CN105130885B - 一种含有联吡啶结构的芳香二胺及其合成方法 - Google Patents
一种含有联吡啶结构的芳香二胺及其合成方法 Download PDFInfo
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- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title abstract description 18
- 150000004984 aromatic diamines Chemical class 0.000 title abstract description 14
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 239000000126 substance Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 47
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 12
- 238000004587 chromatography analysis Methods 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 abstract description 5
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 125000006416 CBr Chemical group BrC* 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YAVVGPBYBUYPSR-UHFFFAOYSA-N benzene;oxygen Chemical compound [O].C1=CC=CC=C1 YAVVGPBYBUYPSR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
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- 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
- C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/65—One oxygen atom attached in position 3 or 5
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- C—CHEMISTRY; METALLURGY
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- Pyridine Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明公开了一种含有联吡啶结构的芳香二胺及其合成方法,其化学结构式如式(1)所示,本发明所制备的含联吡啶单元的芳香二胺是一类新型的含联吡啶单元的二胺单体,作为含氮杂环的单体,相比类似的含苯环的单体,为聚合得到的PI带来了更加显著的性能的改善,包括显著提高了聚合物的热稳定性和玻璃化转变温度,显著改善了聚合物的介电性,总之,本发明的芳香二胺更加有益于改善聚酰亚胺和聚酰胺的应用加工性能及拓展其应用领域。
Description
技术领域
本发明属于有机化合物及其制备方法的技术领域,具体涉及到一种含有联吡啶结构的芳香二胺及其合成方法。
背景技术
聚酰亚胺是一类具有优异的热稳定性、机械性能及电性能的高性能高分子材料,广泛应用于汽车、航空航天、微电子等高科技领域。联吡啶及其衍生物对过渡金属以及稀土金属具有很强的亲和性,能与很多的过渡金属以及稀土金属形成络合物,配合物中存在较强的dπ-pπ反馈键。联吡啶单元的氮杂环引入聚酰亚胺分子中,不仅能提高其玻璃化转变温度、热稳定性以及力学性能,还能赋予其络合功能,形成PI/金属络合交联的功能性高分子材料,在保持其较高热稳定性、优异介电性的同时,且具有低膨胀系数,以期将PI材料的应用领域大幅度拓展。
发明内容
本发明的目的之一在于:提供一种含联吡啶啶结构的芳香二胺,它作为单体,能够为聚合得到的PI带来更加显著的性能改善。
本发明的另一个目的在于:提供一种含联吡啶结构的芳香二胺的合成方法,该方法具有步骤简单,反应产率高,环境友好等优点。
为实现此目的,本发明的技术方案如下:
提供一种含联吡啶结构的芳香二胺,其化学结构式如式(1)所示:
本发明一种优选的方案中,式(1)所示的含联吡啶结构的芳香二胺的氨基在苯氧基苯环上的取代位为4位置。
本发明的另一种优选方案中,式(1)所示的含联吡啶结构的芳香二胺的两端苯环上的氨基取代位置相同。
本发明还提供所述的含联吡啶结构的芳香二胺的制备方法,包括以下步骤:
1)将2,2′-联吡啶与溴发生取代反应得到5,5′-二溴-2,2′-联吡啶;
2)将步骤1)得到的5,5′-二溴-2,2′-联吡啶再与4-氨基苯酚发生亲核取代反应,得到5,5′-双[(4-氨基)苯氧基]-2,2′-联吡啶。
步骤1)所述的取代反应优选2,2′-联吡啶与液溴在反应釜中1.5~2.0大气压下加热反应。
步骤2)所述的反应溶剂为N-甲基吡咯烷酮或者二甲基亚砜。
本发明优选的制备方法如下:
第一步反应:2,2'-联吡啶与液溴物质量比为1:1.5~1:2.5放入反应釜140~160℃下及1.5~2.0大气压反应8~15小时,反应后冷却至室温,把固体粉碎,加入到Na2SO3溶液中搅拌,除去未反应的溴,过滤,再用5%NaOH的溶液碱化除酸,过滤,得到粗产品,用乙酸乙酯/石油醚来进行柱层分离,得到白色5,5'-二溴-2,2'-联吡啶。
第二步反应:5,5'-二溴-2,2'-联吡啶与4-氨基苯酚物质量比为1:2.4~1:3.0加入三颈烧瓶中,再加入除水的N-甲基吡咯烷酮或者二甲基亚砜,加入无水碳酸钾或者氢氧化钠或者氢氧化钾,反应物在170~200℃反应8~12小时,冷却至室温,倒入5%NaOH溶液搅拌1小时,过滤出固体,用蒸馏水反复洗涤几次,用水和乙醇重结晶,得到白色的2,6-双[(4-氨基)苯氧基]-2,2'-联吡啶。
本发明所制备的含联吡啶单元的芳香二胺是一类新型的含联吡啶单元的二胺单体,作为含氮杂环的单体,相比类似的含苯环的单体,为聚合得到的PI带来了更加显著的性能的改善,包括显著提高了聚合物的热稳定性和玻璃化转变温度,显著改善了聚合物的介电性,总之,本发明的芳香二胺更加有益于改善聚酰亚胺和聚酰胺的应用加工性能及拓展其应用领域。
附图说明
图1:5,5′-双[(4-氨基)苯氧基]-2,2′-联吡啶的红外光谱图IR(KBr)。
图2:5,5′-双[(4-氨基)苯氧基]-2,2′-联吡啶的核磁谱图1HMR(DMSO-d6)。
图3:5,5′-双[(4-氨基)苯氧基]-2,2′-联吡啶的核磁谱图13CMR(DMSO-d6)。
具体实施方式
下面将结合附图实施例详细说明本发明所具有的有益效果,旨在帮助阅读者更好地理解本发明的实质,但不能对本发明的实施和保护范围构成任何限定。
实施例1
2,2'-联吡啶(4.99g,0.032mol)和液溴(10.24g,0.064mol)放入反应釜中1.5大气压下150℃反应15小时,反应后冷却至室温,把固体粉碎,加入到Na2SO3溶液中搅拌,除去未反应的溴,过滤,再用5%NaOH的溶液碱化除酸,过滤,得到粗产品,用乙酸乙酯/石油醚来进行柱层分离,得到白色5,5'-二溴-2,2'-联吡啶8.64g,产率86%,m.p.221.6-222.1℃.1H-NMR(400MHz,CDCl3,d):7.95(d,2H),8.28(s,2H),8.71(d,2H);13C-NMR(100MHz,CDCl3,d):121.47(C5),122.25(C3),139.64(C4);150.28(C6),153.64(C2),IR(KBr):3049(C-H,stretching),1562,1453,1356(Ar,stretching),636(C-Br,stretch).Anal.calcd forC10H6N2Br2:C 38.22,H 1.91,N 8.92,Br 50.95;found:C 38.23,H 1.92,N 8.91,Br 50.94。
5,5'-二溴-2,2'-联吡啶(6.28g,0.02mol),4-氨基苯酚(5.23g,0.048mol)加入三颈烧瓶中,再加入100ml除水的N-甲基吡咯烷酮,加入无水碳酸钾K2CO3(2.73g,0.02mol,),反应物在175℃反应12小时,冷却至室温,倒入5%NaOH溶液搅拌1小时,过滤出固体,用蒸馏水反复洗涤几次,用水和乙醇重结晶,得到白色的2,6-双[(4-氨基)苯氧基]-2,2'-联吡啶6.44g,产率87%,m.p.204.0-204.6℃.1H-NMR(400MHz,DMSO-d6,d):5.06(s,4H),6.61(d,4H),6.85(d,4H),7.29(d,2H),8.21(s,2H),8.29(d,2H).13C-NMR(100MHz,DMSO-d6,d):114.89(C3'),120.82(C2’),123.92(C3,C4),138.43(C6),144.75(C4'),146.04(C1'),148.84(C2),155.36(C5).FTIR(KBr):3396,3302(N-H,stretching),1633,1558,1503,1455(Ar,stretching).Anal.calcd for C22H18N4O2:C 71.35,H 4.86,N 15.14,O 8.65;found:C71.33,H 4.87,N15.13,O 8.67。
实施例2
2,2'-联吡啶(4.99g,0.032mol)和液溴(10.24g,0.064mol)放入反应釜中2.0大气压下150℃反应15小时,反应后冷却至室温,把固体粉碎,加入到Na2SO3溶液中搅拌,除去未反应的溴,过滤,再用5%NaOH的溶液碱化除酸,过滤,得到粗产品,用乙酸乙酯/石油醚来进行柱层分离,得到白色5,5'-二溴-2,2'-联吡啶8.64g,产率91%,m.p.221.6-222.1℃.1H-NMR(400MHz,CDCl3,d):7.95(d,2H),8.28(s,2H),8.71(d,2H);13C-NMR(100MHz,CDCl3,d):121.47(C5),122.25(C3),139.64(C4);150.28(C6),153.64(C2),IR(KBr):3049(C-H,stretching),1562,1453,1356(Ar,stretching),636(C-Br,stretch).Anal.calcd forC10H6N2Br2:C 38.22,H 1.91,N 8.92,Br 50.95;found:C 38.23,H 1.92,N 8.91,Br 50.94。
5,5'-二溴-2,2'-联吡啶(6.28g,0.02mol),4-氨基苯酚(5.23g,0.048mol)加入三颈烧瓶中,再加入100ml除水的N-甲基吡咯烷酮,加入无水碳酸钾K2CO3(2.73g,0.02mol,),反应物在175℃反应12小时,冷却至室温,倒入5%NaOH溶液搅拌1小时,过滤出固体,用蒸馏水反复洗涤几次,用水和乙醇重结晶,得到白色的2,6-双[(4-氨基)苯氧基]-2,2'-联吡啶6.44g,产率87%,m.p.204.0-204.6℃.1H-NMR(400MHz,DMSO-d6,d):5.06(s,4H),6.61(d,4H),6.85(d,4H),7.29(d,2H),8.21(s,2H),8.29(d,2H).13C-NMR(100MHz,DMSO-d6,d):114.89(C3'),120.82(C2’),123.92(C3,C4),138.43(C6),144.75(C4'),146.04(C1'),148.84(C2),155.36(C5).FTIR(KBr):3396,3302(N-H,stretching),1633,1558,1503,1455(Ar,stretching).Anal.calcd for C22H18N4O2:C 71.35,H 4.86,N 15.14,O 8.65;found:C71.33,H 4.87,N 15.13,O 8.67。
实施例3
2,2'-联吡啶(4.99g,0.032mol)和液溴(10.24g,0.064mol)放入反应釜中1.5大气压下150℃反应15小时,反应后冷却至室温,把固体粉碎,加入到Na2SO3溶液中搅拌,除去未反应的溴,过滤,再用5%NaOH的溶液碱化除酸,过滤,得到粗产品,用乙酸乙酯/石油醚来进行柱层分离,得到白色5,5'-二溴-2,2'-联吡啶8.64g,产率86%,m.p.221.6-222.1℃.1H-NMR(400MHz,CDCl3,d):7.95(d,2H),8.28(s,2H),8.71(d,2H);13C-NMR(100MHz,CDCl3,d):121.47(C5),122.25(C3),139.64(C4);150.28(C6),153.64(C2),IR(KBr):3049(C-H,stretching),1562,1453,1356(Ar,stretching),636(C-Br,stretch).Anal.calcd forC10H6N2Br2:C 38.22,H 1.91,N 8.92,Br 50.95;found:C 38.23,H 1.92,N 8.91,Br 50.94。
5,5'-二溴-2,2'-联吡啶(6.28g,0.02mol),4-氨基苯酚(5.23g,0.048mol)加入三颈烧瓶中,再加入100ml除水的N-甲基吡咯烷酮,加入无水碳酸钾K2CO3(2.73g,0.02mol,),反应物在195℃反应12小时,冷却至室温,倒入5%NaOH溶液搅拌1小时,过滤出固体,用蒸馏水反复洗涤几次,用水和乙醇重结晶,得到白色的2,6-双[(4-氨基)苯氧基]-2,2'-联吡啶6.44g,产率92%,m.p.204.0-204.6℃.1H-NMR(400MHz,DMSO-d6,d):5.06(s,4H),6.61(d,4H),6.85(d,4H),7.29(d,2H),8.21(s,2H),8.29(d,2H).13C-NMR(100MHz,DMSO-d6,d):114.89(C3'),120.82(C2’),123.92(C3,C4),138.43(C6),144.75(C4'),146.04(C1'),148.84(C2),155.36(C5).FTIR(KBr):3396,3302(N-H,stretching),1633,1558,1503,1455(Ar,stretching).Anal.calcd for C22H18N4O2:C 71.35,H 4.86,N 15.14,O 8.65;found:C71.33,H 4.87,N 15.13,O 8.67。
实施例4
2,2'-联吡啶(4.99g,0.032mol)和液溴(10.24g,0.064mol)放入反应釜中1.5大气压下150℃反应15小时,反应后冷却至室温,把固体粉碎,加入到Na2SO3溶液中搅拌,除去未反应的溴,过滤,再用5%NaOH的溶液碱化除酸,过滤,得到粗产品,用乙酸乙酯/石油醚来进行柱层分离,得到白色5,5'-二溴-2,2'-联吡啶8.64g,产率86%,m.p.221.6-222.1℃.1H-NMR(400MHz,CDCl3,d):7.95(d,2H),8.28(s,2H),8.71(d,2H);13C-NMR(100MHz,CDCl3,d):121.47(C5),122.25(C3),139.64(C4);150.28(C6),153.64(C2),IR(KBr):3049(C-H,stretching),1562,1453,1356(Ar,stretching),636(C-Br,stretch).Anal.calcd forC10H6N2Br2:C 38.22,H 1.91,N 8.92,Br 50.95;found:C 38.23,H 1.92,N 8.91,Br 50.94。
5,5'-二溴-2,2'-联吡啶(6.28g,0.02mol),4-氨基苯酚(5.23g,0.048mol)加入三颈烧瓶中,再加入100ml除水的二甲基亚砜(DMSO),加入无水碳酸钾K2CO3(2.73g,0.02mol,),反应物在185℃反应12小时,冷却至室温,倒入5%NaOH溶液搅拌1小时,过滤出固体,用蒸馏水反复洗涤几次,用水和乙醇重结晶,得到白色的2,6-双[(4-氨基)苯氧基]-2,2'-联吡啶6.44g,产率88%,m.p.204.0-204.6℃.1H-NMR(400MHz,DMSO-d6,d):5.06(s,4H),6.61(d,4H),6.85(d,4H),7.29(d,2H),8.21(s,2H),8.29(d,2H).13C-NMR(100MHz,DMSO-d6,d):114.89(C3'),120.82(C2’),123.92(C3,C4),138.43(C6),144.75(C4'),146.04(C1'),148.84(C2),155.36(C5).FTIR(KBr):3396,3302(N-H,stretching),1633,1558,1503,1455(Ar,stretching).Anal.calcd for C22H18N4O2:C 71.35,H 4.86,N 15.14,O 8.65;found:C 71.33,H 4.87,N 15.13,O 8.67。
实施例5
2,2'-联吡啶(4.99g,0.032mol)和液溴(10.24g,0.064mol)放入反应釜中1.5大气压下150℃反应15小时,反应后冷却至室温,把固体粉碎,加入到Na2SO3溶液中搅拌,除去未反应的溴,过滤,再用5%NaOH的溶液碱化除酸,过滤,得到粗产品,用乙酸乙酯/石油醚来进行柱层分离,得到白色5,5'-二溴-2,2'-联吡啶8.64g,产率86%,m.p.221.6-222.1℃.1H-NMR(400MHz,CDCl3,d):7.95(d,2H),8.28(s,2H),8.71(d,2H);13C-NMR(100MHz,CDCl3,d):121.47(C5),122.25(C3),139.64(C4);150.28(C6),153.64(C2),IR(KBr):3049(C-H,stretching),1562,1453,1356(Ar,stretching),636(C-Br,stretch).Anal.calcd forC10H6N2Br2:C 38.22,H 1.91,N 8.92,Br 50.95;found:C 38.23,H 1.92,N 8.91,Br 50.94。
5,5'-二溴-2,2'-联吡啶(6.28g,0.02mol),4-氨基苯酚(5.23g,0.048mol)加入三颈烧瓶中,再加入100ml除水的二甲基亚砜(DMSO),加入无水碳酸钾K2CO3(2.73g,0.02mol,),反应物在170℃反应12小时,冷却至室温,倒入5%NaOH溶液搅拌1小时,过滤出固体,用蒸馏水反复洗涤几次,用水和乙醇重结晶,得到白色的2,6-双[(4-氨基)苯氧基]-2,2'-联吡啶6.44g,产率82%,m.p.204.0-204.6℃.1H-NMR(400MHz,DMSO-d6,d):5.06(s,4H),6.61(d,4H),6.85(d,4H),7.29(d,2H),8.21(s,2H),8.29(d,2H).13C-NMR(100MHz,DMSO-d6,d):114.89(C3'),120.82(C2’),123.92(C3,C4),138.43(C6),144.75(C4'),146.04(C1'),148.84(C2),155.36(C5).FTIR(KBr):3396,3302(N-H,stretching),1633,1558,1503,1455(Ar,stretching).Anal.calcd for C22H18N4O2:C 71.35,H 4.86,N 15.14,O 8.65;found:C 71.33,H 4.87,N 15.13,O 8.67。
以上所述的实施例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (1)
1.一种5,5'-双[(4-氨基)苯氧基]-2,2'-联吡啶的合成方法,包括以下步骤:
第一步反应:2,2'-联吡啶与液溴物质量比为1:1.5~1:2.5放入反应釜140~160℃下及1.5~2.0大气压反应8~15小时,反应后冷却至室温,把固体粉碎,加入到Na2SO3溶液中搅拌,除去未反应的溴,过滤,再用5%的NaOH溶液碱化除酸,过滤,得到粗产品,用乙酸乙酯/石油醚来进行柱层分离,得到白色5,5'-二溴-2,2'-联吡啶;
第二步反应:5,5'-二溴-2,2'-联吡啶与4-氨基苯酚物质量比为1:2.4~1:3.0加入三颈烧瓶中,再加入除水的N-甲基吡咯烷酮或者二甲基亚砜,加入无水碳酸钾或者氢氧化钠或者氢氧化钾,反应物在170~200℃反应8~12小时,冷却至室温,倒入5%的NaOH溶液搅拌1小时,过滤出固体,用蒸馏水反复洗涤几次,用水和乙醇重结晶,得到白色的5,5'-双[(4-氨基)苯氧基]-2,2'-联吡啶。
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