CN114573514B - Bridged bisbenzimidazole salt, and preparation method and application thereof - Google Patents
Bridged bisbenzimidazole salt, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114573514B CN114573514B CN202210329435.5A CN202210329435A CN114573514B CN 114573514 B CN114573514 B CN 114573514B CN 202210329435 A CN202210329435 A CN 202210329435A CN 114573514 B CN114573514 B CN 114573514B
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- CN
- China
- Prior art keywords
- bridged
- intermediate product
- dicarboxaldehyde
- bisbenzimidazole
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- INAAIJLSXJJHOZ-UHFFFAOYSA-N pibenzimol Chemical class C1CN(C)CCN1C1=CC=C(N=C(N2)C=3C=C4NC(=NC4=CC=3)C=3C=CC(O)=CC=3)C2=C1 INAAIJLSXJJHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 31
- 239000013067 intermediate product Substances 0.000 claims abstract description 29
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 claims abstract description 22
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960000583 acetic acid Drugs 0.000 claims abstract description 16
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- -1 1 ,N 2 -diisopropylbenzene-1, 2-diamine Chemical compound 0.000 claims description 49
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- PXRCFMDCPPRGFL-UHFFFAOYSA-N 3,4-di(propan-2-yl)benzene-1,2-diamine Chemical compound CC(C)C1=CC=C(N)C(N)=C1C(C)C PXRCFMDCPPRGFL-UHFFFAOYSA-N 0.000 claims description 8
- SBRUFOSORMQHES-UHFFFAOYSA-N anthracene-9,10-dialdehyde Chemical compound C1=CC=C2C(C=O)=C(C=CC=C3)C3=C(C=O)C2=C1 SBRUFOSORMQHES-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical group O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 5
- XUFLAVKRRLBIMV-UHFFFAOYSA-N naphthalene-1,4-dicarbaldehyde Chemical compound C1=CC=C2C(C=O)=CC=C(C=O)C2=C1 XUFLAVKRRLBIMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- OTMRXENQDSQACG-UHFFFAOYSA-N thiophene-2,5-dicarbaldehyde Chemical compound O=CC1=CC=C(C=O)S1 OTMRXENQDSQACG-UHFFFAOYSA-N 0.000 claims description 4
- CZSOUHCUPOPPRC-UHFFFAOYSA-N 3-phenylphthalaldehyde Chemical compound O=CC1=CC=CC(C=2C=CC=CC=2)=C1C=O CZSOUHCUPOPPRC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 6
- 150000002460 imidazoles Chemical class 0.000 abstract description 4
- 230000002468 redox effect Effects 0.000 abstract description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 abstract description 3
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical class C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 abstract description 3
- ONQBUHWENXKHHP-UHFFFAOYSA-N 2-phenyl-3,4-dihydro-1h-isoquinoline Chemical compound C1CC2=CC=CC=C2CN1C1=CC=CC=C1 ONQBUHWENXKHHP-UHFFFAOYSA-N 0.000 abstract description 3
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 2
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 238000004949 mass spectrometry Methods 0.000 description 14
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229940125898 compound 5 Drugs 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YYKKBIRETOCLKW-UHFFFAOYSA-N 1,3-di(propan-2-yl)-2h-benzimidazole Chemical compound C1=CC=C2N(C(C)C)CN(C(C)C)C2=C1 YYKKBIRETOCLKW-UHFFFAOYSA-N 0.000 description 1
- GEPFDEGNEBYCSR-UHFFFAOYSA-N 1,3-dimethyl-2h-benzimidazole Chemical compound C1=CC=C2N(C)CN(C)C2=C1 GEPFDEGNEBYCSR-UHFFFAOYSA-N 0.000 description 1
- MHQULXYNBKWNDF-UHFFFAOYSA-N 3,4-dimethylbenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1C MHQULXYNBKWNDF-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- MPIMZAKRTOXRAO-UHFFFAOYSA-N N[C]N Chemical class N[C]N MPIMZAKRTOXRAO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/20—Two benzimidazolyl-2 radicals linked together directly or via a hydrocarbon or substituted hydrocarbon radical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/62—Isoquinoline or hydrogenated isoquinoline ring systems
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1011—Condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Compared with common imidazole salt, the imidazole salt has a more rigid planar bridging framework, an additional redox center and a narrower HOMO-LUMO energy gap. The good redox property enables the bridged bisimidazole salt to be better applied to the solution-type electrochromic device, and can promote the N-phenyl tetrahydroisoquinoline and the diphenyl phosphine oxide to carry out cross dehydrogenation coupling reaction to form carbon-phosphorus bonds. The preparation method comprises mixing N 1 ,N 2 -di-substituent benzene-1, 2-diamine and dicarboxaldehyde with different structures react under the catalysis of glacial acetic acid to obtain an intermediate product A; then the intermediate product A and 2-bromoacetophenone react for 16 to 24 hours in an organic solvent, and then the product B is obtained by separating the products; and finally, reacting the intermediate product B with methyl triflate in an organic solvent, and separating the product to obtain the bridged bisbenzimidazole salt.
Description
Technical Field
The invention belongs to the field of preparation of bridged bisbenzimidazole salts, and particularly relates to a bridged bisbenzimidazole salt, a preparation method and application thereof.
Background
In the early stages of development of the electronic industry, semiconductor materials were mostly inorganic materials such As silicon (Si), germanium (Ge), gallium arsenide (Ga As), etc., and organic materials are often used for insulation, passivation, sacrificial layers, and patterning materials.
Conventionally, organic materials are considered to be insulators based on carbon atoms, and generally do not possess the properties of conductors or semiconductors such as optical, electrical and magnetic. Through years of development, organic semiconductor materials have been widely and deeply applied in the fields of electroluminescence, photovoltaic cells and the like. The bridged bisbenzimidazole salt has oxidation-reduction performance, and can realize two-step reversible oxidation-reduction reaction by organic chemistry, photochemistry, electrochemistry and the like, and simultaneously the color is changed. The organic multi-stage redox system related to electron transfer plays an important role in the aspects of organic materials used for functional dyes, electronic devices, photovoltaic cells, data storage, organic field effect transistors and the like.
In general, the structural features of such redox molecules are composed of two end groups X and a pi-system bond, forming three redox states through the absorption and loss of electrons. Although existing molecules exhibit good redox properties, the wide use of carbon-derived redox molecules in practical applications remains to be developed.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a bridged bisbenzimidazole salt, a preparation method and application thereof, which can be applied to the fields of photocatalysis and electrochromic devices and expands the application of novel organic semiconductor materials in the electrochromic field.
The invention is realized by the following technical scheme:
a bridged bisbenzimidazole salt, which has the following structural formula:
wherein Ar-linker is one of the following groups:
the preparation method of the bridged bisbenzimidazole salt comprises the following steps:
step 1, N is as follows 1 ,N 2 -disubstituted benzene-1, 2-diamine and structurally different dicarboxaldehyde according to (2.5-3): 1 in the molar ratio under the catalysis of glacial acetic acid, wherein the dicarboxaldehyde is terephthalaldehyde, biphenyl dicarboxaldehyde, terphenyl-4, 4' -dicarboxaldehyde, and tiono [3 ],2–b]Thiophene-2, 5-dicarboxaldehyde, 9, 10-anthracene dicarboxaldehyde or 1, 4-naphthalene dicarboxaldehyde to obtain an intermediate product A;
step 2, reacting an intermediate product A and 2-bromoacetophenone in an organic solvent for 16-24 hours, wherein the molar ratio of the intermediate product A to the 2-bromoacetophenone is 2.5:1, separating the product to obtain an intermediate product B;
step 3, reacting an intermediate product B and methyl triflate in an organic solvent at room temperature, wherein the molar ratio of the intermediate product B to the methyl triflate is 2.5:1, and then separating the product to obtain the bridged bisbenzimidazole salt.
Preferably, the molar ratio of glacial acetic acid to the dicarboxaldehyde in step 1 is 0.2.
Preferably, in step 1N 1 ,N 2 -disubstituted benzene-1, 2-diamine and dicarboxaldehyde with different structures react for 16 to 24 hours at the temperature of 20 to 50 ℃.
Preferably, step 1 first uses N 1 ,N 2 -disubstituted benzene-1, 2-diamine, dicarboxaldehyde with different structures and glacial acetic acid are dissolved in methylene dichloride, then the reaction is carried out, and the products in the reaction liquid are separated to obtain an intermediate product A.
Preferably, the organic solvents in step 2 and step 3 are tetrahydrofuran and dichloromethane, respectively.
Preferably, the intermediate product A of the step 2 and 2-bromoacetophenone react at 20-50 ℃, and the obtained reactant is separated by column chromatography to obtain an intermediate product B.
Preferably, the intermediate product B of the step 3 and the methyl triflate react for 12-24 hours at room temperature, and the obtained reactant is separated in a decompression and vacuum mode to obtain the bridged bisbenzimidazole salt.
The application of the bridged bisbenzimidazole salt as a photocatalyst is characterized in that 5-20% of equivalent weight is added into the bridged bisbenzimidazole salt according to the molar ratio, and under the induction of visible light, the following cross dehydrogenation coupling reaction is promoted to construct a carbon-phosphorus bond:
the application of the bridged bisbenzimidazole salt in the electrochromic device is that the bridged bisbenzimidazole salt is dissolved in N, N-dimethylformamide and then is filled in two pieces of glass containing indium tin oxide coating, so that the electrochromic device is obtained.
Compared with the prior art, the invention has the following beneficial technical effects:
the bridged bisbenzimidazole salts of the present invention have a more rigid planar bridging backbone, additional redox centers and a narrower HOMO-LUMO energy gap than conventional imidazole salts. The good redox property enables the bridged bisimidazole salt to be better applied to a solution-type electrochromic device, the bridged bisimidazole salt is dissolved in N, N-dimethylformamide, then the solution-type electrochromic device is filled in two pieces of glass containing indium tin oxide coatings, an external voltage of not more than 2V is applied, obvious color changes are achieved, the device is monitored for multiple color conversion processes under different voltages through an in-situ spectroelectrochemical method, and a good foundation is laid for developing the flexible low-voltage driven electrochromic device as a result. The invention obtains bridged bis-benzimidazole Ar based on the design of N-heterocyclic carbene ligand and the exploration of functionalization, and pi-linking group with diamino carbene as end group i Pr)A 1-6 ·2OTf - Ar (Me) A 1 ·2OTf - Can be successfully applied to the fields of electrochromic and photocatalysis. The color change of the bridged bisbenzimidazole salts is due to intermolecular charge transfer. When a certain voltage is applied to the neutral state bridged bisbenzimidazole salt, the neutral state bridged bisbenzimidazole salt can show a monovalent cation state and a divalent cation state.
The invention relates to a preparation method of bridged bisbenzimidazole salt, which comprises the following steps of N 1 ，N 2 The di-substituent benzene-1, 2-diamine reacts with dicarboxaldehyde with different structures under the catalysis of glacial acetic acid to generate bridged bisbenzimidazole, then reacts with bromoacetophenone to obtain corresponding bromoanion bridged bisbenzimidazole salt, and finally, anions are converted into the bromoanion by trifluoromethyl sulfonic acid methyl esterOTf – Obtaining the target product. The preparation condition is mild and the operation is simple.
The bridged bisbenzimidazole salt can be used as a photocatalyst, and can promote the cross dehydrogenation coupling reaction between N-phenyl tetrahydroisoquinoline and diphenyl phosphine oxide under the induction of visible light to form carbon-phosphorus (C-P) bonds. The method can be particularly used in air, and the yield can reach 80-90% in the presence of white light.
The solution of the bridged bisbenzimidazole salt dissolved in DMF can be injected into the middle of two pieces of glass coated with Indium Tin Oxide (ITO), and when voltage is applied to the glass, three color changes can be observed along with the increase of the voltage, namely red (-0.95V), blue-violet (-0.90V) and deep blue (-0.85V), and more importantly, the glass can be reversibly changed into a colorless state after the voltage is removed. Therefore, the bridged bisbenzimidazole salt has great application potential in the electrochromic field.
Drawings
FIG. 1a is a nuclear magnetic resonance hydrogen spectrum of a bridged bisbenzimidazole salt compound obtained in example 1 of the present invention.
FIG. 1b is a nuclear magnetic resonance hydrogen spectrum of a bridged bisbenzimidazole salt compound obtained in example 2 of the present invention.
FIG. 1c is a nuclear magnetic resonance hydrogen spectrum of a bridged bisbenzimidazole salt compound obtained in example 3 of the present invention.
FIG. 1d is a nuclear magnetic resonance hydrogen spectrum of a bridged bisbenzimidazole salt compound obtained in example 4 of the present invention.
FIG. 1e is a nuclear magnetic resonance hydrogen spectrum of a bridged bisbenzimidazole salt compound obtained in example 5 of the present invention.
FIG. 1f is a nuclear magnetic resonance hydrogen spectrum of a bridged bisbenzimidazole salt compound obtained in example 6 of the present invention.
FIG. 1g is a nuclear magnetic resonance hydrogen spectrum of a bridged bisbenzimidazole salt compound obtained in example 7 of the present invention.
FIG. 2a is a cyclic voltammogram of a bridged bis-benzimidazole salt compound obtained in example 1 of the present invention.
FIG. 2b is a cyclic voltammogram of a bridged bis-benzimidazole salt compound according to example 2 of the present invention.
FIG. 2c is a cyclic voltammogram of a bridged bis-benzimidazole salt compound according to example 3 of the present invention.
FIG. 2d is a cyclic voltammogram of a bridged bis-benzimidazole salt compound obtained in example 4 of the present invention.
FIG. 2e is a cyclic voltammogram of a bridged bis-benzimidazole salt compound obtained in example 5 of the present invention.
FIG. 2f is a cyclic voltammogram of a bridged bis-benzimidazole salt compound according to example 6 of the present invention.
FIG. 2g is a cyclic voltammogram of a bridged bis-benzimidazole salt compound obtained in example 7 of the present invention.
FIG. 3 is an ultraviolet/visible absorption spectrum of bridged bisbenzimidazole salt compounds 1 to 6 obtained in examples 1 to 6 of the present invention.
FIG. 4a is a diagram of a solution type electrochromic device prepared from the bridged bis-benzimidazole salt compound 1 obtained in example 1 of the present invention.
FIG. 4b is a chart showing the ultraviolet-visible spectrum of the bridged bisbenzimidazole salt compound 1 obtained in example 1 of the present invention in DMF.
FIG. 5a is a diagram of a solution type electrochromic device prepared from the bridged bis-benzimidazole salt compound 4 obtained in example 4 of the present invention.
FIG. 5b is a chart showing the ultraviolet-visible spectrum of the bridged bisbenzimidazole salt compound 4 obtained in example 4 of the present invention in DMF.
FIG. 6a is a diagram of a solution electrochromic device prepared from the bridged bis-benzimidazole salt compound 5 obtained in example 6 of the present invention.
FIG. 6b is a chart showing the ultraviolet-visible spectrum of the bridged bisbenzimidazole salt compound 5 obtained in example 6 of the present invention in DMF.
FIG. 7a is a diagram of a solution type electrochromic device prepared from the bridged bis-benzimidazole salt compound 6 obtained in example 5 of the present invention.
FIG. 7b is a UV-visible spectrum of bridged bis-benzimidazole salt compound 6 in DMF according to example 5 of the present invention.
The specific embodiment is as follows:
in order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The idea of the invention is as follows:
first by N 1 ，N 2 -disubstituted benzene-1, 2-diamines with structurally different dicarboxaldehyde (terephthalaldehyde, biphenyldicarboxaldehyde, terphenyl-4, 4 "-dicarboxaldehyde, thiano [3, 2-b)]Thiophene-2, 5-dicarboxaldehyde, 9, 10-anthracene dicarboxaldehyde, 1, 4-naphthalene dicarboxaldehyde) and bromoacetophenone are added to obtain bridged bisbenzimidazole salt (ArA.2Br) with bromine anions - 1-6) and finally converting the anions into (trifluoromethane sulfonate) OTf by means of methyl trifluoromethane sulfonate – (ArA 1-6 ·2OTf - 1-6) to obtain the target product. The specific process is as follows:
the invention is represented by a 9, 10-anthracene dicarboxaldehyde preparation product, and the chemical name of the obtained bridged bisbenzimidazole salt is 2,2' - (anthracene-9, 10-diyl) bis (1, 3-diisopropyl-1H-benzimidazole-3-onium) triflate.
The specific steps for preparing the bridged bisbenzimidazole salt are as follows:
step 1, preparing 9, 10-anthracene dicarboxaldehyde;
N 1 ,N 2 the molar ratio of the di-substituted benzene-1, 2-diamine to the structurally different dicarboxaldehyde is the amine: aldehyde= (2.5-3): 1, a step of;
step 2, stirring in dichloromethaneStirring to make N corresponding to concentration of dicarboxaldehyde 0.19M 1 ,N 2 The di-substituent benzene-1, 2-diamine and 9, 10-anthracene dicarboxaldehyde are completely dissolved, then 0.2eq is added dropwise, glacial acetic acid is used as a catalyst (namely, the molar ratio of the di-substituted benzene-1, 2-diamine and the corresponding dicarboxaldehyde is 0.2), stirring is continued, and after the reaction is carried out for 16 to 24 hours at the temperature of 20 to 50 ℃, the solvent methylene dichloride is removed;
dissolving the obtained intermediate product A in tetrahydrofuran to make the concentration of the intermediate product A be 0.19M, then adding 2-bromoacetophenone, and continuously stirring, wherein the feeding mole ratio of bromoacetophenone to the intermediate product A is bromoacetophenone: intermediate a=2.5: 1, the reaction time is 16-24 hours, the reaction temperature is room temperature-50 ℃, and the intermediate product B is obtained through column chromatography separation;
the obtained intermediate B is dissolved in dichloromethane (0.1M), and methyl triflate is added dropwise, wherein the feeding molar ratio of the intermediate B to the methyl triflate is 1:2.5, stirring for 12-24 hours at normal temperature, and removing solvent dichloromethane to obtain a target product.
The structure is as follows:
wherein Ar-linker has pi-pi conjugated structure, and has excellent photophysical property and electrochemical property. Such compounds are useful as photocatalysts in constructing carbon-phosphorus bonds in the reactions described below. Adding 5-20mol% equivalent of bisbenzimidazole salt as a photocatalyst, and promoting cross dehydrogenation coupling reaction to construct carbon-phosphorus bonds under the induction of visible light;
the bridged bisbenzimidazole salt has excellent electrochemical properties, can be used for electrochromic, and can be used for monitoring various colors of a device under different voltages by means of in-situ spectrum electrochemistry, and the colors can be reversibly converted by changing the voltages.
Ar-linker is used as pi-pi conjugated structure of bridging structure, and is phenyl, biphenyl, terphenyl, naphthyl, anthryl and thiophene, and the structure is as follows:
no metal catalyst was used in the above synthesis method.
1. The specific implementation method for the synthesis of the bridged bisbenzimidazole salt comprises the following steps:
example 1
To N 1 ,N 2 To a solution of diisopropylbenzene-1, 2-diamine (768 mg,4.00 mmol) in dichloromethane (3 mL) was added terephthalaldehyde (1 mmol,134 mg). Then, 0.35mL of glacial acetic acid was added, and the resulting mixed solution was stirred at a rate of 100rpm at 50℃and reacted for 16 hours, and the solvent was removed under reduced pressure and vacuum to give a crude product of 1, 4-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol) -2-yl) benzene.
To a solution of crude 1, 4-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) benzene in tetrahydrofuran (6 mL) was added 2-bromoacetophenone (2.1 mmol,418 mg) and the mixture was stirred at room temperature for 20 hours. The filtrate was removed and the residue was purified by silica gel chromatography (methanol/dichloromethane volume ratio = 1:10) to give Ar @ i Pr)A 1 ·2Br - ，(0.7mmol,334mg)。
Ar is processed at room temperature i Pr)A 1 ·2Br - And methyl triflate (0.95 mmol,156 mg) were mixed in dry dichloromethane (3 mL) and the reaction mixture was stirred at room temperature for 12 hours and the solvent was removed under reduced pressure in vacuo to give Ar as a white solid i Pr)A 1 ·2OTf - The structural formula is as follows:
the target product was subjected to nmr hydrogen spectrum (fig. 1 a) and mass spectrometry according to the conventional method, and the results were as follows:
hydrogen spectrum: 1 H NMR(400MHz,DMSO-d6)：δ8.41-8.39(m,4H,CH-Ar),8.29(s,4H,CH-Ar),7.78-7.75(m,4H,CH-Ar),4.60-4.53(m,4H,CH-iPr),1.68(d,J＝6.8Hz,24H,CH3-iPr).
mass spectrometry: HRMS (ESI) + ):m/z calcd for C 32 H 40 N 4 2+ [M/2] + 240.1621,found 240.1613.
Thus, the objective product was obtained in this example.
Example 2
To N 1 ,N 2 To a solution of diisopropylbenzene-1, 2-diamine (768 mg,4.00 mmol) in dichloromethane (3 mL) was added biphenyl dicarboxaldehyde (1 mmol,210.2 mg). Then, 0.35mL of glacial acetic acid was added, and the resulting mixed solution was stirred at a rate of 100rpm at 50℃for 16 hours, and the solvent was removed under reduced pressure and vacuum to give a crude product of 4,4 '-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) -1,1' -biphenyl.
To a tetrahydrofuran solution (6 mL) of the crude 4,4 '-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) -1,1' -biphenyl was added 2-bromoacetophenone (2.1 mmol,418 mg) and the mixture was stirred at room temperature for 20 hours. The filtrate was removed and the residue was purified by silica gel chromatography (methanol/dichloromethane volume ratio = 1:10) to give Ar @ i Pr)A 2 ·2Br - (0.7mmol,502.3mg)。
Ar is processed at room temperature i Pr)A 2 ·2Br - And methyl triflate (0.95 mmol,156 mg) were mixed in dry dichloromethane (3 mL) and the reaction mixture was stirred at room temperature for 12 hours and the solvent was removed under reduced pressure in vacuo to give Ar as a white solid i Pr)A 2 ·2OTf - The structural formula is as follows:
the target product was subjected to nmr hydrogen spectrum (fig. 1 b) and mass spectrometry according to the conventional method, and the results were as follows:
hydrogen spectrum: 1H NMR (400 MHz, DMSO). Delta.8.28 (dd, J=6.4, 3.2Hz, 4H), 8.17 (d, J=8.0 Hz, 4H), 7.99 (d, J=8.0 Hz, 4H), 7.66 (dd, J=6.0, 3.2Hz, 4H), 4.42 (dt, J=14.0, 7.2Hz, 4H), 1.57 (d, J=6.9 Hz, 24H).
Mass spectrometry: HRMS (ESI) + ):m/z calcd for C 38 H 44 N 4 2+ [M/2] + 278.1778,found 278.1779.
Thus, the objective product was obtained in this example.
Example 3
To N 1 ,N 2 To a solution of diisopropylbenzene-1, 2-diamine (768 mg,4.00 mmol) in methylene chloride (3 mL) was added terphenyl-4, 4 "-dicarboxaldehyde (1 mmol,286.3 mg). Then 0.35mL of glacial acetic acid was added, and the resulting mixed solution was stirred at a rate of 100rpm at 50℃for 16 hours, and the solvent was removed under reduced pressure and vacuum to give a crude product of 4,4 "-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) -1,1':4',1" -terphenyl.
To a solution of 4,4 "-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) -1,1':4',1" -terphenyl crude product in tetrahydrofuran (6 mL) was added 2-bromoacetophenone (2.1 mmol,418 mg) and stirred at room temperature for 20 hours. The filtrate was removed and the residue was purified by silica gel chromatography (methanol/dichloromethane volume ratio = 1:10) to give Ar @ i Pr)A 3 ·2Br - (0.7mmol,554.9mg)。
Ar is processed at room temperature i Pr)A 3 ·2Br - And methyl triflate (0.95 mmol,156 mg) were mixed in dry dichloromethane (3 mL) and the reaction mixture was stirred at room temperature for 12 hours and the solvent was removed under reduced pressure in vacuo to give Ar as a white solid i Pr)A 3 ·2OTf - The structural formula is as follows:
the target product was subjected to nuclear magnetic resonance hydrogen spectrometry (fig. 1 c) and mass spectrometry according to the conventional method, and the results were as follows:
hydrogen spectrum: 1 H NMR(400MHz,DMSO-d6).δ8.37-8.35(m,4H,CH-Ar),8.21-8.19(d,4H,CH-Ar),8.05-8.01(m,8H,CH-Ar)7.74-7.72(m,4H,CH-Ar),4.55-4.48(m,4H,CH-iPr),1.66(d,J＝7.2Hz,24H,CH3-iPr).
mass spectrometry: HRMS (ESI) + ):m/z calcd for C 44 H 48 N 4 2+ [M/2] + 316.1934,found 316.1921.
Thus, the objective product was obtained in this example.
Example 4
To N 1 ,N 2 To a solution of diisopropylbenzene-1, 2-diamine (768 mg,4.00 mmol) in dichloromethane (3 mL) was added 1, 4-naphthalene dicarboxaldehyde (1 mmol,184.2 mg). Then 0.35mL of glacial acetic acid was added, and the resulting mixed solution was stirred at a rate of 100rpm at 50℃and reacted for 16 hours, the solvent was removed under reduced pressure and vacuum to give a crude product of 1, 4-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) naphthalene.
To a tetrahydrofuran solution (6 mL) of the crude 1, 4-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) naphthalene product was added 2-bromoacetophenone (2.1 mmol,418 mg) and the mixture was stirred at room temperature for 20 hours. The filtrate was removed and the residue was purified by silica gel chromatography (methanol/dichloromethane volume ratio = 1:10) to give Ar @ i Pr)A 4 ·2Br - As a white solid (0.7 mmol,483.4 mg).
Ar is processed at room temperature i Pr)A 4 ·2Br - And methyl triflate (0.95 mmol,156 mg) were mixed in dry dichloromethane (3 mL) and the reaction mixture was stirred at room temperature for 12 hours and the solvent was removed under reduced pressure and vacuum to give Ar # i Pr)A 4 ·2OTf - The structural formula is as follows:
the target product was subjected to nuclear magnetic resonance hydrogen spectrometry (fig. 1 d) and mass spectrometry according to the conventional method, and the results were as follows:
hydrogen spectrum: 1 H NMR(400MHz,DMSO-d6).δ8.37-8.34(m,6H,CH-Ar),7.76-7.72(m,4H,CH-Ar),4.77-4.70(m,4H,CH-iPr),1.71(d,J＝6.8Hz,24H,CH3-iPr).
mass spectrometry: HRMS (ESI+): m/z calculated for C 36 H 42 N 4 2+ [M/2] + 265.1699,found 265.1690.
Thus, the objective product was obtained in this example.
Example 5
To N 1 ,N 2 To a solution of diisopropylbenzene-1, 2-diamine (768 mg,4.00 mmol) in methylene chloride (3 mL) was added 9, 10-anthracenedicarboxaldehyde (1 mmol,234.3 mg). Then 0.35mL of glacial acetic acid was added, and the resulting mixed solution was stirred at a rate of 100rpm at 50℃and reacted for 16 hours, the solvent was removed under reduced pressure and vacuum to give a crude product of 9, 10-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) anthracene.
To a tetrahydrofuran solution (6 mL) of the crude 9, 10-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) anthracene product was added 2-bromoacetophenone (2.1 mmol,418 mg) and the mixture was stirred at room temperature for 20 hours. The filtrate was removed and the residue was purified by silica gel chromatography (methanol/dichloromethane volume ratio = 1:10) to give Ar @ i Pr)A 5 ·2Br - (0.7mmol,518.4mg)。
Ar is processed at room temperature i Pr)A 5 ·2Br - And methyl triflate (0.95 mmol,156 mg) were mixed in dry dichloromethane (3 mL) and the reaction mixture was stirred at room temperature for 12 hours and the solvent was removed under reduced pressure in vacuo to give Ar as a pale yellow solid i Pr)A 5 ·2OTf - The structural formula is as follows:
the target product was subjected to nmr hydrogen spectrum (fig. 1 e) and mass spectrometry according to the conventional method, and the results were as follows:
hydrogen spectrum: 1 H NMR(400MHz,DMSO).δ8.49-8.47(m,4H,CH-Ar),7.91-7.89(m,4H,CH-Ar),7.82-7.79(m,8H,CH-Ar)7.73-7.70(m,4H,CH-Ar),4.30-4.23(m,4H,CH-iPr),1.50(d,J＝6.8Hz,24H,CH3-iPr).
mass spectrometry: HRMS (ESI) + ):m/z calcd for C 40 H 44 N 4 2+ [M/2] + 290.1778,found 290.1768.
Thus, the objective product was obtained in this example.
Example 6
To N 1 ,N 2 To a solution of diisopropylbenzene-1, 2-diamine (768 mg,4.00 mmol) in methylene chloride (3 mL) was added thiano [3,2-b ]]Thiophene-2, 5-dicarboxaldehyde (1 mmol,196.2 mg). Then adding 0.35mL of glacial acetic acid, stirring the obtained mixed solution at the speed of 100rpm at 50 ℃ to react for 16 hours, and removing the solvent under reduced pressure and vacuum to obtain 2, 5-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) thieno [3, 2-b)]Crude thiophene products.
Oriented 2, 5-bis (1, 3-diisopropyl-2, 3-dihydro-1H-benzimidazol-2-yl) thieno [3,2-b]To a tetrahydrofuran solution (6 mL) of the crude thiophene was added 2-bromoacetophenone (2.1 mmol,418 mg) and the mixture was stirred at room temperature for 20 hours. The filtrate was removed and the residue was purified by silica gel chromatography (methanol/dichloromethane volume ratio = 1:10) to give Ar @ i Pr)A 6 ·2Br - (0.7mmol,491.8mg)。
Ar is processed at room temperature i Pr)A 6 ·2Br - And methyl triflate (0.95 mmol,156 mg) were mixed in dry dichloromethane (3 mL) and the reaction mixture was stirred at room temperature for 12 hours and the solvent was removed under reduced pressure and vacuum to give Ar # i Pr)A 6 ·2OTf - The structural formula is as follows:
the target product was subjected to nuclear magnetic resonance hydrogen spectrometry (fig. 1 f) and mass spectrometry according to the conventional method, and the results were as follows:
hydrogen spectrum: 1H NMR (400 MHz, DMSO-d 6). Delta.8.37-8.34 (m, 6H, CH-Ar), 7.76-7.72 (m, 4H, CH-Ar), 4.77-4.70 (m, 4H, CH-iPr), 1.71 (d, J=6.8 Hz,24H, CH 3-iPr).
Mass spectrometry: HRMS (ESI) + ):m/z calcd for C 32 H 38 N 4 S 2 2+ [M/2] + 271.1263,found 271.1254.
Thus, the objective product was obtained in this example.
Example 7
To N 1 ,N 2 To a solution of dimethyl benzene-1, 2-diamine (544 mg,4.00 mmol) in methylene chloride (3 mL) was added terephthalaldehyde (1 mmol,134 mg). Then, 0.35mL of glacial acetic acid was added, and the resulting mixed solution was stirred at a rate of 100rpm at 50℃and reacted for 16 hours, and the solvent was removed under reduced pressure and vacuum to give a crude product of 1, 4-bis (1, 3-dimethyl-2, 3-dihydro-1H-benzimidazol) -2-yl) benzene.
To a solution of the crude 1, 4-bis (1, 3-dimethyl-2, 3-dihydro-1H-benzimidazol-2-yl) benzene in tetrahydrofuran (6 mL) was added 2-bromoacetophenone (2.1 mmol,418 mg) and the mixture was stirred at room temperature for 20 hours. The filtrate was removed and the residue was purified by silica gel chromatography (methanol/dichloromethane volume ratio = 1:10) to give Ar (Me) a 1 ·2Br - (0.7mmol,369.8mg)。
Ar (Me) A was taken at room temperature 1 ·2Br - And methyl triflate (0.95 mmol,156 mg) were mixed in dry dichloromethane (3 mL) and the reaction mixture was stirred at room temperature for 12 hours, the solvent was removed under reduced pressure and vacuum to give Ar (Me) A 1 ·2OTf - The structural formula is as follows:
the target product was subjected to nuclear magnetic resonance hydrogen spectrometry (fig. 1 g) and mass spectrometry according to the conventional method, and the results were as follows:
hydrogen spectrum: 1H NMR (400 MHz, DMSO-d 6) delta 8.28 (s, 4H, CH-Ar), 8.20 (d, J=8.2 Hz 4H, CH-Ar), 7.82 (d, J=8.1 Hz,4H, CH-Ar), 4.01 (s, 12H, CH 3 ).
Mass spectrometry: HRMS (ESI) + ):m/z calcd for C 24 H 24 N 4 2+ [M/2] + 184.0995,found 184.0989.
Thus, the objective product was obtained in this example.
2. The application of the bridged bisbenzimidazole salt disclosed by the invention comprises the following contents:
1. based on the application of the bridged bisbenzimidazole salt in visible light catalysis, the preparation method specifically comprises the following steps:
the bridged bisbenzimidazole salt obtained in example 5 was added as a catalyst in an equivalent amount of 5mol% to a reaction for cross dehydrogenation coupling between N-phenyltetrahydroisoquinoline and diphenylphosphine oxide to form carbon-phosphorus (C-P) bonds, and the reaction time was 12 hours, and the progress of the cross dehydrogenation coupling reaction was promoted under the initiation of visible light (white light) to form carbon-phosphorus (C-P) bonds, to give a coupled product with a yield of 93%.
2. Based on the application of the bridged bisbenzimidazole salt in electrochromic devices, the preparation method comprises the following steps:
the bridged bisbenzimidazole salts obtained in examples 1 to 6 above were dissolved in solvent DMF (0.01M), the solution was poured between two pieces of glass containing Indium Tin Oxide (ITO) coating, one of which was initially fluted, and a voltage of 0 to 2V, preferably 0.7V, 0.9V was applied to observe the color change and the corresponding potential.
Described in further detail below:
preparing a visible light photochromic device from the bridged bisbenzimidazole salt compounds 1-6: and (3) attaching two pieces of ITO glass into a device substrate with a cavity of about 0.5mm thickness by using double faced adhesive tape, respectively dissolving 6 bridged bisbenzimidazole salt compounds in DMF, adding the solution into the prepared device cavity, and sealing to obtain the visible photochromic device.
The visible light-induced color device of example 2 and example 3 changed from the original colorless state to black at an external high voltage (1.2V) and could not be recovered upon removal of the potential, which was caused by unstable and easily decomposed bridged bisbenzimidazole salt compound 2, 3.
The invention carries out related tests on 7 bridged bisbenzimidazole salt compounds prepared in the embodiment, and the test results are shown in the following drawings:
the cyclic voltammograms of bridged bisbenzimidazole salt compounds 1-7, respectively, are shown in fig. 2a, 2b, 2c, 2d, 2e, 2f and 2g, indicating that these compounds all have two sets of reversible redox centres, of which compound 5 exhibits excellent redox properties.
Fig. 3 shows the uv/vis absorption spectra of bridged bisbenzimidazole salt compounds 1 to 6, which show the red shift of the maximum absorption wavelength of the bridged bisbenzimidazole salt compounds according to the present invention due to the expansion of the conjugated system.
Referring to fig. 4a, the solution type electrochromic device prepared by bridging bisbenzimidazole salt compound 1 turns pink when a voltage of 0.95V is applied, and the absorption spectrum in fig. 4b shows that the absorption between 500 and 600 is gradually enhanced.
Referring to fig. 5a, the solution type electrochromic device prepared by bridging bisbenzimidazole salt compound 4 turns purple when a voltage of 0.85V is applied, and the absorption spectrum in fig. 5b shows that the absorption between 500 and 600 is gradually enhanced.
Referring to fig. 6a and 6b, the solution type electrochromic device prepared by bridging bisbenzimidazole salt compound 5 turns blue when a voltage of 0.7V is applied, the absorption spectrum shows that the absorption between 500 and 600 is gradually increased, the color becomes red when a voltage of 0.9V is applied, and the absorption between 600 and 700 is gradually increased, so that bridging bisbenzimidazole salt compound 5 is the first imidazole salt having two electrochromic processes.
Referring to fig. 7a, the solution type electrochromic device prepared by bridging bisbenzimidazole salt compound 6 turns deep blue when a voltage of 0.85V is applied, and the absorption spectrum of fig. 7b shows that absorption between 500 and 700 is gradually enhanced.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (7)
1. The preparation method of the bridged bisbenzimidazole salt is characterized in that the bisbenzimidazole salt has the following structural formula:
wherein Ar-linker is one of the following groups:
the method specifically comprises the following steps:
step 1, N is as follows 1 ,N 2 -diisopropylbenzene-1, 2-diamine and structurally different dicarboxaldehyde according to (2.5-3): 1 in the molar ratio under the catalysis of glacial acetic acid, wherein the dicarboxaldehyde is terephthalaldehyde, biphenyl dicarboxaldehyde, terphenyl-4, 4' -dicarboxaldehyde, and tiono [3,2-b ]]Thiophene-2, 5-dicarboxaldehyde, 9, 10-anthracene dicarboxaldehyde or 1, 4-naphthalene dicarboxaldehyde to obtain an intermediate product A, wherein the structural formula of the intermediate product A is as follows:
step 2, reacting an intermediate product A and 2-bromoacetophenone in an organic solvent for 16-24 hours, wherein the molar ratio of the intermediate product A to the 2-bromoacetophenone is 2.5:1, and then separating the product to obtain an intermediate product B, wherein the structural formula of the intermediate product B is as follows:
step 3, reacting an intermediate product B and methyl triflate in an organic solvent at room temperature, wherein the molar ratio of the intermediate product B to the methyl triflate is 2.5:1, and then separating the product to obtain the bridged bisbenzimidazole salt.
2. The process for preparing bridged bisbenzimidazole salt according to claim 1, wherein the molar ratio of glacial acetic acid to dicarboxaldehyde in step 1 is 0.2.
3. The process for preparing bridged bisbenzimidazole salt according to claim 1, wherein N in step 1 1 ,N 2 Reacting diisopropylbenzene-1, 2-diamine with dicarboxaldehyde with different structures at 20-50 ℃ for 16-24 h.
4. The method for preparing bridged bisbenzimidazole salt according to claim 1, wherein step 1 comprises the steps of firstly adding N 1 ,N 2 The diisopropylbenzene-1, 2-diamine, the dicarboxaldehyde with different structures and glacial acetic acid are dissolved in methylene dichloride, then the reaction is carried out, and the products in the reaction liquid are separated to obtain an intermediate product A.
5. The method for preparing bridged bisbenzimidazole salt according to claim 1, wherein the organic solvents in step 2 and step 3 are tetrahydrofuran and dichloromethane, respectively.
6. The preparation method of the bridged bisbenzimidazole salt according to claim 1, wherein the intermediate product A of the step 2 and 2-bromoacetophenone react at 20-50 ℃, and the obtained reactants are separated by column chromatography to obtain the intermediate product B.
7. The preparation method of the bridged bisbenzimidazole salt according to claim 1, wherein the intermediate product B of the step 3 and methyl triflate react for 12-24 hours at room temperature, and the obtained reactants are separated in a decompression vacuum mode to obtain the bridged bisbenzimidazole salt.
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