CN108178744A - 一类新型双功能化紫精离子型化合物及其制备方法 - Google Patents
一类新型双功能化紫精离子型化合物及其制备方法 Download PDFInfo
- Publication number
- CN108178744A CN108178744A CN201711113738.9A CN201711113738A CN108178744A CN 108178744 A CN108178744 A CN 108178744A CN 201711113738 A CN201711113738 A CN 201711113738A CN 108178744 A CN108178744 A CN 108178744A
- Authority
- CN
- China
- Prior art keywords
- purpurine
- ionic compound
- formula
- preparation
- reaction
- 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.)
- Pending
Links
- -1 purpurine ionic compound Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 7
- BBNQQADTFFCFGB-UHFFFAOYSA-N purpurin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 125000006278 bromobenzyl group Chemical group 0.000 claims abstract description 5
- 239000003361 porogen Substances 0.000 claims abstract description 3
- 239000002861 polymer material Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 15
- 238000006467 substitution reaction Methods 0.000 claims description 10
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012456 homogeneous solution Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 150000008040 ionic compounds Chemical class 0.000 abstract description 9
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- CGDKALWGXBQBHQ-UHFFFAOYSA-N CC=1C(=O)CC(CC1C)(C)C.N#CC#N.N#CC#N Chemical compound CC=1C(=O)CC(CC1C)(C)C.N#CC#N.N#CC#N CGDKALWGXBQBHQ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004799 bromophenyl group Chemical group 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 description 1
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
- CVKOOKPNCVYHNY-UHFFFAOYSA-N 3-(bromomethyl)benzonitrile Chemical class BrCC1=CC=CC(C#N)=C1 CVKOOKPNCVYHNY-UHFFFAOYSA-N 0.000 description 1
- XYPVBKDHERGKJG-UHFFFAOYSA-N 4-(bromomethyl)benzaldehyde Chemical compound BrCC1=CC=C(C=O)C=C1 XYPVBKDHERGKJG-UHFFFAOYSA-N 0.000 description 1
- UMLFTCYAQPPZER-UHFFFAOYSA-N 4-(bromomethyl)benzonitrile Chemical class BrCC1=CC=C(C#N)C=C1 UMLFTCYAQPPZER-UHFFFAOYSA-N 0.000 description 1
- SVENKGKXRLHCTC-UHFFFAOYSA-N B(O)(O)O.BrCC=1C=CC=CC1 Chemical class B(O)(O)O.BrCC=1C=CC=CC1 SVENKGKXRLHCTC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- KWGACYZYFZTYRN-UHFFFAOYSA-N OC(C)(C)C(C)(C)O.B(O)(O)O.BrCC1=CC=CC=C1 Chemical class OC(C)(C)C(C)(C)O.B(O)(O)O.BrCC1=CC=CC=C1 KWGACYZYFZTYRN-UHFFFAOYSA-N 0.000 description 1
- CYMXTKNOROVINH-UHFFFAOYSA-N OC(C)(C)C(C)(C)O.C1(=CC=CC=C1)OB(O)O Chemical compound OC(C)(C)C(C)(C)O.C1(=CC=CC=C1)OB(O)O CYMXTKNOROVINH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
-
- 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
-
- 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
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一类新型双功能化紫精离子型化合物及其制备方法，该类紫精离子型化合物的结构如式Ⅰ和式Ⅱ所示，其中功能基团R1和R2为‑CN、‑Br、‑NO2、‑CHO、‑COOH和‑Bpin。该类双功能化紫精离子型化合物的制备方法以4,4’‑联吡啶和R功能基团取代的溴苄为原料，在溶剂热条件下，通过一步季铵化反应制备出高纯度的紫精基离子型化合物。此外功能化紫精离子型化合物，可以直接用作电致变色材料，还可以作为离子单体制备紫精基多孔离子聚合物材料。
Description
技术领域
本发明涉及紫精离子化合物的制备与应用领域，具体涉及一类新型双功能化紫精离子化合物及制备方法。具体地，本发明通过季铵化反应，一步制备双功能化紫精离子化合物，可以用电致变色材料，还可以作为离子单体合成紫精基多孔离子聚合物。本发明还包括对合成的全新紫精离子化合物的结构描述、命名和表征。
背景技术
紫精(viologen)是1,1'-双取代基-4,4'-联吡啶盐的美称，最早在1932年Michaelis 等人发现1,1'-二甲基-4,4'-联吡啶被还原时由无色变成紫色，于是形象称之为紫精(Adv. Mater.,2001,13,783-793)。紫精结构中具有两个N阳离子中心，在不同的氧化态或者还原态可以提供电子和接受电子，可以发生可逆性的氧化还原反应，并伴随着颜色的变化。紫精的颜色变化完全依赖于1,1’位取代基，因此取代基的功能化修饰，在电致变色材料、电子或能量接受体及聚合型紫精材料等领域受到了广泛的关注(化学进展,2013,25, 46-53)。
目前，关于紫精离子单体的制备方法主要为4,4'-联吡啶和相应的二卤代烷烃为原料通过Menschutkin反应制备(也就是季铵化反应)。除此之外，通过4,4'-联吡啶Zincke盐与R基团取代的苯胺发生Zincke反应，制备相应的紫精单体(J.Phys.Chem.B 2012, 116,2842-2849)。前者，合成的方法较为简单，但是制备的紫精大多为烷基取代的，双功能化基团取代的类别较少；后者，可以合成较多功能团取代的紫精，但是合成条件较苛刻，产率低，且产物不易提纯。因此，如何使用一步季铵化反应，高效地合成双功能化基团取代的紫精离子单体，不管在基础研究还是在应用领域中都有着重要意义。
发明内容
本发明的目的之一是提供一类新型的双功能化紫精离子化合物，可以通过调变制备原料R取代溴苄中R基团的种类，从分子水平来设计并制备具有不同功能基团的紫精离子化合物(共12种化合物，其化学结构、编号和英文缩写见结构式)，使紫精离子化合物的阳离子结构具有可设计性，极大地丰富了紫精化合物的种类。
一类新型双功能化紫精离子化合物的结构式如式Ⅰ和Ⅱ所示，
式Ⅰ中，R1为苄基上间位(3位)取代的功能基团，具体为氰基(-CN)、卤素溴(-Br)、硝基(-NO2)、醛基(-CHO)、羧基(-COOH)和硼酸频哪醇酯基(-Bpin)；
式Ⅱ中，R2为苄基上对位(4位)取代的功能基团，具体也为氰基(-CN)、卤素溴(-Br)、硝基(-NO2)、醛基(-CHO)、羧基(-COOH)和硼酸硼酸频哪醇酯基(-Bpin),
本发明的另一个目的是提供一类全新双功能化紫精离子化合物的简便制备方法，其通用的步骤主要包括：
(1)化学计量比称取一定量的4,4’-联吡啶和功能基团取代的溴苄置于在烧杯中，加入一定量的溶剂乙腈使原料完全溶解；
(2)将上述溶液转移到聚四氟乙烯衬里的不锈钢反应釜中，在溶剂热条件下，通过季铵化反应一定时间；
(3)反应结束后，将得到的固体产物通过简单过滤、洗涤和干燥就可以得到纯度大于98％的新型紫精基离子化合物。
本发明涉及的12种新型紫精离子化合物的化学结构式及对应编号和英文缩写
本发明采用溶剂热合成法，通过一步季铵化反应，高效地合成一系列全新双功能化紫精基离子化合物，该方法流程简单、易于操作，具有普遍适用性。
具体实施方式
下面结合实例对本发明涉及的新型紫精离子化合物及详细的制备方法进行说明。但实施的例子仅仅对本发明的优选实例进行描述，并非对本发明的构思和范围进行限定。在不脱离本发明设计思路的前提下，本领域中专业技术人员对新型的化合物中R基团的改变以及对合成的方法进行各种变化，均属于本发明的保护范围。
本发明的关键点在于巧妙使用R基团取代的溴苄与4,4'-联吡啶发生季铵化反应，一步制备新型紫精离子化合物，根据实际应用的需求，可以设计带有特定功能团取代的紫精化合物。本发明所使用的原料均为商业化产品，可以直接使用合成相应的化合物，当然专业技术人员可以自己设计特定R基团取代的溴苄与4,4'-联吡啶反应制备相应的紫精离子化合物。式2所涉及的12种新型紫精离子化合物，均未见文献报道，通过SciFinder 未检出化合物信息。该12种新型紫精离子化合物的合成方法和结构表征的具体实施例子如下：
实施例1：
式3双氰基功能化的紫精离子化合物c1和c2的制备
双氰基功能化的紫精离子化合物c1：D[3-CNBzBpy]Br2和c2：D[4-CNBzBpy]Br2的制备方法和表征。
首先，称取4,4'-联吡啶(10mmol,1.56g)和3-氰基溴苄(20mmol,3.92g)置于在烧杯中，加入30mL溶剂乙腈，搅拌使原料完全溶解。然后，将上述透明溶液转移到50mL聚四氟乙烯衬里的不锈钢反应釜中，放置在烘箱中(80-120℃)，在溶剂热条件下，通过季铵化反应12-24小时。反应结束后，将得到的固体产物通过简单过滤、洗涤和干燥，最后得到黄色固体，即双氰基功能化的紫精离子化合物c1：D[3-CNBzBpy]Br2，产率85％，纯度98％。将3-氰基溴苄换成4-氰基溴苄，使用同样的反应可以制备紫精离子单体c2：D[4-CNBzBpy]Br2(黄色固体，产率90％，纯度98％)，它们的区别在于CN在苯环上的位置不一样，分别为3位和4位。
通过1H NMR、13C NMR和元素分析表征对紫精离子单体c1和c2的化学结构和组成进行了确认。
D[3-CNBzBpy]Br2,1H NMR(300MHz,D6-DMSO):δ9.54～9.56(CH,4H),8.15(CH,2H),7.94-8.00(CH,4H),7.68～7.72(CH,2H),5.96～6.03ppm(CH2,4H).13C NMR(75.5 MHz,D6-DMSO):δ149.72,146.43,135.86,134.45,133.65,133.29,130.92,127.72,118.71,112.54 and 62.85ppm.元素分析，实际值:C,56.52；H,3.86；N,10.29.理论值:C,56.96；H,3.68；N,10.22wt％.
D[4-CNBzBPy]Br2,1H NMR(300MHz,D6-DMSO):δ9.60～9.62(CH,4H),8.84～8.86(CH,4H),7.97～7.99(CH,4H),7.82～7.84(CH,4H)and 6.13ppm(CH2,4H).13C NMR(75.5MHz,D6-DMSO):δ149.75,146.49,139.63,133.54,130.31,127.78,118.75,112.62 and62.85ppm.元素分析，实际值:C,56.95；H,3.72；N,10.21.理论值:C,56.96；H,3.68；N,10.22wt％.
实施例2：
双溴苯基功能化的紫精离子化合物c3：D[3-BrBzBpy]Br2和c4：D[4-BrBzBpy]Br2的制备方法和表征。
首先，称取4,4'-联吡啶(10mmol,1.56g)和3-溴溴苄(20mmol,5.00g)置于在烧杯中，加入30mL溶剂乙腈，搅拌使原料完全溶解。然后，将上述透明溶液转移到50mL 聚四氟乙烯衬里的不锈钢反应釜中，放置在烘箱中(80-120℃)，在溶剂热条件下，通过季铵化反应12-24小时。反应结束后，将得到的固体产物通过简单过滤、洗涤和干燥，最后得到黄色固体，即双溴苯基功能化的紫精离子化合物c3：D[3-CNBzBpy]Br2，产率 86％，纯度98％。将3-溴溴苄换成4-溴溴苄，使用同样的反应可以制备紫精离子单体 c4：D[4-BrBzBpy]Br2(浅黄色固体，产率90％，纯度98％)，它们的区别在于Br在苯环上的位置不一样，分别为3位和4位。
式4双溴苯基功能化的紫精离子化合物c3和c4的制备
通过1H NMR、13C NMR和元素分析表征对紫精离子单体c3和c4的化学结构和组成进行了确认。
D[3-BrBzBPy]Br2,1H NMR(300MHz,D6-DMSO):δ9.57～9.59(CH,4H),8.77～8.79(CH,4H),7.94(CH,2H),7.62～7.68(CH,4H),7.40～7.44(CH,2H)and 5.97ppm(CH2,4H).13C NMR(75.5MHz,D6-DMSO):δ149.72,146.22,136.98,132.88,132.32,131.86,128.70,127.76,122.72 and 62.79ppm.元素分析，测量值:C,45.05；H,2.86；N,4.29.理论值:C,43.94；H,3.07；N,4.27wt％.
D[4-BrBzBPy]Br2,1H NMR(300MHz,D6-DMSO)(Figure S1):δ9.56～9.58(CH,4H),8.79～8.81(CH,4H),7.62～7.70(CH,8H)and 5.98ppm(CH2,4H).13C NMR(75.5MHz, D6-DMSO)(Figure S1):δ149.63,146.19,133.89,132.64,127.69,123.55 and 62.87ppm.元素分析，测量值:C,42.95；H,3.37；N,4.11.理论值:C,43.94；H,3.07；N,4.27wt％.
式5双硝基苯功能化的紫精离子化合物c5和c6的制备
式6双苯甲醛功能化的紫精离子化合物c7和c8的制备
实施例3-6：
采用实施例1和例2类似的方法，实施例3使用3-硝基溴苄(3-NO2BzBr)和4-硝基溴苄(4-NO2BzBr)为原料与4,4'-联吡啶反应，分别制备出两种双硝基苯功能化的紫精离子化合物c5:D[3-NO2BzBpy]Br2和c6:D[4-NO2BzBpy]Br2，反应式如式5所示。
实施例4使用3-溴甲基苯甲醛(3-CHOBzBr)和4-(溴甲基)苯甲醛4-CHOBzBr)为原料与4,4'-联吡啶反应，分别制备出两种双苯甲醛功能化的紫精离子化合物c7: D[3-CHOBzBpy]Br2和c8:D[4-CHOBzBpy]Br2，反应式如式6所示。
实施例5使用3-溴甲基苯甲酸(3-COOHBzBr)和4-溴甲基苯甲酸(4-COOHBzBr) 为原料与4,4'-联吡啶反应，分别制备出两种双苯甲醛功能化的紫精离子化合物c9: D[3-COOHBzBpy]Br2和c10:D[4-COOHBzBpy]Br2，反应式如式6所示。
实施例6使用3-溴甲基苯硼酸频哪醇酯(3-BpinBzBr)和4-溴甲基苯硼酸频哪醇酯(4-BpinBzBr)为原料与4,4'-联吡啶反应，分别制备出两种双苯甲醛功能化的紫精离子化合物c11:D[3-BpinBpy]Br2和c12:D[4-BpinBzBpy]Br2，反应式如式6所示。
通过1H NMR、13C NMR和元素分析表征，确认了上述新型紫精离子化合物的结构。
式7双苯甲酸功能化的紫精离子化合物c9和c10的制备
式8双苯硼酸频哪醇酯功能化的紫精离子化合物c11和c12的制备。
Claims (5)
1.一类新型双功能化紫精离子化合物的结构式如式Ⅰ和Ⅱ所示，
式Ⅰ
式Ⅱ；
式Ⅰ中，R1为苄基上间位（3位）取代的功能基团，具体为氰基（-CN）、卤素溴（-Br）、硝基（-NO2）、醛基（-CHO）、羧基（-COOH）和硼酸频哪醇酯基（-Bpin）；
式Ⅱ中，R2为苄基上对位（4位）取代的功能基团，具体也为氰基（-CN）、卤素溴（-Br）、硝基（-NO2）、醛基（-CHO）、羧基（-COOH）和硼酸硼酸频哪醇酯基（-Bpin）。
2.一种如权利1所要求的新型双功能化紫精离子化合物的制备方法，其特征在于，以下步骤
（1）按化学计算量比（1: 2）称取一定量的4,4’-联吡啶和功能基团（简称R基团）取代的溴苄，在烧杯中搅拌完全溶于一定体积的溶剂乙腈；
（2）将步骤（1）中的均匀溶液转移到聚四氟乙烯衬里的不锈钢反应中，置于烘箱中，在一定反应温度下进行季铵化反应；
（3）反应结束之后，将生成的固体通过过滤分离、用溶剂洗涤、干燥后制得相应R基团双功能化的新型紫精离子单体。
3.根据权利要求2所述的制备方法，其特征在于，所述反应的条件为，使用反应釜的溶剂热合成法，反应温度为80-120 ℃，反应时间为12-24小时。
4.根据权利要求2所述的制备方法，其特征在于，一步法所制备的单体产率在80-95%，产品纯度为98 %以上。
5.如权利要求1要求所述的双功能化紫精离子型化合物，在紫精电致变色材料和制备紫精基多孔离子聚合物材料中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711113738.9A CN108178744A (zh) | 2017-11-13 | 2017-11-13 | 一类新型双功能化紫精离子型化合物及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711113738.9A CN108178744A (zh) | 2017-11-13 | 2017-11-13 | 一类新型双功能化紫精离子型化合物及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108178744A true CN108178744A (zh) | 2018-06-19 |
Family
ID=62544953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711113738.9A Pending CN108178744A (zh) | 2017-11-13 | 2017-11-13 | 一类新型双功能化紫精离子型化合物及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108178744A (zh) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997427A (zh) * | 2018-08-01 | 2018-12-14 | 南方科技大学 | 电致变色化合物、用途以及其制备的电致变色器件和用途 |
| CN110801824A (zh) * | 2019-11-13 | 2020-02-18 | 江苏方时远略科技咨询有限公司 | 一种非金属光催化剂及其制备方法 |
| CN111978516A (zh) * | 2020-07-27 | 2020-11-24 | 大连理工大学 | 一种供体-受体型离子多孔聚合物的制备及其催化应用 |
| CN114031550A (zh) * | 2021-06-22 | 2022-02-11 | 南京米兰达视光科学研究院有限公司 | 一种紫精配位化合物晶体作为光致变色材料的应用 |
| CN114133352A (zh) * | 2021-06-22 | 2022-03-04 | 南京米兰达视光科学研究院有限公司 | 一种紫精配位化合物晶体及其制备方法 |
| CN115536578A (zh) * | 2022-09-23 | 2022-12-30 | 浙江大学 | 一种芳香酯取代紫精类黑色电致变色化合物及其制备方法和应用 |
| CN115651205A (zh) * | 2021-11-02 | 2023-01-31 | 渤海大学 | 基于紫精钴配合物修饰的八钼酸盐晶态材料、合成方法及其应用 |
| KR20230088835A (ko) * | 2020-11-26 | 2023-06-20 | 지앙수 시케신카이 컴퍼니 리미티드 | 자외선 차단 및 청색광 차단 광학 재료 및 이의 제조 방법 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63306448A (ja) * | 1987-06-09 | 1988-12-14 | Fuji Photo Film Co Ltd | ハロゲン化銀カラ−写真感光材料の処理方法 |
-
2017
- 2017-11-13 CN CN201711113738.9A patent/CN108178744A/zh active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63306448A (ja) * | 1987-06-09 | 1988-12-14 | Fuji Photo Film Co Ltd | ハロゲン化銀カラ−写真感光材料の処理方法 |
Non-Patent Citations (4)
| Title |
|---|
| CAMILA P. SOUSA ET AL.: "Chemical modification of a nanocrystalline TiO2 film for efficient electric connection of glucose oxidase", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| KAROL CIEPLUCH ET AL.: "Effect of viologen-phosphorus dendrimers on acetylcholinesterase and butyrylcholinesterase activities", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
| SHENGSHENG ZHANG ET AL.: "Monolayers and Langmuir-Blodgett films of Fe2+-mediated polyelectrolyte with viologen derivatives as linkers at the air-water interface", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 * |
| 游效曾: "《分子材料：光电功能化合物》", 31 October 2001, 上海科学技术出版社 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997427B (zh) * | 2018-08-01 | 2021-06-15 | 南方科技大学 | 电致变色化合物、用途以及其制备的电致变色器件和用途 |
| CN108997427A (zh) * | 2018-08-01 | 2018-12-14 | 南方科技大学 | 电致变色化合物、用途以及其制备的电致变色器件和用途 |
| CN110801824A (zh) * | 2019-11-13 | 2020-02-18 | 江苏方时远略科技咨询有限公司 | 一种非金属光催化剂及其制备方法 |
| CN111978516B (zh) * | 2020-07-27 | 2022-05-10 | 大连理工大学 | 一种供体-受体型离子多孔聚合物的制备及其催化应用 |
| CN111978516A (zh) * | 2020-07-27 | 2020-11-24 | 大连理工大学 | 一种供体-受体型离子多孔聚合物的制备及其催化应用 |
| KR20230088835A (ko) * | 2020-11-26 | 2023-06-20 | 지앙수 시케신카이 컴퍼니 리미티드 | 자외선 차단 및 청색광 차단 광학 재료 및 이의 제조 방법 |
| KR102606185B1 (ko) | 2020-11-26 | 2023-11-23 | 지앙수 시케신카이 컴퍼니 리미티드 | 자외선 차단 및 청색광 차단 광학 재료 및 이의 제조 방법 |
| CN114031550A (zh) * | 2021-06-22 | 2022-02-11 | 南京米兰达视光科学研究院有限公司 | 一种紫精配位化合物晶体作为光致变色材料的应用 |
| CN114133352A (zh) * | 2021-06-22 | 2022-03-04 | 南京米兰达视光科学研究院有限公司 | 一种紫精配位化合物晶体及其制备方法 |
| CN115651205A (zh) * | 2021-11-02 | 2023-01-31 | 渤海大学 | 基于紫精钴配合物修饰的八钼酸盐晶态材料、合成方法及其应用 |
| CN115651205B (zh) * | 2021-11-02 | 2023-10-27 | 渤海大学 | 基于紫精钴配合物修饰的八钼酸盐晶态材料、合成方法及其应用 |
| CN115536578A (zh) * | 2022-09-23 | 2022-12-30 | 浙江大学 | 一种芳香酯取代紫精类黑色电致变色化合物及其制备方法和应用 |
| CN115536578B (zh) * | 2022-09-23 | 2024-03-29 | 浙江大学 | 一种芳香酯取代紫精类黑色电致变色化合物及其制备方法和应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108178744A (zh) | 一类新型双功能化紫精离子型化合物及其制备方法 | |
| JP7433673B2 (ja) | ビフェニルアレーンに基づく大環とかご状分子並びに誘導化合物、及びその合成方法と応用 | |
| Hong et al. | High-dimensional manganese (II) compounds with noncovalent and/or covalent bonds derived from flexible ligands: self-assembly and structural transformation | |
| JP5959171B2 (ja) | π共役有機ホウ素化合物及びその製造方法 | |
| Zhan et al. | Donor-acceptor π-conjugated quinoxaline derivatives exhibiting multi-stimuli-responsive behaviors and polymorphism-dependent multicolor solid-state emission | |
| Sun et al. | Lanthanide organic frameworks for luminescence sensing of nitrobenzene and nitrophenol with high selectivity | |
| Meng et al. | Tetrametallic macrocyclic frameworks constructed from ferrocenedicarboxylato and 2, 2′-bipyridine: synthesis, molecular structures and characteristics | |
| Wang et al. | Multiple stimuli responses of stereo-isomers of AIE-active ethynylene-bridged and pyridyl-modified tetraphenylethene | |
| Yang et al. | Synthesis and properties of aggregation-induced emission enhancement compounds derived from triarylcyclopentadiene | |
| Batsanov et al. | Synthesis and crystal engineering of new halogenated tetrathiafulvalene (TTF) derivatives and their charge transfer complexes and radical ion saltsElectronic supplementary information (ESI) available: a table of intermolecular contacts for compounds 2, 5, 6, 8, 15, 3· TCNQ, 4· TCNQ, 1· 18, 1· 19· 2C4H8O2, 5+˙ I3−· I2 and 16+˙ I3−, and a figure of the crystal structure of complex 1· 18. See http://www. rsc. org/suppdata/jm/b1/b101866n | |
| Nagata et al. | Synthesis of methyl-substituted main-chain-type organoboron quinolate polymers and their emission color tuning | |
| Alidağı et al. | Synthesis and spectral properties of fluorene substituted cyclic and polymeric phosphazenes | |
| Jiang et al. | A Novel d‐f Heterometallic CdII‐EuIII Metal‐organic Framework as a Sensitive Luminescent Sensor for the Dual Detection of Ronidazole and 4‐Nitrophenol | |
| Mistri et al. | Tetracarboxylato-bridged copper (II) complexes with ancillary N-chelating ligands: Syntheses, crystal structures and effect of aromatic compounds on the fluorescence property | |
| Pandey et al. | Luminescent Pyrene-Decorated Organotin Compounds: Observation of Monomer and Excimer Emission | |
| Riefer et al. | Pyridine Adducts of Tricyano‐and Dicyanoboranes | |
| Yang et al. | Self-assembly of two mixed-ligands metal-organic coordination polymers,[MII2 (DPA) 2 (C4O4)(C2O4)](M= Cu, Zn) | |
| JP6815651B2 (ja) | ローダミン系色素化合物及びその製造方法 | |
| Zheng et al. | Synthesis, characterization and thermochemical properties of four new lanthanide complexes with 3, 5-diisopropylsalicylic acid and 1, 10-phenanthroline | |
| Ma et al. | Synthesis, structure, and conformation of ortho-linked oxacalix [n] arene [n] hetarenes | |
| Dang et al. | Two cadmium–thiocyanate coordination polymers with organic cations: Synthesis, crystal structures and luminescent properties | |
| Wesela-Bauman et al. | Synthesis of functionalized diarylborinic 8-oxyquinolates via bimetallic boron–lithium intermediates | |
| Zhao et al. | Efficient Pd-catalyzed coupling reaction of cationic cyclopentadienyliron complexes of chloro-substituted arenes with arylboronic acid | |
| Lü et al. | Luminescent behaviors of salts based on 2–phenyl–1H–benzimidazole | |
| Huang et al. | Synthesis and properties of chiral helical polymers based on optically active polybinaphthyls |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180619 |
|
| RJ01 | Rejection of invention patent application after publication |