CN114853608A - 一种氮杂环卡宾催化的[60]富勒氢衍生物的合成方法 - Google Patents

一种氮杂环卡宾催化的[60]富勒氢衍生物的合成方法 Download PDF

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CN114853608A
CN114853608A CN202210492477.0A CN202210492477A CN114853608A CN 114853608 A CN114853608 A CN 114853608A CN 202210492477 A CN202210492477 A CN 202210492477A CN 114853608 A CN114853608 A CN 114853608A
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刘统信
张朋玲
朱雪
张贵生
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Henan Normal University
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Abstract

本发明公开了一种氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，在氮杂环卡宾催化作用下，不饱和醛类化合物与[60]富勒烯、甲醇进行三组分反应高效合成一系列[60]富勒氢类衍生物。本发明使用氮杂环卡宾催化富勒烯反应，具有操作简单，无污染，后处理简单等优点，而且此发明具有底物范围广泛，官能团兼容性好，产率高，使用有机小分子催化剂，合成工艺绿色环保。

Description

一种氮杂环卡宾催化的[60]富勒氢衍生物的合成方法
技术领域
本发明属于富勒烯衍生物的合成技术领域，具体涉及一种氮杂环卡宾催化的[60]富勒氢衍生物的合成方法。
背景技术
富勒烯的功能化是富勒烯化学的重要研究方向，可以改善富勒烯的溶解度，通过在富勒烯上引入不同功能的基团，制备其它结构和功能新颖的富勒烯衍生物。因此，探索新的富勒烯修饰方法，构建不同的官能团化的富勒烯，对于发展富勒烯衍生物在不同领域中的应用至关重要。
发明内容
本发明解决的技术问题是提供了一种氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，在氮杂环卡宾催化作用下，不饱和醛类化合物与[60]富勒烯、甲醇进行三组分反应高效合成一系列[60]富勒氢类衍生物的新方法。本发明使用氮杂环卡宾催化富勒烯反应，具有操作简单，无污染，后处理简单等优点，而且此发明具有底物范围广泛，官能团兼容性好，产率高，使用有机小分子催化剂，合成工艺绿色环保。
本发明为解决上述技术问题采用如下技术方案，一种氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，其特征在于具体过程为：以α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物、甲醇和[60]富勒烯为反应原料，以氮杂环卡宾为催化剂，以乙酸铯为促进剂，以无水邻二氯苯和无水二氯甲烷为反应溶剂，在惰性气氛下于90-110 ℃发生三组分反应，其中α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物在氮杂环卡宾催化作用下发生极性反转，由亲电性变成亲核性，与[60]富勒烯和甲醇发生反应制得目标产物[60]富勒氢衍生物，合成过程中的反应方程式为：
Figure DEST_PATH_IMAGE002
其中R1为烷基、芳基或杂芳基。
进一步优选，所述的氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，其特征在于具体步骤为：将[60]富勒烯、α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物、氮杂环卡宾、乙酸铯和甲醇置于干燥的史莱克管中，加入无水邻二氯苯和无水二氯甲烷，超声使体系完全溶解，在氮气氛围下于90-110 ℃的油浴锅中反应，反应停止后冷却至室温，滤去不溶物，减压旋出溶剂，先用CS2作为洗脱剂收集未反应的[60]富勒烯，采用湿法上样，用薄层层析硅胶柱分离得到目标产物[60]富勒氢衍生物。
进一步优选，所述[60]富勒烯、α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物、氮杂环卡宾与乙酸铯的投料摩尔比为1.0:3.0:0.2:0.5。
进一步优选，所述α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物为
Figure DEST_PATH_IMAGE004
、
Figure DEST_PATH_IMAGE006
、
Figure DEST_PATH_IMAGE008
、
Figure DEST_PATH_IMAGE010
、
Figure DEST_PATH_IMAGE012
、
Figure DEST_PATH_IMAGE014
、
Figure DEST_PATH_IMAGE016
或
Figure DEST_PATH_IMAGE018
。
进一步优选，所述[60]富勒氢衍生物为
Figure DEST_PATH_IMAGE020
、
Figure DEST_PATH_IMAGE022
、
Figure DEST_PATH_IMAGE024
、
Figure DEST_PATH_IMAGE026
、
Figure DEST_PATH_IMAGE028
、
Figure DEST_PATH_IMAGE030
、
Figure DEST_PATH_IMAGE032
或
Figure DEST_PATH_IMAGE034
。
进一步优选，所述氮杂环卡宾为
Figure DEST_PATH_IMAGE036
或
Figure DEST_PATH_IMAGE038
。
本发明与现有技术相比具有以下优点和有益效果：本发明操作简单，无污染，后处理简单等优点，而且此发明具有底物范围广泛，官能团兼容性好，产率高，使用有机小分子催化剂，合成工艺绿色环保。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
Figure DEST_PATH_IMAGE040
实施例1
制备[60]富勒氢衍生物4aa：
Figure DEST_PATH_IMAGE042
反应步骤：
准确称取0.05 mmol [60]富勒烯，0.15 mmol底物2a
Figure DEST_PATH_IMAGE044
，0.010 mmol催化剂
Figure DEST_PATH_IMAGE045
，0.025 mmol乙酸铯和30 equiv甲醇于25 mL干燥的史莱克管中，加入4mL无水邻二氯苯和1 mL无水二氯甲烷，超声使体系完全溶解。在氮气氛围下于90 ℃的油浴锅中反应1 h，反应停止后，冷却至室温。滤去不溶物，减压旋出溶剂。先用CS2作为洗脱剂收集未反应的[60]富勒烯，采用湿法上样，用薄层层析硅胶柱分离，得到目标产物[60]富勒氢衍生物4aa，产物4aa的相对产率为43%。
4aa:1H NMR (600 MHz, CDCl3/CS2, v/v = 10:1) δ 7.87 (d, J = 7.8 Hz,2H), 7.54 (t, J = 7.8 Hz, 2H), 7.45 (t, J = 7.8 Hz, 1H), 6.68 (s, 1H), 5.16(dd, J = 4.2, 11.4 Hz, 1H), 4.14 (dd, J = 4.2, 15.6 Hz, 1H), 3.86 (dd, J =10.8, 15.6 Hz, 1H), 3.69 (s, 3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ171.99, 153.84, 153.68, 153.51, 147.59, 147.35, 146.93, 146.86, 146.71,146.51, 146.34, 146.27, 146.26，145.82, 145.81, 145.63, 145.52, 145.49,145.48, 145.45, 145.42，144.84, 144.81, 144.58, 144.53, 143.33, 143.31,142.71, 142.70, 142.67, 142.30, 142.26, 142.16, 142.13, 141.74, 141.70,141.65, 141.59, 140.39, 140.37, 139.68, 139.50, 138.54, 136.96, 136.58,136.30, 130.32, 128.95, 128.38, 69.09, 58.49, 55.40, 52.10, 37.89; FT-IR ν/cm-1 (KBr) 1735, 1511, 1428, 1251, 1178, 1020, 904, 765, 729, 700, 662, 573,524; UV-vis (CHCl3) λmax/nm 256, 330, 433, 704; MALDI-TOF MS m/z calcd forC70H12O2[M]-884.0837, found 884.0856。
实施例2
制备[60]富勒氢衍生物4ba：
Figure DEST_PATH_IMAGE047
反应步骤：
准确称取0.05 mmol [60]富勒烯，0.15 mmol底物2b
Figure DEST_PATH_IMAGE049
，0.010mmol催化剂
Figure DEST_PATH_IMAGE050
，0.025 mmol乙酸铯和30 equiv甲醇于25 mL干燥的史莱克管中，加入4 mL无水邻二氯苯和1 mL无水二氯甲烷，超声使体系完全溶解。在氮气氛围下于90 ℃的油浴锅中反应1 h，反应停止后，冷却至室温。滤去不溶物，减压旋出溶剂。先用CS2作为洗脱剂收集未反应的[60]富勒烯，采用湿法上样，用薄层层析硅胶柱分离，得到目标产物[60]富勒氢衍生物4ba，产物4ba的相对产率为46%。
4ba:1H NMR (600 MHz, CDCl3/CS2, v/v = 10:1) δ 7.76 (d, J = 9.0 Hz,2H), 7.03 (d, J = 9.0 Hz, 2H), 6.65 (s, 1H), 5.09 (dd, J = 4.2, 11.4 Hz, 1H),4.09 (dd, J = 4.2, 15.6 Hz, 1H), 3.86 (s, 3H), 3.79 (dd, J = 11.4, 15.6 Hz,1H), 3.68 (s, 3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 170.83, 158.38,152.86, 152.67, 152.61, 152.57, 146.50, 146.26, 145.88, 145.80, 145.67,145.55, 145.44, 145.27, 145.20, 145.18, 144.75, 144.74, 144.55, 144.45,144.40, 144.36, 143.78, 143.74, 143.51, 143.47, 142.27, 142.25, 141.65,141.61, 141.24, 141.20, 141.10, 141.09, 141.07, 140.70, 140.66, 140.60,140.53, 139.33, 139.31, 138.66, 138.47, 135.87, 135.49, 135.27, 135.26,130.23, 129.30, 113.24, 68.33, 57.50, 54.11, 53.67, 50.95, 37.02; FT-IR ν/cm-1 (KBr) 2922, 1731, 1510, 1429, 1247, 1213, 1163, 1031, 988, 828, 806, 766,573, 524; UV-vis (CHCl3) λmax/nm 259, 330, 434, 704; MALDI-TOF MS m/z calcdfor C71H14O3[M]-914.0943, found 914.0956。
实施例3
制备[60]富勒氢衍生物4ca：
Figure DEST_PATH_IMAGE052
反应步骤：
准确称取0.05 mmol [60]富勒烯，0.15 mmol底物2c
Figure DEST_PATH_IMAGE054
，0.010 mmol催化剂
Figure DEST_PATH_IMAGE055
，0.025 mmol乙酸铯和30 equiv甲醇于25 mL 干燥的史莱克管中，加入4 mL无水邻二氯苯和1 mL无水二氯甲烷，超声使体系完全溶解。在氮气氛围下于100 ℃的油浴锅中反应1 h，反应停止后，冷却至室温。滤去不溶物，减压旋出溶剂。先用CS2作为洗脱剂收集未反应的[60]富勒烯，采用湿法上样，用薄层层析硅胶柱分离，得到目标产物[60]富勒氢衍生物4ca，产物4ca的相对产率为38%。
4ca:1H NMR (600 MHz, CDCl3/CS2, v/v = 10:1) δ 8.34 (s, 1H), 8.02-7.97(m, 3H), 7.89 (d, J = 7.8 Hz, 1H), 7.56-7.51 (m, 2H), 6.77 (s, 1H), 5.33 (dd,J = 3.6, 10.8 Hz, 1H), 4.22 (dd, J = 4.2, 16.2 Hz, 1H), 3.97 (dd, J = 10.8,15.6 Hz, 1H), 3.65 (s, 3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ171.86, 153.76, 153.61, 153.45, 147.55, 147.30, 146.89, 146.80, 146.67,146.47, 146.30, 146.23, 145.78, 145.77, 145.62, 145.48, 145.46, 145.44,145.37, 144.80, 144.77, 144.53, 144.48, 143.29, 143.28, 142.68, 142.66,142.64, 142.25, 142.21, 142.12, 142.09, 141.70, 141.66, 141.63, 140.57,140.36, 140.34, 139.71, 139.51, 136.97, 136.56, 136.26, 136.24, 136.18,133.41, 133.18, 129.40, 128.63, 128.31, 128.01, 127.95, 126.60, 126.57,69.17, 58.63, 55.54, 52.06, 37.97; FT-IR ν/cm-1 (KBr) 1731, 1509, 1427, 1253,1215, 1006, 897, 807, 726, 572, 5246; UV-vis (CHCl3) λmax/nm 254, 330, 433,704; MALDI-TOF MS m/z calcd for C74H14O2[M]-934.0994, found 934.0978。
实施例4
制备[60]富勒氢衍生物4da：
Figure DEST_PATH_IMAGE057
反应步骤：
准确称取0.05 mmol [60]富勒烯，0.15 mmol底物2d
Figure DEST_PATH_IMAGE059
，0.010mmol催化剂
Figure DEST_PATH_IMAGE060
，0.025 mmol乙酸铯和30 equiv甲醇于25 mL干燥的史莱克管中，加入4 mL无水邻二氯苯和1 mL无水二氯甲烷，超声使体系完全溶解。在氮气氛围下于100℃的油浴锅中反应1 h，反应停止后，冷却至室温。滤去不溶物，减压旋出溶剂。先用CS2作为洗脱剂收集未反应的[60]富勒烯，采用湿法上样，用薄层层析硅胶柱分离，得到目标产物[60]富勒氢衍生物4da，产物4da的相对产率为30%。
4da:1H NMR (400 MHz, CDCl3/CS2, v/v = 10:1) δ 7.81 (d, J = 8.8 Hz,2H), 7.50 (d, J = 8.4 Hz, 2H), 6.61 (s, 1H), 5.14 (dd, J = 4.0, 11.2 Hz, 1H),4.14 (dd, J = 4.0, 16.0 Hz, 1H), 3.82 (dd, J = 11.2, 16.0 Hz, 1H), 3.70 (s,3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 171.68, 153.50, 153.32,153.02, 152.87, 147.58, 147.33, 146.81, 146.71, 146.50, 146.33, 146.31,146.27, 146.25, 145.76, 145.74, 145.65, 145.52, 145.49, 145.47, 145.44,144.82, 144.79, 144.52, 144.48, 143.32, 143.30, 142.72, 142.70, 142.67,142.24, 142.20, 142.15, 142.09, 141.74, 141.67, 141.65, 141.58, 140.43,140.41, 139.73, 139.53, 137.07, 136.89, 136.62, 136.23, 136.17, 134.45,131.51, 129.11, 68.82, 58.49, 54.84, 52.15, 37.74; FT-IR ν/cm-1 (KBr) 1735,1487, 1429, 1411, 1208, 1164, 1089, 1010, 729, 572, 552, 524; UV-vis (CHCl3)λmax/nm 260, 319, 433, 703; MALDI-TOF MS m/z calcd for C70H11ClO2[M]-918.0448, found 918.0435。
实施例5
制备[60]富勒氢衍生物4ea：
Figure DEST_PATH_IMAGE062
反应步骤：
准确称取0.05 mmol [60]富勒烯，0.15 mmol底物2e
Figure DEST_PATH_IMAGE064
，0.010mmol催化剂
Figure DEST_PATH_IMAGE065
，0.025 mmol乙酸铯和30 equiv甲醇于25 mL干燥的史莱克管中，加入4 mL无水邻二氯苯和1 mL无水二氯甲烷，超声使体系完全溶解。在氮气氛围下于100℃的油浴锅中反应1 h，反应停止后，冷却至室温。滤去不溶物，减压旋出溶剂。先用CS2作为洗脱剂收集未反应的[60]富勒烯，采用湿法上样，用薄层层析硅胶柱分离，得到目标产物[60]富勒氢衍生物4ea，产物4ea的相对产率为40%。
4ea:1H NMR (600 MHz, CDCl3/CS2, v/v = 10:1) δ 7.75 (d, J = 8.4 Hz,2H), 7.65 (d, J = 8.4 Hz, 2H), 6.60 (s, 1H), 5.12 (dd, J = 4.2, 11.4 Hz, 1H),4.14 (dd, J = 4.2, 15.6 Hz, 1H), 3.82 (dd, J = 11.4, 16.2 Hz, 1H), 3.71 (s,3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 170.65, 152.48, 152.31,151.99, 151.85, 146.59, 146.33, 145.81, 145.71, 145.50, 145.35, 145.30,145.27, 145.25, 144.76, 144.74, 144.66, 144.52, 144.47, 144.44, 143.82,143.79, 143.52, 143.48, 142.32, 141.72, 141.70, 141.67, 141.24, 141.20,141.15, 141.09, 140.74, 140.67, 140.65, 140.63, 140.58, 139.43, 139.42,138.74, 138.54, 136.61, 135.91, 135.62, 135.23, 135.17, 131.06, 130.83,113.24, 68.33, 57.49, 54.11，53.67, 50.95, 37.02; FT-IR ν/cm-1 (KBr) 1735,1510, 1484, 1429, 1259, 1209, 1164, 1090, 1007, 984, 963, 798, 761, 573, 524;UV-vis (CHCl3) λmax/nm 253, 313, 433, 703; MALDI-TOF MS m/z calcd forC70H11BrO2[M]-961.9942 , found 961.9928。
实施例6
制备[60]富勒氢衍生物4fa：
Figure DEST_PATH_IMAGE067
反应步骤：
准确称取0.05 mmol [60]富勒烯，0.15 mmol底物2f
Figure DEST_PATH_IMAGE069
，0.010 mmol催化剂
Figure DEST_PATH_IMAGE070
，0.025 mmol乙酸铯和30 equiv甲醇于25 mL干燥的史莱克管中，加入4 mL无水邻二氯苯和1 mL无水二氯甲烷，超声使体系完全溶解。在氮气氛围下于110 ℃的油浴锅中反应1 h，反应停止后，冷却至室温。滤去不溶物，减压旋出溶剂。先用CS2作为洗脱剂收集未反应的[60]富勒烯，采用湿法上样，用薄层层析硅胶柱分离，得到目标产物[60]富勒氢衍生物4fa，产物4fa的相对产率为30%。
4fa: 1H NMR (400 MHz, CDCl3/CS2, v/v = 10:1) δ 7.84 (d, J = 8.0 Hz,2H), 7.60 (d, J = 8.4 Hz, 2H), 6.59 (s, 1H), 5.09 (dd, J = 4.0, 11.2 Hz, 1H),4.11 (dd, J = 4.0, 16.0 Hz, 1H), 3.78 (dd, J = 11.2, 16.0 Hz, 1H), 3.69 (s,3H); 13C NMR (150 MHz, CDCl3/CS2, v/v = 10:1) δ 171.30, 153.36, 153.18,152.87, 152.74, 147.49, 147.24, 146.71, 146.64, 146.42, 146.38, 146.25,146.21, 146.18, 146.15, 145.66, 145.63, 145.58, 145.44, 145.41, 145.37,144.73, 144.70, 144.42, 144.39, 143.23, 143.21, 142.64, 142.59, 142.57,142.15, 142.08, 142.05, 141.99, 141.65, 141.57, 141.52, 141.50, 140.37,140.34, 139.68, 139.49, 138.17, 137.92, 136.82, 136.54, 136.14, 136.08,131.92, 94.87, 68.62, 58.49, 54.96, 51.98, 37.59; FT-IR ν/cm-1 (KBr) 1734,1508, 1428, 1410, 1164, 1046, 1002, 961, 805, 729, 677, 572, 522; UV-vis(CHCl3) λmax/nm 258, 310, 433, 534, 703; MALDI-TOF MS m/z calcd for C70H11IO2[M]-1009.9804, found 1009.9821。
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。

Claims (6)

1.一种氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，其特征在于具体过程为：以α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物、甲醇和[60]富勒烯为反应原料，以氮杂环卡宾为催化剂，以乙酸铯为促进剂，以无水邻二氯苯和无水二氯甲烷为反应溶剂，在惰性气氛下于90-110 ℃发生三组分反应，其中α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物在氮杂环卡宾催化作用下发生极性反转，由亲电性变成亲核性，与[60]富勒烯和甲醇发生反应制得目标产物[60]富勒氢衍生物，合成过程中的反应方程式为：
Figure DEST_PATH_IMAGE001
其中R1为烷基、芳基或杂芳基。
2.根据权利要求1所述的氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，其特征在于具体步骤为：将[60]富勒烯、α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物、氮杂环卡宾、乙酸铯和甲醇置于干燥的史莱克管中，加入无水邻二氯苯和无水二氯甲烷，超声使体系完全溶解，在氮气氛围下于90-110 ℃的油浴锅中反应，反应停止后冷却至室温，滤去不溶物，减压旋出溶剂，先用CS2作为洗脱剂收集未反应的[60]富勒烯，采用湿法上样，用薄层层析硅胶柱分离得到目标产物[60]富勒氢衍生物。
3.根据权利要求1或2所述的氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，其特征在于所述[60]富勒烯、α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物、氮杂环卡宾与乙酸铯的投料摩尔比为1.0:3.0:0.2:0.5。
4.根据权利要求1或2所述的氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，其特征在于所述α,β-不饱和醛类化合物或4-(氯甲基)苯甲醛类化合物为
Figure 351254DEST_PATH_IMAGE002
、
Figure DEST_PATH_IMAGE003
、
Figure 720924DEST_PATH_IMAGE004
、
Figure DEST_PATH_IMAGE005
、
Figure 438344DEST_PATH_IMAGE006
、
Figure DEST_PATH_IMAGE007
、
Figure 521969DEST_PATH_IMAGE008
或
Figure DEST_PATH_IMAGE009
。
5.根据权利要求1或2所述的氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，其特征在于所述[60]富勒氢衍生物为
Figure 539604DEST_PATH_IMAGE010
、
Figure DEST_PATH_IMAGE011
、
Figure 565328DEST_PATH_IMAGE012
、
Figure DEST_PATH_IMAGE013
、
Figure 19312DEST_PATH_IMAGE014
、
Figure DEST_PATH_IMAGE015
、
Figure 421475DEST_PATH_IMAGE016
或
Figure DEST_PATH_IMAGE017
。
6.根据权利要求1或2所述的氮杂环卡宾催化的[60]富勒氢衍生物的合成方法，其特征在于：所述氮杂环卡宾为
Figure 775840DEST_PATH_IMAGE018
或
Figure DEST_PATH_IMAGE019
。
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