CN112778272B - 一种2,2′-联氮杂芳环类双齿配体及其制备方法和应用 - Google Patents
一种2,2′-联氮杂芳环类双齿配体及其制备方法和应用 Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
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- 238000001228 spectrum Methods 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
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- LUYISICIYVKBTA-UHFFFAOYSA-N 6-methylquinoline Chemical compound N1=CC=CC2=CC(C)=CC=C21 LUYISICIYVKBTA-UHFFFAOYSA-N 0.000 description 2
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- UMLDUMMLRZFROX-UHFFFAOYSA-N pyridin-2-ylboronic acid Chemical compound OB(O)C1=CC=CC=N1 UMLDUMMLRZFROX-UHFFFAOYSA-N 0.000 description 2
- 238000012552 review Methods 0.000 description 2
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- KTYAQHYBYRVCGD-UHFFFAOYSA-N [Ir].COC1=CC=CCCCC1 Chemical group [Ir].COC1=CC=CCCCC1 KTYAQHYBYRVCGD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
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Abstract
Description
技术领域
本发明涉及有机合成技术领域,具体涉及一种2,2′-联氮杂芳环类双齿配体及其制备方法和应用。
背景技术
含氮杂环化合物是一类重要的化工中间体,广泛应用于有机合成、涂料、药物和农药等领域(Chem.Soc.Rev.2011,40,2199-2210;Chem.Rev.2019,119,8,5057-5191)。含氮杂环化合物由于具有特殊的螯合作用,可以作为金属催化剂的配体使用,在有机合成领域具有非常广阔的应用前景。尤其是含氮的双齿配体,如联吡啶型配体(Chem.Rev.2002,102,3129-3170;Coordination Chemistry Reviews 2018,375,285-332;ChemCatChem 2020,12,2890-2941),是非常重要的一类配体。
目前,含氮的双齿配体的合成方法多种多样,其中,以2-卤代吡啶类化合物为原料的合成方法(通过Ullmann、Suzuki和Stille等经典有机人名反应合成,CoordinationChemistry Reviews 2019,385,1-19)较为成熟,但该方法需要预先在原料中引入卤素取代基,极大地限制了配体种类的多样性、丰富性和快速合成,且不符合目前绿色化学发展的趋势。
发明内容
本发明的目的在于提供一种2,2′-联氮杂芳环类双齿配体及其制备方法和应用
本发明所采取的技术方案是:
进一步优选的,上述2,2′-联氮杂芳环类双齿配体的制备方法包括以下步骤:保护气氛下将催化剂和添加剂分散在溶剂中,进行交叉偶联反应,反应结束后冷却至室温,真空浓缩,再用有机溶剂进行萃取,收集有机相,用无水硫酸钠干燥,再进行柱层析分离,即得2,2′-联氮杂芳环类双齿配体。
优选的,所述保护气氛为氮气气氛或氩气气氛。
优选的,所述交叉偶联反应在100℃~130℃下进行,反应时间为12h~24h。
优选的,所述催化剂为甲氧基(环辛二烯)合铱二聚体([Ir(COD)Cl2]2)、二氯(五甲基环戊二烯基)合铱二聚体([Cp*IrCl2]2)、十二羰基三钌(Ru3(CO)12)中的至少一种。
进一步优选的,所述催化剂为二氯(五甲基环戊二烯基)合铱二聚体。
优选的,所述添加剂为磷酸钾(K3PO4)、碳酸铯(Cs2CO3)、三氟甲磺酸钠(NaOTf)、三氟甲磺酸镱(Yb(OTf)3)、三氟甲磺酸锌(Zn(OTf)2)、对甲苯磺酸(p-TSA)、三氟乙酸(TFA)、甘氨酸(Glycine)、L-脯氨酸(L-Proline)中的至少一种。
进一步优选的,所述添加剂为L-脯氨酸。
优选的,所述溶剂为叔戊醇、甲苯、1,4-二氧六环、N,N-二甲基甲酰胺、二甲基亚砜、水中的至少一种。
进一步优选的,所述溶剂为1,4-二氧六环和水组成的混合溶剂。
优选的,所述萃取采用的有机溶剂为二氯甲烷或乙酸乙酯。
优选的,所述柱层析分离采用的洗脱液由石油醚和乙酸乙酯按照体积比5:1~50:1组成。
本发明的有益效果是:本发明合成了一系列全新的2,2′-联氮杂芳环双齿配体,且合成方法具有原料廉价易得、反应条件温和、底物适用性广、操作简单、易于工业化生产等优点,在有机合成、涂料、药物和农药等领域具有很好的应用前景。
具体来说:
1)本发明利用非活化芳香氮杂环和含氮杂环的芳基硼酸进行交叉偶联反应(水介导下的析氢反应),合成了一系列全新的2,2′-联氮杂芳环双齿配体(既可以是对称结构,也可以是非对称结构);
2)本发明可以依据含氮杂环和含氮杂环的芳基硼酸结构的不同,合成不同类型的2,2′-联氮杂芳环双齿配体,通过给电子和吸电子基团的取代,调整配体的活性,便于它们在催化反应中的应用;
3)本发明的2,2′-联氮杂芳环类双齿配体在合成时无需使用额外的氧化剂或还原剂,且以水溶液作为溶剂,副产物为氢气和硼酸,后处理简单,适宜于扩大化工业生产。
附图说明
图1为实施例1的2,2′-联氮杂芳环双齿配体的核磁共振氢谱图。
图2为实施例1的2,2′-联氮杂芳环双齿配体的核磁共振碳谱图。
图3为实施例2的2,2′-联氮杂芳环双齿配体的核磁共振氢谱图。
图4为实施例2的2,2′-联氮杂芳环双齿配体的核磁共振碳谱图。
图5为实施例3的2,2′-联氮杂芳环双齿配体的核磁共振氢谱图。
图6为实施例3的2,2′-联氮杂芳环双齿配体的核磁共振碳谱图。
图7为实施例4的2,2′-联氮杂芳环双齿配体的核磁共振氢谱图。
图8为实施例4的2,2′-联氮杂芳环双齿配体的核磁共振碳谱图。
图9为实施例5的2,2′-联氮杂芳环双齿配体的核磁共振氢谱图。
图10为实施例5的2,2′-联氮杂芳环双齿配体的核磁共振碳谱图。
具体实施方式
下面结合具体实施例对本发明作进一步的解释和说明。
实施例1:
一种2,2′-联氮杂芳环双齿配体,其制备方法包括以下步骤:
在氮气气氛下,将0.3mmol的喹啉、0.36mmol的2-吡啶硼酸、0.39mg的[Cp*IrCl2]2和7.75mg的L-脯氨酸分散在1.5mL由1,4-二氧六环和水按照体积比1:10组成的混合溶剂中,再110℃反应24h,冷却至室温,真空浓缩,再用二氯甲烷萃取3次,收集有机相,用无水硫酸钠干燥,再进行柱层析分离,柱层析分离采用的洗脱液由石油醚和乙酸乙酯按照体积比10:1组成,即得2,2′-联氮杂芳环双齿配体(白色固体,熔点94.6℃~95.8℃)。
2,2′-联氮杂芳环双齿配体的核磁共振氢谱图和核磁共振碳谱图分别如图1和图2所示,谱图分析如下:
1H NMR(500MHz,CDCl3):δ8.74(d,J=4.6Hz,1H),8.66(d,J=8.0Hz,1H),8.56(d,J=8.6Hz,1H),8.29(d,J=8.6Hz,1H),8.18(d,J=8.5Hz,1H),7.90-7.85(m,2H),7.74(t,J=7.7Hz,1H),7.56(t,J=7.5Hz,1H),7.38-7.35(m,1H)。
13C NMR(126MHz,CDCl3):δ156.4,156.2,149.2,147.9,137.0,136.8,129.8,129.6,128.3,127.6,126.8,124.0,121.9,119.0。
2,2′-联氮杂芳环双齿配体的高分辨质谱数据如下:
HRMS(ESI-quadrupole)m/z:[M+H]+Calcd.for C14H11N2 207.0917;found:207.0913。
根据以上数据推断所得2,2′-联氮杂芳环双齿配体的结构如下:
实施例2:
一种2,2′-联氮杂芳环双齿配体,其制备方法包括以下步骤:
在氮气气氛下,将0.3mmol的喹啉、0.36mmol的8-喹啉硼酸、0.39mg的[Cp*IrCl2]2和7.75mg的L-脯氨酸分散在1.5mL由1,4-二氧六环和水按照体积比1:10组成的混合溶剂中,再110℃反应24h,冷却至室温,真空浓缩,再用二氯甲烷萃取3次,收集有机相,用无水硫酸钠干燥,再进行柱层析分离,柱层析分离采用的洗脱液由石油醚和乙酸乙酯按照体积比5:1组成,即得2,2′-联氮杂芳环双齿配体(白色固体,熔点120.9℃~121.8℃)。
2,2′-联氮杂芳环双齿配体的核磁共振氢谱图和核磁共振碳谱图分别如图3和图4所示,谱图分析如下:
1H NMR(400MHz,CDCl3):δ8.97(d,J=4.1Hz,1H),8.27-8.23(m,3H),8.22(d,J=8.5Hz,1H),8.14(d,J=8.5Hz,1H),7.92(d,J=8.1Hz,1H),7.89(d,J=8.2Hz,1H),7.77-7.73(m,1H),7.71(t,J=6.1Hz,1H),7.56(t,J=7.5Hz,1H),7.44-7.40(m,1H)。
13C NMR(101MHz,CDCl3):δ158.3,150.4,148.5,146.1,139.5,136.4,134.8,131.5,129.7,129.3,129.1,128.6,127.6,127.4,126.7,126.4,125.0,121.2。
2,2′-联氮杂芳环双齿配体的高分辨质谱数据如下:
HRMS(ESI-quadrupole)m/z:[M+H]+Calcd.for C18H13N2 257.1073;found:257.1067。
根据以上数据推断所得2,2′-联氮杂芳环双齿配体的结构如下:
实施例3:
一种2,2′-联氮杂芳环双齿配体,其制备方法包括以下步骤:
在氮气气氛下,将0.3mmol的6-甲基喹啉、0.36mmol的8-喹啉硼酸、0.43mg的[Cp*IrCl2]2和8.59mg的L-脯氨酸分散在1.5mL由1,4-二氧六环和水按照体积比1:10组成的混合溶剂中,再110℃反应24h,冷却至室温,真空浓缩,再用二氯甲烷萃取3次,收集有机相,用无水硫酸钠干燥,再进行柱层析分离,柱层析分离采用的洗脱液由石油醚和乙酸乙酯按照体积比5:1组成,即得2,2′-联氮杂芳环双齿配体(无色油状液体)。
2,2′-联氮杂芳环双齿配体的核磁共振氢谱图和核磁共振碳谱图分别如图5和图6所示,谱图分析如下:
1H NMR(400MHz,CDCl3):δ8.96(d,J=5.5Hz,1H),8.24(d,J=7.1Hz,1H),8.20(d,J=8.3Hz,1H),8.16(d,J=8.8Hz,2H),8.11(d,J=8.5Hz,1H),7.90(d,J=8.2Hz,1H),7.70(t,J=7.6Hz,1H),7.64(s,1H),7.57(d,J=8.6Hz,1H),7.42-7.38(m,1H),2.56(s,3H)。
13C NMR(101MHz,CDCl3):δ157.3,150.3,147.1,146.1,139.6,136.4,136.2,134.3,131.6,131.5,129.3,129.0,128.6,127.4,126.7,126.4,125.0,121.1,21.7。
2,2′-联氮杂芳环双齿配体的高分辨质谱数据如下:
HRMS(ESI):Calcd.for C17H16N:271.1230;found:271.1224。
根据以上数据推断所得2,2′-联氮杂芳环双齿配体的结构如下:
实施例4:
一种2,2′-联氮杂芳环双齿配体,其制备方法包括以下步骤:
在氮气气氛下,将0.3mmol的喹喔啉、0.36mmol的2-吡啶硼酸、0.39mg的[Cp*IrCl2]2和7.81mg的L-脯氨酸分散在1.5mL由1,4-二氧六环和水按照体积比1:10组成的混合溶剂中,再110℃反应24h,冷却至室温,真空浓缩,再用二氯甲烷萃取3次,收集有机相,用无水硫酸钠干燥,再进行柱层析分离,柱层析分离采用的洗脱液由石油醚和乙酸乙酯按照体积比10:1组成,即得2,2′-联氮杂芳环双齿配体(黄色固体,熔点122.5℃~126.7℃)。
2,2′-联氮杂芳环双齿配体的核磁共振氢谱图和核磁共振碳谱图分别如图7和图8所示,谱图分析如下:
1H NMR(500MHz,CDCl3):δ9.96(s,1H),8.78(d,J=4.6Hz,1H),8.59(d,J=7.9Hz,1H),8.16(d,J=9.3Hz,2H),7.89(t,J=7.7Hz,1H),7.80-7.75(m,2H),7.42-7.39(m,1H)。
13C NMR(126MHz,CDCl3):δ154.5,150.2,149.4,144.2,142.6,141.8,137.1,130.2,130.1,129.7,129.3,124.6,122.1。
2,2′-联氮杂芳环双齿配体的高分辨质谱数据如下:
HRMS(ESI-quadrupole)m/z:[M+H]+Calcd.for C13H10N3 208.0869;found:208.0865。
根据以上数据推断所得2,2′-联氮杂芳环双齿配体的结构如下:
实施例5:
一种2,2′-联氮杂芳环双齿配体,其制备方法包括以下步骤:
在氮气气氛下,将0.3mmol的喹喔啉、0.36mmol的8-喹啉硼酸、0.39mg的[Cp*IrCl2]2和7.81mg的L-脯氨酸分散在1.5mL由1,4-二氧六环和水按照体积比1:10组成的混合溶剂中,再110℃反应24h,冷却至室温,真空浓缩,再用二氯甲烷萃取3次,收集有机相,用无水硫酸钠干燥,再进行柱层析分离,柱层析分离采用的洗脱液由石油醚和乙酸乙酯按照体积比5:1组成,即得2,2′-联氮杂芳环双齿配体(白色固体,熔点182.5℃~183.9℃)。
2,2′-联氮杂芳环双齿配体的核磁共振氢谱图和核磁共振碳谱图分别如图9和图10所示,谱图分析如下:
1H NMR(400MHz,CDCl3):δ9.64(s,1H),8.97(d,J=4.0Hz,1H),8.30(d,J=7.1Hz,1H),8.26(d,J=8.3Hz,1H),8.24-8.19(m,2H),7.99(d,J=8.2Hz,1H),7.81-7.78(m,2H),7.77-7.73(m,1H),7.50-7.46(m,1H)。
13C NMR(101MHz,CDCl3):δ153.3,150.7,148.7,145.9,142.8,141.4,136.4,136.4,131.8,130.0,129.7,129.6,129.6,129.2,128.6,126.8,121.6。
2,2′-联氮杂芳环双齿配体的高分辨质谱数据如下:
HRMS(ESI-quadrupole)m/z:[M+H]+Calcd.for C17H12N3 258.1026;found:258.1021。
根据以上数据推断所得2,2′-联氮杂芳环双齿配体的结构如下:
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (5)
2.根据权利要求1所述的2,2′-联氮杂芳环类双齿配体的制备方法,其特征在于:所述交叉偶联反应在100℃~130℃下进行,反应时间为12h~24h。
5.根据权利要求1所述的2,2′-联氮杂芳环类双齿配体的制备方法,其特征在于:所述溶剂为叔戊醇、甲苯、1,4-二氧六环、N,N-二甲基甲酰胺、二甲基亚砜、水中的至少一种。
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