CN105778890B - Thiophene terpyridine compound two-photon absorption material and preparation method thereof - Google Patents
Thiophene terpyridine compound two-photon absorption material and preparation method thereof Download PDFInfo
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- CN105778890B CN105778890B CN201610136105.9A CN201610136105A CN105778890B CN 105778890 B CN105778890 B CN 105778890B CN 201610136105 A CN201610136105 A CN 201610136105A CN 105778890 B CN105778890 B CN 105778890B
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- thiophene
- terpyridyl
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229930192474 thiophene Natural products 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010521 absorption reaction Methods 0.000 title abstract description 12
- 239000000463 material Substances 0.000 title abstract description 7
- -1 Thiophene terpyridine compound Chemical class 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 12
- 239000011358 absorbing material Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- XNMQTWSIBZKUOA-UHFFFAOYSA-N S1C(=CC=C1)C=O.C1(=CC=CC=C1)NC1=CC=CC=C1 Chemical class S1C(=CC=C1)C=O.C1(=CC=CC=C1)NC1=CC=CC=C1 XNMQTWSIBZKUOA-UHFFFAOYSA-N 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- WMQUKDQWMMOHSA-UHFFFAOYSA-N 1-pyridin-4-ylethanone Chemical class CC(=O)C1=CC=NC=C1 WMQUKDQWMMOHSA-UHFFFAOYSA-N 0.000 claims description 3
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical class BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- 238000007792 addition Methods 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 230000003111 delayed effect Effects 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 150000004694 iodide salts Chemical class 0.000 claims 1
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- 210000003470 mitochondria Anatomy 0.000 abstract description 15
- 210000004027 cell Anatomy 0.000 abstract description 13
- 239000000975 dye Substances 0.000 abstract description 10
- 230000002438 mitochondrial effect Effects 0.000 abstract description 10
- 230000006378 damage Effects 0.000 abstract description 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 abstract 2
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- 230000003834 intracellular effect Effects 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 210000001082 somatic cell Anatomy 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 1
- RUVJFMSQTCEAAB-UHFFFAOYSA-M 2-[3-[5,6-dichloro-1,3-bis[[4-(chloromethyl)phenyl]methyl]benzimidazol-2-ylidene]prop-1-enyl]-3-methyl-1,3-benzoxazol-3-ium;chloride Chemical compound [Cl-].O1C2=CC=CC=C2[N+](C)=C1C=CC=C(N(C1=CC(Cl)=C(Cl)C=C11)CC=2C=CC(CCl)=CC=2)N1CC1=CC=C(CCl)C=C1 RUVJFMSQTCEAAB-UHFFFAOYSA-M 0.000 description 1
- BUGSWHBWBUNUFB-UHFFFAOYSA-N C=O.BrC=1SC=CC1 Chemical compound C=O.BrC=1SC=CC1 BUGSWHBWBUNUFB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 206010010356 Congenital anomaly Diseases 0.000 description 1
- 102000004127 Cytokines Human genes 0.000 description 1
- 108090000695 Cytokines Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 206010056677 Nerve degeneration Diseases 0.000 description 1
- 208000037273 Pathologic Processes Diseases 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 230000001195 anabolic effect Effects 0.000 description 1
- FMYPDZMLNBBLGX-UHFFFAOYSA-N aniline;thiophene Chemical compound C=1C=CSC=1.NC1=CC=CC=C1 FMYPDZMLNBBLGX-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 230000003915 cell function Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 210000003712 lysosome Anatomy 0.000 description 1
- 230000001868 lysosomic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IKEOZQLIVHGQLJ-UHFFFAOYSA-M mitoTracker Red Chemical compound [Cl-].C1=CC(CCl)=CC=C1C(C1=CC=2CCCN3CCCC(C=23)=C1O1)=C2C1=C(CCC1)C3=[N+]1CCCC3=C2 IKEOZQLIVHGQLJ-UHFFFAOYSA-M 0.000 description 1
- 210000003463 organelle Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000009054 pathological process Effects 0.000 description 1
- TUFFYSFVSYUHPA-UHFFFAOYSA-M rhodamine 123 Chemical compound [Cl-].COC(=O)C1=CC=CC=C1C1=C(C=CC(N)=C2)C2=[O+]C2=C1C=CC(N)=C2 TUFFYSFVSYUHPA-UHFFFAOYSA-M 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a thiophene terpyridine compound two-photon absorption material and a preparation method thereof, wherein the thiophene terpyridine compound two-photon absorption material has the structural formula:
Description
First, technical field
Present document relates to a kind of two-photon absorbing material and preparation method thereof, specifically a kind of thiophene terpyridyl chemical combination
Thing two-photon absorbing material and preparation method thereof, thiophene terpyridyl compounds of the present invention are a kind of hypotoxicities, to cell line grain
The two-photon absorbing material of the single-minded identification of body.
2nd, background technology
Mitochondria is the indispensable membranaceous organelle of eukaryotic, is played the part of emphatically in the physiology of cell and pathologic process
The role wanted.It is to provide energy for cell in the major function of physiology course Mitochondria, about 95% in eukaryotic
Energy and ATP are produced by mitochondria, and mitochondria is also modified with intracellular redox equilibrium, liposome, calcium
Balance, cell cycle, congenital immunity etc. are closely related.Therefore mitochondria be otherwise known as intracellular catabolic with it is anabolic
Central hub.Mitochondria produces active oxygen during vital movement, this growth to cell with differentiation, adjust enzyme activity,
Have the function that during adjusting cytokine therapy inflammation and eliminating pathogen and external source particle important.Activity keto concentration
Change can change cell micro-environment, irreversible damage may be caused to cell so as to causing many diseases, including nerve
Degeneration, cardiovascular and cerebrovascular disease etc..Cell occurs to inevitably result in the change of mitochondria shape during lesion, can pass through observation line grain
The form of body determines the state of cell.Therefore, the mitochondrial probe of high selectivity is developed, it is directly perceived by way of biological developing
The form of mitochondria is observed, it is most succinct selection that it is combined with cell function state.Existing commercialization mitochondrial dye
Mainly include Rhodamine 123, Mitotracker Green and Mitotracker Red etc..Although these dyestuffs can be effective
Live body mitochondria is dyed, but their photostability is poor, cannot be irradiated for a long time by laser；More importantly this is several
The complicated of chondrioid dyestuff, cost of manufacture are high and effective two-photon cross-sections value is respectively less than 40GM.Therefore prepare a kind of
Inexpensively, the mitochondrial dye of high selectivity, high brightness and big two photon absorption cross section is the direction of future work.
MOLECULE DESIGN is that applicant uses double ethoxies cheap and easy to get an important factor for restricting commodity application with cost of material
Base diphenylamines, bromothiophene formaldehyde and acetylpyridine are raw material, have simply efficiently synthesized a kind of double ethyoxyls two of D-A configurations
Aniline thiophene terpyridyl.Property research shows that the two photon absorption cross section that the target molecule has maximum in 850nm or so, has
It is 371GM to imitate two photon absorption cross section value, before this document (Simultaneous Imaging of Mitochondria and
Lysosomes by Using Two-Photon Fluorescent Probes, Chem.Eur.J.2012,18,15246) report
The mitochondrial dye in road, its maximum effectively two photon absorption cross section value only half of molecule or so for this.With strong two-photon
Launch fluorescence, good cellular affinity and low cytotoxicity, the active somatic cell mitochondria that applies to that can be safe is shown
Shadow is imaged.This result of study shows that the compound has broad application prospects in life science field.
3rd, the content of the invention
The present invention is intended to provide a kind of thiophene terpyridyl compounds two-photon absorbing material and preparation method thereof, to be solved
Technical problem certainly is the two-photon absorbing material selected by MOLECULE DESIGN to the single-minded identification of cell mitochondrial.
The structural formula of thiophene terpyridyl compounds two-photon absorbing material of the present invention is：
The preparation method of thiophene terpyridyl compounds two-photon absorbing material of the present invention, includes the following steps：
(1) synthesis of diphenylamines thiophenecarboxaldehyde
The DMSO that 100mL is removed water through molecular sieve drying is added into 250mL there-necked flasks, nitrogen protection, stirring is after ten minutes
0.45g (2.3mmol) phenanthroline is added, continues to add 0.46g (2.4mmol) cuprous iodide after stirring 30min, continues to stir
5.00g (36mmol) Anhydrous potassium carbonate is added after 20min, 2.83g (11mmol) double ethoxy diphenyls are added after continuing 20min
Amine, 1.90g (10mmol) bromothiophenes formaldehyde, 0.1g 18-C-6 and 0.2mL Aliquat-336, continue to stir 10min, heating
Reacted 2 days to 95 DEG C；It is cooled to room temperature, filters after reaction, filtrate is poured slowly into the 1000mL large beakers of the water containing 800mL
It is stirred at room temperature 1 day, solution is in Dark grey and has more solid to separate out；Decompression filters, and obtains brown filter residue, column chromatography purifying
(VPetroleum ether/VEthyl acetate=30:1) bright yellow solid --- double oxethyl diphenylamine thiophenecarboxaldehydes are obtained.
Synthetic route is as follows：
(2) diphenylamines thiophene terpyridyl
The double oxethyl diphenylamine thiophenecarboxaldehydes of 3.67g (10mmol), 2.70g are sequentially added into 80mL ethanol solutions
(22mmol) 4- acetylpyridines and 2.90g (50mmol) KOH, the ammonia of 62mL25wt% is added after reacting at room temperature 1h in three batches
Water, 85 DEG C are stirred reaction 4h, are cooled to room temperature after reaction, and decompression filters, and filter residue is washed with isopropanol, and hexichol is obtained after dry
Amine thiophene terpyridyl.
Synthetic route is as follows：
Compared with the prior art, beneficial effects of the present invention are embodied in：
1st, the diphenylamines thiophene terpyridyl that the present invention synthesizes is a kind of two-photon absorption material with biological developing
Material, has the characteristics that hypotoxicity (Fig. 2), good light stability and small to cellular damage, is detected available for active somatic cell, has substantially
Application value.
2nd, the diphenylamines thiophene terpyridyl that the present invention synthesizes single-minded can develop mitochondria, i.e., prepared by the present invention
Compound be a kind of new mitochondrial dye (Fig. 3).Compared with common business mitochondrial dye, have at low concentrations more
High brightness (Fig. 4)
3rd, compound prepared by the present invention has big effective pair in red light district compared with common business mitochondrial dye
Photon absorption cross sections (Fig. 5).
4th, the raw material of compound is easy to get in the present invention, synthesis condition is gentle, yield is high, preparation method is simple and direct.
4th, illustrate
Fig. 1 is the crystal structure schematic diagram (hydrogen atom is deleted) of compound, show the compound be that there is not been reported and
The clear and definite novel substance of structure.
Fig. 2 is the MTT toxotest figures of compound, shows that the toxicity of compound is small, has good biocompatibility.
Fig. 3 is that compound (red) is imaged with commercial fuel (cyan) cell developing common location.Show that compound is contaminated with business
There is the coincidence (Rr=0.9721) of height, i.e. compound on intracellular mitochondria has specific recognition ability.
Fig. 4 is dyeing (scale=10 micron) of the compound under 1-10nM extremely low concentrations to living cells HepG2 mitochondrias,
Show the photostability that the dyestuff has had.
Fig. 5 is effective two photon absorption cross section of compound, shows that the compound has big effective double light in red light district
Sub- absorption cross-section (being twice of document report).
5th, embodiment
1st, the synthesis of diphenylamines thiophenecarboxaldehyde
The DMSO that 100mL is removed water through molecular sieve drying is added into 250mL there-necked flasks, nitrogen protection, stirring is after ten minutes
0.45g (2.3mmol) phenanthroline is added, continues to add 0.46g (2.4mmol) cuprous iodide after stirring 30min, continues to stir
5.00g (36mmol) Anhydrous potassium carbonate is added after 20min, 2.83g (11mmol) double ethoxy diphenyls are added after continuing 20min
Amine, 1.90g (10mmol) bromothiophenes formaldehyde, 0.1g 18-C-6 and 0.2mL Aliquat-336, continue to stir 10min, heating
Reacted 2 days to 95 DEG C；It is cooled to room temperature, filters after reaction, filtrate is poured slowly into the 1000mL large beakers of the water containing 800mL
It is stirred at room temperature 1 day, solution is in Dark grey and has more solid to separate out；Decompression filters, and obtains brown filter residue, column chromatography purifying
(VPetroleum ether/VEthyl acetate=30:1) bright yellow solid --- double oxethyl diphenylamine thiophenecarboxaldehydes are obtained.
M.p.=101 DEG C.1H NMR:(400MHz,d-chloroform),δ(ppm):1.42(t,6H),4.04(q,
4H),6.17(d,1H),6.88(d,4H),7.22(d,4H),7.41(d,1H),9.53(s,1H).13C NMR(150MHz,d6-
acetone):δ(ppm):14.81,63.77,109.09,115.54,127.17,127.99,128.55,138.71,157.39,
166.42,180.95.IR(KBr,cm-1):3058(w),2976(m),2931(w),2895(w),2790(w),1627(s),
1508(s),1443(vs),1420(m),1392(m),1353(m),1244(s),1175(m),1054(m),824(m)
.MALDI-TOF:m/z,cal:367.12,found:367.05[M+].
2nd, diphenylamines thiophene terpyridyl
The double oxethyl diphenylamine thiophenecarboxaldehydes of 3.67g (10mmol), 2.70g are sequentially added into 80mL ethanol solutions
(22mmol) 4- acetylpyridines and 2.90g (50mmol) KOH, the ammonia of 62mL25wt% is added after reacting at room temperature 1h in three batches
Water, 85 DEG C are stirred reaction 4h, are cooled to room temperature after reaction, and decompression filters, and filter residue is washed with isopropanol, and hexichol is obtained after dry
Amine thiophene terpyridyl.
M.p.=157 DEG C of1H NMR(d6- DMSO, 400MHz, ppm) δ=9.43 (d, 2H), 8.66 (d, 2H), 8.61 (s,
2H),8.04(s,2H),7.91(d,1H),7.54(dd,2H),7.19(d,4H),6.96(d,4H),6.23(d,1H),4.03
(q,4H),1.33(t,6H).13C NMR(d6- DMSO, 101MHz, ppm) δ=155.9,154.2,149.9,148.0,139.8,
134.4,133.8,126.0,123.5,115.4,114.0,63.2,14.7.IR(KBr,cm-1):3055(w),3037(w),
2979(m),2930(w),2898(w),2870(w),1601(m),1545(m),1504(s),1469(s),1471(m),1239
(s),1044(w),530(w).Anal.Calcd.for C35H30N4O2S(482.60):C,75.15；H,4.59；N, 11.61%
.Found:C,75.85；H,4.10；N, 11.73%.MALDI-TOF:m/z,cal:570.21,found:570.56[M+]。
Claims (2)
1. a kind of thiophene terpyridyl compounds two-photon absorbing material, it is characterised in that its structural formula is：
2. a kind of preparation method of the thiophene terpyridyl compounds two-photon absorbing material described in claim 1, its feature exist
In including the following steps：
(1) synthesis of diphenylamines thiophenecarboxaldehyde
The DMSO of dry water removal, nitrogen protection are added into 250mL there-necked flasks, stirring adds the adjacent luxuriant and rich with fragrance hello of 2.3mmol after ten minutes
Quinoline, continues to add 2.4mmol cuprous iodides after stirring 30min, continues to add 36mmol Anhydrous potassium carbonates after stirring 20min, after
11mmol double oxethyl diphenylamine, 10mmol bromothiophenes formaldehyde, 0.1g 18-C-6 and 0.2mL are added after continuous 20min
Aliquat-336, continues to stir 10min, is heated to 95 DEG C and reacts 2 days；It is cooled to room temperature, filters after reaction, filtrate is delayed
Slow pour into water containing 800mL is stirred at room temperature 1 day, and solution is in Dark grey and has solid precipitation；Decompression filters, and obtains brown filter residue,
Column chromatography purifies to obtain the as double oxethyl diphenylamine thiophenecarboxaldehydes of bright yellow solid；
(2) diphenylamines thiophene terpyridyl
The double oxethyl diphenylamine thiophenecarboxaldehydes of 10mmol, 22mmol 4- acetylpyridines are sequentially added into 80mL ethanol solutions
And 50mmol KOH, the ammonium hydroxide of addition 62mL 25wt% after 1h is reacted at room temperature, 4h is reacted in 85 DEG C of stirrings, cold after reaction
But filtered to room temperature, decompression, filter residue is washed with isopropanol, and diphenylamines thiophene terpyridyl is obtained after dry；The ammonia of 62mL 25wt%
Three batch additions of the moisture into equivalent.
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