CN111194313A - 闭环反应 - Google Patents
闭环反应 Download PDFInfo
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- CN111194313A CN111194313A CN201880046108.0A CN201880046108A CN111194313A CN 111194313 A CN111194313 A CN 111194313A CN 201880046108 A CN201880046108 A CN 201880046108A CN 111194313 A CN111194313 A CN 111194313A
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- 238000007363 ring formation reaction Methods 0.000 title abstract description 13
- -1 hydrocarbon radicals Chemical class 0.000 claims description 99
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 239000000376 reactant Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 150000003254 radicals Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 12
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 11
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 150000002390 heteroarenes Chemical class 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 241001120493 Arene Species 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 2
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 150000001723 carbon free-radicals Chemical class 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- 229910052732 germanium Inorganic materials 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OQRWNJOAXGZBLH-UHFFFAOYSA-N 1,5-dihydro-s-indacene Chemical group C1=C2CC=CC2=CC2=C1C=CC2 OQRWNJOAXGZBLH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000003541 multi-stage reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000013086 organic photovoltaic Methods 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006467 substitution reaction Methods 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
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VKTQADPEPIVMHK-UHFFFAOYSA-N (2-phenylphenyl)methanol Chemical compound OCC1=CC=CC=C1C1=CC=CC=C1 VKTQADPEPIVMHK-UHFFFAOYSA-N 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- SMUPGNKFSLUSCN-UHFFFAOYSA-N C(C)OC(C1=C(C(=C(C(=O)OCC)C(=C1C=1SC=CC1)F)C=1SC=CC1)F)=O Chemical compound C(C)OC(C1=C(C(=C(C(=O)OCC)C(=C1C=1SC=CC1)F)C=1SC=CC1)F)=O SMUPGNKFSLUSCN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- TXHXKGHPVOLQGK-UHFFFAOYSA-N OCc1cc(-c2cccs2)c(CO)cc1-c1cccs1 Chemical compound OCc1cc(-c2cccs2)c(CO)cc1-c1cccs1 TXHXKGHPVOLQGK-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004001 thioalkyl group Chemical group 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical class C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VCSQHSBVLRYTOO-UHFFFAOYSA-N 2-thiophen-2-ylterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C=2SC=CC=2)=C1 VCSQHSBVLRYTOO-UHFFFAOYSA-N 0.000 description 1
- 125000001331 3-methylbutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 238000006898 Intramolecular Friedel-Crafts reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 125000005248 alkyl aryloxy group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 125000005199 aryl carbonyloxy group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000005200 aryloxy carbonyloxy group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KMBUCYUMFBSKDY-UHFFFAOYSA-N diethyl 2-thiophen-2-ylbenzene-1,4-dicarboxylate Chemical compound C(C)OC(C1=C(C=C(C(=O)OCC)C=C1)C=1SC=CC1)=O KMBUCYUMFBSKDY-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- HKNRNTYTYUWGLN-UHFFFAOYSA-N dithieno[3,2-a:2',3'-d]thiophene Chemical compound C1=CSC2=C1SC1=C2C=CS1 HKNRNTYTYUWGLN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000005553 heteroaryloxy group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds 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
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- MQUPWTBHHPUUMC-UHFFFAOYSA-N isoindole Chemical compound C1=CC=C[C]2C=NC=C21 MQUPWTBHHPUUMC-UHFFFAOYSA-N 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- 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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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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Abstract
本发明涉及一种在合成例如可用作有机半导体材料的稠合芳族或杂芳族环系中有用的闭环反应。
Description
技术领域
本发明涉及一种适用于合成可以例如用作有机半导体材料的稠合芳族或杂芳族环系的闭环反应。
背景
有机电子和光电子应用,例如有机场效应晶体管(OTFT),有机发光二极管(OLED),有机光探测器(OPD)或有机光伏电池(OPV),需要半导体有机化合物,其包含芳族或杂芳族环系,优选稠合(例如多环)的芳族或杂芳族环系。这样的结构的一个示例性类别包含共轭亚芳基和杂亚芳基环,其通过sp3-碳原子互锁或桥连。这样的结构的一个具体实例是1,5-二氢-s-引达省[3,2b;7,6b]二噻吩(IDT),其是卓越的构建基块,导致具有高电子性能的出色半导体有机材料(X.Zhang等,Nat.Commun.,2013,4,2238)。
然而,这种稠合芳族或杂芳族环系的合成可能是更具挑战的。它通常需要多步反应,其中的多个步骤可能必须在苛刻的反应条件下进行和/或可能使用有毒的反应物,并且最重要的,经常导致低的总收率(W.Zhang等,J.Am.Chem.Soc.,2010,132,11437-11439)。尽管在研究阶段通常可以足量合成这种环系,例如以1g至10g或甚至100g的规模,但经常发现扩大这种反应的规模是困难的,尤其是因为有些反应物的高毒性,纯化问题和/或一个或多个合成步骤的低反应收率。
在稠合芳族或杂芳族环系的合成中的一个关键步骤是闭环反应,其形成一个或多个sp3-碳原子桥。希望这种闭环成功,尤其是在温和且良性的反应条件下,以高的收率和/或纯度和/或还使用易得的原料,尤其是不使用有毒的和/或危险的反应物。
芳香稠合的1,5-二氢-s-引达省已经通过不同的多步反应路线预先合成。其中之一,二羧酸前体通过分子内Friedel-Crafts反应和随后使用高毒性的肼的Wolf-Kishner还原转化成相应的二酮(W.Zhang等,J.Am.Chem.Soc.,2010,132,11437-11439)。其他多步反应路线从亚苯基双(叔醇)衍生物起始以进行酸催化的闭环反应。使用Bronsted/Lewis酸的下式(其中R=H或乙酰基)的二苯基醇衍生物的闭环反应例如由G.Li等公开于Tetrahedron,2008,64,9033-9043中。
然而,这些反应要求R1是强给电子甲氧基和R2是芳基。Li等没有观察到对于R1和R2均为H的任何反应,从而限制了可以由该方法制备的化合物尤其是芳香稠合的多环结构例如1,5-二氢-s-引达省的范围。
因此,本申请的一个目的是提供闭环反应,其不具有上述缺点/限制且可以容易地用在商业规模上以制备稠合芳族或杂芳族环系。优选地,这种环闭环反应将赋予期望的产物的良好收率或良好纯度或以上两者。
在一个特定方面,本申请涉及制备稠合的环戊二烯梯结构的简易方法,其中sp3碳原子是未取代的-CH2-基。这些结构是实现对称烷基化的关键前体。
发明概述
本发明人现已惊奇地发现通过本申请的方法可以单独或以任何组合实现上述目的。
因此,本申请提供包含两个相邻部分Ar1和Ar2的反应物在强酸的存在下反应以得到产物的方法,其中
(i)Ar1和Ar2通过碳-碳单键连接;
(ii)Ar1和Ar2每次出现独立地选自芳烃、被Rs取代的芳烃、杂芳烃和被Rs取代的杂芳烃,Rs是卤素或碳基;和
(iii)Ar1和Ar2之一在所述碳-碳单键的邻位具有式-CH2-OH的基团,
在产物中,Ar1和Ar2稠合到五或六元环,其包含所述碳-碳单键和所形成的CH2-桥。
另外,本申请提供由所述方法得到的化合物。
发明详述
为了本申请的目的,术语“芳烃”用于表示单环或多环芳族烃。
为了本申请的目的,术语“杂芳烃”用于表示由芳烃正式衍生的杂环化合物,其通过以保持芳香体系的连续π电子体系的特征和许多对应于Hueckel规则的面外π电子数(4n+2)的方式将一个或多个次甲基(-CH=)和/或乙烯基(-CH=CH-)相应地替换为三价或二价杂原子。还参见International Union of Pure and Applied Chemistry,Compendium ofChemical Technology,Gold Book,第2.3.3版,2014-02-24,第671页。
为了本申请的目的,术语“芳族”用于表示具有比假设的局部(localized)结构显著更大的稳定性的环状共轭分子体。
为了本申请的目的,术语“三氟甲磺酸(triflic acid)”和“三氟甲磺酸(trifluoromethanesulfonic acid)”可替换的使用。
在一般意义上,本方法涉及包含两个部分Ar1和Ar2的反应物在强酸的存在下以在Ar1和Ar2之间形成新的五或六元环并且其中Ar1和Ar2稠合到该新形成的五或六元环上的方式反应,其中Ar1和Ar2之一在邻位上具有羟甲基。换句话说,本发明涉及一种闭环反应,在该反应中形成五或六元环。注意到,在本方法中强酸可能但不必须地充当反应物和溶剂两者。
优选地,强酸选自三氟甲磺酸,多磷酸,氟硫酸,SbF5,BF3,以及包含这些酸中的一种或多种的混合物或由这些酸中的一种或多种组成的混合物。最优选地,强酸是三氟甲磺酸。
在反应物中,Ar1和Ar2通过碳-碳单键连接。为了清楚起见,注意到,Ar1和Ar2包含在相同的分子中。还注意到,碳-碳单键直接连接Ar1和Ar2。
在反应物中,Ar1和Ar2之一在所述碳-碳单键的邻位具有式-CH2-OH的基团
优选地,反应物包含一种或多种具有如上定义的Ar1和Ar2的式(I)的结构单元
相应的产物将包含一种或多种式(II)的结构单元,其通常被描述为二芳基-环戊二烯。
本方法也非常好地适合在相同的反应物中基本上同时进行不止一个的闭环反应,例如在相同的反应物分子中基本上同时进行不止一个的闭环反应。能够基本上同时进行不止一个的闭环反应的示例性反应物选自下式(I-A)、(I-B)和(I-C),且优选式(I-B)(其中两个-CH2-OH基团均在Ar2上)
Ar1和Ar2每次出现独立地如本文所定义,Ar3每次出现独立地如对于Ar1和Ar2的定义,a是选自1,2,3,4和5的整数,且其中相邻的-CH2-OH基团可以彼此呈顺式或反式。还注意到,对于a>1,具有-CH2-OH基团的后续单元可以下式中示意表示的方式取向。
为了本申请的目的,术语“顺式”和“反式”用于表示相邻-CH2-OH基团彼此的相对取向。顺式构型的实例示意性表示于下式(I-A’)至(I-C’)。反式构型的实例示意性表示于下式(I-D’)至(I-F’)。
能够同时进行两个闭环反应的反应物的实例示意性表示于下式(I-A’)至(I-F’)中且相应的产物在式(II-A’)和(II-B’)中。
Ar1和Ar2如本文所定义且Ar3如对于Ar1和Ar2所定义。由于-CH2-OH基团的取向和位置不同,本方法还允许合成广泛的产物,例如其中新形成的五元环相对于彼此成顺式或反式的产物,相应地示意性表示于式(II-A’)和(II-B’)中。相应于(II-A’)和(II-B’)的产物可能通常被描述为二芳基-二氢引达省衍生物。
在反应物中,Ar1和Ar2-如果存在的话-Ar3每次出现独立地选自芳烃和杂芳烃。优选Ar1和Ar2-如果存在的话-Ar3每次出现彼此独立地选自下式(III-1)至(III-11)
其可以任选地被一个或多个基团R5取代,且其中W每次出现独立地选自S,O和Se;且V每次出现独立地为CRs或CR0或N,在这种情况下Rs包括H。
关于式(I)和(II),优选Ar1和Ar2中至少一个选自(III-1),(III-4)和(III-10),且最优选式(III-1),且V优选为CRs,在这种情况下Rs优选选自H、F,具有1至10且优选1至5个碳原子的烷基,该烷基也可以是全部或部分氟代的,和具有1至10且优选1至5个碳原子的烷氧基,Rs更优选选自H、F,和具有1至10且优选1至5个碳原子的烷基,且Rs最优选为H或F。
关于式(I-A)、(I-B)和(I-C),Ar1和Ar3彼此独立地—尽快优选它们是相同的—优选选自式(III-1)、(III-2)、(III-3)、(III-4)和(III-10),更优选选自式(III-1)、(III-2)和(III-3),其中W—如果存在—优选为S,和/或V—如果存在—优选为CRs,在这种情况下Rs优选选自H、F,具有1至10且优选1至5个碳原子的烷基,该烷基也可以是全部或部分氟代的,和具有1至10且优选1至5个碳原子的烷氧基,Rs更优选选自H、F,和具有1至10且优选1至5个碳原子的烷基,且Rs最优选为H或F。
关于式(I-A)、(I-B)和(I-C),Ar2优选选自式(III-1)、(III-2)、(III-3)、(III-4)和(III-10),更优选选自式(III-1)、(III-4)和(III-10),且最优选为式(III-1),其中W—如果存在—优选为S,和/或V—如果存在—优选为CRs,在这种情况下Rs优选选自H、F,具有1至10且优选1至5个碳原子的烷基,该烷基也可以是全部或部分氟代的,和具有1至10且优选1至5个碳原子的烷氧基,Rs更优选选自H、F,和具有1至10且优选1至5个碳原子的烷基,且Rs最优选为H或F。
Rs每次出现独立地为卤素,氟是优选的卤素,或本文定义的碳基,优选选自本文定义的任何基团RT,具有1至40个碳原子的烃基,其中烃基可以进一步被一个或多个基团RT取代,和具有1至40个碳原子的包含一个或多个选自N,O,S,P,Si,Se,As,Te或Ge的杂原子的烃基,N,O和S是优选的杂原子,其中烃基可以进一步被一个或多个基团RT取代。
适合作为Rs的烃基的优选实例可以在每次出现时独立地选自苯基,被一个或多个基团RT取代的苯基,烷基和被一个或多个基团RT取代的烷基,其中烷基具有至少1个且优选至少5个个碳原子,且具有至多40个,更优选至多30或25或20个,甚至更优选至多16个且最优选至多12个碳原子。注意到例如,适合作为Rs的烷基还包括氟代烷基,即其中一个或多个氢原子被氟替代的烷基,和全氟代烷基,即其中全部氢原子被氟替代的烷基。
尤其是,Rs可以选自氟,具有至少1个,优选至少5个碳原子,且具有至多40个,更优选至多30或25或20个,甚至更优选至多16个且最优选至多12个碳原子的烷基,和具有至少1个,优选至少5个碳原子且具有至多40个,更优选至多30或25或20个,甚至更优选至多16个且最优选至多12个碳原子的部分或全部氟代的烷基。
RT每次出现独立地选自F,Br,Cl,-CN,-NC,-NCO,-NCS,-OCN,-SCN,-(O)NR0R00,-C(O)X0,-C(O)R0,-NH2,-NR0R00,-SH,-SR0,-SO3H,-SO2R0,-OH,-OR0,-NO2,-SF5和-SiR0R00R000。优选的RT选自F,Br,Cl,-CN,-NC,-NCO,-NCS,-OCN,-SCN,-(O)NR0R00,-C(O)X0,-C(O)R-0,-NH2,-NR0R00,-SH,-SR0,-OH,-OR0和-SiR0R00R000。最优选的RT为F。
R0,R00和R000每次出现彼此独立地选自H、F、具有1至40个碳原子的烃基,和具有1至40个碳原子其中一个或多个氢被F替代的烃基。所述烃基优选具有至少5个原子。所述烃基优选具有至多30个,更优选至多25或20,甚至更优选至多20,且最优选至多12个碳原子。优选地,R0,R00和R000每次出现彼此独立地选自H,F,烷基,氟代烷基,烯基,炔基,苯基和氟代苯基。更优选地,R0,R00和R000每次出现彼此独立地选自H,F,烷基,氟代优选全氟代烷基,苯基和氟代优选全氟代苯基。
注意到,例如,适合作为R0、R00和R000的烷基还包括全氟代烷基,即其中全部氢原子被氟替代的烷基。适合作为R0、R00和R000的烷基的实例可以选自甲基,乙基,正丙基,异丙基,正丁基,异丁基,叔丁基(或t-丁基),苯基,己基,庚基,辛基,壬基,癸基,十一烷基,十二烷基,十三烷基,十四烷基,十五烷基,十六烷基,十七烷基,十八烷基,十九烷基和二十烷基(-C20H41)。
X0为卤素。优选X0选自F、Cl和Br。
包含结合杂原子的3个或更多个碳原子的链的烃基,其可以是直链,支链和/或环状的,包括螺和/或稠合环。
适合作为Rs,R0,R00和/或R000的烃基可以是饱和或不饱和的。饱和烃基的实例包括烷基。不饱和烃基的实例可以选自烯基(包括无环或环状烯烃),炔基,烯丙基,烷基二烯基,多烯基,芳基和杂芳基。
优选的适合作为Rs,R0,R00和/或R000的烃基包括含有一个或多个杂原子的烃基,且可以例如选自烷氧基,烷基羰基,烷氧基羰基,烷基羰氧基和烷氧基羰氧基,烷基芳氧基,芳基羰基,芳氧基羰基,芳基羰氧基和芳氧基羰氧基。
芳基和杂芳基的优选实例包括单-,二-,三环芳族或杂芳族基团,其也可以包含缩合环。
特别优选的芳基和杂芳基可以选自苯基,其中一个或多个CH基团被N替代的苯基,萘,芴,噻吩,吡咯优选N-吡咯,呋喃,吡啶,优选2-或3-吡啶,嘧啶,哒嗪,三唑,四唑,吡唑,咪唑,异噻唑,噻唑,噻二唑,异唑,唑,二唑,噻吩优选2-噻吩,硒吩优选2-硒吩,噻吩并[3,2-b]噻吩,噻吩并[2,3-b]噻吩,二噻吩并噻吩,呋喃并[3,2-b]呋喃,呋喃并[2,3-b]呋喃,硒吩并[3,2-b]硒吩,硒吩[2,3-b]硒吩,噻吩并[3,2-b]硒吩,噻吩并[3,2-b]呋喃,吲哚,异吲哚,苯并[b]呋喃,苯并[b]噻吩,苯并[1,2-b;4,5-b’]二噻吩,苯并[2,1-b;3,4-b’]二噻吩,醌醇,2-甲基醌醇,异醌醇,喹喔啉,喹唑啉,苯并三唑,苯并咪唑,苯并噻唑,苯并异噻唑,苯并异唑,苯并二唑,苯并唑,苯并噻二唑。
优选的烷氧基,即末端CH2基团被-O-替代的相应的烷基的实例可以是直链或支链的,优选直链(或线性的)。该烷氧基的合适的实例可以选自甲氧基,乙氧基,丙氧基,丁氧基,戊氧基,己氧基,庚氧基,辛氧基,壬氧基,癸氧基,十一烷氧基,十二烷氧基,十三烷氧基,十四烷氧基,十五烷氧基,十六烷氧基,十七烷氧基和十八烷氧基。
优选的烯基,即其中两个相邻的CH2基团被-CH=CH-替代的相应的烷基的实例可以是直链或支链的。优选是直链的。所述烯基优选具有2至10个碳原子。烯基的优选实例可以选自乙烯基,丙-1-烯基或丙-2-烯基,丁-1-烯基,丁-2-烯基或丁-3-烯基,戊-1-烯基,戊-2-烯基,戊-3-烯基或戊-4-烯基,己-1-烯基,己-2-烯基,己-3-烯基,己-4-烯基或己-5-烯基,庚-1-烯基,庚-2-烯基,庚-3-烯基,庚-4-烯基,庚-5-烯基或庚-6-烯基,辛-1-烯基,辛-2-烯基,辛-3-烯基,辛-4-烯基,辛-5-烯基,辛-6-烯基或辛-7-烯基,壬-1-烯基,壬-2-烯基,壬-3-烯基,壬-4-烯基,壬-5-烯基,壬-6-烯基,壬-7-烯基或壬-8-烯基,癸-1-烯基,癸-2-烯基,癸-3-烯基,癸-4-烯基,癸-5-烯基,癸-6-烯基,癸-7-烯基,癸-8-烯基和癸-9-烯基。
特别优选的烯基是C2-C7-1E-烯基,C4-C7-3E-烯基,C5-C7-4-烯基,C6-C7-5-烯基,C7-6-烯基,特别是C2-C7-1E-烯基,C4-C7-3E-烯基,C5-C7-4-烯基。特别优选的烯基的实例是乙烯基,1E-丙烯基,1E-丁烯基,1E-戊烯基,1E-己烯基,1E-庚烯基,3-丁烯基,3E-戊烯基,3E-己烯基,3E-庚烯基,4-戊烯基,4Z-己烯基,4E-己烯基,4Z-庚烯基,5-己烯基,6-庚烯基等。通常优选具有至多5个C原子的烯基。
优选的氧杂烷基,即其中一个非末端CH2基团被-O-替代的相应烷基的实例可以是直链或支链的,优选直链的。氧杂烷基的具体实例可以选自2-氧杂丙基(=甲氧基甲基),2-(=乙氧基甲基)或3-氧杂丁基(=2-甲氧基乙基),2-,3-,或4-氧杂戊基,2-,3-,4-,或5-氧杂己基,2-,3-,4-,5-,或6-氧杂庚基,2-,3-,4-,5-,6-,或7-氧杂辛基,2-,3-,4-,5-,6-,7-或8-氧杂壬基和2-,3-,4-,5-,6-,7-,8-或-9氧杂癸基。
优选的羰氧基或氧羰基,即其中一个CH2基团被-O-替代且与其相邻的一个CH2基团被-C(O)-替代的相应烷基的实例可以选自乙酰氧基,丙酰氧基,丁酰氧基,戊酰氧基,己酰氧基,乙酰氧基甲基,丙酰氧基甲基,丁酰氧基甲基,戊酰氧基甲基,2-乙酰氧基乙基,2-丙酰氧基乙基,2-丁酰氧基乙基,3-乙酰氧基丙基,3-丙酰氧基丙基,4-乙酰氧基丁基,甲氧基羰基,乙氧基羰基,丙氧基羰基,丁氧基羰基,戊氧基羰基,甲氧基羰基甲基,乙氧基羰基甲基,丙氧基羰基甲基,丁氧基羰基甲基,2-(甲氧基羰基)乙基,2-(乙氧基羰基)乙基,2-(丙氧基羰基)乙基,3-(甲氧基羰基)丙基,3-(乙氧基羰基)丙基,和4-(甲氧基羰基)丁基。
优选的硫代烷基(即其中一个CH2基团被-S-替代)的实例可以是直链或支链的,优选直链的。合适的实例可以选自硫代甲基(-SCH3),1-硫代乙基(-SCH2CH3),1-硫代丙基(-SCH2CH2CH3),1-(硫代丁基),1-(硫代戊基),1-(硫代己基),1-(硫代庚基),1-(硫代辛基),1-(硫代壬基),1-(硫代癸基),1-(硫代十一烷基)和1-(硫代十二烷基)。
氟代烷基优选是全氟烷基CiF2i+1,其中i是1至15的整数,特别是CF3,C2F5,C3F7,C4F9,C5F11,C6F13,C7F15或C8F17,非常优选C6F13,或部分氟代的烷基,特别是1,1-二氟烷基,其全部是直链或支链的。
烷基,烷氧基,烯基,氧杂烷基,硫代烷基,羰基和羰氧基可是非手性或手性基团。特别优选的手性基团是2-丁基(=1-甲基丙基),2-甲基丁基,2-甲基戊基,3-甲基戊基,2-乙基己基,2-丙基戊基,2-丁基辛基,2-己基癸基,2-辛基十二烷基,7-癸基十一烷基,特别是例如2-甲基丁基,2-甲基丁氧基,2-甲基戊氧基,3-甲基戊氧基,2-乙基-己氧基,1-甲基己氧基,2-辛氧基,2-氧杂-3-甲基丁基,3-氧杂-4-甲基戊基,4-甲基己基,2-丁基辛基,2-己基癸基,2-辛基十二烷基,7-癸基十一烷基,3,8-二甲基辛基,2-己基,2-辛基,2-壬基,2-癸基,2-十二烷基,6-甲基-氧辛氧基,6-甲基辛氧基,6-甲基辛酰氧基,5-甲基庚氧基羰基,2-甲基丁酰氧基,3-甲基戊酰氧基,4-甲基己酰氧基,2-氯丙酰氧基,2-氯-3-甲基丁酰氧基,2-氯-4-甲基戊酰氧基,2-氯-3-甲基戊酰氧基,2-甲基-3-氧杂戊基,2-甲基-3-氧杂-己基,1-甲氧基丙基-2-氧基,1-乙氧基丙基-2-氧基,1-丙氧基丙基-2-氧基,1-丁氧基丙基-2-氧基,2-氟辛氧基,2-氟癸氧基,1,1,1-三氟-2-辛氧基,1,1,1-三氟-2-辛基,2-氟甲基辛氧基。最优选的是2-乙基己基。
优选的非手性支链基团是异丙基,异丁基(=甲基丙基),异戊基(=3-甲基丁基),叔丁基,异丙氧基,2-甲基-丙氧基和3-甲基丁氧基。
在一个优选的实施方案中,有机基团彼此独立地选自具有1至30个C原子的伯、仲或叔烷基或烷氧基,其中一个或多个H原子任选地被F替代,或任选地烷基化或烷氧基化且具有4至30个环原子的芳基,芳氧基,杂芳基或杂芳氧基。这种类型的非常优选的基团选自含有下式的基团
其中“ALK”表示任选地氟代的,优选线性的,具有1至20个优选且1至12个C原子的烷基或烷氧基,在叔基团非常优选1至9个C原子的情况下,虚线表示与这些基团结合的环的连接。在这些基团中尤其优选的是所有ALK子基团相同的那些。
三氟甲磺酸与反应物中包含的-CH2-OH基团数量的摩尔比优选为至少1,更优选至少5,甚至更优选至少10并且最优选至少15。
本方法在优选至多50℃(例如至多45℃或40℃或35℃或30℃或25℃或20℃或15℃或10℃)的温度下进行。
优选的反应物、产物和相应的反应的实例可以选自以下,其任选地可以被Rs取代
非常优选的反应物、产物和相应的反应的实例可以选自以下,其任选地可以被Rs取代
最优选的反应物(左栏)、产物(右栏)和相应的反应的实例可以选自以下,其中最优选的Rs是H或F。
本方法的优点可以从其通用性中看出,即允许通过非常简单的方法得到广泛的反应物和因此广泛的产物的可能性。本方法还允许从实验室规模至商业规模的比较容易的规模扩大。
从本方法获得的产物是有用的,例如作为有机半导体、有机光伏电池,有机发光二级管的材料的组分或前体,仅举几例。最重要的,这些产物是合成新型有机半导体材料的单体的通用构建模块或前体。
实施例
所有反应物和溶剂从商业来源获得,除非另外说明。2,5-二-噻吩并[3,2-b]噻吩-2-基-对苯二甲酸二乙酯根据由C.Wang等.在WO2013010614中公开的合成来合成。2,5-二噻吩-2-基-1,4-苯二甲醇,通过使用1,4-二乙酯-2,5-二-2-噻吩-1,4-苯二甲酸替代2,5-二-噻吩并[3,2-b]噻吩-2-基-对苯二甲酸二乙酯以与化合物1相同的方式制备。1,4-二乙酯-2,5-二-2-噻吩-1,4-苯二甲酸,根据由S.Chen等在Macromolecules,2016,49(2),527-536中公开的合成来合成。2,5-二氟-3,6-二噻吩-2-基-对苯二甲酸二乙酯,根据由M.D’Lavari等在WO2015154845中公开的合成来合成。联苯-2-基-甲醇从Sigma-Aldrich获得。
实施例1
化合物1
在0℃下,向2,5-二-噻吩并[3,2-b]噻吩-2-基-对苯二甲酸二乙酯(25.2g,50.0mmol)和无水四氢呋喃(1000cm3)的混合物中在30分钟内逐滴加入氢化二异丁基铝(200cm3,250mmol,在己烷中25%w/w)。反应混合物在0℃下搅拌4小时并缓慢温热17小时至23℃。将反应混合物冷却至0℃并加入浓盐酸直至反应混合物呈酸性。在真空中除去挥发物,残余物用甲醇(500cm3)磨碎并通过过滤收集固体。用盐酸水溶液(100cm3,2%),甲醇(100cm3)洗涤固体且然后重结晶(四氢呋喃/甲醇)以得到黄色固体的化合物1(19.4g,94%)。
1H-NMR(400MHz,DMSO)7.69-7.74(6H,m),7.49-7.51(2H,m),5.46(2H,s),4.69(4H,s).
化合物2
在-5℃下,向三氟甲磺酸(10cm3,120mmol)中加入化合物1(1.25g,3.02mmol)超过1小时。然后将混合物在-5℃下搅拌6小时并用冷却浴自然温热至23℃,然后搅拌60小时。将混合物倒到碎冰(50g)上并通过过滤收集固体。固体用水(50cm3),乙酸钠的饱和溶液(50cm3),水(50cm3)和甲醇(50cm3)洗涤。产物在沸腾的氯苯(50cm3)中加热并过滤热溶液。对固体进行另外三次萃取过程并收集滤液。在真空中除去溶剂以得到黄色固体的化合物2(0.71g,62%)。
1H-NMR(400MHz,o-DCB,120℃)7.38(2H,s),7.13(4H,m),3.60(4H,s)
实施例2
化合物3
将三氟甲磺酸(30cm3,370mmol)用丙酮-冰浴冷却10分钟(外部-7℃)。在冷却下向搅拌的酸中以小份加入2,5-二噻吩-2-基-1,4-苯二甲醇(1.51g,5.0mmol)。将混合物在冷却浴下搅拌6小时并且然后倒到100g碎冰上且通过过滤收集固体。将固体用水(100cm3),乙酸钠的饱和溶液(100cm3),水(100cm3)和甲醇(100cm3)洗涤。固体在氯仿(75cm3)中沸腾并且然后通过硅胶垫吸滤。在真空中除去溶剂以得到淡黄色固体的化合物3(277mg,21%)。
1H-NMR(400MHz,CDCl3)7.54(2H,s),7.22(2H,d,J 4.9),7.05(2H,d,J 4.9),3.67(4H,s)。
实施例3
9H-芴
在-5℃下,向三氟甲磺酸(30cm3,370mmol)中以小份加入联苯-2-基-甲醇(1.5g,8.1mmol)超过1小时。然后将混合物在-5℃下搅拌6小时并缓慢温热至23℃并且然后搅拌超过17小时。将混合物倒到碎冰(50g)上并通过过滤收集固体。将固体用水(50cm3)和甲醇(50cm3)洗涤以得到浅黄色固体。粗黄色固体的GCMS在4.37mins(166g/mol,9H-芴)显示出相应于4%的不纯的收率。
实施例4
化合物5
在-78℃,向2,5-二氟-3,6-二噻吩-2-基-对苯二甲酸二乙酯(2.00g,4.73mmol)的无水四氢呋喃溶液(10cm3))中逐滴加入氢化二异丁基铝溶液(23.7ml,23.7mmol,以1M在四氢呋喃中)超过30分钟。然后将反应混合物温热至23℃并搅拌17小时。缓慢加热盐酸(200cm3,2M)并且将混合物搅拌20分钟。加入浓盐酸(2cm3)并且将混合物再搅拌20分钟。产物用二乙醚(2100cm3)萃取并将收集的有机相用水(100cm3)和盐水(100cm3)洗涤。然后将有机相用无水硫酸镁干燥,在真空中过滤并除去溶剂以得到米白色固体的化合物5(1.45g,91%)。
1H-NMR(400MHz,DMSO)7.81(2H,dd,J 5.12.1),7.38(2H,dd,J3.511.2),7.25(2H,dd,J 5.13.5),5.32(2H,t,J 50),4.36-4.42(4H,m)。
19F-NMR(400MHz,DMSO)-119.4.
化合物6
将三氟甲磺酸(14.5cm3,150mmol)用丙酮-冰浴冷却10分钟(外部-7℃)。在冷却下,向搅拌的酸中以小份加入化合物5(1.45g,4.3mmol)。将混合物缓慢温热至23℃并搅拌17小时。将混合物倒到100g碎冰上并通过过滤收集固体。将固体用水(100cm3)、乙酸钠的饱和溶液(100cm3)、水(100cm3)和甲醇(100cm3)洗涤。将固体在氯仿(2×50cm3)中沸腾,然后通过过滤收集以得到棕色固体的化合物6(1.07g,83%)。
1H-NMR(400MHz,CDCl3)7.43(2H,d,J 4.9),7.17(2H,d,J 4.9),3.86(4H,s)。
19F-NMR(400MHz,DMSO-d6)-131.7。
Claims (10)
1.使包含两个相邻部分Ar1和Ar2的反应物在强酸的存在下反应以得到产物的方法,其中
(i)Ar1和Ar2通过碳-碳单键连接;
(ii)Ar1和Ar2每次出现独立地选自芳烃,被Rs取代的芳烃,杂芳烃和被Rs取代的杂芳烃,Rs是卤素或碳基;和
(iii)Ar1和Ar2之一在所述碳-碳单键的邻位具有式-CH2-OH的基团,
在产物中,Ar1和Ar2稠合到五或六元环上,其包含所述碳-碳单键和所形成的CH2-桥。
2.根据权利要求1的方法,其中所述强酸是三氟甲磺酸、多磷酸、氟硫酸、SbF5、BF3、或包含上述酸中的一种或多种的混合物,或包含中性溶剂例如二氯甲烷、氯仿、和上述酸的混合物。
7.根据上述权利要求的任一项或多项的方法,其中Rs每次出现独立地选自任何RT基团,具有1至40个碳原子的烃基,其中所述烃基可以进一步被一个或多个RT基团取代,和具有1至40个碳原子的包含一个或多个选自N,O,S,P,Si,Se,As,Te或Ge的杂原子的烃基,其中N、O和S是优选的杂原子,其中烃基可以进一步被一个或多个基团RT取代,RT每次出现独立地选自F,Br,Cl,-CN,-NC,-NCO,-NCS,-OCN,-SCN,-(O)NR0R00,-C(O)X0,-C(O)R0,-NH2,-NR0R00,-SH,-SR0,-SO3H,-SO2R0,-OH,-OR0,-NO2,-SF5和-SiR0R00R000,R0,R00和R000每次出现彼此独立地选自H,F,具有1至40个碳原子的烃基,和具有1至40个碳原子其中一个或多个氢被F替代的烃基。
9.根据上述权利要求的任一项或多项的方法,其中三氟甲磺酸与反应物-CH2OH基团的数量的摩尔比至少为1。
10.根据上述权利要求的任一项或多项的方法,其中所述方法在至多50℃的温度下进行。
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