CN109651239A - 一种多齿配体三联吡啶双乙酸及其制备方法 - Google Patents
一种多齿配体三联吡啶双乙酸及其制备方法 Download PDFInfo
- Publication number
- CN109651239A CN109651239A CN201910013862.0A CN201910013862A CN109651239A CN 109651239 A CN109651239 A CN 109651239A CN 201910013862 A CN201910013862 A CN 201910013862A CN 109651239 A CN109651239 A CN 109651239A
- Authority
- CN
- China
- Prior art keywords
- terpyridyl
- diacetic acid
- ethyl alcohol
- aqueous solution
- multidentate ligand
- 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
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003446 ligand Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- KDPAWGWELVVRCH-UHFFFAOYSA-M bromoacetate Chemical compound [O-]C(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-M 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000013256 coordination polymer Substances 0.000 abstract description 7
- 229920001795 coordination polymer Polymers 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000696 magnetic material Substances 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 150000004696 coordination complex Chemical class 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- -1 rare earth ion Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical group N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 1
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical group N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07D213/24—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 with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pyridine Compounds (AREA)
Abstract
一种多齿配体三联吡啶双乙酸,分子式C25H20N4O4,分子量440。化合物名称:4’‑p‑N,N‑二(羧乙基)胺基苯基‑2,2’:6,2”‑三联吡啶。本发明的三联吡啶双乙酸的配位能力强,配位方式多样。本发明的三联吡啶双乙酸的制备方法操作简单,易于纯化,产率高。以三联吡啶或羧酸为配体的金属配合物种类繁多,应用广泛。依托本发明的三联吡啶双乙酸的合成方法,并以之为多齿配体与合适的金属离子在特定条件下反应,可获得一系列适宜于发光材料、磁性材料以及催化剂研究的配位聚合物。
Description
技术领域
本发明涉及一种发光材料领域,特别是一种多齿配体三联吡啶双乙酸及其制备方法。
背景技术
将含有3d、4d电子的金属离子以及4f电子的稀土离子通过有机共轭配体桥联形成的配位聚合物,不仅结构新颖奇特,往往还呈现出特殊的光、电、磁以及催化性能。d-f型的异核配合物更是能实现这些性能的复合优化,在新型发光材料领域有着潜在应用前景。在构筑这些配位聚合物的独特结构时,桥联配体的选择至关重要。2,2’:6’,2”-三联吡啶基团依靠{N,N,N}配位,具有良好的配位能力,在光电子领域有着很好的应用[U.S.Schubertet.al.,Chem.Soc.Rev.,2011,40,1459-1511]。三联吡啶分子结构中的芳香环便于结构修饰,可在多个位置连接给电子/吸电子基团,或者生物相容性的大分子基团,从而可进一步优化三联吡啶配合物的性能[G.R.Newkome et.al.,Chem.Soc.Rev.,2018,47,3991-4016]。羧酸基团中的两个O原子可以通过单配、双配甚至桥联的方式与金属离子结合,得到多种配位结构共存的配合物[A.A.Sidorov et.al.,Russ.J.Coord.Chem.,2016,42,621-634],这些结构的配合物在催化、磁性材料等领域应用广泛。如何将三联吡啶配合物与羧酸配合物的优势结合起来是一个巨大的挑战,目前常见的做法是将两种配体同时与金属离子反应,或者分步反应以实现混配,这些方法的副反应较多,提纯步骤复杂,产率不高。
发明内容
本发明要解决的技术问题是针对现有技术的不足,提出了一种配位能力强,配位方式多样的多齿配体三联吡啶双乙酸。本发明另一要解决的技术问题是提出了一种该多齿配体三联吡啶双乙酸的制备方法。
本发明要解决的技术问题是通过以下技术方案米实现的,一种多齿配体三联吡啶双乙酸,其特点是具有如下结构:
分子式C25H20N4O4,分子量440。
化合物名称:4’-p-N,N-二(羧乙基)胺基苯基-2,2’:6,2”-三联吡啶。
缩写词:TPYPDCA。
上述多齿配体三联吡啶双乙酸的一种制备方法,其特点是包括如下步骤:
(1)、将苯胺、碳酸钾、碘化钾按照1∶1~3∶1~3的摩尔比配成混合物,在氮气保护下搅拌10~30分钟;
缓慢的将溴乙酸乙酯的乙腈溶液滴加到上述混合物中,其中溴乙酸乙酯与乙腈的体积比为1∶3~5,滴加的量按苯胺与溴乙酸乙酯的摩尔比为1∶2~3.5计量;
在90~120℃下搅拌6~12小时,反应结束后蒸除溶剂,将余渣溶解在二氯甲烷中,并用水洗涤,取下层有机层用无水硫酸钠干燥;过滤后浓缩,然后用中性氧化铝色谱柱提纯,收集淡黄色产物得到p-N,N-二酯基苯胺;
(2)、将p-N,N-二酯基苯胺、三氯氧磷、N,N-二甲基甲酰胺按质量比为1∶1.0~1.2∶1.0~1.5的比例混合后,在-10~10℃条件下搅拌0.5~1小时后升温至80~100℃,反应3~8小时;
冷却至室温,调节pH=7~9;
然后用二氯甲烷萃取,有机层水洗后用无水硫酸钠干燥;过滤后浓缩,然后用中性氧化铝色谱柱提纯,收集淡黄色产物得到p-N,N-二酯基苯甲醛;
(3)、将p-N,N-二酯基苯甲醛、2-乙酰基吡啶溶解于乙醇中,再加入氢氧化钠水溶液进行混和;
其中p-N,N-二酯基苯甲醛、2-乙酰基吡啶、NaOH水溶液、乙醇的质量比为1∶1.0~1.5∶1.0~1.3∶4.0~7.0,其中氢氧化钠水溶液的浓度为10mol/L;
室温搅拌2~3小时后,-4℃冷冻0.5~2小时,除去上层液体;室温下,对下层有机物再加入乙醇并搅拌至黑红色油状物全部溶解;
然后再加入NaOH水溶液和氨水,其中加入NaOH水溶液和氨水的量与上述2-乙酰基吡啶用量三者的质量比为1.0~1.5∶10~15∶1,其中氢氧化钠的水溶液的浓度为10mol/L,氨水的质量百分比浓度为25%;
在80~120℃条件下反应3~8小时,反应完成后,将混合物倒入冷水中冷却,调节pH至3.5~6.5,得到黄色沉淀,离心分离后的固体用乙醇和无水乙醚的混合溶剂洗涤,其中乙醇和无水乙醚的体积比为1∶10~20;过滤后干燥,得到三联吡啶双乙酸。
本发明要解决的技术问题还可以通过以下技术方案来进一步实现,用中性氧化铝色谱柱提纯时使用的洗脱液为石油醚与乙酸乙酯或乙醇的混合液,其中石油醚∶乙酸乙酯或乙醇的体积比为1∶1~1.5。
本发明要解决的技术问题还可以通过以下技术方案来进一步实现,步骤(1)中蒸除溶剂的方法采用减压蒸馏法,其压力为-0.09~-0.1MPa。
本发明通过在苯环的对位上分别连接一个三联吡啶以及一个胺基二乙酸基团,得到多齿配体三联吡啶双乙酸。三联吡啶对大部分d过渡金属,特别是Zn(II)、Ru(II)、Ir(III)、Re(I)等离子具有良好亲和性,羧基能和部分d过渡金属离子离子,特别是Zn(II)、Sn(IV),以及稀土离子,特别是Eu(III)、Tb(III)配位。通过控制三联吡啶双乙酸与金属离子的反应配比,调节合适的反应条件,如温度、溶剂、反应时间、pH值等,可以便捷的得到多种结构的同核和异核的d-d型或d-f型配位聚合物。
与现有技术相比,本发明的三联吡啶双乙酸的配位能力强,配位方式多样。本发明的三联吡啶双乙酸的制备方法操作简单,易于纯化,产率高。以三联吡啶或羧酸为配体的金属配合物种类繁多,应用广泛。依托本发明的三联吡啶双乙酸的合成方法,并以之为多齿配体与合适的金属离子在特定条件下反应,可获得一系列适宜于发光材料、磁性材料以及催化剂研究的配位聚合物。
附图说明
图1为本发明的核磁氢谱;
图2为本发明的电喷雾质谱;
图3为本发明的红外光谱;
图4为本发明的荧光光谱图;
图5为本发明的锌配合物的荧光光谱图;
图6为本发明制备步骤中的合成路线图;
图7为本发明的锌配合物的单晶X-射线衍射图。
具体实施方式
以下进一步描述本发明的具体技术方案,以便于本领域的技术人员进一步地理解本发明,而不构成对其权利的限制。
一种多齿配体三联吡啶双乙酸,其特点是具有如下结构:
分子式C25H20N4O4,分子量440。
化合物名称:4’-p-N,N-二(羧乙基)胺基苯基-2,2’:6,2”-三联吡啶,缩与词:TPYPDCA。
上述多齿配体三联吡啶双乙酸的一种制备方法,包括如下步骤:
(1)、将苯胺、碳酸钾、碘化钾按照1∶1~3∶1~3的摩尔比配成混合物,在氮气保护下搅拌10~30分钟;
缓慢的将溴乙酸乙酯的乙腈溶液滴加到上述混合物中,其中溴乙酸乙酯与乙腈的体积比为1∶3~5,滴加的量按苯胺与溴乙酸乙酯的摩尔比为1∶2~3.5计量;
在90~120℃下搅拌6~12小时,反应结束后蒸除溶剂,将余渣溶解在二氯甲烷中,并用水洗涤两次,除去上层液,包括反应不完全的无机盐类;
取下层有机层用无水硫酸钠干燥,看不到水层为止,干燥时间为4~6小时;过滤后浓缩,然后用中性氧化铝色谱柱提纯,洗脱液为石油醚∶乙酸乙酯或乙醇=1∶1~1.5,收集淡黄色产物得到p-N,N-二酯基苯胺;
(2)、将p-N,N-二酯基苯胺、三氯氧磷、N,N-二甲基甲酰胺按质量比为1∶1.0~1.2∶1.0~1.5的比例混合后,在-10~10℃条件下搅拌0.5~1小时后升温至80~100℃,反应3~8小时;
冷却至室温,用醋酸钠或碳酸钠或氢氧化钠中的一种或几种调节pH=7~9;
然后用二氯甲烷萃取,有机层水洗后用无水硫酸钠干燥;过滤后浓缩,然后用中性氧化铝色谱柱提纯,洗脱液为石油醚∶乙酸乙酯或乙醇=1∶1~2.5,收集淡黄色产物得到p-N,N-二酯基苯甲醛;
(3)、将p-N,N-二酯基苯甲醛、2-乙酰基吡啶溶解于乙醇中,再加入氢氧化钠水溶液进行混和;
其中p-N,N-二酯基苯甲醛、2-乙酰基吡啶、NaOH水溶液、乙醇的质量比为1∶1.0~1.5∶1.0~1.3∶4.0~7.0,其中氢氧化钠水溶液的浓度为10mol/L;
室温搅拌2~3小时后,-4℃冷冻0.5~2小时,除去上层液体;室温下,对下层有机物再加入乙醇并搅拌至黑红色油状物全部溶解;
然后再加入NaOH水溶液和氨水,其中加入NaOH水溶液和氨水的量与上述2-乙酰基吡啶用量三者的质量比为1.0~1.5∶10~15∶1,其中氢氧化钠的水溶液的浓度为10mol/L,氨水的质量百分比浓度为25%;
在80~120℃条件下反应3~8小时,反应完成后,将混合物倒入冷水中冷却,用稀HCl、稀硫酸或者醋酸中一种或几种调节pH至3.5~6.5,得到黄色沉淀,离心分离后的固体用乙醇和无水乙醚的混合溶剂洗涤,其中乙醇和无水乙醚的体积比为1∶10~20;过滤后干燥,得到三联吡啶双乙酸。
用中性氧化铝色谱柱提纯时使用的洗脱液为石油醚与乙酸乙酯或乙醇的混合液,其中石油醚∶乙酸乙酯或乙醇的体积比为1∶1~1.5。步骤(1)中蒸除溶剂的方法采用减压蒸馏法,其压力为-0.09~-0.1MPa。
应用:利用本发明的三联吡啶双乙酸与Zn2+通过溶剂热(甲醇∶DMF=1∶1~1.5,温度100~140℃,聚四氟乙烯内衬的25mL不锈钢反应釜)反应,可以得到五配位结构的Zn(II)配位聚合物,三联吡啶基团近似平行。该锌配合物具有较好的发光性能,荧光激发峰为347nm,发射峰为469nm,相比本发明的三联吡啶双乙酸的荧光光谱(激发峰为339nm,发射峰为450nm)均有明显的红移。本发明的多齿配体三联吡啶双乙酸可作为桥联配体,用于构筑独特结构的Zn(II)配位聚合物,在新型发光材料研究领域具有潜在的应用价值。
图1解析:化学位移的归属如下:12.99(s,2H,-COOH);8.77(d,2H,H6,6’’);8.66(d,4H,H3,3”+H3’,5’);8.03(m,2H,H4,4”);7.80(d,2H,benzene-H);7.53(m,2H,H5,5”);6.73(d,2H,benzene-H);4.21(s,4H,-CH2-)。
图2解析:TPYPDCA的分子量M=440,质荷比为439.145(-p)的峰可以归属为[M-H]-,质荷比为219.435(-p)的峰可以归属为[M-2H]2-,
图3解析:3424归属为羧基中的O-H的伸缩振动峰,2943归属为烷基(-CH2-)的C-H伸缩振动峰,1599归属为吡啶环中C=N和C=C的伸缩振动峰,1584,1526归属为C=C的面内振动峰,1389归属为O-H的变形振动峰,1214归属为C-N的伸缩振动峰,792归属为苯环中C-H的变形振动峰。
图4解析:三联吡啶双乙酸在丙酮中的最佳激发峰为339nm,荧光发射峰为450nm。
图5解析:三联吡啶双乙酸的锌配合物在丙酮中的最佳激发峰为347nm,荧光发射峰为469nm。
图6解析:本发明的制备步骤图。
图7解析:晶体属斜方晶系,空间群为P-1,R1[I>2σ(I)]=0.064,wR2[I>2σ(I)]=0.1813。晶胞参数: α=90°,β=90°,γ=90°,
Claims (4)
1.一种多齿配体三联吡啶双乙酸,其特征在于具有如下结构:
分子式C25H20N4O4,分子量440。
2.一种权利要求1所述的多齿配体三联吡啶双乙酸的制备方法,其特征在于包括如下步骤:
(1)、将苯胺、碳酸钾、碘化钾按照1∶1~3∶1~3的摩尔比配成混合物,在氮气保护下搅拌10~30分钟;
缓慢的将溴乙酸乙酯的乙腈溶液滴加到上述混合物中,其中溴乙酸乙酯与乙腈的体积比为1∶3~5,滴加的量按苯胺与溴乙酸乙酯的摩尔比为1∶2~3.5计量;
在90~120℃下搅拌6~12小时,反应结束后蒸除溶剂,将余渣溶解在二氯甲烷中,并用水洗涤,取下层有机层用无水硫酸钠干燥;过滤后浓缩,然后用中性氧化铝色谱柱提纯,收集淡黄色产物得到p-N,N-二酯基苯胺;
(2)、将p-N,N-二酯基苯胺、三氯氧磷、N,N-二甲基甲酰胺按质量比为1∶1.0~1.2∶1.0~1.5的比例混合后,在-10~10℃条件下搅拌0.5~1小时后升温至80~100℃,反应3~8小时;
冷却至室温,调节pH=7~9;
然后用二氯甲烷萃取,有机层水洗后用无水硫酸钠干燥;过滤后浓缩,然后用中性氧化铝色谱柱提纯,收集淡黄色产物得到p-N,N-二酯基苯甲醛;
(3)、将p-N,N-二酯基苯甲醛、2-乙酰基吡啶溶解于乙醇中,再加入氢氧化钠水溶液进行混和;
其中p-N,N-二酯基苯甲醛、2-乙酰基吡啶、NaOH水溶液、乙醇的质量比为1∶1.0~1.5∶1.0~1.3∶4.0~7.0,其中氢氧化钠水溶液的浓度为10mol/L;
室温搅拌2~3小时后,-4℃冷冻0.5~2小时,除去上层液体;
室温下,对下层有机物再加入乙醇并搅拌至黑红色油状物全部溶解;
然后再加入NaOH水溶液和氨水,其中加入NaOH水溶液和氨水的量与上述2-乙酰基吡啶用量三者的质量比为1.0~1.5∶10~15∶1.0,其中氢氧化钠的水溶液的浓度为10mol/L,氨水的质量百分比浓度为25%;
在80~120℃条件下反应3~8小时,反应完成后,将混合物倒入冷水中冷却,调节pH至3.5~6.5,得到黄色沉淀,离心分离后的固体用乙醇和无水乙醚的混合溶剂洗涤,其中乙醇和无水乙醚的体积比为1∶10~20;过滤后干燥,得到三联吡啶双乙酸。
3.根据权利要求2所述的多齿配体三联吡啶双乙酸的制备方法,其特征在于:用中性氧化铝色谱柱提纯时使用的洗脱液为石油醚与乙酸乙酯或乙醇的混合液,其中石油醚∶乙酸乙酯或乙醇的体积比为1∶1~1.5。
4.根据权利要求2所述的多齿配体三联吡啶双乙酸的制备方法,其特征在于:步骤(1)中蒸除溶剂的方法采用减压蒸馏法,其压力为-0.09~-0.1MPa。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910013862.0A CN109651239A (zh) | 2019-01-07 | 2019-01-07 | 一种多齿配体三联吡啶双乙酸及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910013862.0A CN109651239A (zh) | 2019-01-07 | 2019-01-07 | 一种多齿配体三联吡啶双乙酸及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109651239A true CN109651239A (zh) | 2019-04-19 |
Family
ID=66119479
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910013862.0A Pending CN109651239A (zh) | 2019-01-07 | 2019-01-07 | 一种多齿配体三联吡啶双乙酸及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109651239A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111875624A (zh) * | 2020-06-06 | 2020-11-03 | 桂林理工大学 | 一种基于bteb的四核锌配合物的制备、结构和荧光应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102584686A (zh) * | 2012-01-11 | 2012-07-18 | 淮海工学院 | 一种水溶性三联吡啶荧光化合物及其制备方法 |
CN102924524B (zh) * | 2012-10-29 | 2015-02-04 | 安徽大学 | 一种具有活体细胞显影功能的锰配合物双光子吸收材料及其合成方法 |
-
2019
- 2019-01-07 CN CN201910013862.0A patent/CN109651239A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102584686A (zh) * | 2012-01-11 | 2012-07-18 | 淮海工学院 | 一种水溶性三联吡啶荧光化合物及其制备方法 |
CN102924524B (zh) * | 2012-10-29 | 2015-02-04 | 安徽大学 | 一种具有活体细胞显影功能的锰配合物双光子吸收材料及其合成方法 |
Non-Patent Citations (1)
Title |
---|
XIAOHE TIAN,ET AL.: "Halides tuning the subcellular-targeting in two-photon emissive complexes via different uptake mechanisms", 《CHEMICAL COMMUNICATIONS》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111875624A (zh) * | 2020-06-06 | 2020-11-03 | 桂林理工大学 | 一种基于bteb的四核锌配合物的制备、结构和荧光应用 |
CN111875624B (zh) * | 2020-06-06 | 2022-06-14 | 桂林理工大学 | 一种基于bteb的四核锌配合物的制备、结构和荧光应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103408445B (zh) | 一种芳胺类衍生物及其制备方法 | |
CN107935926B (zh) | 能够识别芳香酸异构体的凝胶因子及其超分子聚合物凝胶的制备和应用 | |
CN102965099B (zh) | 新型稀土/三联吡啶功能化离子液体发光材料 | |
CN115368272A (zh) | 一种4-氰基-2-甲氧基苯甲醛的制备方法 | |
CN109651239A (zh) | 一种多齿配体三联吡啶双乙酸及其制备方法 | |
CN102584686B (zh) | 一种水溶性三联吡啶荧光化合物及其制备方法 | |
CN101987823B (zh) | N,n’-双苯基-n-(9,9-二甲基-2-芴基)-n’-(9’,9’-二甲基-7’-(2’’-萘基)-2’-芴基)-联苯胺及其合成方法 | |
CN107556155B (zh) | 一种合成α,β-双溴化合物的方法 | |
CN109111357A (zh) | 一种可量产辛酸铑二聚体的合成方法 | |
Politeo et al. | The first coordination compound of 6-fluoronicotinate: the crystal structure of a one-dimensional nickel (II) coordination polymer containing the mixed ligands 6-fluoronicotinate and 4, 4′-bipyridine | |
CN102417486B (zh) | 一种缬沙坦的合成方法 | |
CN110950778A (zh) | 制备芳族丙二腈的方法和催化剂体系 | |
CN102030702B (zh) | 一种空穴传输材料及其合成方法 | |
CN110526886A (zh) | 一种合成1-氧代-1,3-二氢-3-羟基苯并呋喃-5-甲酸的方法 | |
CN109706323A (zh) | 苯并杂环类化合物及其应用 | |
CN102516133A (zh) | 一种苯甲磺酸衍生物的制备方法 | |
CN109456275A (zh) | 一种1h-1,2,3-三氮唑的制备方法 | |
CN101696153B (zh) | 3,3-二甲基-1-丁醇的制备方法 | |
CN104817589A (zh) | 一种双烷基次膦酸类化合物或其盐及其制备方法 | |
CN106188085A (zh) | 一种制备荧光素的工艺方法 | |
CN105152903A (zh) | 一种脂肪族二元羧酸的制备方法 | |
CN111233753A (zh) | 一种aie金属有机凝胶的制备方法 | |
CN109485550A (zh) | 用离子液体制备苯乙烯衍生物的方法 | |
CN110172076A (zh) | 一种含环外双键喹啉衍生物及其制备方法 | |
CN104230926A (zh) | 米诺膦酸关键中间体的制备方法 |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190419 |