl groups having a branched or linear structure at the 3-position, 6-position, 11-position, and 14-position, and having halogeno groups at the 8-position or 9-position, and the 1-position or 16-position, respectively, examples of the halogen include fluorine, chlorine, bromine, and iodine. Among these, bromine and iodine are preferred because they facilitate the lithium-halogen exchange reaction. Substituents such as alkyl groups, allyl groups, aryl groups, alkenyl groups, alkynyl groups, halogeno groups, hydroxyl groups, alkyl ether groups, polyoxyalkylene groups, amide groups, and amino groups may be present at other substitution positions. Specific examples of the dibenzo[g,p]chrysene derivative include, for example,
etc.
前記ジベンゾ［ｇ，ｐ］クリセン誘導体は、たとえば以下の製造方法によって作製することができる。
（Ｘ）分岐構造を有するアルキル基、アルケニル基、および、アルキニル基からなる群から選択される置換基と、ハロゲノ基を有する９―フルオレノン誘導体を二量化し、スピロケトン誘導体を作製する工程、
（Ｙ）得られたスピロケトン誘導体を還元してスピロアルコール誘導体を作製する工程、および、
（Ｚ）得られたスピロアルコール誘導体を脱水し、ジベンゾ［ｇ，ｐ］クリセン誘導体を得る工程
The dibenzo[g,p]chrysene derivative can be prepared, for example, by the following production method.
(X) a step of dimerizing a 9-fluorenone derivative having a halogeno group and a substituent selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group having a branched structure to prepare a spiroketone derivative;
(Y) reducing the resulting spiroketone derivative to produce a spiroalcohol derivative; and
(Z) A step of dehydrating the obtained spiro alcohol derivative to obtain a dibenzo[g,p]chrysene derivative.
９―フルオレノン誘導体における分岐構造または直鎖構造を有するアルキル基等の置換基、ハロゲノ基は、前述した置換基と同じ置換基である。また、これらの置換基の置換位置は、目的とするジベンゾ［ｇ，ｐ］クリセン誘導体に対応する置換位置に置換されている必要がある。 The substituents such as alkyl groups having a branched or straight chain structure and halogeno groups in the 9-fluorenone derivatives are the same as the substituents described above. In addition, the substitution positions of these substituents must be those corresponding to the substitution positions of the desired dibenzo[g,p]chrysene derivative.
工程（Ｘ）におけるフルオレノン誘導体の二量化方法は特に限定されず、亜リン酸トリアルキルなどの酸素親和性の高いルイス塩基試薬の存在下で行う方法が挙げられる。亜リン酸トリアルキルなどの活性化試薬は２当量以上が好ましい。反応温度は特に限定されず、９０～２００℃が好ましい。 The method for dimerizing the fluorenone derivative in step (X) is not particularly limited, and examples thereof include a method in the presence of a Lewis base reagent with high oxygen affinity, such as trialkyl phosphite. The amount of the activation reagent, such as trialkyl phosphite, is preferably 2 equivalents or more. The reaction temperature is not particularly limited, and is preferably 90 to 200°C.
工程（Ｙ）におけるスピロケトン誘導体の還元法は特に限定されず、水素化ホウ素ナトリウム、水素化アルミニウムリチウム、水素ガスを用いた接触還元法などが挙げられる。 The method for reducing the spiroketone derivative in step (Y) is not particularly limited, and examples include catalytic reduction using sodium borohydride, lithium aluminum hydride, and hydrogen gas.
工程（Ｚ）におけるスピロアルコール誘導体の脱水法は特に限定されず、二塩化エチルアルミニウム、三塩化アルミニウム、濃塩酸、塩酸、メタンスルホン酸、パラトルエンスルホン酸、ベンゼンスルホン酸、酢酸、トリフルオロメタンスルホン酸などが挙げられる。 The method for dehydrating the spiro alcohol derivative in step (Z) is not particularly limited, and examples include ethylaluminum dichloride, aluminum trichloride, concentrated hydrochloric acid, hydrochloric acid, methanesulfonic acid, paratoluenesulfonic acid, benzenesulfonic acid, acetic acid, trifluoromethanesulfonic acid, etc.
工程（Ａ）で使用するジアルキルカーボネート化合物としては、ジメトキシカーボネート、ジエトキシカーボネートなどが挙げられる。これらのジアルキルカーボネート化合物とジベンゾ［ｇ，ｐ］クリセン誘導体αをｎ－ＢｕＬｉ、メチルリチウム、フェニルリチウム、ノルマルヘキシルリチウムなどの有機リチウム化合物の存在下でリチウムハロゲン交換反応させて、ハロゲノ基をエステル基に変換し、ジベンゾ［ｇ，ｐ］クリセン誘導体βを合成する。 The dialkyl carbonate compound used in step (A) includes dimethoxy carbonate, diethoxy carbonate, etc. These dialkyl carbonate compounds and dibenzo[g,p]chrysene derivative α are subjected to a lithium halogen exchange reaction in the presence of an organolithium compound such as n-BuLi, methyllithium, phenyllithium, or normal hexyllithium to convert the halogeno group to an ester group, thereby synthesizing dibenzo[g,p]chrysene derivative β.
工程（Ｂ）
工程（Ａ）で得たジベンゾ［ｇ，ｐ］クリセン誘導体βは、酸または塩基の存在下で加水分解し、アルキルまたはアリールエステル基をカルボキシル基に変換して、ジベンゾ［ｇ，ｐ］クリセン誘導体γを合成する。塩基としては、ｔ－ＢｕＯＫ、ｔ－ＢｕＯＮａなどが挙げられる。
Step (B)
The dibenzo[g,p]chrysene derivative β obtained in step (A) is hydrolyzed in the presence of an acid or a base to convert the alkyl or aryl ester group to a carboxyl group, thereby synthesizing the dibenzo[g,p]chrysene derivative γ. Examples of the base include t-BuOK and t-BuONa.
工程（Ｃ）
工程（Ｂ）で得たジベンゾ［ｇ，ｐ］クリセン誘導体γは、Ｎ，Ｎ－ジメチルホルムアミド存在下においてチオニルクロライドと反応させて、カルボキシ基を酸ハライド基に変換し、ジベンゾ［ｇ，ｐ］クリセン誘導体δを合成する。
Step (C)
The dibenzo[g,p]chrysene derivative γ obtained in step (B) is reacted with thionyl chloride in the presence of N,N-dimethylformamide to convert the carboxy group to an acid halide group, thereby synthesizing the dibenzo[g,p]chrysene derivative δ.
工程（Ｄ）
工程（Ｃ）で得たジベンゾ［ｇ，ｐ］クリセン誘導体δは、三塩化アルミニウムや三フッ化ホウ素や三塩化鉄やゼロ価鉄などのルイス酸の存在下でフリーデルクラフツ反応を行って環化し、２つのベイ領域に５員環を形成した目的のジベンゾ［ｇ，ｐ］クリセン誘導体を合成することができる。
Step (D)
The dibenzo[g,p]chrysene derivative δ obtained in step (C) can be cyclized by Friedel-Crafts reaction in the presence of a Lewis acid such as aluminum trichloride, boron trifluoride, iron trichloride, or zero-valent iron to synthesize the desired dibenzo[g,p]chrysene derivative having five-membered rings formed in the two bay regions.
（化１）～（化２）で表される化合物は、いずれも本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する（化３）で表される化合物の製造方法における中間体として生成する新規物質である。（化１）で表される化合物は、本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格の誘導体の製造方法における還元工程（ａ）において、出発物質であるインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン－４，１１－ジ－オンと１，３－プロパンジチオールを反応させることによって合成することができる。（化２）で表される化合物は、（化１）で表される化合物とトリアルキルヨードシラン、トリアルキルブロモシラン、トリアルキルクロロシランなどのハロシリル化剤と、ヨウ化ナトリウム、臭化ナトリウム、ヨウ化ナトリウムなどのハロゲン化剤を組み合わせて反応させることにより合成することができる。 The compounds represented by (Chemical formula 1) and (Chemical formula 2) are all new substances produced as intermediates in the manufacturing method of the compound represented by (Chemical formula 3) having the diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton of the present invention. The compound represented by (Chemical formula 1) can be synthesized by reacting the starting material indeno[7,1,2-ghi:7',1',2'-pqr]chrysene-4,11-dione with 1,3-propanedithiol in the reduction step (a) in the manufacturing method of the derivative of the diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton of the present invention. The compound represented by (Chemical formula 2) can be synthesized by combining and reacting the compound represented by (Chemical formula 1) with a halosilylating agent such as trialkyliodosilane, trialkylbromosilane, or trialkylchlorosilane, and a halogenating agent such as sodium iodide, sodium bromide, or sodium iodide.
本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物は、高分子材料、高耐熱性樹脂、光機能性材料、有機エレクトロニクス材料、化学センサー材料、高機能炭素材料、分子ナノカーボン材料、グラフェンナノリボン材料の分野に適用される。具体的には、低伝送損失基板材料、低誘電・光接着ポリイミド樹脂用原料、リソグラフィー用材料、レジスト材料、有機ＥＬ用材料、接着剤等の樹脂用材料、スーパーエンジニアリングプラスチック用材料、有機半導体材料、有機態様電池用材料、フレキシブルプリント基板等が挙げられる。特に、薄膜トランジスターの正孔輸送物質や有機発光ダイオードの発光素子や、その前駆体の化合物として応用可能である。また、屈折率が高く、プラスチックレンズなどの高屈折率材料や光学材料として応用可能である。 The compound having the diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton of the present invention is applicable in the fields of polymer materials, high heat resistant resins, optical functional materials, organic electronics materials, chemical sensor materials, high performance carbon materials, molecular nano carbon materials, and graphene nanoribbon materials. Specific examples include low transmission loss substrate materials, raw materials for low dielectric and optically adhesive polyimide resins, materials for lithography, resist materials, materials for organic electroluminescence, resin materials such as adhesives, materials for super engineering plastics, organic semiconductor materials, materials for organic mode batteries, and flexible printed circuit boards. In particular, it can be used as a hole transport material for thin film transistors, a light emitting element for organic light emitting diodes, or a precursor compound thereof. In addition, it has a high refractive index and can be used as a high refractive index material for plastic lenses and optical materials.
以下、本発明の実施例について説明するが、本発明は、以下の実施例に限定されない。 The following describes examples of the present invention, but the present invention is not limited to the following examples.
実施例において、禁水反応はアルゴンまたは窒素雰囲気下で行なっており、特に断りのない限り実験は禁水条件で実施した。購入した無水溶媒・試薬は、改めて精製して純度を向上させることなく使用した。薄層クロマトグラフィーとしてＭｅｒｃｋ ｓｉｌｉｃａ ６０Ｆ２５４を使用し、カラムクロマトグラフィーとしてシリカゲル６０Ｎ（関東化学（株）製）を用いた。高分解能質量測定（ＨＲＭＳ）として飛行時間型質量分析法（ＭＡＬＤＩ－ＴＯＦまたはＬＣＭＳ－ＩＴ－ＴＯＦ）または直接質量分析法（ＤＡＲＴ－ＭＳ）のいずれかを用いた。 In the examples, reactions without water were carried out under an argon or nitrogen atmosphere, and experiments were carried out under water-free conditions unless otherwise specified. Purchased anhydrous solvents and reagents were used without further purification to improve purity. Merck Silica 60F 254 was used for thin-layer chromatography, and silica gel 60 N (Kanto Chemical Co., Ltd.) was used for column chromatography. For high-resolution mass spectrometry (HRMS), either time-of-flight mass spectrometry (MALDI-TOF or LCMS-IT-TOF) or direct mass spectrometry (DART-MS) was used.
１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲスペクトルについては、５ｍｍのＱＮＰプローブを用い、それぞれ４００ＭＨｚ、１００ＭＨｚで測定した。化学シフト値はδ（ｐｐｍ）で示しており、それぞれの溶媒中での基準値は１Ｈ－ＮＭＲ：ＣＨＣｌ３（７．２６），ＣＨ２Ｃｌ２（５．３２）、ＤＭＳＯ（２．５０）；１３Ｃ－ＮＭＲ：ＣＤＣｌ３（７７．０）、ＤＭＳＯ（３９．５）としている。分裂のパターンは、ｓ：単一線、ｄ：二重線、ｔ：三重線、ｑ：四重線、ｍ：多重線、ｂｒ：幅広線で示す。 1 H-NMR and 13 C-NMR spectra were measured at 400 MHz and 100 MHz, respectively, using a 5 mm QNP probe. Chemical shift values are shown in δ (ppm), and the reference values in each solvent are 1 H-NMR: CHCl 3 (7.26), CH 2 Cl 2 (5.32), DMSO (2.50); 13 C-NMR: CDCl 3 (77.0), DMSO (39.5). Splitting patterns are indicated as s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, and br: broad line.
以下の実施例で言及する化合物と化合物番号を以下に示す。
本発明の製造方法で使用する出発物質である化合物１６の化合物１２からの合成スキームを以下に示す。
合成例１
４－ブロモ－２、７－ジ－ｔｅｒｔ－ブチルフルオレノン（化合物１０）の合成
空気下、２００ｍＬの一径フラスコに４－ブロモフルオレン（５．７２ｇ，１６ｍｍｏｌ）とピリジン（３２ｍＬ）と塩化鉄（ＩＩＩ）六水和物（８６４ｍｇ，３．２ｍｍｏｌ）を加えた。ｔｅｒｔ－ブチルペルオキシド（６．６ｍＬ，４８ｍｍｏｌ，７０％水溶液）を滴下後、８０℃に昇温した。反応１時間後、さらにｔｅｒｔ－ブチルペルオキシド（２．２ｍＬ，１６ｍｍｏｌ）を滴下し、原料の完全消失を確認した。反応溶液を濾過、除媒濃縮後、得られた黄色固体を塩化メチレンに溶かし抽出操作を行った。合わせた有機層を飽和食塩水で洗浄、芒硝乾燥、除媒濃縮後、黄色の粗生成物を得た。これをイソプロピルアルコールで再結晶操作を行い、化合物１０を５．２２ｇ（８８％）の黄色の結晶として得た。
Synthesis Example 1
Synthesis of 4-bromo-2,7-di-tert-butylfluorenone (compound 10) In a 200 mL one-neck flask, 4-bromofluorene (5.72 g, 16 mmol), pyridine (32 mL), and iron (III) chloride hexahydrate (864 mg, 3.2 mmol) were added under air. tert-butyl peroxide (6.6 mL, 48 mmol, 70% aqueous solution) was added dropwise, and the temperature was raised to 80°C. After 1 hour of reaction, tert-butyl peroxide (2.2 mL, 16 mmol) was further added dropwise to confirm complete disappearance of the raw material. The reaction solution was filtered and concentrated to remove the solvent, and the resulting yellow solid was dissolved in methylene chloride and subjected to extraction. The combined organic layer was washed with saturated saline, dried over sodium sulfate, and concentrated to remove the solvent, to obtain a yellow crude product. This was recrystallized with isopropyl alcohol to obtain 5.22 g (88%) of compound 10 as yellow crystals.
化合物１０の分析データ
Ｒｆ ｖａｌｕｅ ０．３７（Ｈｅｘａｎｅ／ＥｔＯＡｃ＝１９／１）；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）８．１８（ｄ，Ｊ＝８．０Ｈｚ，１Ｈ），
７．７３（ｄ，Ｊ＝２．０Ｈｚ，１Ｈ），７．６６（ｄ，Ｊ＝１．７Ｈｚ，１Ｈ），７．５６（ｄ，Ｊ＝１．７Ｈｚ，１Ｈ），７．５５（ｄｄ，Ｊ＝８．０，２．０Ｈｚ，１Ｈ），１．３５（ｓ，９Ｈ），１．３３（ｓ，９Ｈ）ｐｐｍ；
１３ＣＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）１９３．６，１５４．２，１５３．１，１４１．４，１４０．２，１３７．３，１３６．３，１３４．８，１３１．９，１２３．１，１２１．９，１２０．９，１１７．３，３５．３３，３５．３０，３１．４，３１．３ｐｐｍ；
ＭＳ（ＤＡＲＴ－ＴＯＦＭＳ）ｍ／ｚ：３７１［ＭＨ］＋；
ＩＲ（ｎｅａｔ）：２９６０，１７１４（Ｃ＝Ｏ），１６０６，１４７５，１３６０，１１４８，８２６，７７８，５６３ｃｍ－１；
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦＭＳ）ｃａｌｃｄ ｆｏｒ Ｃ２１Ｈ２４ＢｒＯ：３７１．１０１１［ＭＨ］＋，Ｆｏｕｎｄ：３７１．１００９；
Ａｎａｌ． Ｃａｌｃｄ ｆｏｒ Ｃ２１Ｈ２３ＢｒＯ：Ｃ，６７．９３；Ｈ，６．２４．Ｆｏｕｎｄ：Ｃ，６７．７３；Ｈ，６．１０．
Analytical data for compound 10: Rf value 0.37 (Hexane/EtOAc=19/1);
1H NMR (400MHz, CDCl3 ) 8.18 (d, J = 8.0Hz, 1H),
7.73 (d, J = 2.0 Hz, 1H), 7.66 (d, J = 1.7 Hz, 1H), 7.56 (d, J = 1.7 Hz, 1H), 7.55 (dd, J = 8.0, 2.0 Hz, 1H), 1.35 (s, 9H), 1.33 (s, 9H) ppm;
13C NMR (100 MHz, CDCl3 ) 193.6, 154.2, 153.1, 141.4, 140.2, 137.3, 136.3, 134.8, 131.9, 123.1, 121.9, 120.9, 117.3, 35.33, 35.30, 31.4, 31.3 ppm;
MS (DART-TOFMS) m/z: 371 [MH]+;
IR(neat): 2960, 1714 (C=O), 1606, 1475, 1360, 1148, 826, 778, 563 cm-1 ;
HRMS (DART-TOFMS) calculation for C21H24BrO : 371.1011 [MH]+, Found: 371.1009;
Anal. Calcd for C21H23BrO : C, 67.93 ; H, 6.24. Found: C, 67.73; H, 6.10.
合成例２
スピロケトン誘導体（化合物１１、化合物ｉｓｏ－１１）の合成
空気下、一径フラスコに化合物１０（４－ブロモ－２、７－ジ－ｔｅｒｔ－ブチルフルオレノン）（６．６８ｇ，１６ｍｍｏｌ）と亜リン酸トリエチル（６．２ｍＬ，３６ｍｍｏｌ）を加え、室温下のオイルバスに浸し１７５℃に昇温した。６０時間撹拌後、６０℃に自然降温した。水道水（６．５ｍＬ，３６０ｍｍｏｌ）を添加後、再び８０℃に昇温した。２時間撹拌後、減圧濾取し、水と冷メタノールで洗浄した。２００ｍＬの一径フラスコにメタノールを加え、９５℃で加熱還流した。３０分撹拌後、室温に自然降温、減圧濾取し、冷メタノールで洗浄した。加熱真空乾燥後、黄白色の粗生成物を５．１７ｇ（７９％，異性体比５０：５０）得た。その内５００ｍｇを用いてシリカゲルクロマトグラフィー（展開溶媒はヘキサン／トルエン＝１／１）を行い、化合物１１を２０９ｍｇ（２８％）、化合物ｉｓｏ－１１を１７８ｍｇ（３３％）の白色固体として得た。化学構造は、Ｘ線結晶構造解析により決定した。
Synthesis Example 2
Synthesis of spiroketone derivative (compound 11, compound iso-11) Compound 10 (4-bromo-2,7-di-tert-butylfluorenone) (6.68 g, 16 mmol) and triethyl phosphite (6.2 mL, 36 mmol) were added to a single-neck flask under air, and the mixture was immersed in an oil bath at room temperature and heated to 175°C. After stirring for 60 hours, the temperature was naturally lowered to 60°C. Tap water (6.5 mL, 360 mmol) was added, and the temperature was again raised to 80°C. After stirring for 2 hours, the mixture was filtered under reduced pressure and washed with water and cold methanol. Methanol was added to a 200 mL single-neck flask and refluxed at 95°C. After stirring for 30 minutes, the mixture was naturally cooled to room temperature, filtered under reduced pressure, and washed with cold methanol. After heating and vacuum drying, 5.17 g (79%, isomer ratio 50:50) of a yellowish white crude product was obtained. 500 mg of the mixture was subjected to silica gel chromatography (eluent: hexane/toluene=1/1) to obtain 209 mg (28%) of compound 11 and 178 mg (33%) of compound iso-11 as white solids. Their chemical structures were determined by X-ray crystal structure analysis.
化合物１１の分析データ
Ｒｆ ｖａｌｕｅ ０．７０（Ｈｅｘａｎｅ／Ｔｏｌｕｅｎｅ＝１／１）；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）８．７２（ｄ，Ｊ＝８．５Ｈｚ，１Ｈ），８．４２（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），７．８２（ｄｄ，Ｊ＝８．５，２．３Ｈｚ，１Ｈ），７．７２（ｄ，Ｊ＝２．３Ｈｚ，１Ｈ），７．６５（ｄ，Ｊ＝２．０Ｈｚ，１Ｈ），７．５０（ｄ，Ｊ＝１．６Ｈｚ，１Ｈ）７．４２（ｄｄ，Ｊ＝８．３，２．０Ｈｚ，１Ｈ），６．８４（ｄ，Ｊ＝１．６Ｈｚ，１Ｈ），６．８２（ｄ，Ｊ＝１．８Ｈｚ，１Ｈ），６．６６（ｄ，Ｊ＝１．８Ｈｚ，１Ｈ），１．３２（ｓ，９Ｈ），１．１５（ｓ，９Ｈ），１．１３（ｓ，９Ｈ），１．０９（ｓ，９Ｈ）ｐｐｍ；
１３ＣＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）１９８．３，１５２．５，１５２．１，１５２．０，１５１．４，１４８．０，１４５．８，１４０．７，１３８．０，１３７．３，１３４．９，１３２．９，１３２．６，１３０．６，１３０．５，１２９．７，１２８．６，１２５．３，１２５．１，１２４．９，１２３．４，１２２．４，１２２．２，１２０．７，１１６．６，７０．３，３５．１，３５．０（ｔｗｏ ｐｅａｋｓ ａｒｅ ｏｖｅｒｌａｐｐｅｄ），３４．９，３１．５，３１．４，３１．３，３１．１ｐｐｍ；
ＭＳ（ＤＡＲＴＴＯＦ）ｍ／ｚ：７２７［ＭＨ］＋；
ＩＲ（ｎｅａｔ）：２９５９，１７０２（Ｃ＝Ｏ），１４５４，１３６２，１２２９，８２９，７５３ｃｍ－１；
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦ）ｃａｌｃｄ ｆｏｒ Ｃ４２Ｈ４７Ｂｒ２Ｏ：７２７．１９７３ ［Ｈ］＋，Ｆｏｕｎｄ：７２７．１９７１；
Ａｎａｌ．Ｃａｌｃｄ ｆｏｒ Ｃ４２Ｈ４６Ｂｒ２Ｏ：Ｃ，６９．４２；Ｈ，６．３８．Ｆｏｕｎｄ：Ｃ，６９．３５；Ｈ，６．３４．
Analytical data for compound 11: Rf value 0.70 (Hexane/Toluene=1/1);
1H NMR (400 MHz, CDCl3 ) 8.72 (d, J = 8.5 Hz, 1H), 8.42 (d, J = 8.3 Hz, 1H), 7.82 (dd, J = 8.5, 2.3 Hz, 1H), 7.72 (d, J = 2.3 Hz, 1H), 7.65 (d, J = 2.0 Hz, 1H), 7.50 (d, J = 1.6 Hz, 1H) 7.42 (dd, J = 8.3, 2.0 Hz, 1H), 6.84 (d, J = 1.6 Hz, 1H), 6.82 (d, J = 1.8 Hz, 1H), 6.66 (d, J = 1.8 Hz, 1H), 1.32 (s, 9H), 1.15 (s, 9H), 1.13 (s, 9H), 1.09 (s, 9H) ppm;
13C NMR (100MHz, CDCl3 ) 198.3, 152.5, 152.1, 152.0, 151.4, 148.0, 145.8, 140.7, 138.0, 137.3, 134.9, 132.9, 132.6, 130.6, 130.5, 129.7, 128.6, 125.3, 125.1, 124.9, 123.4, 122.4, 122.2, 120.7, 116.6, 70.3, 35.1, 35.0 (two peaks are overlapped), 34.9, 31.5, 31.4, 31.3, 31.1 ppm;
MS (DARTTOF) m/z: 727 [MH]+;
IR(neat): 2959, 1702 (C=O), 1454, 1362, 1229, 829, 753 cm-1 ;
HRMS (DART-TOF) calculation for C42H47Br2O : 727.1973 [H] + , Found: 727.1971;
Anal. Calcd for C42H46Br2O : C , 69.42 ; H,6.38. Found: C, 69.35; H, 6.34.
化合物ｉｓｏ－１１の分析データ
Ｒｆ ｖａｌｕｅ ０．７４（Ｈｅｘａｎｅ／Ｔｏｌｕｅｎｅ＝１／１）；
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）８．５５（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．４４（ｄ，Ｊ＝８．３Ｈｚ，１Ｈ），８．０３（ｄ，Ｊ＝２．０Ｈｚ，１Ｈ），７．７１（ｄ， Ｊ＝２．０Ｈｚ，１Ｈ），７．５２（ｄ，Ｊ＝１．５Ｈｚ，１Ｈ），７．４３（ｄｄ，Ｊ ＝８．３，２．０Ｈｚ，１Ｈ），７．４１（ｄ，Ｊ＝８．３，２．１Ｈｚ，１Ｈ），７．０４－７．０３（ｍ，２Ｈ），６．８２（ｄ，Ｊ＝２．１Ｈｚ，１Ｈ），１．３０（ｓ，９Ｈ），１．１９（ｓ，９Ｈ）１．１８（ｓ，９Ｈ），１．１４（ｓ，９Ｈ）ｐｐｍ；
１３ＣＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）１９８．０，１５２．８，１５２．３，１５１．９，１５１．２，１４７．２，１４４．９，１３８．１，１３８．０，１３７．７，１３７．４，１３６．１，１３４．０，１３０．５，１２８．９，１２８．８，１２５．２，１２５．１，１２４．９，１２４．４，１２３．４，１２２．９，１２２．７，１１９．５，１１６．６，６９．９，３５．１（ｆｏｕｒ ｐｅａｋｓ ａｒｅ ｏｖｅｒｌａｐｐｅｄ），３１．５２，３１．４５，３１．３，３１．１ｐｐｍ；
ＭＳ（ＤＡＲＴ－ＴＯＦ）ｍ／ｚ：７２７［ＭＨ］＋；
ＩＲ（ｎｅａｔ）：２９５９，１６９９（Ｃ＝Ｏ），１４４７，１３６２，１２３４，１１５７，８３０，７４６，６９５ｃｍ－１；
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦ）ｃａｌｃｄ ｆｏｒ Ｃ４２Ｈ４７Ｂｒ２Ｏ：７２７．１９７３［ＭＨ］＋，Ｆｏｕｎｄ：７２７．１９８８；
Ａｎａｌ． Ｃａｌｃｄ ｆｏｒ Ｃ４２Ｈ４６Ｂｒ２Ｏ：Ｃ，６９．４２；Ｈ，６．３８． Ｆｏｕｎｄ：Ｃ，６９．５９；Ｈ，６．４１．
Analytical data for compound iso-11: Rf value 0.74 (Hexane/Toluene=1/1);
1H NMR (400 MHz, CDCl3 ) 8.55 (d, J = 8.3 Hz, 1H), 8.44 (d, J = 8.3 Hz, 1H), 8.03 (d, J = 2.0 Hz, 1H), 7.71 (d, J = 2.0 Hz, 1H), 7.52 (d, J = 1.5 Hz, 1H), 7.43 (dd, J = 8.3, 2.0 Hz, 1H), 7.41 (d, J = 8.3, 2.1 Hz, 1H), 7.04-7.03 (m, 2H), 6.82 (d, J = 2.1 Hz, 1H), 1.30 (s, 9H), 1.19 (s, 9H) 1.18 (s, 9H), 1.14 (s, 9H) ppm;
13C NMR (100MHz, CDCl3 ) 198.0, 152.8, 152.3, 151.9, 151.2, 147.2, 144.9, 138.1, 138.0, 137.7, 137.4, 136.1, 134.0, 130.5, 128.9, 128.8, 125.2, 125.1, 124.9, 124.4, 123.4, 122.9, 122.7, 119.5, 116.6, 69.9, 35.1 (four peaks are overlapped), 31.52, 31.45, 31.3, 31.1 ppm;
MS (DART-TOF) m/z: 727 [MH]+;
IR(neat): 2959, 1699 (C=O), 1447, 1362, 1234, 1157, 830, 746, 695 cm-1 ;
HRMS (DART-TOF) calculation for C42H47Br2O : 727.1973 [MH] + , Found: 727.1988;
Anal. Calcd for C42H46Br2O : C , 69.42 ; H,6.38. Found: C, 69.59; H, 6.41.
合成例３
ジベンゾ［ｇ，ｐ］クリセン誘導体（化合物１２、ｉｓｏ－１２）混合物の合成
空気下、二径フラスコに化合物ｉｓｏ－１１（５４１ｍｇ，０．７４ｍｍｏｌ）、トルエン（３．０ｍＬ）、メタノール（０．６ｍＬ）を加え、４５℃に昇温した。水素化ホウ素ナトリウム（２８ｍｇ，０．７４ｍｍｏｌ）を２０分かけて添加後、３０分間攪拌した。アセトン（０．５ｍＬ）を加え、３０分間攪拌後、室温に自然降温した。有機層を水で洗浄し、飽和食塩水で洗浄、芒硝乾燥、除媒濃縮を経て黄白色の粗生成物５２０ｍｇを得た。得られた粗生成物は精製することなくそのまま次のステップに供した。
Synthesis Example 3
Compound iso-11 (541 mg, 0.74 mmol), toluene (3.0 mL), and methanol (0.6 mL) were added to a two-neck flask under synthetic air of a mixture of dibenzo[g,p]chrysene derivatives (compound 12, iso-12), and the temperature was raised to 45°C. Sodium borohydride (28 mg, 0.74 mmol) was added over 20 minutes, and the mixture was stirred for 30 minutes. Acetone (0.5 mL) was added, and the mixture was stirred for 30 minutes, and the temperature was naturally lowered to room temperature. The organic layer was washed with water, washed with saturated saline, dried over sodium sulfate, and concentrated to remove the solvent, to obtain 520 mg of a yellowish-white crude product. The obtained crude product was directly used in the next step without purification.
得られた粗生成物（２５０ｍｇ、０．３４ｍｍｏｌ）のトルエン（２．５ｍＬ）溶液にヘキサフルオロ－２－イソプロパノール（２．５ｍＬ）と濃塩酸（０．０２ｍＬ，０．２１ｍｍｏｌ，３５％水溶液）を加えた。１時間攪拌後、０℃で飽和炭酸水素ナトリウム水溶液を加えて反応停止操作を行った。得られた有機層を飽和食塩水で洗浄、芒硝乾燥、除媒濃縮を行い、白色の粗生成物を得た。シリカゲルを用いた濾過カラム精製を行い、白色固体の混合物（化合物１２：化合物ｉｓｏ－１２＝９１：９）を２２１ｍｇ（９１％）で得た。 Hexafluoro-2-isopropanol (2.5 mL) and concentrated hydrochloric acid (0.02 mL, 0.21 mmol, 35% aqueous solution) were added to a solution of the obtained crude product (250 mg, 0.34 mmol) in toluene (2.5 mL). After stirring for 1 hour, a saturated aqueous solution of sodium bicarbonate was added at 0°C to stop the reaction. The obtained organic layer was washed with saturated saline, dried over sodium sulfate, and concentrated to remove the solvent, yielding a white crude product. Filtration column purification using silica gel was performed to obtain 221 mg (91%) of a white solid mixture (compound 12: compound iso-12 = 91:9).
合成例４
ジベンゾ［ｇ，ｐ］クリセン誘導体（化合物１３、ｉｓｏ－１３）混合物の合成
アルゴン雰囲気下、二径フラスコに、合成例３で合成した化合物１２（３．２０ｇ，４．５ｍｍｏｌ）と無水ジエチルエーテル（８０ｍＬ）を加えた。ノルマルブチルリチウム（１０．４ｍＬ，１６．２ｍｍｏｌ，１．５６Ｍヘキサン溶液）を－７８℃下で滴下し、１５分間撹拌後、炭酸ジメチル（１．９ｍＬ，２２．５ｍｍｏｌ）を加えた。反応溶液を３０分間撹拌後、室温へ昇温した後にさらに２時間攪拌を行い、１Ｍ塩酸を加えて反応停止操作を行った。水層に対してトルエンで抽出操作を行い、飽和食塩水で洗浄、芒硝乾燥、真空乾燥後、粗生成物を得た。シリカゲルを用いたカラム精製操作を行い、１．７５ｇ（５８％，異性体比５７：４３）の化合物１３を白色固体として得た。
Synthesis Example 4
Synthesis of dibenzo[g,p]chrysene derivative (compound 13, iso-13) mixture: Compound 12 (3.20 g, 4.5 mmol) synthesized in Synthesis Example 3 and anhydrous diethyl ether (80 mL) were added to a two-neck flask under an argon atmosphere. Normal butyl lithium (10.4 mL, 16.2 mmol, 1.56 M hexane solution) was added dropwise at -78°C, and after stirring for 15 minutes, dimethyl carbonate (1.9 mL, 22.5 mmol) was added. The reaction solution was stirred for 30 minutes, warmed to room temperature, and further stirred for 2 hours, and 1 M hydrochloric acid was added to stop the reaction. The aqueous layer was extracted with toluene, washed with saturated saline, dried with sodium sulfate, and dried in vacuum to obtain a crude product. A column purification operation using silica gel was performed to obtain 1.75 g (58%, isomer ratio 57:43) of compound 13 as a white solid.
化合物１３の分析データ
Ｍ．ｐ．２５０℃．
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）８．７８（ｄ，Ｊ＝２．０Ｈｚ，２Ｈ），８．６２（ｄ，Ｊ＝２．０Ｈｚ，２Ｈ），８．６１（ｄ，Ｊ＝２．０Ｈｚ，２Ｈ），８．４５（ｄ，Ｊ＝２．０Ｈｚ，２Ｈ），８．０４（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．０３（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．８６（ｄ，Ｊ＝２．０Ｈｚ，２Ｈ），７．８１（ｄ，Ｊ＝２．０Ｈｚ，２Ｈ），７．５９（ｄｄ，Ｊ＝２．０，８．６Ｈｚ，４Ｈ），４．０５（ｓ，６Ｈ），４．０４（ｓ，６Ｈ），１．４７－１．４０（ｍ，７２Ｈ）ｐｐｍ．
１３ＣＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）１７３．３，１７３．１，１５０．３，１５０．２，１４９．１，１４９．０，１３１．２，１３０．８４，１３０．８０，１３０．３，１３０．２１，１３０．１８，１３０．１，１２９．０，１２８．１，１２７．４９，１２７．４６，１２７．２，１２７．１，１２７．０１，１２７．０，１２６．９，１２６．７，１２６．０，１２５．６，１２５．２，１２４．８，１２４．０，１２３．８，５３．０７，５３．０５，３５．５２，３５．４７（ｔｗｏ ｐｅａｋｓ ａｒｅ ｏｖｅｒｌａｐｐｅｄ），３５．４３，３１．８４，３１．８２（ｔｗｏ ｐｅａｋｓ ａｒｅ ｏｖｅｒｌａｐｐｅｄ），３１．８０ｐｐｍ．
ＭＳ（ＤＡＲＴ－ＴＯＦ）ｍ／ｚ：６６９［ＭＨ］＋．
ＩＲ（ｎｅａｔ）：２９５２，１７１８（Ｃ＝Ｏ），１５９９，１４３２，１２４０，１１４１， ８８２ｃｍ－１．
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦ）ｃａｌｃｄ．ｆｏｒ Ｃ４６Ｈ５３Ｏ４［ＭＨ］＋：６６９．３９４４，ｆｏｕｎｄ：６６９．３９２４．
Analytical data for compound 13: M.p. 250°C.
1 HNMR (400 MHz, CDCl 3 ) 8.78 (d, J = 2.0 Hz, 2H), 8.62 (d, J = 2.0 Hz, 2H), 8.61 (d, J = 2.0 Hz, 2H), 8.45 (d, J = 2.0 Hz, 2H), 8.04 (d, J = 8.6 Hz, 2H), 8.03 (d, J = 8.6 Hz, 2H), 7.86 (d, J = 2.0 Hz, 2H), 7.81 (d, J = 2.0 Hz, 2H), 7.59 (dd, J = 2.0, 8.6 Hz, 4H), 4.05 (s, 6H), 4.04 (s, 6H), 1.47-1.40 (m, 72H) ppm.
13CNMR (100MHz, CDCl3 ) 173.3, 173.1, 150.3, 150.2, 149.1, 149.0, 131.2, 130.84, 130.80, 130.3, 130.21, 130.18, 130.1, 129.0, 128.1, 127.49, 127.46, 127.2, 127.1, 127.01, 127.0, 126.9, 126.7, 126.0, 125.6, 125.2, 124.8, 124.0, 123.8, 53.07, 53.05, 35.52, 35.47 (two peaks are overlapped), 35.43, 31.84, 31.82 (two peaks are overlapped), 31.80 ppm.
MS (DART-TOF) m/z: 669 [MH] + .
IR(neat): 2952, 1718 (C=O), 1599, 1432, 1240, 1141, 882 cm -1 .
HRMS (DART-TOF) calcd. for C46H53O4 [MH ]+ : 669.3944 , found: 669.3924.
合成例５
ジベンゾ［ｇ，ｐ］クリセン誘導体（化合物１４、ｉｓｏ－１４）混合物の合成
アルゴン雰囲気下、一径フラスコにカリウムターシャリーブトキシド（１２．０ｇ，１０７ｍｍｏｌ）と無水テトラヒドロフラン（１５０ｍＬ）を加えた。この反応溶液に、０℃下にて蒸留水（０．４９ｍＬ，２７．３ｍｍｏｌ）を加え、５分撹拌後、化合物１３（８．２９ｇ，１２．４ｍｍｏｌ）を加えた。反応溶液を７０℃まで昇温し、１時間撹拌後、３Ｍ塩酸で反応停止操作を行った。水層に対して酢酸エチルで抽出操作を行い、合わせた有機層を飽和食塩水で洗浄、芒硝乾燥、除媒濃縮、真空乾燥後、化合物１４（異性体比５２：４８）を定量的に得た。
Synthesis Example 5
Synthesis of dibenzo[g,p]chrysene derivative (compound 14, iso-14) mixture Under an argon atmosphere, potassium tert-butoxide (12.0 g, 107 mmol) and anhydrous tetrahydrofuran (150 mL) were added to a one-neck flask. Distilled water (0.49 mL, 27.3 mmol) was added to this reaction solution at 0°C, and after stirring for 5 minutes, compound 13 (8.29 g, 12.4 mmol) was added. The reaction solution was heated to 70°C, stirred for 1 hour, and then the reaction was stopped with 3M hydrochloric acid. The aqueous layer was extracted with ethyl acetate, and the combined organic layer was washed with saturated saline, dried with sodium sulfate, concentrated to remove the solvent, and dried in vacuum to quantitatively obtain compound 14 (isomer ratio 52:48).
化合物１４の分析データ
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）８．７０（ｄ，Ｊ＝１．８Ｈｚ，２Ｈ），８．５５（ｄ，Ｊ＝１．８Ｈｚ，２Ｈ），８．５４（ｄ，Ｊ＝１．８Ｈｚ，２Ｈ），８．４０（ｄ，Ｊ＝１．８Ｈｚ，２Ｈ），８．３４（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．３２（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．８９（ｄ，Ｊ＝１．８Ｈｚ，２Ｈ），７．８４（ｄ，Ｊ＝１．８Ｈｚ，２Ｈ），７．５３（ｄｄ，Ｊ＝８．６，１．８Ｈｚ，４Ｈ），１．４２－１．３５（ｍ，７２Ｈ）ｐｐｍ．
ＭＳ（ＤＡＲＴ－ＴＯＦ）ｍ／ｚ：６３９［Ｍ－Ｈ］－．
ＩＲ（ｎｅａｔ）：３０６０，２９５２，２６３０，１６９０（Ｃ＝Ｏ），１２４９，８８６，７１４ｃｍ－１．
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦ）ｃａｌｃｄ．ｆｏｒ Ｃ４４Ｈ４７Ｏ４［Ｍ－Ｈ］－：６３９．３４７４，ｆｏｕｎｄ：６３９．３４６０．
Analytical data for compound 14
1 HNMR (400 MHz, CDCl 3 ) 8.70 (d, J = 1.8 Hz, 2H), 8.55 (d, J = 1.8 Hz, 2H), 8.54 (d, J = 1.8 Hz, 2H), 8.40 (d, J = 1.8 Hz, 2H), 8.34 (d, J = 8.6 Hz, 2H), 8.32 (d, J = 8.6 Hz, 2H), 7.89 (d, J = 1.8 Hz, 2H), 7.84 (d, J = 1.8 Hz, 2H), 7.53 (dd, J = 8.6, 1.8 Hz, 4H), 1.42-1.35 (m, 72H) ppm.
MS (DART-TOF) m/z: 639 [M−H] − .
IR(neat): 3060, 2952, 2630, 1690 (C=O), 1249, 886, 714 cm -1 .
HRMS (DART-TOF) calcd. for C44H47O4 [M-H ]- : 639.3474 , found: 639.3460.
合成例６
ジベンゾ［ｇ，ｐ］クリセン誘導体（化合物１５、ｉｓｏ－１５）混合物の合成
アルゴン雰囲気下、化合物１４（９．６１ｇ，１５ｍｍｏｌ）の塩化チオニル（９６ｍＬ，１．３ｍｏｌ）溶液に、室温下でＤＭＦを少量加えた。反応溶液を３０分間攪拌後に除媒し、真空乾燥後、化合物１５（異性体比５０：５０）を定量的に得た。
Synthesis Example 6
Synthesis of a mixture of dibenzo[g,p]chrysene derivatives (compound 15, iso-15) A small amount of DMF was added to a solution of compound 14 (9.61 g, 15 mmol) in thionyl chloride (96 mL, 1.3 mol) at room temperature under an argon atmosphere. The reaction solution was stirred for 30 minutes, and then the solvent was removed. After drying in vacuum, compound 15 (isomer ratio 50:50) was quantitatively obtained.
化合物１５の分析データ
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）８．８６（ｄ，Ｊ＝１．９Ｈｚ，２Ｈ），８．６３（ｄ，Ｊ＝１．９Ｈｚ，２Ｈ），８．６２（ｄ，Ｊ＝１．９Ｈｚ，２Ｈ），８．４１（ｄ，Ｊ＝１．９Ｈｚ，２Ｈ），８．２５（ｄ，Ｊ＝８．６Ｈｚ，４Ｈ），８．０４（ｄ，Ｊ＝１．９Ｈｚ，２Ｈ），７．９８（ｄ，Ｊ＝１．９Ｈｚ，２Ｈ），７．６９（ｄｄ，Ｊ＝８．６，１．９Ｈｚ，４Ｈ），１．５０－１．４１（ｍ，７２Ｈ）ｐｐｍ．
１３ＣＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）１７２．２，１７２．１，１５１．５，１５１．２，１４９．５，１４９．３，１３５．７，１３５．３，１３１．７，１３０．４，１３０．３，１３０．２２，１３０．１７，１２９．９，１２９．２，１２９．１，１２８．９，１２８．８，１２６．５，１２６．３，１２６．２，１２６．１，１２６．０，１２５．８，１２５．４，１２５．３，１２４．８（ｔｗｏ ｐｅａｋｓ ａｒｅ ｏｖｅｒｌａｐｐｅｄ），１２４．５，３５．７，３５．６３，３５．６１，３５．５７，３１．７８（ｔｗｏ ｐｅａｋｓ ａｒｅ ｏｖｅｒｌａｐｐｅｄ），３１．７５（ｔｗｏ ｐｅａｋｓ ａｒｅ ｏｖｅｒｌａｐｐｅｄ）ｐｐｍ．
ＭＳ（ＤＡＲＴ－ＴＯＦ）ｍ／ｚ：６７６［Ｍ］＋．
ＩＲ（ｎｅａｔ）：２９５６，１７７０（Ｃ＝Ｏ），９３３，７４２，７２７，６０７ｃｍ－１．
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦ）ｃａｌｃｄ．ｆｏｒ Ｃ４４Ｈ４６Ｃｌ２Ｏ２［Ｍ］＋：６７６．２８７５，ｆｏｕｎｄ：６７６．２８６２．
Analytical data for compound 15
1 HNMR (400 MHz, CDCl 3 ) 8.86 (d, J=1.9 Hz, 2H), 8.63 (d, J=1.9 Hz, 2H), 8.62 (d, J=1.9 Hz, 2H), 8.41 (d, J=1.9 Hz, 2H), 8.25 (d, J=8.6 Hz, 4H), 8.04 (d, J=1.9 Hz, 2H), 7.98 (d, J=1.9 Hz, 2H), 7.69 (dd, J=8.6, 1.9 Hz, 4H), 1.50-1.41 (m, 72H) ppm.
13C NMR (100MHz, CDCl3) 172.2, 172.1, 151.5, 151.2, 149.5, 149.3, 135.7, 135.3, 131.7, 130.4 , 130.3, 130.22, 130.17, 129.9, 129.2, 129.1, 128.9, 128.8, 126.5, 126.3, 126.2, 126.1, 126.0, 125.8, 125.4, 125.3, 124.8 (two peaks are overlapped), 124.5, 35.7, 35.63, 35.61, 35.57, 31.7 ... peaks are overlapped), 31.75 (two peaks are overlapped) ppm.
MS (DART-TOF) m/z: 676 [M] + .
IR(neat): 2956, 1770 (C=O), 933, 742, 727, 607 cm-1 .
HRMS (DART-TOF) calcd. for C44H46Cl2O2 [ M ]+ : 676.2875 , found: 676.2862.
合成例７
２，６，９，１３－ｔｅｔｒａ－ｔｅｒｔ－ｂｕｔｙｌｄｉｉｎｄｅｎｏ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］ｃｈｒｙｓｅｎｅ－４，１１－ｄｉ－ｏｎｅ（２，６，９，１３－テトラ－ターシャリー－ブチルジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン－４，１１－ジ－オン）（化合物１６）の合成
アルゴン雰囲気下、一径フラスコに原料の化合物１５（６．３７ｇ，９．４ｍｍｏｌ）と無水塩化メチレン（８６ｍＬ）を加えた。この溶液に、０℃下で塩化アルミニウム（３．７６ｇ，２８．２ｍｍｏｌ）を加え、３０分間攪拌後、水を加えて反応停止操作を行った。有機層を分離し、水層に対してクロロホルムで抽出操作を行った。合わせた有機層を飽和食塩水で洗浄、芒硝乾燥、真空乾燥後、６．０３ｇの粗生成物を得た。シリカゲルを用いたカラム精製操作を行い、５．２２ｇ（９２％）の化合物１６を黄色固体として得た。
Synthesis Example 7
Synthesis of 2,6,9,13-tetra-tert-butyldiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene-4,11-di-one (compound 16) In an argon atmosphere, the raw material compound 15 (6.37 g, 9.4 mmol) and anhydrous methylene chloride (86 mL) were added to a one-neck flask. To this solution, aluminum chloride (3.76 g, 28.2 mmol) was added at 0°C, and the mixture was stirred for 30 minutes, after which water was added to stop the reaction. The organic layer was separated, and the aqueous layer was extracted with chloroform. The combined organic layer was washed with saturated saline, dried over sodium sulfate, and vacuum dried to give 6.03 g of a crude product, which was purified using a silica gel column to give 5.22 g (92%) of compound 16 as a yellow solid.
化合物１６の分析データ
Ｍ．ｐ．＞３５０℃．
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）９．０６（ｓ，４Ｈ），８．０６（ｓ，４Ｈ），１．５７（ｓ，３６Ｈ）ｐｐｍ．
１３ＣＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）１９４．７，１５３．４，１３７．８，１３３．８，１２８．８，１２７．９，１２７．０，１２１．７，３６．６，３２．３ｐｐｍ．
ＭＳ（ＤＡＲＴ－ＴＯＦＭＳ）ｍ／ｚ：６０５［ＭＨ］＋．
ＩＲ（ｎｅａｔ）：２９５２，１７１４（Ｃ＝Ｏ），１３６３，１２０４，８７７，７７４ｃｍ－１．
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦ）ｃａｌｃｄ．ｆｏｒ Ｃ４４Ｈ４５Ｏ２［ＭＨ］＋：６０５．３４２０，ｆｏｕｎｄ：６０５．３３９７．
Ａｎａｌ．Ｃａｌｃｄ．ｆｏｒ Ｃ４４Ｈ４４Ｏ２；Ｃ，８７．３８；Ｈ，７．３３．Ｆｏｕｎｄ： Ｃ，８７．４６；Ｈ，７．２５．
Analytical data for compound 16: M.p. >350°C.
1H NMR (400 MHz, CDCl3 ) 9.06 (s, 4H), 8.06 (s, 4H), 1.57 (s, 36H) ppm.
13C NMR (100 MHz, CDCl3 ) 194.7, 153.4, 137.8, 133.8, 128.8, 127.9, 127.0, 121.7, 36.6, 32.3 ppm.
MS (DART-TOFMS) m/z: 605 [MH] + .
IR(neat): 2952, 1714 (C=O), 1363, 1204, 877, 774 cm -1 .
HRMS (DART-TOF) calcd. for C44H45O2 [MH ]+ : 605.3420 , found: 605.3397.
Anal. Calcd. for C44H44O2 ; C ,87.38 ; H,7.33. Found: C, 87.46; H, 7.25.
化合物１６から本発明の化合物１、２、３の合成スキームを以下に示す。
実施例１
化合物１の合成
アルゴン雰囲気下、ジケトン体である化合物１６（２．０ｇ、３．３ｍｍｏｌ）、無水塩化メチレン（５００ｍＬ）を加え、室温で１０分攪拌した。１，３－プロパンジチオール（３．３ｍＬ，３３ｍｍｏｌ）、三フッ化ホウ素ジエチルエーテル錯体（６．７ｍＬ，５３ｍｍｏｌ）を加え、室温で１時間攪拌後、水を加えて反応停止操作を行った。有機層を分離し、水層に対してクロロホルムで抽出操作を行った。合わせた有機層を飽和食塩水で洗浄、芒硝乾燥、真空乾燥後、粗生成物を得た。シリカゲルによる濾過カラム精製操作を行い、化合物１を１．８ｇの白色固体として得た（収率７０％）。
Example 1
Synthesis of Compound 1: Under an argon atmosphere, compound 16 (2.0 g, 3.3 mmol), which is a diketone, and anhydrous methylene chloride (500 mL) were added and stirred at room temperature for 10 minutes. 1,3-propanedithiol (3.3 mL, 33 mmol) and boron trifluoride diethyl ether complex (6.7 mL, 53 mmol) were added and stirred at room temperature for 1 hour, after which water was added to stop the reaction. The organic layer was separated, and the aqueous layer was extracted with chloroform. The combined organic layer was washed with saturated saline, dried over sodium sulfate, and dried in vacuum to obtain a crude product. Filtration and purification using a silica gel column were performed to obtain compound 1 as 1.8 g of a white solid (yield 70%).
化合物１のデータ
Ｍ．ｐ．３０２℃（ｄｅｃ．）．
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）９．１１（ｓ，４Ｈ），８．１８（ｓ，４Ｈ），３．５１（ｔ，Ｊ＝５．７Ｈｚ，８Ｈ），２．５４－２．５３（ｍ，４Ｈ），１．６３（ｓ，３６Ｈ） ｐｐｍ．
１３ＣＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）１５１．７，１４８．３，１３２．６，１２９．９，１２７．６，１２２．９，１１９．３，５５．７，３６．５，３２．７，２８．３，２５．１ｐｐｍ．
ＭＳ（ＤＡＲＴ－ＴＯＦＭＳ）ｍ／ｚ：７８５［ＭＨ］＋．
ＩＲ（ｎｅａｔ）２９５８，１５９５，１４１５，１２７１，１２０３，７５４，７３１，６６５ｃｍ－１．
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦ）ｃａｌｃｄ．ｆｏｒ Ｃ５０Ｈ５７Ｓ４：７８５．３３３８［ＭＨ］＋，ｆｏｕｎｄ：７８５．３３２９．
Data for compound 1 M.p. 302°C (dec.).
1 HNMR (400 MHz, CDCl 3 ) 9.11 (s, 4H), 8.18 (s, 4H), 3.51 (t, J=5.7 Hz, 8H), 2.54-2.53 (m, 4H), 1.63 (s, 36H) ppm.
13C NMR (100 MHz, CDCl3 ) 151.7, 148.3, 132.6, 129.9, 127.6, 122.9, 119.3, 55.7, 36.5, 32.7, 28.3, 25.1 ppm.
MS (DART-TOFMS) m/z: 785 [MH] + .
IR(neat) 2958, 1595, 1415, 1271, 1203, 754, 731, 665 cm -1 .
HRMS (DART-TOF) calcd. for C50H57S4 : 785.3338 [MH ] + , found: 785.3329.
実施例２
化合物２の合成
アルゴン雰囲気下、化合物１（４５０ｍｇ，０．５７ｍｍｏｌ）、無水塩化メチレン（３２４ｍＬ）を加えて室温で２０分間攪拌した。ヘアドライヤーで加熱して溶液に近い無色曇状に誘導した。その後、ヨウ化ナトリウム（８．５ｇ，５７ｍｍｏｌ）を加え、続いてトリメチルクロロシラン（７．２ｍＬ，５７ｍｍｏｌ）を添加した。室温下８９時間攪拌した後に、水を加えて加水分解を行い、３０分攪拌した。飽和チオ硫酸ナトリウム水溶液を加えて反応停止操作を行った。有機層を分離し、水層に対してクロロホルムで抽出操作を行った。合わせた有機層を飽和食塩水で洗浄、芒硝乾燥、真空乾燥後、粗生成物を得た。シリカゲルによる濾過カラム精製操作を行い、化合物２を２４２ｍｇの白色固体として得た（収率７４％）。
Example 2
Synthesis of Compound 2 Compound 1 (450 mg, 0.57 mmol) and anhydrous methylene chloride (324 mL) were added under an argon atmosphere and stirred at room temperature for 20 minutes. The mixture was heated with a hair dryer to induce a colorless cloudy state close to a solution. Sodium iodide (8.5 g, 57 mmol) was then added, followed by trimethylchlorosilane (7.2 mL, 57 mmol). After stirring at room temperature for 89 hours, water was added to perform hydrolysis, and the mixture was stirred for 30 minutes. A saturated aqueous sodium thiosulfate solution was added to stop the reaction. The organic layer was separated, and the aqueous layer was extracted with chloroform. The combined organic layer was washed with saturated saline, dried with sodium sulfate, and dried in vacuum to obtain a crude product. A silica gel filtration column purification operation was performed to obtain compound 2 as a white solid of 242 mg (yield 74%).
化合物２のデータ
Ｍ．ｐ．２１４－２１９℃．
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）９．１７（ｓ，４Ｈ），７．９２（ｓ，４Ｈ），４．４３（ｓ，４Ｈ），１．６３（ｓ，３６Ｈ）ｐｐｍ．
１３ＣＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）１５０．７，１４２．０，１３６．８，１２９．９，１２７．５，１２０．８，１２０．２，３７．９，３６．４，３２．８ｐｐｍ．
ＭＳ（ＤＡＲＴ－ＴＯＦＭＳ）ｍ／ｚ：５７７［ＭＨ］＋．
ＩＲ（ｎｅａｔ）２９５２，１５９９，１４１２，１３６０，１２７６，１２１４，８４６，７５６，７３２，６６５ｃｍ－１．
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦ）ｃａｌｃｄ．ｆｏｒ Ｃ４４Ｈ４９：５７７．３８２９［ＭＨ］＋， ｆｏｕｎｄ：５７７．３８０２．
Data for compound 2 M.p. 214-219°C.
1H NMR (400 MHz, CDCl3 ) 9.17 (s, 4H), 7.92 (s, 4H), 4.43 (s, 4H), 1.63 (s, 36H) ppm.
13C NMR (100 MHz, CDCl3 ) 150.7, 142.0, 136.8, 129.9, 127.5, 120.8, 120.2, 37.9, 36.4, 32.8 ppm.
MS (DART-TOFMS) m/z: 577 [MH] + .
IR(neat) 2952, 1599, 1412, 1360, 1276, 1214, 846, 756, 732, 665 cm -1 .
HRMS (DART-TOF) calcd. for C44H49 : 577.3829 [MH] + , found: 577.3802.
実施例３
化合物３の合成
アルゴン雰囲気下、化合物２（１．４ｇ，２．４ｍｍｏｌ）のベンゼン（３８ｍＬ）懸濁液に、室温下、三塩化アルミニウム（７７０ｍｇ，５．８ｍｍｏｌ）を加えた。反応溶液を室温で３０ 分攪拌後、０℃下で蒸留水（６０ｍＬ）を３分かけて加え、反応停止操作を行った。有機層を分離し、水層に対して塩化メチレンで抽出操作を行った。合わせた有機層を飽和食塩水で洗浄、芒硝乾燥、除媒濃縮、真空乾燥を行い、粗生成物を得た。シリカゲルによる濾過カラム精製操作を行い、化合物３を６２４ｍｇの白色固体として得た（収率７３％）。
Example 3
Synthesis of Compound 3 Under an argon atmosphere, aluminum trichloride (770 mg, 5.8 mmol) was added to a suspension of compound 2 (1.4 g, 2.4 mmol) in benzene (38 mL) at room temperature. After stirring the reaction solution at room temperature for 30 minutes, distilled water (60 mL) was added at 0°C over 3 minutes to stop the reaction. The organic layer was separated, and the aqueous layer was extracted with methylene chloride. The combined organic layer was washed with saturated saline, dried with sodium sulfate, concentrated to remove the solvent, and dried in vacuum to obtain a crude product. A silica gel filtration column purification operation was performed to obtain compound 3 as a white solid (624 mg, 73% yield).
化合物３のデータ
Ｍ．ｐ．２６８－２７４℃．
１ＨＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）９．１１（ｄｄ，Ｊ＝６．４Ｈｚ，６．４Ｈｚ，４Ｈ），７．８５－７．８１（ｍ，８Ｈ），４．４７（ｓ，４Ｈ）ｐｐｍ．
１３ＣＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３）１４２．１，１３８．７，１２９．１，１２８．２，１２７．７，１２４．６，１２２．１，３７．８ｐｐｍ．
ＭＳ（ＤＡＲＴ－ＴＯＦＭＳ）ｍ／ｚ：３５３［ＭＨ］＋．
ＩＲ（ｎｅａｔ）２９２３，１４９４，１４４２，１４１８，１３９３，１０８５，１０２７，９３７，８２１，７６７，７０８，６１９，４７５ｃｍ－１．
ＨＲＭＳ（ＤＡＲＴ－ＴＯＦ）ｃａｌｃｄ．ｆｏｒ Ｃ２８Ｈ１７：３５３．１３２５［ＭＨ］＋， ｆｏｕｎｄ：３５３．１３１４．
Data for compound 3 M.p. 268-274°C.
1 HNMR (400 MHz, CDCl 3 ) 9.11 (dd, J=6.4 Hz, 6.4 Hz, 4H), 7.85-7.81 (m, 8H), 4.47 (s, 4H) ppm.
13C NMR (100 MHz, CDCl3 ) 142.1, 138.7, 129.1, 128.2, 127.7, 124.6, 122.1, 37.8 ppm.
MS (DART-TOFMS) m/z: 353 [MH] + .
IR(neat) 2923, 1494, 1442, 1418, 1393, 1085, 1027, 937, 821, 767, 708, 619, 475 cm -1 .
HRMS (DART-TOF) calcd. for C28H17 : 353.1325 [MH] + , found: 353.1314.
本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物は、高分子材料、高耐熱性樹脂、光機能性材料、有機エレクトロニクス材料、化学センサー材料、高機能炭素材料、分子ナノカーボン材料、グラフェンナノリボン材料の分野に適用可能である。具体的には、低伝送損失基板材料、低誘電・光接着ポリイミド樹脂用原料、リソグラフィー用材料、レジスト材料、有機ＥＬ用材料、接着剤等の樹脂用材料、スーパーエンジニアリングプラスチック用材料、有機半導体材料、有機態様電池用材料、フレキシブルプリント基板等が挙げられる。特に、薄膜トランジスターの正孔輸送物質や有機発光ダイオードの発光素子や、その前駆体の化合物として応用可能である。また、屈折率が高く、プラスチックレンズなどの高屈折率材料、光学材料として応用可能である。また、本発明のジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物の製造方法は、薄膜トランジスターの正孔輸送物質や有機発光ダイオードの発光素子として有用なジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物の製造方法として適用可能である。 The compound having the diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton of the present invention can be applied in the fields of polymer materials, high heat resistance resins, optical functional materials, organic electronics materials, chemical sensor materials, high-performance carbon materials, molecular nanocarbon materials, and graphene nanoribbon materials. Specific examples include low transmission loss substrate materials, raw materials for low dielectric and optically adhesive polyimide resins, materials for lithography, resist materials, materials for organic EL, resin materials such as adhesives, materials for super engineering plastics, organic semiconductor materials, materials for organic mode batteries, and flexible printed circuit boards. In particular, it can be applied as a hole transport material for thin film transistors, a light emitting element for organic light emitting diodes, or a precursor compound thereof. In addition, it has a high refractive index and can be applied as a high refractive index material for plastic lenses and optical materials. In addition, the method for producing a compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton of the present invention can be used as a method for producing a compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton that is useful as a hole transport material for thin-film transistors or a light-emitting element for organic light-emitting diodes.
本発明の最も重要な要素は、ジベンゾ［ｇ，ｐ］クリセンが持つ２箇所のベイ領域を、メチレン基を用いて架橋した４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンを合成したことである。その主たる効果は、以下の通りである。
（１）バックミンスターフラーレン（Ｃ６０）の部分構造である４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンを初めて合成し、全く新しい物質を発明したことである。Ｃ６０は特徴的な物理化学的性質（例えば高い電子受容性など）を有するため、その部分構造も機能性の高い有機分子として期待される。
（２）液相条件下にてボトムアップ合成したことである。原料となるジケトン化合物は、複数個のｔｅｒｔ－Ｂｕ基を持つため、有機溶媒には問題なく溶ける。そのため、本発明にて標的とする化合物を液相合成することが可能となり、純度の高い物質合成を達成できる。量的供給も十分に可能である。
The most important element of the present invention is the synthesis of 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene, in which two bay regions of dibenzo[g,p]chrysene are bridged with methylene groups. The main effects of this are as follows.
(1) We have invented a completely new substance by synthesizing 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene, a partial structure of Buckminsterfullerene (C60), for the first time. Because C60 has unique physicochemical properties (e.g., high electron-accepting ability), its partial structure is also expected to be a highly functional organic molecule.
(2) Bottom-up synthesis under liquid-phase conditions. The diketone compound used as the raw material has multiple tert-Bu groups, so it dissolves in organic solvents without any problems. This makes it possible to synthesize the target compound in the present invention in liquid phase, achieving the synthesis of a substance with high purity. It is also possible to supply it in sufficient quantity.
Claims (4)
１位と１６位の炭素原子、および、８位と９位の炭素原子が、それぞれ１個のメチレン基、または、１，３－ジチアノ基がスピロ構造を保持して結合した炭素原子を介して５員環構造を形成したジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセン骨格を有する化合物。 a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group at the 3-, 6-, 11- and 14-positions;
A compound having a diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene skeleton in which the carbon atoms at the 1st and 16th positions, and the carbon atoms at the 8th and 9th positions each form a 5-membered ring structure via a carbon atom to which one methylene group or one 1,3-dithiano group is bonded while maintaining a spiro structure.
または
or
（ｂ）得られた３，６，１１，１４位に、アルキル基、アルケニル基またはアルキニル基を有する４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンを脱アルキル化、脱アルケニル化または脱アルキニル化する工程
を含む４，１１－ジヒドロジインデノ［７，１，２－ｇｈｉ：７’，１’，２’－ｐｑｒ］クリセンの製造方法。 (a) reducing diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene-4,11-dione having substituents selected from an alkyl group, an alkenyl group, or an alkynyl group at the 3-, 6-, 11-, and 14-positions; and
(b) a method for producing 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene, which comprises a step of dealkylating, dealkenylating or dealkynylating the obtained 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene having alkyl groups, alkenyl groups or alkynyl groups at the 3, 6, 11 and 14 positions.
The method for producing 4,11-dihydrodiindeno[7,1,2-ghi:7',1',2'-pqr]chrysene according to claim 3, wherein in the reduction step (a), diindeno[7,1,2-ghi:7',1',2'-pqr]chrysene-4,11-di-one having substituents selected from an alkyl group, an alkenyl group, or an alkynyl group at the 3-, 6-, 11-, and 14-positions is reacted with an alkanedithiol and a Lewis acid, and then reacted with a halosilylating agent and a halogenating agent.
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