CN107759597A - 一种咔唑类化合物及其用途 - Google Patents
一种咔唑类化合物及其用途 Download PDFInfo
- Publication number
- CN107759597A CN107759597A CN201710959580.0A CN201710959580A CN107759597A CN 107759597 A CN107759597 A CN 107759597A CN 201710959580 A CN201710959580 A CN 201710959580A CN 107759597 A CN107759597 A CN 107759597A
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- Prior art keywords
- compound
- added
- alkyl
- ethyl acetate
- carbazole compound
- Prior art date
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 31
- -1 carbazole compound Chemical class 0.000 title claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 150000003254 radicals Chemical class 0.000 claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 3
- 150000005840 aryl radicals Chemical class 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 40
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 43
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000004440 column chromatography Methods 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000003208 petroleum Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 15
- 239000012043 crude product Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
- 229940126086 compound 21 Drugs 0.000 description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002024 ethyl acetate extract Substances 0.000 description 3
- 238000003810 ethyl acetate extraction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002240 furans Chemical class 0.000 description 3
- 150000004694 iodide salts Chemical class 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 2
- 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 2
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 2
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- 229940126142 compound 16 Drugs 0.000 description 2
- 229940125961 compound 24 Drugs 0.000 description 2
- 229940125851 compound 27 Drugs 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 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 1
- 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 1
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
- 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 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- USUPCWCZFHDYTI-UHFFFAOYSA-N COc(cc1)ccc1-c(cc1)ccc1Nc(cc1)ccc1-c(cc1)ccc1OC Chemical compound COc(cc1)ccc1-c(cc1)ccc1Nc(cc1)ccc1-c(cc1)ccc1OC USUPCWCZFHDYTI-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 0 OS(c(cc1)ccc1OCC1*C1)O Chemical compound OS(c(cc1)ccc1OCC1*C1)O 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126208 compound 22 Drugs 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- SWGQITQOBPXVRC-UHFFFAOYSA-N methyl 2-bromobenzoate Chemical class COC(=O)C1=CC=CC=C1Br SWGQITQOBPXVRC-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- H—ELECTRICITY
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Abstract
本发明公开了一种咔唑类化合物及其用途。所说的咔唑类化合物具有式(I)所示结构:式(I)中:R1为C1~C12烃基或C1~C12烷氧基或C4~C20杂环基,其中所说杂环基的杂原子为N或S或O;R2为C1~C12烃基;R3为芳香烃基或杂环芳香烃基。本发明所说的化合物可作为染料敏化太阳电池的敏化剂。
Description
技术领域
本发明涉及一种有机化合物及其用途,具体地说,涉及一种咔唑类化合物及其用途。
背景技术
伴随着人类工业文明的迅速发展,煤、石油和天然气等矿物资源日益枯竭,由此引发的能源危机和环境污染已成为亟待解决的严重问题。因此人们迫切需要寻找其他新的可替代能源。有机薄膜太阳能电池,特别是染料敏化太阳能电池,因其低成本,具有潜在的实用价值。在上述光伏器件中,有机分子作为敏化染料极大影响着器件的性能。咔唑类化合物由于具有较好的光学性能以及较合适的能级结构,在上述材料中得到广泛应用。但是现有咔唑类化合物仍然存在一个重要缺陷:化合物的吸收光谱范围较窄,导致其作为染料敏化太阳电池的敏化剂光捕获能力较弱,浪费了大量的太阳光能。这个问题直接影响了基于咔唑类化合物的有机分子在上述器件中的性能,很大程度上限制了咔唑类有机分子在上述器件中的应用。因此,如何通过分子工程,调控咔唑类染料分子结构,拓展其吸收光谱范围,提高其光捕获能力,受到科学家们的广泛关注。
发明内容
本发明的目的在于提供一种咔唑类化合物,其具有较好平面性以及较高的光捕获能力。
本发明的目的还在于提供该咔唑类化合物的用途。
实现本发明的目的采取的技术方案如下:所说的咔唑类化合物,其结构式如式(I)所示:
式(I)中:R1为C1~C12烃基或C1~C12烷氧基或C4~C20杂环基,其中所说杂环基的杂原子为N或S或O;R2为C1~C12烃基;R3为芳香烃基或杂环芳香烃基。
在本发明的优选技术方案中,R1为C1~C8烷基或C1~C8烷氧基或C4~C10杂环基;R2为C1~C8烃基;R3为苯系芳香烃基。
更优选的R1为C1~C6烷基或C1~C6烷氧基或C5~C6杂环基,其中所说杂环基的杂原子为N;R2为C4~C8烃基;R3为单环苯系芳香烃基。
最佳的技术方案:R1为己氧基;R2为正辛基;R3为苯基。
本发明所说的咔唑类化合物的用途包括但不仅限于作为染料敏化太阳电池的敏化剂。
附图说明
图1为实施例2所制备染料(化合物21)在甲醇溶液中的紫外吸收谱图(3×10-5mol/L)。
图2为实施例2所制备染料(化合物21)吸附在二氧化钛电极上的紫外吸收谱图。
图3为实施例2所制备染料(化合物21)作为敏化剂的染料敏化太阳电池I-V曲线图。
制备本发明所说的咔唑类化合物,合成路线如下所示:
上述合成路线R1、R2和R3的含义与前文所述相同。
制备本发明所说的咔唑类化合物的方法,包括如下步骤:
(1)将咔唑[式(A)所示化合物]和邻溴苯甲酸甲酯[式(B)所示化合物]在碘化亚铜催化下,在邻二氯苯中回流反应12小时得到式(C)所示化合物;
(2)将式(C)所示化合物与R2基溴化镁通过格氏反应得到式(D)所示化合物;
(3)将式(D)所示化合物和三氟化硼的乙醚溶液在有惰性存在条件下反应5小时得粗产物,所得产物用乙酸乙酯/石油醚进行柱层析可得式(E)所示化合物;
(4)将式(E)所示化合物用NBS进行溴代反应,得到式(F)所示化合物;
(5)将式(F)所示化合物在-78℃下用丁基锂与硼酸三甲酯进行反应,得到式(G)所示化合物;
(6)将式(G)所示化合物与式(H)所示化合物进行Suzuki偶联反应,得到目标产物[式(I)所示化合物]。
本发明所说的咔唑类化合物,即式(I)所示化合物可作为染料敏化太阳电池中的敏化剂使用。
具体实施方式
下面通过实例对本发明作进一步的阐述,目的在于更好理解本发明的内容。因此,所举之例并不限制本发明的保护范围。
实施例1合成(R1=R2=CH3,R3=苯环)
在100mL单口瓶中,加入1.00g(5.99mmol)咔唑,用四氢呋喃将其溶解,并将单口瓶置于冰浴中且避光,然后将2.67g(15mmol)NBS用四氢呋喃溶解倒入恒压滴液漏斗中缓慢滴入100ml单口瓶中,氮气保护下冰浴搅拌4h。反应物倒入100mL水中,用乙酸乙酯萃取三次,得到的液体旋干,用乙酸乙酯:石油醚=1:200进行柱层析得到1.56g(4.8mmol)白色固体,化合物2,产率80%。1H NMR(500Hz,CDCl3)δ8.16(s,2H),8.09(s,1H),7.55(d,J=8.5Hz,2H),7.33(d,J=8.5Hz,2H)。
在250mL单口瓶中,加入3.35g(10.31mmol)化合物2,3.37g(24.76mmol)化合物3,碳酸钠5.66g(41.01mmol),水14ml,乙醇26ml,然后加入溶剂甲苯30ml,然后鼓泡30min除去氧气,然后加入0.3g(0.26mmol)四三苯基磷钯,在氮气保护下80℃回流搅拌12h,冷却后加入二氯甲烷20ml,有机相用冰水洗涤3次,用无水硫酸钠干燥,然后过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:200进行柱层析得到2.61g(7.5mmol)化合物4,产率73%。1HNMR(500Hz,CDCl3)δ8.27(s,2H),8.06(s,1H),7.63(d,J=8.5Hz,6H),7.47(d,J=8.5Hz,2H),7.01(d,J=8.5Hz,4H),2.40(s,6H)。
在100mL单口瓶中,分别加入2.61g(7.5mmol)g化合物4与1.61g(7.49mmol)化合物5以及0.48g铜粉(7.5mmol)和1.43g(7.53mmol)碘化亚铜和1.56g(11.30mmol)碳酸钾,然后加入溶剂邻二氯苯50ml,氮气保护下升温至180℃回流搅拌22h。反应完毕减压蒸馏去掉溶剂邻二氯苯,冷却后加入二氯甲烷20ml,有机相用冰水洗涤3次,用无水硫酸钠干燥,然后过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:100进行柱层析得到2.52g(5.24mmol)浅黄色固体,化合物6,产率70%。1H NMR(500Hz,CDCl3)δ8.36(s,2H),8.17(d,J=8.5Hz,1H),7.80(t,J=7.5Hz,1H),7.68-7.61(m,8H),7.20(d,J=8.5Hz,2H),7.05(d,J=8.5Hz,4H),3.32(s,3H),2.40(s,6H)。
在25ml的单口瓶中2.37g(4.92mmol)化合物6,然后加入10ml甲基溴化鎂,在氮气保护下升温至80℃回流搅拌12h,反应完毕用饱和的氯化铵溶液洗涤,乙酸乙酯萃取3次,然后用无水硫酸钠干燥,过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:100进行柱层析得到2.20g(4.56mmol)化合物7,产率92.83%.1H NMR(500Hz,CDCl3)δ8.32(s,2H),7.98(d,J=8Hz,1H),7.63(d,J=8.5Hz,4H),7.58(d,J=8Hz,3H),7.42(t,J=7.5Hz,1H),7.05-7.01(m,7H),2.41(s,6H),1.44(s,6H)。
在50mL单口烧瓶中,分别加入2.20g(4.56mmol)化合物7、1gAmberlyst15、25ml甲苯,在氮气保护下加上分水器升温至120℃回流20h,反应完毕抽滤除去催化剂,然后将液体旋干,用乙酸乙酯:石油醚=1:300进行柱层析得到1.65g(3.55mmol)浅黄色固体为目标产物化合物8,产率78%。1H NMR(500Hz,CDCl3)δ8.33(s,1H),8.19(d,J=8.5Hz,1H),8.11(d,J=8.5Hz,1H),8.08(s,1H),7.75(d,J=10.5Hz,1H),7.68(s,1H),7.67-7.64(m,5H),7.39(t,J=7.5Hz,1H),7.19(t,J=7.5Hz,1H),7.04(d,J=8.5Hz,4H),2.41(s,6H),1.82(s,6H)。
在50mL单口烧瓶中,加入0.08g(0.17mmol)化合物8用二氯将其溶解,并将单口瓶置于冰浴中且避光,然后将0.04g(0.22mmol)NBS用乙腈溶解倒入恒压滴液漏斗中缓慢滴入50ml单口瓶中,氮气保护下冰浴搅拌4h。反应物倒入100mL水中,用二氯萃取三次,得到的液体旋干,用乙酸乙酯:石油醚=1:200进行柱层析得到0.06g白色固体,化合物9,产率73%。1H NMR(500Hz,CDCl3)δ9.14(s,1H),8.15(d,J=8.5Hz,1H),8.01(d,J=8.5Hz,1H),7.72(s,1H),7.81(s,1H),7.68(d,J=8.5Hz,2H),7.53(s,1H),7.46(d,J=8.5Hz,2H),7.42(s,1H),7.05-7.08(m,5H),2.43(s,6H),1.85(s,6H)。
在50mL三口瓶中,加入0.16g(0.30mmol)化合物9,然后将其溶于30ml干燥的四氢呋喃中,插上低温温度计,在氮气保护下将其置于低温槽中,当温度低于-78℃时,用针管滴加正丁基锂3ml,缓慢滴加维持温度低于-78℃,滴加完丁基锂后搅拌2h,开始滴加硼酸三异丙脂1ml,滴加完毕再搅拌1h,然后从低温槽中取出,让其升到室温搅拌过夜。反应完毕水洗,乙酸乙酯萃取3次,然后用无水硫酸钠干燥,过滤蒸发滤液得到粗产物10,直接进行下一步反应。
在100ml单口瓶中,加入上一步的产物15,然后再加入0.13g(0.33mmol)化合物16,加入2mol/L的碳酸钾4ml,加入50ml的四氢呋喃,然后鼓泡30min除去氧气,然后加入0.1g(0.09mmol)四三苯基膦钯,在氮气保护下80℃回流搅拌12h,冷却后加入乙酸乙酯20ml,有机相用冰水洗涤3次,用无水硫酸钠干燥,然后过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:100进行柱层析得到163mg化合物17,产率68%。1H NMR(500Hz,CDCl3)δ8.36(s,2H),8.20-8.24(m,4H),8.11(s,1H),8.08(d,J=8.5Hz,2H),8.02(s,1H),7.87(s,2H),7.80(s,1H),7.62-7.70(m,5H),7.03-7.06(m,4H),2.39(s,6H),1.75(s,6H)。
实施例2合成(R1=OC8H17,R2=CH3,R3=苯环)
在250mL单口瓶中,加入3.35g(10.31mmol)化合物2,6.19g(24.76mmol)化合物13,碳酸钠5.66g(41.01mmol),水14ml,乙醇26ml,然后加入溶剂甲苯30ml,然后鼓泡30min除去氧气,然后加入0.3g(0.26mmol)四三苯基磷钯,在氮气保护下80℃回流搅拌12h,冷却后加入二氯甲烷20ml,有机相用冰水洗涤3次,用无水硫酸钠干燥,然后过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:200进行柱层析得到4.32g(7.5mmol)化合物14,产率73%。1HNMR(500Hz,CDCl3)δ8.27(s,2H),8.06(s,1H),7.63(d,J=8.5Hz,6H),7.47(d,J=8.5Hz,2H),7.01(d,J=8.5Hz,4H),4.02(t,J=6.5Hz,4H),1.85-1.80(m,4H),1.52-1.46(m,4H),1.38-1.31(m,16H),0.90(t,J=6.5Hz,6H)。
在100mL单口瓶中,分别加入4.32(7.5mmol)g化合物14与1.61g(7.49mmol)化合物5以及0.48g铜粉(7.5mmol)和1.43g(7.53mmol)碘化亚铜和1.56g(11.30mmol)碳酸钾,然后加入溶剂邻二氯苯50ml,氮气保护下升温至180℃回流搅拌22h。反应完毕减压蒸馏去掉溶剂邻二氯苯,冷却后加入二氯甲烷20ml,有机相用冰水洗涤3次,用无水硫酸钠干燥,然后过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:100进行柱层析得到3.72g(5.24mmol)浅黄色固体,化合物16,产率70%。1H NMR(500Hz,CDCl3)δ8.36(s,2H),8.17(d,J=8.5Hz,1H),7.80(t,J=7.5Hz,1H),7.68-7.61(m,8H),7.20(d,J=8.5Hz,2H),7.05(d,J=8.5Hz,4H),4.06(t,J=6.5Hz,4H),3.32(s,3H),1.89-1.83(m,4H),1.56-1.50(m,4H),1.43-1.35(m,16H),0.94(t,J=6Hz,6H)。
在25ml的单口瓶中3.49g(4.92mmol)化合物11,然后加入10ml甲基溴化鎂,在氮气保护下升温至80℃回流搅拌12h,反应完毕用饱和的氯化铵溶液洗涤,乙酸乙酯萃取3次,然后用无水硫酸钠干燥,过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:100进行柱层析得到3.24g(4.56mmol)化合物12,产率92.83%.1H NMR(500Hz,CDCl3)δ8.32(s,2H),7.98(d,J=8.5Hz,1H),7.63(d,J=8.5Hz,4H),7.58(d,J=8.5Hz,3H),7.42(t,J=7.5Hz,1H),7.05-7.01(m,7H),4.03(t,J=6.5Hz,4H),1.86-1.78(m,4H),1.51-1.48(m,4H),1.44(s,6H),1.39-1.32(m,16H),0.91(t,J=6.5Hz,6H)。
在50mL单口烧瓶中,分别加入3.24g(4.56mmol)化合物17、1gAmberlyst15、25ml甲苯,在氮气保护下加上分水器升温至120℃回流20h,反应完毕抽滤除去催化剂,然后将液体旋干,用乙酸乙酯:石油醚=1:300进行柱层析得到2.46g(3.55mmol)浅黄色固体,为目标化合物18,产率78%。1H NMR(500Hz,CDCl3)δ8.33(s,1H),8.19(d,J=8.5Hz,1H),8.11(d,J=8.5Hz,1H),8.08(s,1H),7.75(d,J=10.5Hz,1H),7.68(s,1H),7.67-7.64(m,5H),7.39(t,J=7.5Hz,1H),7.19(t,J=7.5Hz,1H),7.04(d,J=8.5Hz,4H),,4.04(t,J=6.5Hz,4H),1.85-1.82(m,4H),1.82(s,6H),1.52-1.49(m,4H),1.37-1.31(m,16H),0.91(t,J=6.5Hz,6H)。
在50mL单口烧瓶中,加入0.12g(0.17mmol)化合物18用二氯将其溶解,并将单口瓶置于冰浴中且避光,然后将0.04g(0.22mmol)NBS用乙腈溶解倒入恒压滴液漏斗中缓慢滴入50ml单口瓶中,氮气保护下冰浴搅拌4h。反应物倒入100mL水中,用二氯萃取三次,得到的液体旋干,用乙酸乙酯:石油醚=1:200进行柱层析得到0.1g白色固体,化合物19,产率77%。1H NMR(500Hz,CDCl3)δ9.14(s,1H),8.14(d,J=8.5Hz,1H),8.01(d,J=8.5Hz,1H),7.71(s,1H),7.81(s,1H),7.67(d,J=8.5Hz,2H),7.49(s,1H),7.42(d,J=8.5Hz,2H),7.40(s,1H),7.05-7.00(m,5H),4.03(t,J=6.5Hz,4H),1.85-1.82(m,4H),1.82(s,6H),1.52-1.49(m,4H),1.37-1.31(m,16H),0.91(t,J=6.5Hz,6H)。
在50mL三口瓶中,加入0.23g(0.30mmol)化合物19,然后将其溶于30ml干燥的四氢呋喃中,插上低温温度计,在氮气保护下将其置于低温槽中,当温度低于-78℃时,用针管滴加正丁基锂3ml,缓慢滴加维持温度低于-78℃,滴加完丁基锂后搅拌2h,开始滴加硼酸三异丙脂1ml,滴加完毕再搅拌1h,然后从低温槽中取出,让其升到室温搅拌过夜。反应完毕水洗,乙酸乙酯萃取3次,然后用无水硫酸钠干燥,过滤蒸发滤液得到粗产物20,直接进行下一步反应。
在100ml单口瓶中,加入上一步的产物20,然后再加入0.13g(0.31mmol)化合物11,加入2mol/L的碳酸钾4ml,加入50ml的四氢呋喃,然后鼓泡30min除去氧气,然后加入0.1g(0.09mmol)四三苯基膦钯,在氮气保护下80℃回流搅拌12h,冷却后加入乙酸乙酯20ml,有机相用冰水洗涤3次,用无水硫酸钠干燥,然后过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:100进行柱层析得到177mg目标化合物21,产率63%。1H NMR(500Hz,CDCl3)δ8.36(s,2H),8.25-8.21(m,4H),8.11(s,1H),8.08(d,J=8.5Hz,2H),8.02(s,1H),7.87(s,2H),7.78(s,1H),7.72-7.69(m,5H),7.08-7.06(m,4H),4.07(t,J=6.5Hz,4H),1.92(s,6H),1.87(t,J=6.5Hz,4H),1.55-1.51(m,4H),1.42-1.35(m,16H),0.95(t,J=6.5Hz,6H)。
实施例3合成(R1=OCH3,R2=CH3,R3=苯环)
在250mL单口瓶中,加入3.35g(10.31mmol)化合物2,3.8g(25mmol)化合物22,碳酸钠5.66g(41.01mmol),水14ml,乙醇26ml,然后加入溶剂甲苯30ml,然后鼓泡30min除去氧气,然后加入0.3g(0.26mmol)四三苯基磷钯,在氮气保护下80℃回流搅拌12h,冷却后加入二氯甲烷20ml,有机相用冰水洗涤3次,用无水硫酸钠干燥,然后过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:200进行柱层析得到3.37g化合物23,产率64%。1H NMR(500Hz,CDCl3)δ8.27(s,2H),8.06(s,1H),7.63(d,J=8.5Hz,6H),7.47(d,J=8.5Hz,2H),7.01(d,J=8.5Hz,4H),3.77(s,6H)。
在100mL单口瓶中,分别加入2.84g(7.5mmol)化合物23与1.61g(7.49mmol)化合物5以及0.48g铜粉(7.5mmol)和1.43g(7.53mmol)碘化亚铜和1.56g(11.30mmol)碳酸钾,然后加入溶剂邻二氯苯50ml,氮气保护下升温至180℃回流搅拌22h。反应完毕减压蒸馏去掉溶剂邻二氯苯,冷却后加入二氯甲烷20ml,有机相用冰水洗涤3次,用无水硫酸钠干燥,然后过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:100进行柱层析得到2.33g浅黄色固体,化合物24,产率63%。1H NMR(500Hz,CDCl3)δ8.36(s,2H),8.17(d,J=8.5Hz,1H),7.80(t,J=7.5Hz,1H),7.68-7.61(m,8H),7.20(d,J=8.5Hz,2H),7.05(d,J=8.5Hz,4H),3.84(s,6H),3.32(s,3H)。
在25ml的单口瓶中2.00g(3.90mmol)化合物24,然后加入10ml甲基溴化鎂,在氮气保护下升温至80℃回流搅拌12h,反应完毕用饱和的氯化铵溶液洗涤,乙酸乙酯萃取3次,然后用无水硫酸钠干燥,过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:100进行柱层析得到2.11g化合物25,产率91%.1H NMR(500Hz,CDCl3)δ8.32(s,2H),7.98(d,J=8.5Hz,1H),7.63(d,J=8.5Hz,4H),7.58(d,J=8.5Hz,3H),7.42(t,J=7.5Hz,1H),7.05-7.01(m,7H),3.98(s,6H),1.44(s,6H)。
在50mL单口烧瓶中,分别加入2.00g(3.90mmol)化合物25、1g Amberlyst15、25ml甲苯,在氮气保护下加上分水器升温至120℃回流20h,反应完毕抽滤除去催化剂,然后将液体旋干,用乙酸乙酯:石油醚=1:300进行柱层析得到1.51g(3.04mmol)浅黄色固体,为目标化合物26,产率78%。1H NMR(500Hz,CDCl3)δ8.33(s,1H),8.19(d,J=8.5Hz,1H),8.11(d,J=8.5Hz,1H),8.08(s,1H),7.75(d,J=10.5Hz,1H),7.68(s,1H),7.67-7.64(m,5H),7.39(t,J=7.5Hz,1H),7.19(t,J=7.5Hz,1H),7.04(d,J=8.5Hz,4H),3.88(s,6H),1.82(s,6H)。
在50mL单口烧瓶中,加入1.51g(3.04mmol)化合物26用二氯将其溶解,并将单口瓶置于冰浴中且避光,然后将0.6g(3.20mmol)NBS用乙腈溶解倒入恒压滴液漏斗中缓慢滴入50ml单口瓶中,氮气保护下冰浴搅拌4h。反应物倒入100mL水中,用二氯萃取三次,得到的液体旋干,用乙酸乙酯:石油醚=1:200进行柱层析得到1.44g白色固体,化合物27,产率83%。1H NMR(500Hz,CDCl3)δ9.14(s,1H),8.14(d,J=8.5Hz,1H),8.01(d,J=8.5Hz,1H),7.71(s,1H),7.81(s,1H),7.67(d,J=8.5Hz,2H),7.49(s,1H),7.42(d,J=8.5Hz,2H),7.40(s,1H),7.05-7.00(m,5H),3.87(s,6H)1.82(s,6H)。
在50mL三口瓶中,加入1.44g(2.52mmol)化合物27,然后将其溶于30ml干燥的四氢呋喃中,插上低温温度计,在氮气保护下将其置于低温槽中,当温度低于-78℃时,用针管滴加正丁基锂3ml,缓慢滴加维持温度低于-78℃,滴加完丁基锂后搅拌2h,开始滴加硼酸三异丙脂1ml,滴加完毕再搅拌1h,然后从低温槽中取出,让其升到室温搅拌过夜。反应完毕水洗,乙酸乙酯萃取3次,然后用无水硫酸钠干燥,过滤蒸发滤液得到粗产物28,直接进行下一步反应。
在100ml单口瓶中,加入上一步的产物28,然后再加入1.05g(2.48mmol)化合物11,加入2mol/L的碳酸钾4ml,加入50ml的四氢呋喃,然后鼓泡30min除去氧气,然后加入0.1g(0.09mmol)四三苯基膦钯,在氮气保护下80℃回流搅拌12h,冷却后加入乙酸乙酯20ml,有机相用冰水洗涤3次,用无水硫酸钠干燥,然后过滤蒸发滤液得到粗产物,用乙酸乙酯:石油醚=1:100进行柱层析得到1.16目标终产物29,产率61%。1H NMR(500Hz,CDCl3)δ8.36(s,2H),8.25-8.21(m,4H),8.11(s,1H),8.08(d,J=8.5Hz,2H),8.02(s,1H),7.87(s,2H),7.78(s,1H),7.72-7.69(m,5H),7.08-7.06(m,4H),3.83(s,6H),1.92(s,6H)。
实施例4所说的咔唑类化合物21应用于染料敏化太阳电池并对其进行光伏性能测试
以化合物21作为光敏化剂制备染料敏化太阳电池器件:将烧制好的纳米二氧化钛电极(二氧化钛厚度:6微米)加热到80℃后,在化合物18配制成的3×10-4mol/L甲醇溶液中浸泡敏化6小时。敏化完成后取出,用无水甲醇冲洗掉未吸附的染料,吹干得到染料敏化的二氧化钛电极。将此敏化电极和镀铂的玻璃电极面对面组合得到染料敏化太阳电池器件。向其注入事先配好的电解质溶液并对其进行测量。电解质溶液的组成:0.6mol/L的3-甲基-1-丁基咪唑碘、0.05mol/L的I2、0.1mol/L的LiI、0.5mol/L的叔丁基吡啶和用乙腈作为溶剂。在太阳模拟器100mW/cm-2光源照射下测定其开路电压为0.653V,短路电流为14.29mAcm-2,填充因子为0.690,光电转化效率为6.44%。其光电流和光电压曲线见图3。图3表明:相比传统结构的咔唑敏化剂,本发明所说的咔唑类化合物21应用于染料敏化太阳电池能够在较薄的二氧化钛电极条件下即可产生更高的短路电流(J.Am.Chem.Soc.,2006,128,14256-14257;J.Photochem.Photobio A:Chemistry,2011,223,57-64)和较高的开路电压,从而得到较高的光电转换效率,证明其相比传统结构的咔唑敏化剂更适合作为染料敏化太阳电池中的敏化剂使用。
Claims (5)
1.一种咔唑类化合物,其特征在于具有式(I)所示结构:
式(I)中:R1为C1~C12烃基或C1~C12烷氧基或C4~C20杂环基,其中,所说杂环基的杂原子为N或S或O;R2为C1~C12烃基;R3为芳香烃基或杂环芳香烃基。
2.根据权利要求1所说的咔唑类化合物,其特征在于:R1为C1~C8烷基或C1~C8烷氧基或C4~C10杂环基;R2为C1~C8烃基;R3为苯系芳香烃基。
3.根据权利要求1所说的咔唑类化合物,其特征在于:R1为C1~C6烷基或C1~C6烷氧基或C5~C6杂环基,其中所说杂环基的杂原子为N;R2为C4~C8烃基;R3为单环苯系芳香烃基。
4.根据权利要求1所说的咔唑类化合物,其特征在于,其中R1为己氧基;R2为正辛基;R3为苯基。
5.分子结构中包含如权利要求1~4中任意一项所说的咔唑类化合物的用途,其特征在于用作染料敏化太阳电池的敏化剂。
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