CN105968130B - Two pyrroles's methine derivatives and preparation method thereof are complexed containing double center boron fluorides of carbazole and bridge linkage group in a kind of middle position - Google Patents
Two pyrroles's methine derivatives and preparation method thereof are complexed containing double center boron fluorides of carbazole and bridge linkage group in a kind of middle position Download PDFInfo
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- CN105968130B CN105968130B CN201610535707.1A CN201610535707A CN105968130B CN 105968130 B CN105968130 B CN 105968130B CN 201610535707 A CN201610535707 A CN 201610535707A CN 105968130 B CN105968130 B CN 105968130B
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- carbazole
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 150000003233 pyrroles Chemical class 0.000 title claims abstract description 25
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- -1 pinacol boron ester Chemical class 0.000 claims abstract description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 101000933296 Homo sapiens Transcription factor TFIIIB component B'' homolog Proteins 0.000 claims description 12
- 101001087412 Homo sapiens Tyrosine-protein phosphatase non-receptor type 18 Proteins 0.000 claims description 12
- 102100026002 Transcription factor TFIIIB component B'' homolog Human genes 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000975 dye Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 8
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical class C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 claims description 7
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- RMCPHJRABSGLSX-UHFFFAOYSA-N 1,2-dibromo-9-octylcarbazole Chemical class C1=C(Br)C(Br)=C2N(CCCCCCCC)C3=CC=CC=C3C2=C1 RMCPHJRABSGLSX-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical class BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical class BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 17
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 16
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 150000002240 furans Chemical class 0.000 abstract description 8
- 229930192474 thiophene Natural products 0.000 abstract description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 150000003235 pyrrolidines Chemical class 0.000 abstract description 2
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical class BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract 1
- IFCBYLWQBDFAHD-UHFFFAOYSA-N [Br].C=1C=COC=1 Chemical class [Br].C=1C=COC=1 IFCBYLWQBDFAHD-UHFFFAOYSA-N 0.000 abstract 1
- 230000031709 bromination Effects 0.000 abstract 1
- 238000005893 bromination reaction Methods 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 48
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- AZKACZGHQQSQGL-UHFFFAOYSA-N [amino-(4-hydroxyphenyl)-phosphonomethyl]phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(N)C1=CC=C(O)C=C1 AZKACZGHQQSQGL-UHFFFAOYSA-N 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000009102 absorption Effects 0.000 description 7
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003480 eluent Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical class O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 125000001544 thienyl group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 208000030208 low-grade fever Diseases 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- MFYGWCVLNPQWRR-UHFFFAOYSA-N 3,6-dibromo-9-octylcarbazole Chemical class BrC1=CC=C2N(CCCCCCCC)C3=CC=C(Br)C=C3C2=C1 MFYGWCVLNPQWRR-UHFFFAOYSA-N 0.000 description 1
- GFBVUFQNHLUCPX-UHFFFAOYSA-N 5-bromothiophene-2-carbaldehyde Chemical compound BrC1=CC=C(C=O)S1 GFBVUFQNHLUCPX-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(CC)C(C(*1)=CC=C*1*1N)=C2*1=CC=C2 Chemical compound CCC(CC)C(C(*1)=CC=C*1*1N)=C2*1=CC=C2 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- BFMYDTVEBKDAKJ-UHFFFAOYSA-L disodium;(2',7'-dibromo-3',6'-dioxido-3-oxospiro[2-benzofuran-1,9'-xanthene]-4'-yl)mercury;hydrate Chemical compound O.[Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C([O-])C([Hg])=C1OC1=C2C=C(Br)C([O-])=C1 BFMYDTVEBKDAKJ-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/12—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being branched "branched" means that the substituent on the polymethine chain forms a new conjugated system, e.g. most trinuclear cyanine dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Indole Compounds (AREA)
Abstract
Two pyrroles's methine derivatives and preparation method thereof are complexed containing double center boron fluorides of carbazole and bridge linkage group the invention discloses a kind of middle position.It is using carbazole as starting material, successively by bromination, the octylatcd reactions of N, it carries out after Suzuki coupling reactions that twain-aldehyde compound compound is obtained by the reaction with 4 bromobenzaldehydes, 5 bromothiophene, 2 formaldehyde, 5 bromine furans, 2 formaldehyde etc. respectively again with duplex pinacol boron ester again, then with pyrroles to react synthesis double（Two pyrrolidines）Compound most obtains several novel double center BODIPY dyestuffs containing carbazole and different bridge linkage groups through boron trifluoride ether fluorine boronation afterwards.After carbazole and five-ring heterocycles thiophene and furans are introduced into double BODIPY structures, red shift occurs for the UV absorption of the analog derivative, and derivative is with good stability.The preparation method of the present invention is simple, and yield is high, can efficiently synthesize and be widely used.
Description
Technical field
Two pyrroles's methine derivatives are complexed containing double center boron fluorides of carbazole and bridge linkage group the present invention relates to a kind of middle position
And preparation method thereof, the analog derivative can be applied to fluorescent dye, luminescent material, photovoltaic material, life science, analysis science,
The fields such as environmental energy science.
Background technology
Two pyrroles's methines of boron fluoride complexing (4,4 '-Difluoro-4-bora-3a, 4a-diaza-sindacene, referred to as
BODIPY just received significant attention after) fluorochrome is reported for the first time from nineteen sixty-eight, because its have higher photostability,
Stronger spectral absorption has been applied to the fields such as life science, analytical chemistry, environmental energy science.
For the novel B ODIPY derivant materials being had excellent performance, Many researchers select the pyrroles in BODIPY parent nucleus
It is modified on ring, extends system conjugate length, increases molecular rigidity structure etc..Research shows that in BODIPY parent nucleus meso-
After introducing aromatic functional group, it is difficult to form effective conjugation with BODIPY core planes, the spectrum property variation of molecule is little, because
This, the BODIPY class dyestuffs of meso- modifications, the research of double center fluoroboric dyes of especially meso- modification at present is reported
It is considerably less.The present invention devise a kind of meso- containing the distinct fragrances type such as carbazole and benzene, thiophene and furans group replace it is double in
Heart BODIPY derivatives.Carbazole molecules have very strong electron donation, are a kind of special rigid condensed cyclic structures, have higher
Thermal stability, photochemical stability and preferable hole transport performance, introduce it into BODIPY, molecule can be increased
ICT effects effectively widen the absorption spectrum of molecule.
The present invention introduces the bridge linkage groups such as carbazole and benzene, thiophene and furans simultaneously for the first time, investigates the light of this kind of structural material
Electric physical property, and existing one-pot synthesis is improved, reaction yield is made to have obtained effective raising.
Invention content
It is an object of the invention to the angle from structure design, with reference to the excellent properties of donor monomer carbazole, design
Synthesize double center boron fluorides containing bridge linkage groups such as benzene, thiophene, furans and two pyrroles's methine new derivatives are complexed, make its tool
There are excellent photoelectric properties.
Another object of the present invention is to provide a kind of middle position containing double center boron fluorides of carbazole and bridge linkage group complexing two
The preparation method of pyrroles's methine derivative.
In order to achieve the above objectives, this invention takes following technical solutions：A kind of pair of middle position containing carbazole and bridge linkage group
Two pyrroles's methine derivatives are complexed in center boron fluoride, have the chemical constitution of general formula I,
,
In formula 。
In above-mentioned technical proposal, two pyrroles are complexed containing double center boron fluorides of carbazole and bridge linkage group in a kind of middle position
The preparation method of methine derivative, includes the following steps：
Carbazole is reacted with N- bromo-succinimides in tetrahydrofuran solution, obtains 3,6- dibromo carbazoles；
3,6- dibromo carbazoles are reacted with 1- bromine normal octanes, obtain 3,6-, bis- bromo- 9- octylcarbazols；
With duplex pinacol boron ester coupling reaction occurs for 3,6- bis- bromo- 9- octylcarbazols, obtains 3,6- bis- (4,4,5,5- tetra-
Methyl-1,3,2- dioxaborolans) -9- octylcarbazols；
3,6- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolans) -9- octylcarbazols respectively with 4- bromobenzaldehydes,
5- bromothiophene -2- formaldehyde and the reaction of 5- bromine furans -2- formaldehyde, respectively obtain product 3,6- bis- (4- aldehyde radicals phenyl) -9- octyl group clicks
Azoles, (5- formylthiophenes the base) -9- octylcarbazols of 3,6- bis- and 3,6- bis- (5- aldehyde radicals furyl) -9- octylcarbazols；
3,6- bis- (4- aldehyde radicals phenyl) -9- octylcarbazols, (5- formylthiophenes the base) -9- octylcarbazols of 3,6- bis- and 3,6- bis-
(5- aldehyde radicals furyl) -9- octylcarbazols are respectively in InCl3Catalysis under steam pyrroles with new and react, generate 3,6-, bis- [4- respectively
(two pyrrolylmethyls) phenyl] -9- octylcarbazols, [5- (two pyrrolylmethyls) the thienyl] -9- octylcarbazols of 3,6- bis- and 3,6- bis-
[5- (two pyrrolylmethyls) furyl] -9- octylcarbazols；
3,6- bis- [4- (two pyrrolylmethyls) phenyl] -9- octylcarbazols, 3,6- bis- [5- (two pyrrolylmethyls) thienyl] -9-
Octylcarbazol and 3,6- bis- [5- (two pyrrolylmethyls) furyl] -9- octylcarbazols are respectively in boron trifluoride ether/triethylamine body
It is reacted in system, generates target dyestuff BDP1, BDP2 and BDP3 respectively；
Reaction medium in reaction step (1)-(6) is n-hexane, tetrahydrofuran, dichloromethane, dimethyl sulfoxide (DMSO), first
One or more of mixing of benzene, chloroform, petroleum ether, ethyl acetate, ethyl alcohol.
Catalyst in reaction step (3), (4), (5) is InCl3, Pd (dppf) Cl2, Pd (PPh3)4In it is any one
Kind.
Reaction temperature in reaction step (1), (3), (4) is 80-150 DEG C, and the reaction temperature in (2), (5), (6) is room
- 100 DEG C of temperature.
Reaction time in reaction step (1), (3), (4) is 12-36h, and the reaction time in (2), (5), (6) is 2-
10h。
The preparation of partial target dyestuff BDP1, BDP2 and BDP3 according to the present invention can use following chemical equation
To represent：
。
The beneficial effects of the present invention are：（1）The present invention is by first synthesizing containing the bridgings such as carbazole and benzene, thiophene, furans
The Symmetrical Dialdehydes class compound of group, then generation is double under indium trichloride catalysis with pyrroles（Two pyrrolidines）Compound most passes through afterwards
Tetrachloroquinone oxidation obtains contaminating containing double center BODIPY of carbazole and different bridge linkage groups from boron trifluoride ether chelatropic reaction
Material.
（2）It is employed in synthetic method provided by the invention and quickly crosses column method, the target product made from the method synthesizes
At low cost, comprehensive yied higher.
（3）It is analyzed by the spectrum to several target products and electrochemical data, it can be seen that such double center BODIPY
There is compound relatively stable wide spectrum to absorb, after introducing carbazole and five-ring heterocycles thiophene and furans in molecule, fluorescent emission
Apparent red shift occurs for peak, and with the enhancing of system conjugation, Stokes displacements are bigger, and fluorescence generation is significantly quenched.
Description of the drawings:
Fig. 1: BDP11H NMR nuclear magnetic spectrums.
Fig. 2: BDP21H NMR nuclear magnetic spectrums.
Fig. 3: BDP31H NMR nuclear magnetic spectrums.
Fig. 4: BDP113C NMR nuclear magnetic spectrums.
Fig. 5: BDP213C NMR nuclear magnetic spectrums.
Fig. 6: BDP313C NMR nuclear magnetic spectrums.
Fig. 7:BDP1 mass-spectrograms.
Fig. 8:BDP2 mass-spectrograms.
Fig. 9:BDP3 mass-spectrograms.
Specific embodiment
Technical solution for a better understanding of the present invention is made detailed below by way of partial derivatives specific embodiment and attached drawing
Thin description.
Embodiment 1.
The synthesis of BDP1.
(1) intermediate 1（3,6- dibromo carbazoles）Synthesis.
4 g of carbazole is added in 250 mL single port bottles（24.0 mmol）, 8.5 g of N- bromo-succinimides（48.0
mmol）, 80 mL anhydrous tetrahydro furans, under argon gas protection, reaction system is heated to 80 DEG C of magnetic agitation reactions for 24 hours, stops anti-
Should, reaction mixture is poured into after being cooled to room temperature in 200 mL distilled water, is extracted with ethyl acetate 3 times, organic layer uses saturation again
Salt is washed 3 times, merges organic phase, and anhydrous sodium sulfate is dried overnight.Rotary evaporation removes solvent, and residue is through silica gel column layer
Analysis, with petroleum ether：Ethyl acetate=30:1 is eluant, eluent, isolated 6.1 g of white solid, yield 78%.1H NMR (600
MHz, CDCl3) δ: 8.13 (s, 2H), 8.10 (s, 1H), 7.52 (d, J = 6.8 Hz, 2H), 7.30 (d,J = 8.6 Hz, 2H).13C NMR (151 MHz, CDCl3) δ 138.37, 129.34, 124.12, 123.29,
112.66, 112.25。
(2) intermediate 2（Bis- bromo- 9- octylcarbazols of 3,6-）Synthesis.
In 250 mL there-necked flasks, 5 g (15.4 mmol) intermediate 1 is sequentially added（3,6- dibromo carbazoles）、100
ML DMSO, 0.25 g (1.1 mmol) TEBA and 25 mL sodium hydroxide solutions (50 wt%), in 0.5 h under magnetic agitation
Interior dropwise addition 3.3 g (16.9 mmol) 1- bromine normal octanes, react at room temperature 8 h, stop reaction, and adding in hydrochloric acid in reaction solution is adjusted
PH=7 are extracted with ethyl acetate (3 × 50 mL), merge organic layer and with saturated common salt water washing 3 times, anhydrous magnesium sulfate
It is dried overnight, distilling off solvent after filtering, residue is eluant, eluent column chromatography for separation with petroleum ether, obtains 5.4 g of white crystal, is received
Rate 80%.1H NMR (600 MHz, CDCl3) δ: 8.08 (s, 2H), 7.52 (d, J = 8.7 Hz, 2H), 7.21
(d, J = 8.7 Hz, 2H), 4.15 (t, J = 7.3 Hz, 2H), 1.82–1.72 (m, 2H), 1.37–1.11
(m, 10H), 0.88 (t, J = 7.1 Hz, 3H).13C NMR (151 MHz, CDCl3) δ: 139.25, 128.97,
123.39, 123.20, 111.91, 110.36, 43.30, 31.80, 29.34, 29.19, 28.87, 27.25,
22.64, 14.13。
（3）Intermediate 3（3,6- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolans) -9- octylcarbazols）Conjunction
Into.
Intermediate 2 is added in 250 mL single port bottles（Bis- bromo- 9- octylcarbazols of 3,6-）2 g（4.6 mmol）, duplex frequency
Any alcohol boron ester 2.6 g（10.1 mmol）, 2.6 g of potassium acetate（27.6 mmol）、Pd(dppf)Cl2 150 mg (0.21
Mmol) and 80 mL DMF, vacuumize, under argon gas protection, control 95 DEG C of oil bath temperature, magnetic agitation is reacted for 24 hours.Stop anti-
Should, reaction mixture is poured into after being cooled to room temperature in 300 mL water, with dichloromethane extraction three times（60 mL × 3）, then use
Saturated common salt water washing for several times, merges organic phase, anhydrous magnesium sulfate drying.Remove solvent, residue petroleum ether under reduced pressure：Acetic acid
Ethyl ester=15:1 carries out silica gel for eluant, eluent（200-300 mesh）Column chromatography for separation, obtains 1.7 g of white solid, and yield is
69.6%。1H NMR (600 MHz, CDCl3) δ: 8.66 (s, 2H), 7.90 (d, J = 9.1 Hz, 2H), 7.39
(d, J = 8.2 Hz, 2H), 4.30 (t, J = 7.3 Hz, 2H), 1.91–1.78 (m, 2H), 1.39 (s,
24H), 1.36–1.15 (m, 10H), 0.85 (t, J = 7.1 Hz, 3H).13C NMR (151 MHz, CDCl3) δ:
142.64, 131.97, 128.08, 122.82, 108.14, 83.54, 43.15, 31.79, 29.72, 29.36,
29.15, 28.92, 27.24, 24.95, 22.61。
（4）Intermediate 4a（3,6- bis- (4- aldehyde radicals phenyl) -9- octylcarbazols）Synthesis.
In 250 mL single port bottles, intermediate 3 is sequentially added（(4,4,5,5- tetramethyl -1,3,2- the dioxas of 3,6- bis-
Pentaborane) -9- octylcarbazols）2 g（3.8 mmol）, 1.55 g of 4- bromobenzaldehydes（8.4 mmol）, four（Triphenylphosphine）Palladium 0.1
g（0.09 mmol）, 50 mL toluene and 30 mL（2 mol/L）Sodium carbonate liquor excludes air, argon gas protection, control reaction
Temperature is at 90 DEG C, magnetic agitation reaction 36h.Stop reaction, reaction mixture is cooled to room temperature, pour into 200 mL distillations
In water, with chloroform extraction for several times, organic layer uses saturated common salt water washing three times again（150 mL × 3）, merge organic phase,
Anhydrous magnesium sulfate is dried overnight.Remove solvent, residue petroleum ether under reduced pressure：Dichloromethane：Ethyl acetate=10:2:1 is
Eluant, eluent carries out silica gel（200-300 mesh）Column chromatography for separation purifies, and obtains faint yellow fluorescence solid, yield 72%.1H NMR
(600 MHz, CDCl3) δ: 10.08 (s, 2H), 8.45 (s, 2H), 7.99 (d, J = 8.2 Hz, 4H),
7.90 (d, J = 8.2 Hz, 4H), 7.81 (dd, J = 8.5, 1.7 Hz, 2H), 7.53 (d, J = 8.5
Hz, 2H), 4.37 (t, J = 7.2 Hz, 2H), 1.97–1.91 (m, 2H), 1.37–1.20 (m, 10H),
0.87 (t, J = 7.0 Hz, 3H).13C NMR (151 MHz, CDCl3) δ: 191.93, 147.99, 141.15,
134.62, 131.06, 130.40, 127.58, 125.67, 123.58, 119.42, 109.56, 43.50, 31.78,
29.36, 29.16, 29.05, 27.32, 22.60, 14.05. MALDI-TOF-MS, m/z: calcd for
C34H33NO2: 487.251, found: 487.310 [M]+。
（5）Intermediate 5a（3,6- bis- [4- (two pyrrolylmethyls) phenyl] -9- octylcarbazols）Synthesis.
Intermediate 4a is sequentially added in 100 mL there-necked flasks（3,6- bis- (4- aldehyde radicals phenyl) -9- octylcarbazols）0.8 g
（1.6 mmol）17 mL of pyrroles is steamed with new（250 mmol）, air in system is extracted, is passed through argon gas protection, low-grade fever is stirred to react
After 10min, InCl is rapidly added into reaction system3100 mg（0.45 mmol）, continue under the conditions of low-grade fever to be protected from light magnetic force and stir
4h is mixed, solution becomes dark from fluorescence is faint yellow, adds in 1 g of NaOH（25 mmol）Solid particle terminates reaction, is further continued for stirring
Mix 30min.Solid is filtered to remove, filtrate decompression is distilled, recycles the pyrroles of distillation, the crude product petroleum ether in reaction bulb：
Ethyl acetate=10:1, as the separation of eluant, eluent silica gel column chromatography, obtains bottle-green solid 0.97g, yield 82%.1H NMR
(600 MHz, CDCl3) δ: 8.32 (s, 2H), 8.01 (s, 4H), 7.70 (d, J = 8.4 Hz, 2H),
7.66 (d, J = 8.1 Hz, 4H), 7.46 (d, J = 8.5 Hz, 2H), 7.31 (d, J = 8.1 Hz, 4H),
6.72 (d, J = 1.4 Hz, 4H), 6.19 (d, J = 2.9 Hz, 4H), 5.99 (s, 4H), 5.54 (s,
2H), 4.32 (t, J = 7.2 Hz,2H), 1.92–1.87 (m, 2H), 1.34–1.22 (m, 10H), 0.86 (t,J = 6.9 Hz, 3H).13C NMR (151 MHz, CDCl3) δ: 140.77, 140.42, 140.25, 132.58,
131.94, 128.86, 127.47, 125.27, 123.47, 118.80, 117.25, 109.13, 108.48,
107.25, 62.22, 43.69, 31.81, 29.40, 29.20, 29.08, 27.36, 20.84, 14.09. MALDI-
TOF-MS, m/z: calcd for C50H49N5: 719.399, found: 718.781 [M]+。
（6）The synthesis of BDP1.
Intermediate 5a is sequentially added in 100 mL there-necked flasks（3,6- bis- [4- (two pyrrolylmethyls) phenyl] -9- octyl groups
Carbazole）0.5 g（0.7 mmol）, 0.37 g of tetrachloroquinone（1.5 mmol）With the dichloromethane of 50 mL dryings, at room temperature magnetic
Power stirs, fully oxidized 6h.Then air in reaction system is taken out to the greatest extent, is passed through argon gas protection, three second are slowly added dropwise through syringe
Amine takes boron trifluoride ether to be added dropwise followed in turn by syringe, and the reaction process heat release is violent, need to strictly control boron trifluoride
The rate of addition of ether continues magnetic agitation reaction 4h after being added dropwise to complete.Stop reaction, reaction mixture is poured into 200 mL
In 0.1M NaOH aqueous solutions, with dichloromethane extracted several times, it is washed with water three times, merges organic phase, anhydrous sodium sulfate is dried
Night.Filtrate is collected by filtration, removes solvent, residue petroleum ether under reduced pressure：Ethyl acetate=5:1 is eluant, eluent silica gel column chromatography
It isolates and purifies, obtains 0.38 g of solid of aubergine, yield 68.5%.1H NMR (600 MHz, CDCl3) δ: 8.49 (s,
2H), 7.97 (s, 4H), 7.91 (d, J = 8.0 Hz, 4H), 7.84 (d, J = 8.5 Hz, 2H), 7.71
(d, J = 8.0 Hz, 4H), 7.57 (d, J = 8.5 Hz, 2H), 7.07 (d, J = 3.7 Hz, 4H), 6.58
(d, J = 2.7 Hz, 4H), 4.40 (t, J = 7.1 Hz, 2H), 1.98–1.95 (m, 2H), 1.48–1.23
(m, 10H), 0.88 (t, J = 6.7 Hz, 3H).13C NMR (151 MHz, CDCl3) δ: 147.43, 144.68,
143.89, 141.02, 134.94, 132.02, 131.51, 131.33, 127.11, 125.50, 123.65,
119.18, 118.49, 110.00, 109.62, 43.53, 31.80, 29.71, 29.20, 29.11, 27.36,
22.62, 14.07. MALDI-TOF-MS, m/z: calcd for C50H43B2F4N5: 811.364, found:
792.371 [M-F]+。
Embodiment 2.
The synthesis of BDP2.
（1）Intermediate 4b（3,6- bis- (5- formylthiophenes base) -9- octylcarbazols）Synthesis.
3,6- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolans) -9- is sequentially added into 100 mL there-necked flasks
2 g of octylcarbazol（3.8 mmol）, 1.6 g of 5- bromothiophene -2- formaldehyde（8.4 mmol）, with the method for similar synthetic intermediate 4a
Obtain intermediate 4b, orange-yellow fluorescence solid, yield 68%.1H NMR (600 MHz, CDCl3) δ: 8.41 (s, 2H),
7.81 (d, J = 8.5 Hz, 2H), 7.77 (d, J = 3.8 Hz, 2H), 7.47 (d, J = 3.8 Hz, 2H),
7.44 (d, J = 8.5 Hz, 2H), 4.31 (t, J = 7.2 Hz, 2H), 1.93–1.84 (m, 2H), 1.39–
1.22 (m, 10H), 0.86 (t, J = 6.9 Hz, 2H).13C NMR (151 MHz, CDCl3) δ: 182.59,
155.71, 141.57, 137.78, 126.47, 125.16, 124.89, 123.26, 123.15, 118.69,
109.78, 43.54, 31.75, 29.31, 29.13, 29.00, 27.26, 22.58, 14.04。
（2）Intermediate 5b（3,6- bis- [5- (two pyrrolylmethyls) thienyl] -9- octylcarbazols）Synthesis.
0.5 g of 3,6- bis- (5- formylthiophenes base) -9- octylcarbazols is sequentially added into 100ml there-necked flasks（1 mmol）With
10.4 mL of pyrroles（150 mmol）, intermediate 5b, auburn solid are obtained with the synthetic method of similar synthetic intermediate 5a
0.62 g, yield 85%.1H NMR (600 MHz, CDCl3) δ: 8.23 (s, 2H), 8.12 (s, 4H), 7.64
(d, J = 10.2 Hz, 2H), 7.32 (d, J = 8.5 Hz, 2H), 7.17 (d, J = 3.6 Hz, 2H),
6.86 (d, J = 3.4 Hz, 2H), 6.71 (s, 4H), 6.20 (d, J = 2.9 Hz, 4H), 6.12 (s,
4H), 5.74 (s, 2H), 4.23 (t, J = 7.1 Hz, 2H), 1.87–1.79 (m, 2H), 1.32–1.19 (m,
10H), 0.85 (t, J = 7.0 Hz, 3H). 13C NMR (151 MHz, CDCl3) δ: 144.78, 143.96,
140.37, 131.98, 126.53, 125.83, 124.16, 123.17, 121.44, 117.66, 117.49,
109.18, 108.50, 107.09, 62.23, 43.32, 31.79, 29.36, 29.18, 29.03, 27.29,
20.85, 14.10。
（3）The synthesis of BDP2.
Intermediate 5b and boron trifluoride ether are sequentially added into there-necked flask, target is obtained with the method for similar synthesis BDP1
Product BDP2, wine-colored 0.37 g of solid, yield 65.6%.1H NMR (600 MHz, CDCl3) δ: 8.47 (s, 2H),
7.94 (s, 4H), 7.85 (d, J = 8.5 Hz, 2H), 7.66 (d, J = 3.8 Hz, 2H), 7.57 (d, J
= 3.8 Hz, 2H), 7.50 (d, J = 8.5 Hz, 2H), 7.45 (d, J = 4.0 Hz, 4H), 6.62 (d, J
= 4.0 Hz, 4H), 4.37 (t, J = 7.2 Hz, 2H), 1.96–1.91 (m, 2H), 1.43–1.23 (m,
10H), 0.87 (t, J = 6.9 Hz, 3H).13C NMR (151 MHz, CDCl3) δ: 152.97, 143.15,
141.43, 139.59, 135.06, 134.01, 132.94, 130.99, 124.94, 124.82, 123.69,
123.37, 118.52, 118.25, 109.89, 43.60, 31.76, 29.34, 29.15, 29.05, 27.29,
22.59, 14.05. MALDI-TOF-MS, m/z: calcd for C46H39B2F4N5S2: 823.277, found:
823.283 [M]+。
Embodiment 3.
The synthesis of BDP3.
（1）Intermediate 4c（3,6- bis- (5- aldehyde radicals furyl) -9- octylcarbazols）Synthesis.
3,6- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborolans) -9- is sequentially added into 100 mL there-necked flasks
2 g of octylcarbazol（3.8 mmol）, 1.47 g of 5- bromine furans -2- formaldehyde（8.4 mmol）, with the side of similar synthetic intermediate 4a
Method obtains intermediate 4c, orange-yellow fluorescence solid, yield 70.7%.1H NMR (600 MHz, CDCl3) δ: 9.64 (s,
2H), 8.53 (s, 2H), 7.89 (d, J = 8.5 Hz, 2H), 7.37 (t, J = 5.6 Hz, 4H), 6.85
(d, J = 3.6 Hz, 2H), 4.23 (t, J = 7.2 Hz, 2H), 1.93–1.74 (m, 2H), 1.36–1.19
(m, 10H), 0.86 (t, J = 7.0 Hz, 3H).13C NMR (151 MHz, CDCl3) δ: 176.73, 160.76,
151.60, 141.51, 123.84, 123.09, 120.69, 118.03, 109.48, 106.39, 43.40, 31.75,
29.29, 29.15, 28.97, 27.23, 22.59, 14.07. MALDI-TOF-MS, m/z: calcd for
C30H29NO4: 467.210, found: 467.244 [M]+。
（2）Intermediate 5c（3,6- bis- [5- (two pyrrolylmethyls) furyl] -9- octylcarbazols）Synthesis.
With the method for similar synthetic intermediate 5a, by 3,6- bis- (5- aldehyde radicals furyl) -9- octylcarbazols, 0.5 g（1.1
mmol）With 11.1 mL of pyrroles（160 mmol）Intermediate 5c, 0.6 g of solid of Dark grey, yield 83.5% is obtained by the reaction.1H
NMR (600 MHz, CDCl3) δ: 8.41 (s, 2H), 8.16 (s, 4H), 7.77 (d, J = 9.7 Hz, 2H),
7.37 (d, J = 8.6 Hz, 2H), 6.73 (d, J = 1.3 Hz, 4H), 6.63 (d, J = 3.1 Hz, 2H),
6.24 (d, J = 2.8 Hz, 4H), 6.22 (d, J = 3.1 Hz, 2H), 6.13 (s, 4H), 5.62 (s,
2H), 4.25 (t, J = 5.9 Hz, 2H), 1.89–1.84 (m, 2H), 1.33–1.25 (m, 10H), 0.91
(t, J = 7.0 Hz, 3H). 13C NMR (151 MHz, CDCl3) δ: 154.61, 153.28, 140.25,
130.33, 123.08, 122.55, 122.42, 117.73, 115.92, 109.29, 109.17, 108.37,
107.04, 104.09, 62.27, 43.27, 31.84, 29.41, 29.22, 29.05, 27.31, 20.86,
14.15. MALDI-TOF-MS, m/z: calcd for C46H45N5O2: 699.357, found: 698.670 [M]+。
（3）The synthesis of BDP3.
Intermediate 5c and boron trifluoride ether are sequentially added into there-necked flask, target is obtained with the method for similar synthesis BDP1
Product BDP3, the solid of aubergine, yield 65%.1H NMR (600 MHz, CDCl3) δ: 8.59 (s, 2H), 8.00
(d, J = 10.2 Hz, 2H), 7.90 (s, 4H), 7.61 (d, J = 4.0 Hz, 4H), 7.56 (d, J =
8.6 Hz, 2H), 7.47 (d, J = 3.7 Hz, 2H), 7.08 (d, J = 3.7 Hz, 2H), 6.63 (d, J =
5.9 Hz, 4H), 4.39 (t, J = 7.3 Hz, 2H), 1.97–1.93 (m, 2H), 1.43–1.23 (m, 10H),
0.87 (t, J = 6.8 Hz, 3H). 13C NMR (151 MHz, CDCl3) δ: 153.89, 147.78, 141.45,
138.86, 134.52, 131.90, 129.48, 128.65, 125.00, 123.00, 120.60, 120.29,
118.00, 110.13, 109.63, 43.35, 31.94, 29.79, 29.33, 29.08, 27.28, 22.60,
14.13. MALDI-TOF-MS, m/z: calcd for C46H39B2F4N5O2: 791.323, found: 791.368 [M
]+。
Target product BDP1-3 is in CH in above-described embodiment2Cl2In solution and solid film on ultraviolet-visible absorption spectroscopy and
Fluorescence spectrum the results are shown in Table 1, and the related data of target product BDP1-3 electrochemical properties is shown in Table 2 in embodiment.
。
。
b E ox onset, onset oxidation potential. c.E ox p, oxidation peak potential.d E redonset reduction potential. e E HOMO = [-(E ox onset -0.53)-4.8] eV, E LUMO = [-
(E red onset -0.53)-4.8] eV。
Table 1 is the results show that several target products mainly have 280-350 nm and 450-680 nm two in ultraviolet-visible light area
A absorption band.280-350 nm absorption bands be carbazole unit feature π-π * transition absorptions, 450-680 nm absorption bands by
ICT effects cause between BODIPY parent nucleus and meso- donors.The maximum absorption wavelength of three kinds of dyestuffs be respectively 501nm,
512nm and 525nm, dyestuff BDP3 and BDP2 24 nm and 11 nm of the absorbing wavelength red shift than BDP1 respectively, this is because thiophene
The coplanarity of fen ring, furan nucleus and fluorine boron parent nucleus is more preferable than the coplanarity of phenyl ring and fluorine boron parent nucleus, and dyestuff BDP3 compares dyestuff
13 nm of the maximum absorption wavelength red shift of BDP2, this is because the coplanarity of the entire molecules of BDP3 is more preferable, intramolecular electronics supplies
More efficiently intramolecular charge transport can be formed between body and electron acceptor.
There are two fluorescence emission peaks, respectively 528 nm and 634 nm in dyestuff BDP1；Bridge linkage group is the dye of thiphene ring
The maximum emission wavelength for expecting BDP2 is 648 nm；When furans is as bridge linkage group, the coplanar degree bigger of system, electron transfer is more
Smooth, fluorescence emission wavelengths red shift amplitude bigger reaches 650 nm.As it can be seen that in excitation state, more smooth molecular structure is conducive to
The energy and charge migration of intramolecular.
2 data of table show, the first oxidizing potential of target dyestuff BDP1-BDP3 be respectively 1.11 eV, 1.21 eV and
1.32 eV, corresponding HOMO energy levels be respectively -5.38 eV, -5.48 eV and -5.59 eV, lumo energy be respectively -
3.39 eV, the eV of -3.50eV and -3.56.In addition to there was only the BDP of carbazole bridge linkage group, tri- kinds of target products of BDP1-BDP3
First oxidizing potential, HOMO energy levels and lumo energy are increased slightly successively with the change of bridge linkage group.Phenyl ring, thiophene and furan
It mutters the electron donation of these three groups and the conjugated degree difference of entire molecule results in the stability of three kinds of target dyestuffs not
Together, when bridge linkage group is furans, the planar conjugate effect formed with BODIPY basic structures is stronger, and stability is more preferable, therefore oxygen
Change current potential and HOMO energy levels are relatively higher.
The present invention illustrates the detailed synthetic method of the present invention by above-described embodiment, but the invention is not limited in above-mentioned
Method does not mean that the present invention has to rely on above-mentioned reaction condition and could implement.Person of ordinary skill in the field should
Understand, any improvement in the present invention, the change of equivalence replacement and reaction actual conditions to reaction dissolvent catalyst of the present invention
Deng all falling within protection scope of the present invention and the open scope.
Claims (6)
1. two pyrroles's methine derivatives are complexed containing double center boron fluorides of carbazole and bridge linkage group in a kind of middle position, it is characterised in that tool
There is the chemical constitution of general formula I,
In formula,R=CnH2n+1, n=8.
Spread out 2. two pyrroles's methines are complexed containing double center boron fluorides of carbazole and bridge linkage group in a kind of middle position as described in claim 1
The preparation method of biology, it is characterised in that comprise the steps of：
(1) 3,6- dibromo carbazoles are obtained by the reaction with N- bromo-succinimides in carbazole in tetrahydrofuran, and structure is：
(2) 3,6- dibromo carbazole are reacted with 1- bromine normal octanes, obtain 3,6-, bis- bromo- 9- octylcarbazols, and structure is：
Bis- bromo- 9- octylcarbazols of (3) 3,6- are reacted with duplex pinacol boron ester, obtain 3,6- bis- (4,4,5,5- tetramethyls -1,3,
2- dioxaborolans) -9- octylcarbazols, structure is：
(4) 3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborolans) -9- octylcarbazols are reacted with 4- bromobenzaldehydes,
Product 3,6- bis- (4- aldehyde radicals phenyl) -9- octylcarbazols are respectively obtained, structure is：
(4- aldehyde radicals the phenyl) -9- octylcarbazols of (5) 3,6- bis- are reacted with new steaming pyrroles, generate [4- (the two pyrroles's first of 3,6- bis- respectively
Base) phenyl] -9- octylcarbazols, structure is：
(6) 3,6- bis- [4- (two pyrrolylmethyls) phenyl] -9- octylcarbazols react life in boron trifluoride ether/triethylamine system
Into target dyestuff BDP1, structure is：
3. two pyrroles's methines are complexed containing double center boron fluorides of carbazole and bridge linkage group in a kind of middle position according to claim 2
The preparation method of derivative, it is characterised in that reaction medium in reaction step (1)-(6) is n-hexane, tetrahydrofuran,
One or more of mixing of dichloromethane, dimethyl sulfoxide (DMSO), toluene, chloroform, petroleum ether, ethyl acetate, ethyl alcohol.
4. two pyrroles's methines are complexed containing double center boron fluorides of carbazole and bridge linkage group in a kind of middle position according to claim 2
The preparation method of derivative, it is characterised in that the catalyst in the reaction step (3), (4), (5) is InCl3, Pd (dppf)
Cl2, Pd (PPh3)4In any one.
5. two pyrroles's first are complexed containing double centre type boron fluorides of carbazole and bridge linkage group in a kind of middle position according to claim 2
The preparation method of river derivative, it is characterised in that the reaction temperature in the reaction step (1), (3), (4) is 80-150 DEG C,
(2), the reaction temperature in (5), (6) is -100 DEG C of room temperature.
6. two pyrroles's first are complexed containing double centre type boron fluorides of carbazole and bridge linkage group in a kind of middle position according to claim 2
The preparation method of river derivative, it is characterised in that reaction time in the reaction step (1), (3), (4) is 12-36h, (2),
(5), the reaction time in (6) is 2-10h.
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