CN106699786A - 一种季铵盐型水溶性氮杂Aza‑BODIPY及合成方法 - Google Patents
一种季铵盐型水溶性氮杂Aza‑BODIPY及合成方法 Download PDFInfo
- Publication number
- CN106699786A CN106699786A CN201611169559.2A CN201611169559A CN106699786A CN 106699786 A CN106699786 A CN 106699786A CN 201611169559 A CN201611169559 A CN 201611169559A CN 106699786 A CN106699786 A CN 106699786A
- Authority
- CN
- China
- Prior art keywords
- bodipy
- aza
- reaction
- mol ratio
- bis
- 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.)
- Granted
Links
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 title abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title abstract description 5
- OVTCUIZCVUGJHS-UHFFFAOYSA-N dipyrrin Chemical compound C=1C=CNC=1C=C1C=CC=N1 OVTCUIZCVUGJHS-UHFFFAOYSA-N 0.000 title abstract 2
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000003747 Grignard reaction Methods 0.000 claims abstract description 5
- 239000000543 intermediate Substances 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 25
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 150000003233 pyrroles Chemical class 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 8
- 235000005513 chalcones Nutrition 0.000 claims description 8
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 claims description 8
- RSHBAGGASAJQCH-UHFFFAOYSA-N 1-iodo-3-methoxybenzene Chemical class COC1=CC=CC(I)=C1 RSHBAGGASAJQCH-UHFFFAOYSA-N 0.000 claims description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 6
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 5
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- FKZSPBKGUNSVCV-UHFFFAOYSA-N 2-dodecoxybenzaldehyde Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1C=O FKZSPBKGUNSVCV-UHFFFAOYSA-N 0.000 claims description 2
- CYMHIEKFNUNIBB-UHFFFAOYSA-N N1C=CC=CC=C1.[B] Chemical compound N1C=CC=CC=C1.[B] CYMHIEKFNUNIBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000006396 nitration reaction Methods 0.000 abstract description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- -1 aldehyde ketone Chemical class 0.000 abstract description 2
- 238000005956 quaternization reaction Methods 0.000 abstract description 2
- ULUNQYODBKLBOE-UHFFFAOYSA-N 2-(1h-pyrrol-2-yl)-1h-pyrrole Chemical compound C1=CNC(C=2NC=CC=2)=C1 ULUNQYODBKLBOE-UHFFFAOYSA-N 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 50
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 210000003739 neck Anatomy 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 230000009102 absorption Effects 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- NHJRXMJGDMOERY-UHFFFAOYSA-N 2,4-dimethylpyrrole Chemical compound CC1=CN=C(C)[CH]1 NHJRXMJGDMOERY-UHFFFAOYSA-N 0.000 description 1
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 150000001538 azepines Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ILBIXZPOMJFOJP-UHFFFAOYSA-N n,n-dimethylprop-2-yn-1-amine Chemical compound CN(C)CC#C ILBIXZPOMJFOJP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 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
- C09B57/00—Other synthetic dyes of known constitution
-
- 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
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
- C09K2211/1085—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with other heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
本发明涉及一种季铵盐型水溶性氮杂Aza‑BODIPY及制备方法;通过分子改性,进过醛酮缩合反应、硝化反应、并环反应、格氏反应,最后经过季铵化反应等多步反应,开发一种季铵盐型水溶性Aza‑BODIPY,命名为4,4‑二‑(3‑三甲基碘化铵‑1‑丙炔)‑1,7‑二(4‑十二烷氧基苯基)‑3,5‑二(2‑二甲氧基‑4‑碘苯)‑氮杂硼二吡咯。该化合物不单具有良好的水溶性,而且分子具有活泼的碘原子,具有广阔的分子修饰前景。该种Aza‑BODIPY的最大紫外吸收峰接近近红外区域,并且具有很好的水溶性。所以相比于一些其他普通Aza‑BODIPY,在近红外材料应用等领域具有更广阔地应用。
Description
技术领域
本发明涉及一种季铵盐型水溶性氮杂Aza-BODIPY及制备方法。
背景技术
近些年,氟硼二吡咯甲川类荧光染料(BODIPY),由于其优异的光谱、应用性质而被广泛研究[Chem Soc Rev,2013,42,77-88]。但是由于BODIPY自身结构的限制,例如普通BODIPY的水溶性差,吸收峰可见光范围附近,所以其应用范围也受到很大的制约[Chemistry,2014,20,12933-12944]。为了改良BODIPY的性质,很多新型的BODIPY也被报道出了很多。由于近红外材料在基本有机化工、精细化工、生命科学、制药、医学临床、农业等多方面对于科研和国家国防水平的重要作用。所谓近红外材料是能与近红外光(780~2526nm)相互作用,或在其他条件如光、温度、电场、自身状态及化学反应等作用后,发出近红外光的一类物质[化工新型材料,2016,04,41-43]。
相对于普通BODIPY,氮杂BODIPY(Aza-BODIPY)在近红外区域的强烈的吸收。所以在一些近红外材料应用的诸多领域,Aza-BODIPY具有更好的应用前。所以近些年,Aza-BODIPY的研究也颇为广泛,各种新结构、新用途的Aza-BODIPY也陆续被报道。Donal F.O’Shea在2004年报道了吸收峰在650and 700nm,摩尔消光系数在75000to 85000M-1cm-1的Aza-BODIPY。该物质作为光敏剂应用于临床医学的Aza-BODIPY的结构、光谱研究、以及与海拉细胞相互作用的研究,并且取得了很明显的效果[Journal of the American ChemicalSociety,2004,126,10619-10631]。HorsBoris Le Guennic课题组在2011年,报道了最大吸收峰在650-827nm的Aza-BODIPY。通过对已合成出来的Aza-BODIPY的研究与计算模拟,他们提出了另外一些近红外吸收氮杂BODIPY的结构预测,这为其它氮杂BODIPY的设计和制备提供了很有价值的参考[Phys Chem Chem Phys,2012,14,157-164];Klaus Mullen课题组2014年合成了一类具有二聚型Aza-BODIPY内核化合物,并研究了该物质在二氯甲烷中的光谱性质[Chem Commun(Camb),2014,50,11540-11542]。
虽然这些Aza-BODIPY具有某些应用和研究价值,但是通过其结构可以看出,普通Aza-BODIPY没有亲水基团,所以其水溶性不好。这就导致了普通Aza-BODIPY不能应用在水环境中。有很多的学者也发现这一问题,并提出了很多对普通Aza-BODIPY的改性方法。例如Kevin Burgess在2015年报道了一种通过对Aza-BODIPY引入磺酸基和酰胺基取代基,到达增强Aza-BODIPY水溶性的目的[Chem Commun(Camb),2015,51,10664-10667]。该方法虽然可以提高Aza-BODIPY在水中的溶解性,但是合成步骤较为繁琐。
发明内容
本发明开发出一种季铵盐型水溶性Aza-BODIPY,该方法通过对Aza-BODIPY进行季铵化,大大提高了Aza-BODIPY的溶解性,并且其制备过程简单,更易于工业化生产。通过分子改性,进过醛酮缩合反应、硝化反应、并环反应、格氏反应,最后经过季铵化反应等多步反应,开发一种季铵盐型水溶性Aza-BODIPY。该化合物不单具有良好的水溶性,而且分子具有活泼的碘原子,具有广阔的分子修饰前景。该种Aza-BODIPY的最大紫外吸收峰接近近红外区域,并且具有很好的水溶性。所以相比于一些其他普通Aza-BODIPY,该种Aza-BODIPY在近红外材料应用等领域具有更广阔地应用。
本发明的技术方案如下:
一种季铵盐型水溶性Aza-BODIPY,其特征是结构如下:
采用IUPAC有机物命名名称为:4,4-二-(3-三甲基碘化铵-1-丙炔)-1,7-二(4-十二烷氧基苯基)-3,5-二(2-二甲氧基-4-碘苯)-氮杂硼二吡咯。
英文为:4,4-bis-(3-trimethylaminoiodine-1-propynyl)-1,7-bis(4-dodecyloxyphenyl)-3,5-bis(2-methoxyl-4-I-phenyl)-8-N-4-bora-3a,4a-diaza-s-indacene。
本发明的季铵盐型水溶性Aza-BODIPY;其1H NMR(400MHz,CDCl3)图谱为:8.11(d,J=8.1Hz,2H),8.02(d,J=8.7Hz,4H),7.39(d,J=8.1Hz,2H),7.22(s,2H),6.98(d,J=8.7Hz,4H),6.80(s,2H),4.05(t,J=6.5Hz,4H),3.78(s,6H),2.93(s,4H),2.04(s,12H),1.86(dd,J=14.1,7.1Hz,4H),1.55–1.47(m,4H),1.33(d,J=28.5Hz,32H),0.90(t,J=6.6Hz,6H)。13C NMR(101MHz,CDCl3),如图4所示,160.00(s),158.02(s),142.97(s),133.79(s),130.60(s),129.10(s),120.08(s),114.55(s),68.16(s),56.04(s),48.66(s),43.82(s),31.94(s),29.80–29.07(m),26.09(s),22.71(s),14.14(s)。
本发明通过有目的分子设计,利用醛酮缩合反应、硝化反应、并环反应、格氏反应,最后经过季铵化反应制备一种季铵盐型水溶性Aza-BODIPY。
本发明的季铵盐型水溶性Aza-BODIPY的制备方法,其步骤如下:
1)在二硫化碳作溶剂,无水三氯化铝催化下,控制3-碘苯甲醚和三氯化铝的摩尔比为1:(1~1.18),控制3-碘苯甲醚和乙酰氯的摩尔比为1:(0.9~1),室温反应制备中间体A;
2)将A和对十二烷氧基苯甲醛按照摩尔比1:(1~1.11),溶解在乙醇,冰浴后,滴加氢氧化钾水溶液;滴毕,室温搅拌过夜;反应毕,过滤得到查尔酮B;
3)在二乙胺和甲醇的体系中,控制化合物B:硝基甲烷的摩尔比为1:(3~5),进行回流,反应毕后处理得到化合物C;
4)控制C与乙酸铵的摩尔比在1:(20~35),回流反应,制备中间体D;
5)氮气保护的条件下,四氢呋喃作为溶剂,N,N-二异丙基乙胺作为碱,控制化合物D与三氟化硼***的摩尔比为1:(5~8),室温下;通过一锅法反应制备Aza-BODIPY中间体E;
6)Aza-BODIPY中间体E通过格氏反应,制备Aza-BODIPY中间体F:控制Aza-BODIPY与格氏试剂的摩尔比在1:(7~10),温度控制在58~62℃;
7)Aza-BODIPY中间体F进行季铵化得到水溶性季铵盐型Aza-BODIPY:以***为溶剂,控制Aza-BODIPY F与碘甲烷的摩尔比为1:(6~12)。
本发明的效果如下:
1)季铵盐型水溶性Aza-BODIPY的合成方法简单,易于操作,最后季铵化步骤收率84.23%较高;
2)该方法合成的季铵盐型Aza-BODIPY,可溶于水,同时在水和乙醇复配体系中溶解度更高,可达10-4M。对于研究Aza-BODIPY在细胞成像、生物活体染色等生物性能方面具有巨大的优势;
3)该方法合成的季铵盐型Aza-BODIPY在水中的最大吸收峰为653nm,接近近红外,在一些例如显示屏幕、高倍像素成像器件等近红外材料的研究具有很好前景。
本发明的制备方法收率比较高;过程简单,便于操作;最后的季铵化不需要过柱子,便于工业化生产;反应条件比较温和,易于进行;使用范围比较广泛;所带活泼原子,也便于后期分子改性。
附图说明
图1 Aza-BODIPY中间体E1的1H核磁谱图;
图2 Aza-BODIPY中间体E1的13C核磁谱图;
图3 Aza-BODIPY中间体F1的1H核磁谱图;
图4 Aza-BODIPY中间体F1的13C核磁谱图;
图5 Aza-BODIPY 1的1H核磁谱图;
图6 Aza-BODIPY 1的13C核磁谱图;
图7 Aza-BODIPY在水和乙醇中的紫外吸收光谱谱图
具体实施方式
具体说明如下:
一种季铵盐型水溶性Aza-BODIPY,合成路线如下:
I:CS2,AlCl3,CH3COOCl,rt;II:CH3CH2OH,KOH,rt,16h;III:CH3OH,(CH3CH2)2NH,CH3NO2,回流20h;IV:NH4OOCCH3,C4H9OH,回流56h;V:CF3COOH,2,4-Dimethylpyrrole,DCM,rt,rt 30min;DDQ,rt,30min;DIEA,BF3Et2O,rt,2h;VI:EtMgBr,THF,1-dimethylamino-2-propyne,55~60℃,0.5h;VII:Et2O,CH3I,rt,20h.
本发明的一种季铵盐型水溶性氮杂BODIPY的制备方法,其特征是步骤如下:
实施例1
步骤(1.1)
2-甲氧基-4-碘苯乙酮(中间体A1)的制备:在将3-碘苯甲醚(5.00g,21.40mmol,1eq)溶于10mL二硫化碳中,冰浴。向体系中,缓慢分批加入无水三氯化铝(3.33g,25.25mmol,1.18eq),加入乙酰氯(1.69g,21.40mmol,1eq),室温反应,反应毕,浓缩过柱得到3.14g中间体A1,收率53.13%;
步骤(1.2)
3-(4-十二烷氧基苯基)-1-(4-碘-2-甲氧基苯基)-2-丙烯-1-酮(中间体B1)的合成:原料2-甲氧基-4-碘苯乙酮(1.00g,3.60mmol,1eq),4-十二烷氧基苯甲醛(1.16g,4.00mmol,1.11eq),溶解在乙醇20ml。冰浴后,滴加氢氧化钾(2.80g)水溶液(20ml,2.5M),滴毕室温搅拌过夜。过滤重得到1.85g类白色结晶状查尔酮B1,收率92.96%。
步骤(1.3)
3-(4-十二烷氧基苯基)-1-(4-碘-2-甲氧基苯基)-4-硝基丁基-1-酮(中间体C1)的制备:将中间体B1(1.70g,3.10mmol,1eq),二乙胺(1.14g,15.50mmol,5eq)硝基甲烷(0.95g,15.50mmol,5eq)溶于甲醇150ml中,回流20h,冷却至0℃。加入盐酸100ml,2.5M,淬灭反应。过滤,用甲醇和戊烷洗,甲醇重结晶后得到1.80g白色固体硝化查尔酮C1,收率95.24%。
步骤(1.4)
1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂二吡咯甲川(中间体D1)的制备:C1(1.60g,2.63mmol,1eq),乙酸铵(7.09g,92.05mmol,35eq),氮保,丁醇(50ml,bp117℃)加热回流56h,降温,浓缩后,加水100mL用100mL×3萃取,浓缩,得到中间体D1蓝色固体1.32g,收率89.24%。
步骤(1.5)
4,4-二氟-1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂氟硼二吡咯的制备(Aza-BODIPY中间体E1):将D1(1.30g,1.15mmol,1eq)加入到两颈瓶中抽真空,N2保护,置换三次。加入新蒸的二氯甲烷(20mL),加入4mL的DIEA和46.80%的三氟化硼***(2.79g,9.20mmol,8eq),室温反应2h。30mL×3水洗,30mL×1盐水洗,有机层经无水硫酸镁干燥,过滤,浓缩后,通过柱层析(二氯甲烷/正己烷=1:1)提纯,得到固体E1,(0.85g,Y=55.55%)。1H NMR(400MHz,CDCl3),如图1所示,8.04(d,J=8.7Hz,4H),7.59(d,J=8.2Hz,2H),7.39(d,J=8.2Hz,2H),7.30(s,2H),6.99(d,J=8.7Hz,4H),6.89(s,2H),4.06(t,J=6.5Hz,4H),3.84(s,6H),1.91–1.81(m,4H),1.57–1.46(m,4H),1.34(d,J=28.2Hz,32H),0.91(t,J=6.7Hz,6H)。13C NMR(101MHz,CDCl3),如图2所示,160.45(s),158.08(s),155.03(s),144.94(s),142.91(s),132.68(s),130.86(s),129.91(s),125.25(s),120.92(s),120.68(s),119.40(s),114.68(s),97.51(s),68.21(s),56.17(s),31.95(s),29.89–29.14(m),26.09(s),22.72(s),14.15(s)。
步骤(1.6)
4,4-二-(3-二甲氨基-1-丙炔)-1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂氟硼二吡咯(Aza-BODIPY中间体F1)的制备:将两颈瓶中抽真空,N2保护,置换三次。加入新蒸的四氢呋喃(THF:3mL),加入N,N-二甲基丙炔胺(0.28g,3.32mmol,7.58eq),1M的乙基溴化镁的THF溶液(3.06mL,3.06mmol,7eq),此时会有大量气泡(乙烷)生成。55℃反应2h,制得格氏试剂溶液。将格氏试剂加入到已经氮保好的氮杂BODIPY中间体E1(0.52g,0.44mmol,1eq)的THF(2mL)溶液中,升温至58℃,反应0.5h。TLC检测反应毕,浓缩后,加入30mL水和50mL二氯甲烷,30mL×3的二氯甲烷萃取,合并有机层后,使用无水硫酸镁干燥有机层,再经过过滤,浓缩后,使用硅胶柱层析方法提纯(甲醇/二氯甲烷=1:3),得到蓝色固体中间体F1(0.49g,Y=85.68%)。1H NMR(400MHz,CDCl3),如图3所示,8.11(d,J=8.1Hz,2H),8.02(d,J=8.7Hz,4H),7.39(d,J=8.1Hz,2H),7.22(s,2H),6.98(d,J=8.7Hz,4H),6.80(s,2H),4.05(t,J=6.5Hz,4H),3.78(s,6H),2.93(s,4H),2.04(s,12H),1.86(dd,J=14.1,7.1Hz,4H),1.55–1.47(m,4H),1.33(d,J=28.5Hz,32H),0.90(t,J=6.6Hz,6H)。13C NMR(101MHz,CDCl3),如图4所示,160.00(s),158.02(s),142.97(s),133.79(s),130.60(s),129.10(s),120.08(s),114.55(s),68.16(s),56.04(s),48.66(s),43.82(s),31.94(s),29.80–29.07(m),26.09(s),22.71(s),14.14(s)。
步骤(1.7)
4,4-二-(3-三甲氨基-1-丙炔)-1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂氟硼二吡咯染料(Aza-BODIPY 1)的制备:将F1(0.15g,0.12mmol,1eq)加入***(30mL)中,加入碘甲烷(0.10g,0.72mmol,6eq),避光室温反应20h,TLC检测反应毕,使用微量过滤器加上有机滤膜过滤。滤饼再使用二氯甲烷和***进行重结晶得到蓝色固体氮杂Aza-BODIPY 1(180.02mg,Y=84.23%)。1H NMR(400MHz,CDCl3),如图5所示,8.02(d,J=8.2Hz,4H),7.74(s,2H),7.58(s,4H),6.98(d,J=8.3Hz,4H),6.73(s,2H),4.48(s,4H),4.04(s,4H),3.92(d,J=25.0Hz,6H),3.29(s,18H),1.84(s,4H),1.46(d,J=28.0Hz,4H),1.29(s,32H),0.90(t,J=6.4Hz,6H)。13C NMR(101MHz,CDCl3),如图6所示,160.99(s),158.62(s),156.57(s),142.55(d,J=11.5Hz),132.67(s),131.31(s),129.13(s),124.76(s),121.49(d,J=5.9Hz),120.73(s),115.69(s),99.16(s),85.86(s),68.45(s),57.21(s),56.74(s),52.21(s),40.88–40.51(m),40.43(s),40.27(s),40.10(s),39.93(s),39.77(s),31.99(s),29.70(dd,J=4.9,3.1Hz),29.38(t,J=9.8Hz),26.18(s),22.78(s),14.60(s).该Aza-BODIPY在水和乙醇中的紫外吸收光谱谱图如图7所示,在水中的最大吸收峰为653nm,在乙醇中最大吸收峰为610nm。
实施例2
步骤(2.1)
2-甲氧基-4-碘苯乙酮(中间体A2)的制备:在将3-碘苯甲醚(5.00g,21.40mmol,1eq)溶于10mL二硫化碳中,冰浴。向体系中,缓慢分批加入无水三氯化铝(2.82g,21.40mmol,1eq),加入乙酰氯(1.69g,21.40mmol,0.9eq),室温反应,反应毕,浓缩过柱得到2.85g中间体A1,收率48.21%;
步骤(2.2)
3-(4-十二烷氧基苯基)-1-(4-碘-2-甲氧基苯基)-2-丙烯-1-酮(中间体B2)的合成:原料2-甲氧基-4-碘苯乙酮(1.00g,3.60mmol,1eq),4-十二烷氧基苯甲醛(1.04g,3.60mmol,1eq),溶解在乙醇20ml。冰浴后,滴加氢氧化钾(2.80g)水溶液(20ml,2.5M),滴毕室温搅拌过夜。过滤重得到1.71g类白色结晶状查尔酮B2,收率86.75%。
步骤(2.3)
3-(4-十二烷氧基苯基)-1-(4-碘-2-甲氧基苯基)-4-硝基丁基-1-酮(中间体C2)的制备:将中间体B2(1.70g,3.10mmol,1eq),二乙胺(1.14g,15.50mmol,5eq)硝基甲烷(0.57g,9.30mmol,3eq)溶于甲醇150ml中,回流20h,冷却至0℃。加入盐酸100ml,2.5M,淬灭反应。过滤,用甲醇和戊烷洗,甲醇重结晶后得到1.70g白色固体硝化查尔酮C2,收率90.10%。
步骤(2.4)
1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂二吡咯甲川(中间体D2)的制备:C2(1.60g,2.63mmol,1eq),乙酸铵(4.05g,52.60mmol,20eq),氮保,丁醇(50ml,bp117℃)加热回流56h,降温,浓缩后,加水100mL用100mL×3萃取,浓缩,得到中间体D2蓝色固体1.12g,收率75.12%。
步骤(2.5)
4,4-二氟-1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂氟硼二吡咯的制备(BODIPY中间体E2):将D2(1.30g,1.15mmol,1eq)加入到两颈瓶中抽真空,N2保护,置换三次。加入新蒸的二氯甲烷(20mL),加入4mL的DIEA和46.80%的三氟化硼***(1.74g,5.75mmol,5eq),室温反应2h。30mL×3水洗,30mL×1盐水洗,有机层经无水硫酸镁干燥,过滤,浓缩后,通过柱层析(二氯甲烷/正己烷=1:1)提纯,得到固体E2,(0.61g,Y=45.18%)。
步骤(2.6)
4,4-二-(3-二甲氨基-1-丙炔)-1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂氟硼二吡咯(氮杂BODIPY中间体F2)的制备:将两颈瓶中抽真空,N2保护,置换三次。加入新蒸的四氢呋喃(THF:3mL),加入N,N-二甲基丙炔胺(0.41g,4.82mmol,11eq),1M的乙基溴化镁的THF溶液(4.40mL,4.40mmol,10eq),此时会有大量气泡(乙烷)生成。55℃反应2h,制得格氏试剂溶液。将格氏试剂加入到已经氮保好的氮杂BODIPY中间体E2(0.52g,0.44mmol,1eq)的THF(2mL)溶液中,升温至60℃,反应0.5h。TLC检测反应毕,浓缩后,加入30mL水和50mL二氯甲烷,30mL×3的二氯甲烷萃取,合并有机层后,使用无水硫酸镁干燥有机层,再经过过滤,浓缩后,使用硅胶柱层析方法提纯(甲醇/二氯甲烷=1:3),得到蓝色固体中间体F2(0.50g,Y=87.21%)。
步骤(2.7)
4,4-二-(3-三甲氨基-1-丙炔)-1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂氟硼二吡咯染料(Aza-BODIPY 2)的制备:将F2(0.15g,0.12mmol,1eq)加入***(30mL)中,加入碘甲烷(0.20g,1.44mmol,12eq),避光室温反应20h,TLC检测反应毕,使用微量过滤器加上有机滤膜过滤。滤饼再使用二氯甲烷和***进行重结晶得到蓝色固体氮杂Aza-BODIPY 2(174.27mg,Y=81.54%)。
实施例3
步骤(3.1)
2-甲氧基-4-碘苯乙酮(中间体A3)的制备:在将3-碘苯甲醚(5.00g,21.40mmol,1eq)溶于10mL二硫化碳中,冰浴。向体系中,缓慢分批加入无水三氯化铝(3.11g,23.54mmol,1.10eq),加入乙酰氯(1.59g,20.33mmol,0.95eq),室温反应,反应毕,浓缩过柱得到2.51g中间体A3,收率42.50%;
步骤(3.2)
3-(4-十二烷氧基苯基)-1-(4-碘-2-甲氧基苯基)-2-丙烯-1-酮(中间体B3)的合成:原料2-甲氧基-4-碘苯乙酮(1.00g,3.60mmol,1eq),4-十二烷氧基苯甲醛(1.10g,3.78mmol,1.05eq),溶解在乙醇20ml。冰浴后,滴加氢氧化钾(2.80g)水溶液(20ml,2.5M),滴毕室温搅拌过夜。过滤重得到1.62g类白色结晶状查尔酮B3,收率82.11%。
步骤(3.3)
3-(4-十二烷氧基苯基)-1-(4-碘-2-甲氧基苯基)-4-硝基丁基-1-酮(中间体C3)的制备:将中间体B3(1.70g,3.10mmol,1eq),二乙胺(1.14g,15.50mmol,5eq)硝基甲烷(0.76g,12.40mmol,4eq)溶于甲醇150ml中,回流20h,冷却至0℃。加入盐酸100ml,2.5M,淬灭反应。过滤,用甲醇和戊烷洗,甲醇重结晶后得到1.66g白色固体硝化查尔酮C3,收率88.15%。
步骤(3.4)
1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂二吡咯甲川(中间体D3)的制备:C3(1.60g,2.63mmol,1eq),乙酸铵(6.08g,78.90mmol,30eq),氮保,丁醇(50ml,bp117℃)加热回流56h,降温,浓缩后,加水100mL用100mL×3萃取,浓缩,得到中间体D3蓝色固体1.15g,收率77.55%。
步骤(3.5)
4,4-二氟-1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂氟硼二吡咯的制备(BODIPY中间体E3):将D3(1.30g,1.15mmol,1eq)加入到两颈瓶中抽真空,N2保护,置换三次。加入新蒸的二氯甲烷(20mL),加入4mL的DIEA和46.80%的三氟化硼***(2.09g,6.90mmol,6eq),室温反应2h。30mL×3水洗,30mL×1盐水洗,有机层经无水硫酸镁干燥,过滤,浓缩后,通过柱层析(二氯甲烷/正己烷=1:1)提纯,得到固体E3,(0.66g,Y=48.55%)。
步骤(3.6)
4,4-二-(3-二甲氨基-1-丙炔)-1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂氟硼二吡咯(氮杂BODIPY中间体F3)的制备:将两颈瓶中抽真空,N2保护,置换三次。加入新蒸的四氢呋喃(THF:3mL),加入N,N-二甲基丙炔胺(0.33g,3.86mmol,8.8eq),1M的乙基溴化镁的THF溶液(3.52mL,3.52mmol,8eq),此时会有大量气泡(乙烷)生成。55℃反应2h,制得格氏试剂溶液。将格氏试剂加入到已经氮保好的氮杂BODIPY中间体E3(0.52g,0.44mmol,1eq)的THF(2mL)溶液中,升温至60℃,反应0.5h。TLC检测反应毕,浓缩后,加入30mL水和50mL二氯甲烷,30mL×3的二氯甲烷萃取,合并有机层后,使用无水硫酸镁干燥有机层,再经过过滤,浓缩后,使用硅胶柱层析方法提纯(甲醇/二氯甲烷=1:3),得到蓝色固体中间体F3(0.48g,Y=84.27%)。
步骤(3.7)
4,4-二-(3-三甲氨基-1-丙炔)-1,7-二(4-十二烷氧基苯基)-3,5-二(2-甲氧基-4-碘苯基)-8-氮杂氟硼二吡咯染料(Aza-BODIPY 3)的制备:将F3(0.15g,0.12mmol,1eq)加入***(30mL)中,加入碘甲烷(0.17g,1.20mmol,10eq),避光室温反应20h,TLC检测反应毕,使用微量过滤器加上有机滤膜过滤。滤饼再使用二氯甲烷和***进行重结晶得到蓝色固体氮杂Aza-BODIPY 3(177.34mg,Y=82.94%)。
Claims (4)
1.一种季铵盐型水溶性Aza-BODIPY,其特征是结构如下:
2.如权利要求1所述是的季铵盐型水溶性Aza-BODIPY;其特征是IUPAC有机物命名名称为:4,4-二-(3-三甲基碘化铵-1-丙炔)-1,7-二(4-十二烷氧基苯基)-3,5-二(2-二甲氧基-4-碘苯)-氮杂硼二吡咯。
3.如权利要求1所述是的季铵盐型水溶性Aza-BODIPY;其特征是1H NMR(400MHz,CDCl3)图谱为:8.11(d,J=8.1Hz,2H),8.02(d,J=8.7Hz,4H),7.39(d,J=8.1Hz,2H),7.22(s,2H),6.98(d,J=8.7Hz,4H),6.80(s,2H),4.05(t,J=6.5Hz,4H),3.78(s,6H),2.93(s,4H),2.04(s,12H),1.86(dd,J=14.1,7.1Hz,4H),1.55–1.47(m,4H),1.33(d,J=28.5Hz,32H),0.90(t,J=6.6Hz,6H);其13C NMR(101MHz,CDCl3)图谱为:160.00(s),158.02(s),142.97(s),133.79(s),130.60(s),129.10(s),120.08(s),114.55(s),68.16(s),56.04(s),48.66(s),43.82(s),31.94(s),29.80–29.07(m),26.09(s),22.71(s),14.14(s)。
4.权利要求1的季铵盐型水溶性Aza-BODIPY的制备方法,其特征是步骤如下:
1)在二硫化碳作溶剂,无水三氯化铝催化下,控制3-碘苯甲醚和三氯化铝的摩尔比为1:(1~1.18),控制3-碘苯甲醚和乙酰氯的摩尔比为1:(0.9~1),室温反应制备中间体A;
2)将A和对十二烷氧基苯甲醛按照摩尔比1:(1~1.11),溶解在乙醇,冰浴后,滴加氢氧化钾水溶液;滴毕,室温搅拌过夜;反应毕,过滤得到查尔酮B;
3)在二乙胺和甲醇的体系中,控制化合物B:硝基甲烷的摩尔比为1:(3~5),进行回流,反应毕后处理得到化合物C;
4)控制C与乙酸铵的摩尔比在1:(20~35),回流反应,制备中间体D;
5)氮气保护的条件下,四氢呋喃作为溶剂,N,N-二异丙基乙胺作为碱,控制化合物D与三氟化硼***的摩尔比为1:(5~8),室温下;通过一锅法反应制备Aza-BODIPY中间体E;
6)Aza-BODIPY中间体E通过格氏反应,制备Aza-BODIPY中间体F:控制Aza-BODIPY与格氏试剂的摩尔比在1:(7~10),温度控制在58~62℃;
7)Aza-BODIPY中间体F进行季铵化得到水溶性季铵盐型Aza-BODIPY:以***为溶剂,控制Aza-BODIPY F与碘甲烷的摩尔比为1:(6~12)。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611169559.2A CN106699786B (zh) | 2016-12-16 | 2016-12-16 | 一种季铵盐型水溶性氮杂Aza-BODIPY及合成方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611169559.2A CN106699786B (zh) | 2016-12-16 | 2016-12-16 | 一种季铵盐型水溶性氮杂Aza-BODIPY及合成方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106699786A true CN106699786A (zh) | 2017-05-24 |
CN106699786B CN106699786B (zh) | 2019-04-16 |
Family
ID=58938442
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611169559.2A Expired - Fee Related CN106699786B (zh) | 2016-12-16 | 2016-12-16 | 一种季铵盐型水溶性氮杂Aza-BODIPY及合成方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106699786B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111253296A (zh) * | 2020-02-19 | 2020-06-09 | 天津大学 | 一种过渡金属络合氮杂二吡咯甲川两亲性近红外染料及其制备方法 |
CN114450353A (zh) * | 2019-08-08 | 2022-05-06 | 阿尔卑斯格勒诺布尔大学 | 氮杂氟硼荧型荧光团化合物作为短波红外区造影剂的用途 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010075512A1 (en) * | 2008-12-23 | 2010-07-01 | Michigan Technological University | Polymers with bodipy-based backbone for solar cells |
CN103865289A (zh) * | 2014-02-26 | 2014-06-18 | 天津大学 | 含有亲水基团的氟化硼二吡咯荧光染料及其制备方法 |
CN105566941A (zh) * | 2016-01-05 | 2016-05-11 | 天津大学 | 一类两亲性氮杂氟硼二吡咯荧光染料及其制备方法 |
CN105753892A (zh) * | 2016-03-22 | 2016-07-13 | 天津大学 | 一类具有不同疏水链的水溶性bodipy衍生物及制备方法 |
-
2016
- 2016-12-16 CN CN201611169559.2A patent/CN106699786B/zh not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010075512A1 (en) * | 2008-12-23 | 2010-07-01 | Michigan Technological University | Polymers with bodipy-based backbone for solar cells |
CN103865289A (zh) * | 2014-02-26 | 2014-06-18 | 天津大学 | 含有亲水基团的氟化硼二吡咯荧光染料及其制备方法 |
CN105566941A (zh) * | 2016-01-05 | 2016-05-11 | 天津大学 | 一类两亲性氮杂氟硼二吡咯荧光染料及其制备方法 |
CN105753892A (zh) * | 2016-03-22 | 2016-07-13 | 天津大学 | 一类具有不同疏水链的水溶性bodipy衍生物及制备方法 |
Non-Patent Citations (1)
Title |
---|
陈志坚等: "水溶性氟硼二吡咯类染料的合成及其应用研究进展", 《化工新型材料》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114450353A (zh) * | 2019-08-08 | 2022-05-06 | 阿尔卑斯格勒诺布尔大学 | 氮杂氟硼荧型荧光团化合物作为短波红外区造影剂的用途 |
CN111253296A (zh) * | 2020-02-19 | 2020-06-09 | 天津大学 | 一种过渡金属络合氮杂二吡咯甲川两亲性近红外染料及其制备方法 |
CN111253296B (zh) * | 2020-02-19 | 2023-01-10 | 天津大学 | 一种过渡金属络合氮杂二吡咯甲川两亲性近红外染料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN106699786B (zh) | 2019-04-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109400899B (zh) | 一种铅配位聚合物及其制备方法和应用 | |
CN106543177B (zh) | 聚集诱导发红光材料及其制备方法 | |
CN111995580B (zh) | 四苯乙烯并咪唑环结构的荧光染料及其应用 | |
CN102321109A (zh) | 1,3,5,7-四甲基-8-三苯胺基吡咯甲川-二氟化硼络合物及其制备方法 | |
CN107602600A (zh) | 氨基取代氮杂氟硼二吡咯近红外pH荧光探针及其制法和用途 | |
CN104877674B (zh) | 一种可激发产生白色荧光的水溶液及配制方法 | |
CN108997391B (zh) | 一种三聚茚基bodipy-富勒烯星型化合物的制备方法 | |
CN106699786B (zh) | 一种季铵盐型水溶性氮杂Aza-BODIPY及合成方法 | |
CN110283586B (zh) | 一种近红外荧光染料及其制备方法 | |
CN102702208A (zh) | 一种含溴吲哚[3,2-b]咔唑衍生物及其制备方法 | |
CN105753892A (zh) | 一类具有不同疏水链的水溶性bodipy衍生物及制备方法 | |
CN103923481B (zh) | 一种金刚烷基修饰的近红外方酸染料及其制备和应用 | |
CN112851556B (zh) | 新型聚集诱导发光高尔基体荧光探针及其制备方法与应用 | |
CN102827195B (zh) | 以间苯二甲酸和2-吡啶甲酸为混合配体构筑的稀土有机配位聚合物及其制备方法与应用 | |
CN105985363A (zh) | 一类氟硼类荧光染料的合成及其应用 | |
CN105223171B (zh) | 一种近红外磷光铱配合物的合成及其荧光检测成像应用 | |
CN111574578B (zh) | 具有智能响应多色转变的圆偏振发光材料及其制备方法和应用 | |
CN110066287A (zh) | 一种edot-喹喔啉-edot衍生物及其制备方法与应用 | |
CN102993206A (zh) | 一种一步法合成四苯基卟啉金属配合物的方法 | |
CN105001141A (zh) | 一种氟代苯基吲哚类化合物,其作为红色有机发光材料的应用及其制备方法 | |
CN105837568B (zh) | 一种芴基β‑咔啉类化合物,其作为有机发光材料和聚集诱导荧光增强材料的应用及制备方法 | |
CN115197260B (zh) | 一种具有j聚集效应的炔基偶联双bodipy类近红外荧光染料及其制备方法 | |
CN108558834B (zh) | 一种哒嗪酮基三色荧光发射有机发光材料及其应用 | |
CN103183696A (zh) | 氮杂氟硼二吡咯化合物及其合成方法 | |
CN104387790B (zh) | 一种含噻吩基团的苯并吲哚盐染料及其制备方法和用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190416 Termination date: 20201216 |
|
CF01 | Termination of patent right due to non-payment of annual fee |