CN102030701A - Fluoradene derivative and preparation method thereof - Google Patents
Fluoradene derivative and preparation method thereof Download PDFInfo
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- CN102030701A CN102030701A CN 201010530888 CN201010530888A CN102030701A CN 102030701 A CN102030701 A CN 102030701A CN 201010530888 CN201010530888 CN 201010530888 CN 201010530888 A CN201010530888 A CN 201010530888A CN 102030701 A CN102030701 A CN 102030701A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- HQJPYLIAWVSUHC-UHFFFAOYSA-N ctk1a2241 Chemical class C12=CC=CC=C2C2=CC=CC3=C2C1C1=CC=CC=C31 HQJPYLIAWVSUHC-UHFFFAOYSA-N 0.000 title claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 29
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims abstract description 14
- ICZIGRGFOIYYPA-UHFFFAOYSA-N 1-hexyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CCCCCC ICZIGRGFOIYYPA-UHFFFAOYSA-N 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 46
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 41
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 28
- 150000001412 amines Chemical class 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- OWWDMZCHFSXLIF-UHFFFAOYSA-N 9-(2-bromophenyl)-9H-fluoren-1-ol Chemical compound BrC1=C(C=CC=C1)C1C2=CC=CC=C2C=2C=CC=C(C12)O OWWDMZCHFSXLIF-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 23
- 235000017550 sodium carbonate Nutrition 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- 150000002475 indoles Chemical class 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- IIQWSBJDXPXJNJ-UHFFFAOYSA-M azane;benzyl(triethyl)azanium;chloride Chemical compound N.[Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 IIQWSBJDXPXJNJ-UHFFFAOYSA-M 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 238000005829 trimerization reaction Methods 0.000 claims description 12
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical group BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims description 11
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 8
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 claims description 6
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 230000031709 bromination Effects 0.000 claims description 6
- 238000005893 bromination reaction Methods 0.000 claims description 6
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000006254 arylation reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229960004839 potassium iodide Drugs 0.000 claims description 3
- 235000007715 potassium iodide Nutrition 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000002837 carbocyclic group Chemical group 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000012433 hydrogen halide Substances 0.000 abstract description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 abstract 2
- 238000010276 construction Methods 0.000 abstract 2
- 150000001717 carbocyclic compounds Chemical class 0.000 abstract 1
- 238000012512 characterization method Methods 0.000 abstract 1
- 150000001923 cyclic compounds Chemical class 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 abstract 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 abstract 1
- 230000005693 optoelectronics Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 238000005481 NMR spectroscopy Methods 0.000 description 22
- 238000000967 suction filtration Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 238000000605 extraction Methods 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000012074 organic phase Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- -1 3 Chemical compound 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 9
- KDDHMFGABWFXGD-UHFFFAOYSA-N 9-(2-bromophenyl)fluoren-9-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1(O)C1=CC=CC=C1Br KDDHMFGABWFXGD-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- SHUQFBKCOHURJQ-UHFFFAOYSA-N 9-hexylcarbazole Chemical compound C1=CC=C2N(CCCCCC)C3=CC=CC=C3C2=C1 SHUQFBKCOHURJQ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- CDKBZLHZLOFNHR-UHFFFAOYSA-N BrC1=C(C=CC=C1)C1C2=CC=CC=C2C=2C=CC=C(C12)C1=CC=CC=2C3=CC=CC=C3N(C12)CCCCCC Chemical compound BrC1=C(C=CC=C1)C1C2=CC=CC=C2C=2C=CC=C(C12)C1=CC=CC=2C3=CC=CC=C3N(C12)CCCCCC CDKBZLHZLOFNHR-UHFFFAOYSA-N 0.000 description 5
- GEYBMYRBIABFTA-UHFFFAOYSA-N O-methyltyrosine Chemical compound COC1=CC=C(CC(N)C(O)=O)C=C1 GEYBMYRBIABFTA-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- IKBRTTRENJAGSP-UHFFFAOYSA-N 3-[9-(2-bromophenyl)-9H-fluoren-1-yl]-9-hexylcarbazole Chemical compound BrC1=C(C=CC=C1)C1C2=CC=CC=C2C=2C=CC=C(C12)C=1C=CC=2N(C3=CC=CC=C3C2C1)CCCCCC IKBRTTRENJAGSP-UHFFFAOYSA-N 0.000 description 3
- KWSQYVPIKHBAQV-UHFFFAOYSA-N 3-diazenyl-1H-indol-2-ol Chemical compound Oc1[nH]c2ccccc2c1N=N KWSQYVPIKHBAQV-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- GMGLGUFSJCMZNT-UHFFFAOYSA-N BrCCCCCC.BrCCCCCC Chemical compound BrCCCCCC.BrCCCCCC GMGLGUFSJCMZNT-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- QNLOWBMKUIXCOW-UHFFFAOYSA-N indol-2-one Chemical compound C1=CC=CC2=NC(=O)C=C21 QNLOWBMKUIXCOW-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920001088 polycarbazole Polymers 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JQEFMAADBIZPEB-UHFFFAOYSA-N tetracyclo[3.3.1.03,9.07,9]nonane Chemical compound C1C2CC3CC4C32C1C4 JQEFMAADBIZPEB-UHFFFAOYSA-N 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IHMXVSZXHFTOFN-UHFFFAOYSA-N 2-ethyloxolane Chemical compound CCC1CCCO1 IHMXVSZXHFTOFN-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- RZSJZEHKTBMMDZ-UHFFFAOYSA-N azanium;1,2,3-triethylbenzene;chloride Chemical compound [NH4+].[Cl-].CCC1=CC=CC(CC)=C1CC RZSJZEHKTBMMDZ-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000007051 intramolecular arylation reaction Methods 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一类Fluoradene衍生物及其制备方法，其制备方法是在化合物咔唑、己基咔唑、三苯胺及己基三聚吲哚上引入了fluoradene环，通过钯催化分子内碳-氢键活化和卤化氢消除反应并高效构建碳环或杂环化合物，尤其是结构新颖的碳环的构建；本发明致力于含有Fluoradene结构单元的大张力环状化合物的合成和表征，这类新颖的含Fluoradene结构单元的化合物有望用于有机光电材料领域。The invention discloses a class of fluorodene derivatives and a preparation method thereof. The preparation method is to introduce a fluorodene ring into the compound carbazole, hexylcarbazole, triphenylamine and hexyltrimeric indole, and catalyze intramolecular carbon-hydrogen bonds through palladium. Activation and hydrogen halide elimination reaction and efficient construction of carbocyclic or heterocyclic compounds, especially the construction of carbocyclic rings with novel structures; the present invention is dedicated to the synthesis and characterization of large strained cyclic compounds containing Fluoradene structural units, such novel containing Compounds of Fluoradene structural units are expected to be used in the field of organic optoelectronic materials.
Description
Technical field
The present invention relates to the organic chemistry synthesis technical field, specifically class Fluoradene derivative and preparation method thereof.
Background technology
In Synthetic Organic Chemistry, hightension aromatic nucleus molecule for example fenestrane theoretical or experimentally all be to have very big challenge.And wherein fluoradene (in the accompanying drawing 1 a), two indenes rings are shared quaternary carbons in a kind of acidic molecular and the molecule.To the structural analysis of Fluradene is hydrocarbon polymer C from the unknown
19H
10The C-C key of the aromatic nucleus of (b in the accompanying drawing 1) ([1] A.Streiweiser Jr.Tetrahedron Lett.1960, (6), 23.) gains enlightenment.Up to the present, be that considerably less ([3] are H.Rapoprt (a), and G.Smolinsky, J.Am.Chem.Soc.1958,80,2910 to the report of fluorandene; (b) H.Rapoprt, and G.Smolinsky, J.Am.Chem.Soc.1960,82,934; (c) G.Baum and H.Shecter, J.Org.Chem.1976,41,2120; (d) H.Dietrich, D.Bladauski, M.Grosse, K.Roth and D.Rewichi, Chem.Ber.1975,108,1807; (e) W.Burger, D.Bladauski, M.Grosse and D.Rewicki, Chem.Ber.1982,115,209; (f) S.Murata, T.Sugawara and H.Iwamura, J.Am.Chem.Soc.1985,107,6317.).Fluorandene has characteristic and thereby its interior clearly outside makes it to form stable compound on the structure with metal-complexing.The synthetic of the 7b position substitutive derivative of Fluorandene also was not in the news, up to the present have only two compound 7b-triisopropylsilylfluorandene and 7b-(2,4-dinitrophenyl)-crystalline structure of fluorandene was in the news, but ([4] are A.Xia (a) not relate to any concrete synthetic details, J.P.Selegue, A.Carrillo, B.O.Patrick, S.Parkinand C.P.Brock, Acta Crystallographica 2001, B57,507; (b) L.Fabian and A.Kalman, ActaCrystallographica 2004, B60, p548; (c) C.P.Brock, and B.O.Patrick, Mol.Cryst.Liq.Cryst.2002,389,79.).The phenyl derivatives of other fluorandene is phenylfluoradene and its derivative for example, they are considered to can be via tetrabenzo[5.5.5.5] fenestrane derives and obtains, but all be unknown material also never appear in the newspapers (referring to the c and the d of accompanying drawing 1).
Summary of the invention
Class Fluoradene derivative that provides at the deficiencies in the prior art and preparation method thereof is provided, eliminate reaction by C-H activation and hydrogen halide in the palladium catalytic molecular and can efficiently make up carbocyclic ring or heterogeneous ring compound, especially the isocyclic of novel structure makes up, and is devoted to contain hightension ring compound synthetic of Fluoradene structural unit and characterizes.
The present invention synthesizes various fluorandene derivatives with conventional palladium catalytic molecular intramolecular cyclization arylation methodology of organic synthesis first, promptly at 3 of carbazole and N-alkyl carbazole, 6,2 of the 4-position of the phenyl ring of triphenylamine and N-alkyl trimerization indoles, introduced fluorandene substituted radical structure for 7,12.
The object of the present invention is achieved like this:
One class fluoradene derivative, characteristics are: introduced the fluoradene ring on compound carbazole, hexyl carbazole, triphenylamine and hexyl trimerization indoles, it has following structure:
A kind of preparation method of said derivative, this method comprises following concrete steps:
A, preparation intermediate 9-(2-bromophenyl) fluorenol
(1), o-bromoaniline is dissolved in the 12mol/L hydrochloric acid, place-5～0 ℃, add sodium nitrite solution, reacted 1～2 hour, add liquor kalii iodide again, reacted 2 hours heat temperature raising to 60～70 ℃, obtains adjacent bromo-iodobenzene; Wherein: the mol ratio of o-bromoaniline, Sodium Nitrite and potassiumiodide is 1: (1.2～1.3): (1.4～1.5);
(2), adjacent bromo-iodobenzene that step (1) is obtained is dissolved in the tetrahydrofuran (THF), adds sec.-propyl bromination magnesium again ,-50～-40 ℃ of reactions 3 hours add the Fluorenone that is dissolved in tetrahydrofuran (THF) inward.Get midbody product 9-(2-bromophenyl) fluorenol; Wherein: the mol ratio of adjacent bromo-iodobenzene, sec.-propyl bromination magnesium and Fluorenone is 1: 1: (0.6～1); The quality of adjacent bromo-iodobenzene and the volume ratio 1 of tetrahydrofuran (THF): (5～7);
B, Fu Ke alkylated reaction
(1), 9-(2-bromophenyl) fluorenol and triphenylamine be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 3～5 hours; Wherein: when the mol ratio of triphenylamine, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～2.5), obtain compound (12); When the mol ratio of triphenylamine, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is (2～2.5): (0.9～1.3): in the time of 1, obtain compound (10);
(2), 9-(2-bromophenyl) fluorenol and carbazole be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 6～8 hours; Wherein: when the mol ratio of carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～3), obtain compound (3);
(3), 9-(2-bromophenyl) fluorenol and hexyl carbazole be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 5～7 hours; Wherein: when the mol ratio of hexyl carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～2.5), obtain compound (8); When the mol ratio of hexyl carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (0.8～1.2), obtain compound (6);
(4), 9-(2-bromophenyl) fluorenol and hexyl trimerization indoles be dissolved in solvent, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 5～7 hours; When 5,10, the mol ratio of 15-three hexyl trimerization indoles, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (3～3.5), obtain compound (18);
Appearance agent described in b step (1), (2), (3) and (4) is 1,4-dioxane or methylene dichloride; Holding the volume of agent and the mass ratio of 9-(2-bromophenyl) fluorenol is (10～20): 1;
C, synthetic fluoradene derivative
With the synthetic fluoradene ring of arylation in the palladium catalytic molecular, its reaction conditions is:
Pd (OAc)
2/ PPh
3/ Na
2CO
3/ BuEt
3NCl/DMA or Pd (OAc)
2/ PPh
3/ Na
2CO
3/ BuEt
3NCl/DMF;
(1), compound and palladium, yellow soda ash, triphenyl phosphorus and the benzyl triethyl ammonium ammonia chloride that the b step is obtained is dissolved in the solvent reheat to 140～170 ℃ reaction 4～6 hours; Said solvent is N, dinethylformamide or N,N-dimethylacetamide;
The mol ratio of compound (3), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.3): (0.2～0.7): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (3) is (50-60): 1; Obtain compound 3,6-difluoradenyl-9H-carbazole (4);
The mol ratio of compound (6), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.2): (0.2-0.24): (4-5): (0.5-1); The mass ratio of the volume of solvent and compound (6) is (30-50): 1; Obtain compound 3-fluoradenyl-9-hexylcarbazole (7);
The mol ratio of compound (8), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.3): (0.2～0.66): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (8) is (30～50): 1; Obtain compound 3,6-difluoradene-9-hexylcarbazole (9);
The mol ratio of compound (10), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.05～0.2): (0.1～0.44): (4～6): (0.5～1); The mass ratio of the volume of solvent and compound (10) is (30～50): 1; Obtain compound tris[(4-fluoradenyl) phenyl] amine (11);
The mol ratio of compound (12), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.3): (0.2～0.7): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (12) is (40～60): 1; Obtain compound tris[(4,4 '-difluoradene) phenyl] amine (13);
The mol ratio of compound (18), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.3～0.5): (0.6～1): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (18) is (40～60): 1; Obtain compound 5,10,15-trihexyl-2,7,12-trifluoradenyl-10,15-dihydro-5H-diindolo[3,2-a; 3 ', 2 '-c] carbazole (19).
The present invention makes the carbon-hydrogen activation on the aromatic nucleus realize intramolecular arylation with palladium catalyst.This catalyzer is common palladium [Pd (OAc)
2], palladium salt such as two (tricyclohexyl phosphine) Palladous chloride [(Cy
3P)
2PdCl
2], two (triphenylphosphine) Palladous chloride [(Ph
3P)
2PdCl
2], tetrakis triphenylphosphine palladium [(Ph
3P)
4Pd] etc., the solvent of using is generally polar solvent such as tetrahydrofuran (THF), dioxane, N, dinethylformamide (DMF), N,N-dimethylacetamide (DMA), preferred N, dinethylformamide (DMF), N,N-dimethylacetamide (DMA).
The present invention is the reaction of carrying out with 9-(2-bromophenyl)-9-fluorenol and various substrate.For four kinds of substrate N-hexyl carbazoles that relate in the reaction, carbazole, they all contain the N atom triphenylamine and trimerization indoles, and the lone-pair electron on this N atom participate in conjugation.In final compound (4), contain two fluorandene structures, contain a fluorandene structure in the compound (7), (9) contain two fluorandene structures, (11) contain a fluorandene structure in, contain two fluorandene structures and (20) in (13) and contain three fluorandene structures.All be to carry out the Fu Shi alkylated reaction as catalyzer in the reaction with Lewis acid three fluosulfonic acid, solvent generally is polar solvent such as tetrahydrofuran (THF), 1,4-dioxane etc. first-selected 1, the 4-dioxane, heat up again after being added dropwise to complete under the general first normal temperature of operation about 40 ℃-100 ℃ first-selected 70-80 ℃ and reacted 1-10 hour preferred 4-5 hour down.Its solvability variation of increase along with fluoradene substituted radical number, three [4,4 ', 4 " three (9-(2-bromophenyl) fluorenyl) phenyl] the via palladium-catalyzed product that obtains of amine can't obtain pure product because of its solvability is too poor; and the bis[(4 that three [4; 4 ' two (9-(2-bromophenyl) fluorenyl) phenyl] amine (12) obtains via palladium catalysis, 4 '-difluoradene) phenyl] amine (13) also can't pass through because of the solvability extreme difference
13C NMR detects.Sp in the various final fluorandene derivatives
3The quaternary carbon of hydridization exists
13Generally about 60ppm, we finally determine its structure by the X-single crystal diffraction to data among the C NMR.
Fluoradene derivative provided by the invention is because of having specific luminescent properties and good thermostability, so the compound that contains the Fluoradene structural unit of this class novelty is expected to be used for the organic photoelectrical material field.
Description of drawings
Fig. 1 is several Fluoradene derivant structure figure, and wherein a is known; B, c and d are unknown compound
Fig. 2-7 is the preparation flow figure of the embodiment of the invention
Fig. 8 is the single crystal structure figure of The compounds of this invention (7)
Embodiment
The invention is further illustrated by the following examples
Adopt reagent: Sodium Nitrite, 1,4-epoxy hexane, dehydrated alcohol, THF, analytical pure, Shanghai Shang Si Fine Chemical Co., Ltd; O-bromoaniline, bromohexane, three fluosulfonic acid, isatin, sodium hydride, analytical pure, Shanghai reaches auspicious fine chemistry company limited; Fluorenone, carbazole, triphenylamine, hydrazine hydrate, oxo phosphorus chloride, triphenyl phosphorus, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group produces; Yellow soda ash, potassiumiodide, analytical pure, Shanghai reagent one factory; Concentrated hydrochloric acid, analytical pure, Shanghai reagent four Kunshan subsidiary factories of factory; Sec.-propyl bromination magnesium, analytical pure, ladder is uncommon likes that (Shanghai) changes into industrial development company limited; Palladium, analytical pure, chemical industry company limited is reached in Shaanxi; The phenyl triethyl ammonium chloride, analytical pure, Shanghai chemical reagents corporation of Chinese Medicine group.
1), the preparation of 2-bromo iodobenzene (1)
(5g 29.06mmol) is dissolved in the 50mL water, the 15mL concentrated hydrochloric acid is added wherein again, is cooled to 0 ℃ with o-bromoaniline.With NaNO
2(2.41g 34.87mmol) is dissolved in the 50mL water, slowly is added drop-wise in the above-mentioned solution.When solid all after the dissolving, (7.23g 43.59mmol) joins in the above-mentioned solution slowly, and it is blood red that solution is will to be dissolved in the KI of 11mL water.Stir 0.5h under the room temperature.Be warming up to 70 ℃ of stirring 0.5h.Cool off, add the Na of 0.43mol/L
2SO
3Solution 20mL neutralization.Use dichloromethane extraction, organic phase washes with water, passes through anhydrous MgSO again
4Dry.Remove behind the suction filtration and desolvate, again underpressure distillation obtain light yellow liquid (3.85g, yield:77.0%).
1H?NMR(CDCl
3，500MHz)：δ7.88-7.86(dd，J＝8.0Hz，J＝1.4Hz?1H)；7.64-7.62(dd，J＝8.0Hz，J＝1.4Hz，1H)；7.30-7.20(td，J＝7.9Hz，J＝1.4Hz?1H)；7.02-6.99(td，J＝7.8Hz，J＝1.4Hz，1H).
2), the preparation of 9-(2-bromophenyl)-9-fluorenol (2)
Under the nitrogen protection with adjacent bromo-iodobenzene (6.98g; 24.67mmol) be dissolved in the 25mL tetrahydrofuran (THF) (THF); be cooled to-40 ℃; slowly in reaction flask, drip 24mL1.0M sec.-propyl bromination magnesium solution; dropwising the back keeps this temperature to stir 3h; then with Fluorenone (2.88g; 16.00mmol) splash in the above-mentioned solution in tetrahydrofuran (THF) (15ml); stir 0.5h; continue to stir 12h after slowly being warming up to room temperature; the gained reaction mixture dilutes with saturated ammonium chloride solution, with ethyl acetate (3 * 100ml) extractions, the anhydrous MgSO of organic phase
4Drying, suction filtration is spin-dried for the back resistates and carries out recrystallization with ethyl acetate and sherwood oil and obtain white solid (3.51g, productive rate: 65.0%) .Mp:142-144 ℃;
1H NMR (CDCl
3, 500MHz): δ 8.48 (br, 1H); 7.56 (d, J=7.6Hz, 2H); 7.50 (s, 1H); 7.45-7.40 (m, 3H); 7.26 (t, J=7.7Hz, 2H); 7.19 (t, J=7.7Hz, 3H); 2.43 (br, 1H).
13C?NMR(CDCl
3，125MHz)：δ：120.24?120.92?124.00?127.07?128.35?129.10?129.23?134.39?140.83141.35?148.69
3) 3, the 6-two (preparation of 9-(2-bromophenyl)-9-fluorenyl carbazole (3)
Under the nitrogen protection with carbazole (0.50g, 2.97mmol) and 9-(2-bromophenyl)-9-fluorenol (2.0g 5.93mmol) is dissolved in 25mL 1, and in the 4-dioxane, (0.89g 5.93mmol) slowly splashes in the above-mentioned solution with three fluosulfonic acid then.Be warming up to 80 ℃ of reacting by heating 7h again.Cooling is poured reaction solution in the water into, suction filtration, oven dry.Use sherwood oil: ethyl acetate=cross post at 5: 1, obtain crude product (0.36g), directly throw next step.
4) 3, the preparation of 6-difluoradenyl-9H-carbazole (4)
Under the nitrogen protection with 3; 6-two (9-(2-bromophenyl)-9 fluorenyl carbazoles (0.36g, 0.45mmol), palladium (30mg; 0.13mmol); triphenyl phosphorus (70mg, 0.29mmol) and yellow soda ash (240mg, 2.25mmol); triethylbenzene ammonium chloride (100mg; 0.45mmol) be dissolved in the 20mL N,N-dimethylacetamide, be heated to 140 ℃ of about 5h of reaction.After the cooling reaction solution is poured in the water, with methylene dichloride (3 * 30mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use sherwood oil: ethyl acetate=cross post obtain white solid (0.16g, productive rate 55.2%) at 1: 1.Mp＞350℃。
1H?NMR(DMSO，500MHz)：δ11.01(s，1H)；8.25(d，J＝7.5Hz，4H)；7.74(d，J＝7.5Hz，4H)；7.69(s，2H)；7.56(d，J＝7.5Hz，4H)；7.48(d，J＝7.5Hz，2H)；7.38-7.34(m，6H)；7.28(t，J＝7.5Hz，4H)；7.17(d，J＝7.5Hz，2H).
13C?NMR(DMSO，125MHz)：δ66.10?110.93?115.96?119.68?121.54?122.00?124.27?126.19?126.50127.84?130.94?134.95?138.65?139.78?143.30?152.23?165.78.
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) preparation of 9-hexyl carbazole (5)
Under the nitrogen protection with NaH (1.74g, 60%w/w dispersion in mineral oil 44.0mmol) pour in 20mLN is housed, in the round-bottomed flask of N-N,N-DIMETHYLACETAMIDE, N
2Protection.(5.52g 33.0mmol) is dissolved in the 60mL N,N-dimethylacetamide and splashes in the above-mentioned solution and stir 0.5h with carbazole.Drip inside again hexyl bromide 1 bromohexane (6.54g, 39.6mmol), reflux 5h.During cooling is fallen back, with methylene dichloride (3 * 50mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use ethyl alcohol recrystallization, obtain white solid (6.39g, productive rate 77.0%).Mp：64-66℃
4) preparation of 3-(9-(2-bromophenyl) fluorenyl)-9-hexyl carbazole (6)
Under the nitrogen protection with N-hexyl carbazole (2.80g; 11.12mmol) and three fluosulfonic acid (0.67g; 4.45mmol) be dissolved in 10mL1; in the 4-dioxane; then with 9-(2-bromophenyl)-9-fluorenol (1.5g 4.45mmol) is dissolved in 10mL 1, in the 4-dioxane in; and splash into slowly in the above-mentioned solution, and then be warming up to 90 ℃ of reacting by heating 5h.After the cooling reaction solution is poured in the water, with methylene dichloride (3 * 100mL) extractions, organic phase MgSO
4Drying is spin-dried for behind the suction filtration.Use sherwood oil: ethyl acetate=cross post obtain white solid (2.8g, productive rate 51.2%) at 40: 1.Mp：181-183℃
1H?NMR(CDCl
3?500MHz)：δ7.89(d，J＝7.9Hz，1H)；7.84(s，1H)；7.77(d，J＝6.2Hz，2H)；7.71(br，1H)；7.62(br，1H)；7.55(d，J＝7.9Hz，1H)；7.42(d，J＝8.8Hz，1H)；7.40-7.36(m，3H)；7.33(d，J＝8.3Hz，1H)；7.28(br，1H)；7.25(t，J＝4.3Hz，2H)；7.20(d，J＝7.7Hz，1H)；7.13-7.10(m，2H)；7.08-7.05(m，1H)；4.22(t，J＝7.3Hz，2H)；1.84-1.79(m，2H)；1.37-1.35(m，2H)；1.29-1.25(m，4H)；0.85(t，J＝6.8Hz，3H).
13C?NMR(CDCl
3，125MHz)：δ13.98?22.51?26.93?28.92?31.52?43.12?66.39?108.44?108.58?118.51119.04?120.25?120.31?122.57?122.80?123.54?125.43?126.13?126.21?126.31?126.92?127.49?128.30134.56?135.83?139.28?140.69?144.32?151.40
5) preparation of 3-fluoradenyl-9-hexylcarbazole (7)
Under the nitrogen protection with 3-(9-(2-bromophenyl) fluorenyl)-9-hexyl carbazole (0.57g; 1.00mmol); palladium (50mg; 0.20mmol), triphenyl phosphorus (120mg, 0.44mmol) and yellow soda ash (530mg; 5mmol); (110mg 0.5mmol) is dissolved in 20mLN to the phenyl triethyl ammonium chloride, is heated to 140 ℃ of about 5h in the N-N,N-DIMETHYLACETAMIDE.After the cooling reaction solution is poured in the water, with methylene dichloride (3 * 30mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use sherwood oil: ethyl acetate=cross post at 20: 1 obtains white solid (0.4g, productive rate 81.8%).Mp：206-208℃
1H?NMR(DMSO，500MHz)：δ8.33(d，J＝7.5Hz，2H)；8.10(s，1H)；7.99(d，J＝7.8Hz，1H)；7.74(d，J＝7.4Hz，2H)；7.58(d，J＝7.4Hz，2H)；7.51-7.46(m，3H)；7.39-7.31(m，4H)；7.28(t，J＝7.4Hz，2H)；7.11(t，J＝7.4Hz，1H)；4.22(t，J＝7.0Hz，2H)；1.63-1.61(m，2H)；1.17-1.14(m，6H)；0.75(t，J＝6.8Hz，3H)；
13C?NMR(CDCl
3，125MHz)：δ：13.97?22.45?26.86?28.87?31.51?42.99?66.62?108.48?117.63?118.43119.29.120.26?121.88?122.43?122.69?124.59?125.38?126.01?126.37?127.77?130.64?134.46?139.05140.14?140.69?144.31?152.52?167.23
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) with (3) among the embodiment 2
4) 3, the preparation of 6-two [9-(2-bromophenyl) fluorenyl]-9-hexyl carbazole (8)
Under the nitrogen protection with N-hexyl carbazole (1.29g, 5.19mmol) and 9-(2-bromophenyl)-9-fluorenol (3.5g 10.37mmol) is dissolved in 50mL 1; in the 4-dioxane, (1.48g 9.86mmol) splashes in the above-mentioned solution slowly with three fluosulfonic acid then; be warming up to 80 ℃ again, heating 5h.Cooling is poured reaction solution in the water into, suction filtration, oven dry.Use sherwood oil: methylene dichloride=cross post at 4: 1 obtains white solid (2.0g, productive rate 43.3%).
1H?NMR(CDCl
3?500MHz)：δ7.75(s，4H)；7.69(br，2H)；7.59(s，2H)；7.51(d，J＝7.0Hz，4H)；7.40-7.36(m，6H)；7.25(t，J＝7.5Hz，4H)；7.19(d，J＝9.0Hz，2H)；7.12-7.08(m，4H)；7.06-7.03(m，2H)；4.14(t，J＝7.5Hz，2H)；1.76-1.72(m，2H)；1.30-1.23(m，6H)；0.83(t，J＝7.0Hz，3H).
13C?NMR(CDCl
3，125MHz)：δ13.97?22.49?26.90?28.93?31.49?43.18?66.31?108.39?119.15?120.24122.60?126.31?126.88?127.39?128.26?132.14?134.27?135.69?139.56?140.69?144.26?148.08?151.17151.79.
5) 3, the preparation of 6-difluoradene-9-hexylcarbazole (9)
Under the nitrogen protection with 3,6-two [9-(2-bromophenyl) fluorenyl]-9-hexyl carbazole (0.50g, 0.56mmol); palladium (40mg; 0.17mmol), triphenyl phosphorus (100mg, 0.37mmol) and yellow soda ash (240mg; 2.24mmol); (130mg 0.56mmol) is dissolved in the 20mL N,N-dimethylacetamide phenyl triethyl ammonium chloride; be heated to 140 ℃, about 5h.After the cooling reaction solution is poured in the water, with methylene dichloride (3 * 30mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use sherwood oil: methylene dichloride=cross post at 2: 1 obtains white solid (0.29g, productive rate 71.3%).Mp(dec)：325℃
1H?NMR(DMSO-d
6，500MHz)：δ8.24(d，J＝7.5Hz，4H)；7.75(d，J＝7.5Hz，4H)；7.68(S，2H)；7.57(d，J＝7.4Hz，4H)；7.49(t，J＝7.4Hz，2H)；7.36(t，J＝7.6Hz，6H)；7.28(t，J＝7.4Hz，4H)；7.20(d，J＝8.8Hz，2H)；4.06(t，J＝7.2Hz，2H)；1.50(m，2H)；1.08(m，6H)；0.70(t，J＝6.5Hz，3H).
13C?NMR(CDCl
3，125MHz)：δ13.96?22.39?26.73?28.79?31.45?42.83?66.64?108.35?117.50?119.27121.82?122.18?124.42?126.13?126.29?127.73?130.58?133.93139.16?140.05?144.34?152.47?167.31
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) preparation of three [4-(9-(2-bromophenyl) fluorenyl) phenyl] amine (10)
Under the nitrogen protection with triphenylamine (6.51mmol, 1.60) and three fluosulfonic acid (0.44g 2.96mmol) is dissolved in 10mL 1, in the 4-dioxane, N
2Protection.With 9-(2-bromophenyl)-9-fluorenol (1.0g 2.96mmol) is dissolved in 10mL 1, in the 4-dioxane in, and splash into slowly in the above-mentioned solution, be warming up to 90 ℃ again, heating 5h.Cooling is poured reaction solution in the water into, with methylene dichloride (3 * 50mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use sherwood oil: ethyl acetate=cross post at 40: 1 obtains white solid (1.01g, productive rate 60.5%).
1H?NMR(CDCl
3?500MHz)：δ7.75(d，J＝7.5Hz，2H)；7.56(d，J＝7.1Hz，2H)；7.54(d，J＝7.6Hz，1H)；7.37(t，J＝7.4Hz，2H)；7.27(d，J＝7.7Hz，3H)；7.20(t，J＝7.7Hz，4H)；7.14(s，2H)；7.07(dd，J＝8.5Hz，J＝7.7Hz，6H)；6.97(t，J＝7.4Hz，2H)；6.90(d，J＝8.6Hz，2H).
13C?NMR(CDCl
3，125MHz)：δ119.28?121.84?122.65?123.21?124.26?126.00?126.40?127.13?127.86129.07?120.68?137.75?140.00?144.38?146.00?147.57?151.86
4) phenyl tris[(4-fluoradenyl)] preparation of amine (11)
Under the nitrogen protection with three [4-(9-(2-bromophenyl) fluorenyl) phenyl] amine (0.56g; 1.0mmol); palladium (50mg 0.20mmol); triphenyl phosphorus (120mg, 0.44mmol) and yellow soda ash (530mg, 5.0mmol); phenyl triethyl ammonium chloride (110mg; 0.50mmol) be dissolved in the 20mL N,N-dimethylacetamide, be heated to 140 ℃ of about 4h of reaction.After the cooling reaction solution is poured in the water, with methylene dichloride (3 * 30mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use sherwood oil: ethyl acetate=cross post at 20: 1 obtains white solid (0.18g, productive rate 37.2%).Mp：256-259℃
1H?NMR(CDCl
3?500MHz)：δ7.84(d，J＝7.5Hz，2H)；7.50(d，J＝7.5Hz，2H)；7.35(t，J＝7.5Hz，5H)；7.24(d，J＝7.5Hz，2H)；7.16(t，J＝8.0Hz，4H)；7.03(d，J＝4.3Hz，2H)；6.97-6.92(m，6H)；6.77(d，J＝9.0Hz，2H).
13C?NMR(CDCl
3，125MHz)：δ65.78?120.22?122.66?123.40?123.47?124.25?126.16?126.99?127.54127.58?128.40?128.62?129.13?135.88?137.95?140.66?143.74?146.13?147.66?150.65
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) preparation of three [4,4 '-two (9-(2-bromophenyl) fluorenyl) phenyl] amine (12)
Under the nitrogen protection with triphenylamine (2.04mmol; 0.5g) and three fluosulfonic acid (0.67g; 4.48mmol) be dissolved in 20mL 1; in the 4-dioxane, (1.51g 4.48mmol) is dissolved in 10mL 1 with 9-(2-bromophenyl)-9-fluorenol; in the 4-dioxane; and slowly splash in the above-mentioned solution, be warming up to 90 ℃ again, reacting by heating 5h.Cooling is poured reaction solution in the water into, with methylene dichloride (3 * 50mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use sherwood oil: methylene dichloride=cross post at 3: 1 obtains white solid (0.62g, productive rate 34.4%).
1H?NMR(CDCl
3，500MHz)：δ7.73(d，J＝7.5Hz，4H)；7.56-7.51(m，6H)；7.35(t，J＝7.3Hz，4H)；7.25(d，J＝7.0Hz，2H)；7.17(t，J＝8.2Hz，2H)；7.11-7.07(m，4H)；7.06-7.01(m，8H)；6.93(t，J＝7.2Hz，1H)；6.87(d，J＝8.7Hz，4H)；
13C?NMR(CDCl
3，125MHz)：δ：65.74?120.19?122.77?123.39?123.44?124.23?124.53?126.13?126.97127.52?127.55?128.37?128.54?129.08?129.12?131.73?135.85?137.89?140.61?143.71?145.93?147.41150.62.
4) tris[(4,4 '-difluoradene) phenyl] preparation of amine (13)
Under the nitrogen protection with three [4; 4 '-two (9-(2-bromophenyl) fluorenyl) phenyl] and amine (0.50g, 0.57mmol), palladium (40mg; 0.17mmol); triphenyl phosphorus (100mg, 0.37mmol) and yellow soda ash (240mg, 2.26mmol); phenyl triethyl ammonium chloride (130mg; 0.57mmol) be dissolved in the 20mL N,N-dimethylacetamide, be heated to 140 ℃ of about 5h of reaction.After the cooling reaction solution is poured in the water, with methylene dichloride (3 * 30mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use sherwood oil: methylene dichloride=cross post at 1: 1 obtains white solid (0.29g, productive rate 71.1%).Mp：346-349℃
1H?NMR(CDCl
3，500MHz)：δ7.78(d，J＝7.5Hz，4H)；7.58(d，J＝7.5Hz，4H)；7.31(t，J＝6.5Hz，10H)；7.20(t，J＝7.5Hz，4H)；7.06(t，J＝8.0Hz，2H)；6.93(d，J＝8.5Hz，4H)；6.87-6.83(m，3H)；6.63(d，J＝8.5Hz，4H).
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) preparation of isatin-3-hydrazone (14)
(3.75g 25.4mmol) is dissolved in the 30mL methyl alcohol isatin, drips 2.91g hydrazine hydrate (massfraction 85%) inward.The about 1h of mild heat.Cool off in ice-water bath, suction filtration gets yellow solid (3.68g, productive rate 89.5%).Mp(dec)：225℃
4) preparation of 2-indolone (15)
1.2g Na is dissolved in the ethanol of 30mL, is stirred to molten entirely.And toward isatin-3-hydrazone (3g slowly drips in 18.6mmol), is warming up to 60-70 ℃, is back to no N
2Till the generation.Cooling adds 10%HCl and is adjusted to pH=1.Use dichloromethane extraction, organic phase MgSO
4Drying is spin-dried for behind the suction filtration.Get light yellow solid (2.08g, productive rate 69.3%) with methylene dichloride and sherwood oil recrystallization.Mp：125-128℃
5) preparation of trimerization indoles (16)
(1.0g 7.5mmol) adds 4mL POCl toward the 2-indoles down in nitrogen protection
3, be heated to 120 ℃ of reactions and distill away unnecessary POCl behind the 15h
3, resistates is poured in the water, with in the yellow soda ash and back ethyl acetate (3 * 50ml) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use P: A=4: 1 crosses post, obtains yellow solid (0.07g, productive rate 8.1%).Mp＞350℃
1H?NMR(DMSO-d
6，500MHz)：δ11.45(s，1H)；7.58(d，J＝8.0Hz，1H)；7.43(d，J＝8.0Hz，1H)；7.15-7.07(m，2H).
6) 5,10, the preparation of 15-three hexyl trimerization indoles (17)
Under the nitrogen protection with NaH (4.06mmol, 60%w/w dispersion in mineral oil 0.16g) is suspended among the 5mLDMF, drip inward three polycarbazoles be dissolved in 15mL DMF (0.4g, 1.16mmol), stirring at normal temperature 0.5h.(0.76g 4.63mmol) is added dropwise to wherein, heating reflux reaction 1h with hexyl bromide 1 bromohexane again.Cooling is poured reaction in the water into, with methylene dichloride (3 * 50mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use ethyl alcohol recrystallization, obtain yellow solid (0.39g, productive rate 98.1%).Mp：131-133℃
1H?NMR(CDCl
3，500MHz)：δ7.41-7.37(m，6H)；7.19(t，J＝7.6Hz，3H)；7.10(t，J＝7.2Hz，3H)；4.27-4.15(m，6H)；1.48-1.47(m，3H)；1.34-1.32(m，3H)；0.61-0.51(m，18H)；0.44(t，J＝6.3Hz，9H).
13C?NMR(CDCl3，125MHz)：δ：13.80?21.56?25.70?29.17?31.15?44.76?107.14?110.30?118.79119.80?120.96?127.47?137.25?138.29
7) 5,10,15-three hexyls-2,7, the preparation of 12-three [9-bromophenyl) fluorenyl] trimerization indoles (18)
With 5,10, (0.6g, 1.0mmol), (1.18g, 3.5mmol) in 20mL 1,4-dioxy hexamethylene six encircles 9-(bromophenyl) 9-fluorenol 15-three hexyls three polycarbazoles under the nitrogen protection.Drip inward three fluosulfonic acid (0.53g, 3.5mmol).Reflux, reaction 5h.Cooling is poured reaction in the water into, with methylene dichloride (3 * 100mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use sherwood oil: ethyl acetate=3: 1, obtain crude product (0.72g), directly throw next step.
8) 5,10,15-trihexyl-2,7,12-trifluoradenyl-10,15-dihydro-5H-diindolo[3,2-a; 3 ', 2 '-c] preparation of carbazole (19)
Under the nitrogen protection with 5,10,15-three hexyls-2; 7, and 12-three [the 9-bromophenyl) fluorenyl] the trimerization indoles (0.50g, 0.32mmol); palladium (30mg, 0.15mmol), triphenyl phosphorus (80mg; 0.32mmol) and yellow soda ash (140mg, 1.28mmol), phenyl triethyl ammonium chloride (70mg; 0.32mmol) be dissolved in 20mL N; in the N-N,N-DIMETHYLACETAMIDE, be heated to 140 ℃, about 5h.After the cooling reaction solution is poured in the water, with methylene dichloride (3 * 50mL) extractions, organic phase MgSO
4Drying, suction filtration is spin-dried for.Use sherwood oil: methylene dichloride=cross post at 20: 1 obtains yellow solid (0.35g, productive rate 83.3%).
1H?NMR(CDCl3，500MHz)：δ7.81-7.77(m，6H)；7.57(d，J＝7.0Hz，6H)；7.34-7.25(m，48H，CDCl3overlap)；7.16(t，J＝7.0Hz，18H)；6.99(s，3H)；6.80(s，6H)；3.74-3.67(m，6H)；0.97-0.95(m，6H)；0.45-0.24(m，27H).
13C?NMR(CDCl3，125MHz)：δ13.60?21.36?25.13?28.70?30.70?44.26?66.87?106.09?108.02?118.22118.80?119.18?119.21?121.71?125.79?125.91?126.00?126.20?127.67?130.51?136.77?136.85?138.26139.96?140.01?144.39?152.52?167.24.
Claims (2)
1. a class fluoradene derivative, it is characterized in that: introduced the fluoradene ring on compound carbazole, hexyl carbazole, triphenylamine and hexyl trimerization indoles, it has following structure.
2. the preparation method of the described derivative of claim 1 is characterized in that this method comprises following concrete steps:
A, preparation intermediate 9-(2-bromophenyl) fluorenol
(1), o-bromoaniline is dissolved in the hydrochloric acid of 12mol/L, place-5～0 ℃, add sodium nitrite solution, reacted 1～2 hour, add liquor kalii iodide again, reacted 2 hours heat temperature raising to 60～70 ℃, obtains adjacent bromo-iodobenzene; Wherein: the mol ratio of o-bromoaniline, Sodium Nitrite and potassiumiodide is 1: (1.2～1.3): (1.4～1.5);
(2), adjacent bromo-iodobenzene that step (1) is obtained is dissolved in the tetrahydrofuran (THF), adds sec.-propyl bromination magnesium again, places-50～-40 ℃ of reactions 3 hours, adds the Fluorenone solution that is dissolved in tetrahydrofuran (THF) more inward, midbody product 9-(2-bromophenyl) fluorenol; Wherein: the mol ratio of adjacent bromo-iodobenzene, sec.-propyl bromination magnesium and Fluorenone is 1: 1: (0.6～1); The quality of adjacent bromo-iodobenzene and the volume ratio 1 of tetrahydrofuran (THF): (5～7);
B, Fu Ke alkylated reaction
(1), 9-(2-bromophenyl) fluorenol and triphenylamine be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 3～5 hours; Wherein: when the mol ratio of triphenylamine, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～2.5), obtain compound (12); When the mol ratio of triphenylamine, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is (2～2.5): (0.9～1.3): in the time of 1, obtain compound (10);
(2), 9-(2-bromophenyl) fluorenol and carbazole be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 6～8 hours; Wherein: when the mol ratio of carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～3), obtain compound (3);
(3), 9-(2-bromophenyl) fluorenol and hexyl carbazole be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 5～7 hours; Wherein: when the mol ratio of hexyl carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～2.5), obtain compound (8); When the mol ratio of hexyl carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (0.8～1.2), obtain compound (6);
(4), 9-(2-bromophenyl) fluorenol and hexyl trimerization indoles be dissolved in solvent, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 5～7 hours; When 5,10, the mol ratio of 15-three hexyl trimerization indoles, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (3～3.5), obtain compound (18);
Appearance agent described in b step (1), (2), (3) and (4) is 1,4-dioxane or methylene dichloride; Holding the volume of agent and the mass ratio of 9-(2-bromophenyl) fluorenol is (10～20): 1;
C, synthetic fluoradene derivative
With the synthetic fluoradene ring of arylation in the palladium catalytic molecular, its reaction conditions is:
Pd (OAc)
2/ PPh
3/ Na
2CO
3/ BuEt
3NCl/DMA or Pd (OAc)
2/ PPh
3/ Na
2CO
3/ BuEt
3NCl/DMF;
(1), compound and palladium, yellow soda ash, triphenyl phosphorus and the benzyl triethyl ammonium ammonia chloride that the b step is obtained is dissolved in the solvent reheat to 140～170 ℃ reaction 4～6 hours; Said solvent is N, dinethylformamide or N,N-dimethylacetamide;
The mol ratio of compound (3), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.3): (0.2～0.7): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (3) is (50-60): 1; Obtain compound 3,6-difluoradenyl-9H-carbazole (4);
The mol ratio of compound (6), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.2): (0.2-0.24): (4-5): (0.5-1); The mass ratio of the volume of solvent and compound (6) is (30-50): 1; Obtain compound 3-fluoradenyl-9-hexylcarbazole (7);
The mol ratio of compound (8), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.3): (0.2～0.66): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (8) is (30～50): 1; Obtain compound 3,6-difluoradene-9-hexylcarbazole (9);
The mol ratio of compound (10), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.05～0.2): (0.1～0.44): (4～6): (0.5～1); The mass ratio of the volume of solvent and compound (10) is (30～50): 1; Obtain compound tris[(4-fluoradenyl) phenyl] amine (11);
The mol ratio of compound (12), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.3): (0.2～0.7): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (12) is (40～60): 1; Obtain compound tris[(4,4 '-difluoradene) phenyl] amine (13);
The mol ratio of compound (18), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.3～0.5): (0.6～1): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (18) is (40～60): 1; Obtain compound 5,10,15-trihexyl-2,7,12-trifluoradenyl-10,15-dihydro-5H-diindolo[3,2-a; 3 ', 2 '-c] carbazole (19).
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