CN110343064A - 一种[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法 - Google Patents

一种[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法 Download PDF

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CN110343064A
CN110343064A CN201910701178.1A CN201910701178A CN110343064A CN 110343064 A CN110343064 A CN 110343064A CN 201910701178 A CN201910701178 A CN 201910701178A CN 110343064 A CN110343064 A CN 110343064A
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fullerene
indole derivatives
tetrahydro cyclopentyl
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CN110343064B (zh
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刘统信
张朋玲
张贵生
危娟
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Henan Normal University
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    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract

本发明公开了一种[60]富勒烯并四氢环戊[2,3‑b]吲哚衍生物的合成方法，属于富勒烯衍生物的合成技术领域。本发明的技术方案要点为：一种[60]富勒烯并四氢环戊[2,3‑b]吲哚衍生物的合成方法，具体合成过程为：以碘化铜为催化剂，以无水氯苯为溶剂，[60]富勒烯与C2‑取代的吲哚类化合物在4‑二甲氨基吡啶和过氧化二叔丁基的作用下，通过在氮气保护下于40~85℃直接氧化脱氢发生自由基加成反应实现C‑C键构建合成目标产物[60]富勒烯并四氢环戊[2,3‑b]吲哚衍生物。本发明具有较高的原子经济性，底物范围广，通过直接氧化脱氢的方法一锅法合成目标产物，与PCBM具有相近的还原电势，可成为有机太阳能电池潜在的受体材料。

Description

一种[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法
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[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法。
背景技术
自1985年富勒烯发现以来，富勒烯化学的骨架修饰一直是人们研究的热点领域。迄今为止，多种结构新颖、功能独特的富勒烯衍生物已被合成并广泛应用于太阳能电池、生物医药、纳米材料、光电材料等领域。因此，发展简单、高效的新方法合成结构新颖的富勒烯衍生物来实现富勒烯的功能化是至关重要的。
发明内容
本发明解决的技术问题是提供了一种原子经济性高且底物适用范围广的[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法。
本发明为解决上述技术问题采用如下技术方案，一种[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法，其特征在于具体合成过程为：以碘化铜为催化剂，以无水氯苯为溶剂，[60]富勒烯与C2-取代的吲哚类化合物在4-二甲氨基吡啶和过氧化二叔丁基的作用下，通过在氮气保护下于40～85℃直接氧化脱氢发生自由基加成反应实现C-C键构建合成目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物；
该合成过程中生成[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的反应方程式为：
其中R1为芳基、杂芳基、烯基或取代氨基，R2为H、甲氧基或氯。
进一步优选，所述的[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法，其特征在于具体合成步骤为：将C60富勒烯、碘化铜、C2-取代的吲哚类化合物和4-二甲氨基吡啶置于干燥的Schlenk tube中，再加入溶剂无水氯苯和97wt％的过氧化二叔丁基水溶液密封，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrektube中的溶剂完全解冻后置于40～85℃的油浴中反应3～5h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先准备好的薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物，所述的C2-取代的吲哚类化合物为
进一步优选，所述[60]富勒烯、碘化铜、C2-取代的吲哚类化合物、4-二甲氨基吡啶与过氧化二叔丁基的投料摩尔比为1:0.2:2.0:0.5:4.0。
本发明与现有技术相比具有以下有益效果：本发明具有较高的原子经济性，底物范围广，通过直接氧化脱氢的方法一锅法合成目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物，与PCBM具有相近的还原电势，可成为有机太阳能电池潜在的受体材料。
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。
实施例1
制备[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2a：
反应步骤：
准确称取C60富勒烯(36.0mg,0.05mmol)，碘化铜(1.9mg,0.01mmol)，1a(0.1mmol)和DMAP(3.1mg,0.025mmol)于25mL干燥的Schlenk tube中，再加入6mL溶剂无水氯苯和97wt％的过氧化二叔丁基(0.2mmol)水溶液密闭，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrek tube中的溶剂完全解冻后置于85℃的油浴中反应3h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先准备好的薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用尽可能少的二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2a，产物2a的相对产率为36％。
2a:1H NMR(400MHz,CD2Cl2/CS2)δ8.39(s,1H),7.94(d,J＝8.0Hz,1H),7.69(d,J＝7.2Hz,2H),7.57(d,J＝8.0Hz,1H),7.44(t,J＝8.0Hz,2H),7.40-7.29(m,2H),7.21(td,J＝7.2,0.8Hz,1H),6.50(s,1H)。
13C NMR(150MHz,CDCl3/CS2with Cr(acac)3as relaxation reagent,all 1Cunless indicated)δ157.42,154.27,157.33,152.51,147.50,147.25,146.11,146.09,146.04,146.03,146.01,145.97,145.93,145.90,145.81,145.66,145.59,145.31,145.28,145.24,145.23,145.20,145.09,145.07,145.00,144.50,144.48,144.45,144.33,143.07,142.63,142.58,142.55,142.53,142.50,142.13,142.06,142.02,141.79,141.76,141.69,141.57,140.80,140.71,140.49,140.20,139.92,139.12,136.57,135.61,135.48,135.14,129.82,129.20,128.31,123.59,122.97,122.81,120.99,118.94,112.75,82.29,70.33,57.52。
FT-IRν/cm-1(KBr)3430,1510,1449,1461,736,715,699,574,526。
UV-vis(CHCl3)λmax/nm 256,430,703；MALDI-TOF MS m/z calcd for C75H11N[M]+925.0886,found 925.0856。
实施例2
制备[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2b：
反应步骤：
准确称取C60富勒烯(36.0mg,0.05mmol)，碘化铜(1.9mg,0.01mmol)，1b(0.1mmol)和DMAP(3.1mg,0.025mmol)于25mL干燥的Schlenk tube中，再加入6mL溶剂无水氯苯和97wt％的过氧化二叔丁基(0.2mmol)水溶液密闭，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrek tube中的溶剂完全解冻后置于65℃的油浴中反应4h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先将薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用尽可能少的二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2b，产物2b的相对产率为37％。
2b:1H NMR(400MHz,CDCl3/CS2)δ8.33(s,1H),8.16(s,1H),8.05(d,J＝7.6Hz,1H),7.94–7.83(m,4H),7.59(d,J＝8.0Hz,1H),7.53–7.51(m,2H),7.38(t,J＝8.0Hz,1H),7.30(t,J＝7.6Hz,1H),6.65(s,1H)。
13C NMR(150MHz,DMSO-d6/CS2with Cr(acac)3as relaxation reagent)δ157.19,153.92,152.99,152.20,146.50,146.26,145.26,145.17,145.09,145.07,145.05,145.01,144.91,144.82,144.75,144.41,144.34,144.31,144.28,144.22,144.16,144.13,144.01,143.61,143.57,143.55,143.43,142.33,142.16,142.10,141.87,141.85,141.61,141.58,141.55,141.24,141.20,141.18,141.14,141.09,140.86,140.79,140.76,140.62,140.37,139.82,139.60,138.96,138.21,137.75,135.81,134.62,134.42,134.33,132.52,132.04,127.89,127.36,126.99,125.69,125.56,122.53,121.45,120.02,119.42,117.55,112.32,81.52,69.58,56.60。
FT-IRν/cm-1(KBr)3428,1510,1447,1309,1244,1187,860,818,739,574,526。
UV-vis(CHCl3)λmax/nm 253,431,704；MALDI-TOF MS m/z calcd for C79H13N[M]+975.1043,found 975.1029。
实施例3
制备[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2c：
反应步骤：
准确称取C60富勒烯(36.0mg,0.05mmol)，碘化铜(1.9mg,0.01mmol)，1c(0.1mmol)和DMAP(3.1mg,0.025mmol)于25mL干燥的Schlenk tube中，再加入6mL溶剂无水氯苯和97wt％的过氧化二叔丁基(0.2mmol)水溶液密闭，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrek tube中的溶剂完全解冻后置于40℃的油浴中反应3h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先准备好的薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用尽可能少的二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2c，产物2c的相对产率为40％。
2c:1H NMR(600MHz,CDCl3/CS2)δ8.46(s,1H),8.01(d,J＝7.8Hz,1H),7.61(d,J＝8.4Hz,1H),7.38–7.36(m,3H),7.28(t,J＝7.2Hz,1H),7.09(s,1H),6.77(s,1H)。
13C NMR(150MHz,CDCl3/CS2with Cr(acac)3as relaxation reagent)δ156.64,153.25,153.14,152.13,147.42,147.17,146.28,146.07,146.03,146.01,145.98,145.92,145.88,145.82,145.65,145.58,145.35,145.25,145.17,145.15,145.10,145.04,144.95,144.40,144.34,144.28,143.30,142.98,142.56,142.54,142.48,142.45,142.35,142.09,142.07,141.98,141.94,141.90,141.76,141.71,141.60,141.59,141.44,140.66,140.41,139.93,139.85,138.94,136.78,135.59,135.37,135.18,127.78,127.56,126.40,123.42,123.23,122.43,121.08,119.09,82.40,69.89,52.46。
FT-IRν/cm-1(KBr)3426,1511,1447,1427,1309,1244,1187,854,738,700,574,526。
Uv-vis(CHCl3)λmax/nm 255,430,703；MALDI-TOF MS m/z calcd for C73H9NS[M]+931.0450,found 931.0444。
实施例4
制备[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2d：
反应步骤：
准确称取C60富勒烯(36.0mg,0.05mmol)，碘化铜(1.9mg,0.01mmol)，1d(0.1mmol)和DMAP(3.1mg,0.025mmol)于25mL干燥的Schlenk tube中，再加入6mL溶剂无水氯苯和97wt％的过氧化二叔丁基(0.2mmol)水溶液密闭，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrek tube中的溶剂完全解冻后置于60℃的油浴中反应4h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先将薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用尽可能少的二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2d，产物2d的相对产率为35％。
2d:1H NMR(600MHz,CDCl3/CS2)δ8.38(s,1H),7.93(d,J＝7.8Hz,1H),7.57(d,J＝8.4Hz,1H),7.46(s,1H),7.33(t,J＝7.8Hz,1H),7.22(d,J＝7.8Hz,1H),6.61(d,J＝2.4Hz,1H),6.58(s,1H),6.43(s,1H)。
13C NMR(150MHz,DMSO-d6/CS2with Cr(acac)3as relaxation reagent)δ156.27,153.05,152.66,152.53,151.97,146.44,146.18,145.59,145.13,145.10,145.03,145.00,144.94,144.88,144.80,144.73,144.68,144.54,144.24,144.18,144.14,144.12,144.09,144.03,143.50,143.47,143.43,142.07,142.04,142.02,141.77,141.71,141.59,141.50,141.19,141.18,141.04,140.99,140.77,140.75,140.71,140.67,140.63,139.71,139.48,138.75,137.98,137.49,135.71,134.56,134.39,134.33,122.36,121.46,119.57,119.32,117.43,112.28,110.22,108.69,80.81,69.12,49.87。
FT-IRν/cm-1(KBr)3433,1705,1448,1427,1358,1314,1245,1187,1147,1074,1011,739,575,527。
UV-vis(CHCl3)λmax/nm 257,429,700；MALDI-TOF MS m/z calcd for C73H9NO[M]+915.0679,found 915.0675。
实施例5
制备[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2e：
反应步骤：
准确称取C60富勒烯(36.0mg,0.05mmol)，碘化铜(1.9mg,0.01mmol)，1e(0.1mmol)和DMAP(3.1mg,0.025mmol)于25mL干燥的Schlenk tube中，再加入6mL溶剂无水氯苯和97wt％的过氧化二叔丁基(0.2mmol)水溶液密闭，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrek tube中的溶剂完全解冻后置于75℃的油浴中反应4h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先准备好的薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用尽可能少的二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2e，产物2e的相对产率为41％。
2e:1H NMR(600MHz,CDCl3/CS2)δ8.33(s,1H),7.89(d,J＝7.8Hz,1H),7.55(d,J＝7.8Hz,1H),7.30(t,J＝7.8Hz,1H),7.20(t,J＝7.8Hz,1H),6.66–6.60(m,1H),5.79(d,J＝9.0Hz,1H),5.73(d,J＝16.8Hz,1H),5.54(d,J＝10.2Hz,1H)。
13C NMR(100MHz,DMSO-d6/CS2with Cr(acac)3as relaxation reagent)δ157.13,153.68,152.85,152.48,146.67,146.42,146.00,145.44,145.39,145.36,145.23,145.21,145.16,145.09,145.06,145.04,144.71,144.48,144.45,144.42,144.40,144.31,144.28,143.76,143.72,143.67,142.34,142.30,142.29,142.08,141.99,141.82,141.80,141.75,141.71,141.39,141.38,141.29,141.26,141.13,141.08,141.04,140.96,140.93,140.41,139.85,139.79,139.11,138.63,137.16,136.01,134.55,134.41,122.72,121.36,119.43,118.30,118.16,117.56,112.34,79.95,69.55,55.08。
FT-IRν/cm-1(KBr)3433,1511,1447,1427,1310,1244,1187,1016,986,925,861,737,575,526。
UV-vis(CHCl3)λmax/nm 257,430,702；MALDI-TOF MS m/z calcd for C71H9N[M]-875.0740,found 875.0765。
实施例6
制备[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2f：
反应步骤：
准确称取C60富勒烯(36.0mg,0.05mmol)，碘化铜(1.9mg,0.01mmol)，1f(0.1mmol)和DMAP(3.1mg,0.025mmol)于25mL干燥的Schlenk tube中，再加入6mL溶剂无水氯苯和97wt％的过氧化二叔丁基(0.2mmol)水溶液密闭，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrek tube中的溶剂完全解冻后置于65℃的油浴中反应4h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先准备好的薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用尽可能少的二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2f，产物2f的相对产率为38％。
2f:1H NMR(600MHz,CDCl3/CS2)δ8.38(s,1H),7.93(d,J＝7.8Hz,1H),7.57(d,J＝8.4Hz,1H),7.46(s,1H),7.33(t,J＝7.8Hz,1H),7.22(d,J＝7.8Hz,1H),6.61(d,J＝2.4Hz,1H),6.58(s,1H),6.43(s,1H)。
13C NMR(150MHz,DMSO-d6/CS2with Cr(acac)3as relaxation reagent)δ156.27,153.05,152.66,152.53,151.97,146.44,146.18,145.59,145.13,145.10,145.03,145.00,144.94,144.88,144.80,144.73,144.68,144.54,144.24,144.18,144.14,144.12,144.09,144.03,143.50,143.47,143.43,142.07,142.04,142.02,141.77,141.71,141.59,141.50,141.19,141.18,141.04,140.99,140.77,140.75,140.71,140.67,140.63,139.71,139.48,138.75,137.98,137.49,135.71,134.56,134.39,134.33,122.36,121.46,119.57,119.32,117.43,112.28,110.22,108.69,80.81,69.12,49.87。
FT-IRν/cm-1(KBr)3433,1705,1448,1427,1358,1314,1245,1187,1147,1074,1011,739,575,527。
UV-vis(CHCl3)λmax/nm 257,429,700；MALDI-TOF MS m/z calcd for C73H9NO[M]+915.0679,found 915.0675。
实施例7
制备[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2g：
反应步骤：
准确称取C60富勒烯(36.0mg,0.05mmol)，碘化铜(1.9mg,0.01mmol)，1g(0.1mmol)和DMAP(3.1mg,0.025mmol)于25mL干燥的Schlenk tube中，再加入6mL溶剂无水氯苯和97wt％的过氧化二叔丁基(0.2mmol)水溶液密闭，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrek tube中的溶剂完全解冻后置于85℃的油浴中反应3h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先准备好的薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用尽可能少的二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2g，产物2g的相对产率为38％。
2g:1H NMR(600MHz,CDCl3/CS2)δ8.39(s,1H),8.03(d,J＝7.8Hz,1H),7.61(d,J＝8.4Hz,1H),7.48(s,1H),7.39(t,J＝7.8Hz,1H),7.32–7.26(m,5H),6.84(t,J＝6.6Hz,1H),3.34(s,3H)。
13C NMR(150MHz,CDCl3/CS2with Cr(acac)3as relaxation reagent)δ156.67,153.25,153.16,152.20,147.47,147.22,146.34,146.13,146.09,146.07,146.04,145.99,145.95,145.88,145.70,145.64,145.39,145.32,145.24,145.21,145.16,145.11,145.10,144.99,144.45,144.40,144.34,143.27,143.04,142.62,142.60,142.54,141.51,142.50,142.35,142.15,142.12,142.04,142.00,141.97,141.82,141.77,141.66,141.65,141.50,140.72,140.47,139.91,139.87,139.01,136.86,135.62,135.39,135.20,127.76,127.59,126.43,123.46,123.32,122.52,122.17,119.15,112.54,82.43,69.92,52.48。
FT-IRν/cm-1(KBr)3432,1594,1500,1447,1381,1307,1244,1187,1102,944,740,690,574,526。
UV-vis(CHCl3)λmax/nm 257,429,702；MALDI-TOF MS m/z calcd for C76H14N2[M]+954.1151,found 954.1149。
实施例8
制备[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2h：
反应步骤：
准确称取C60富勒烯(36.0mg,0.05mmol)，碘化铜(1.9mg,0.01mmol)，1h(0.1mmol)和DMAP(3.1mg,0.025mmol)于25mL干燥的Schlenk tube中，再加入6mL溶剂无水氯苯和97wt％的过氧化二叔丁基(0.2mmol)水溶液密闭，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrek tube中的溶剂完全解冻后置于85℃的油浴中反应4h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先准备好的薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用尽可能少的二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2h，产物2h的相对产率为25％。
2h:1H NMR(600MHz,CDCl3/CS2)δ8.37(s,1H),8.01(d,J＝7.8Hz,1H),7.62(d,J＝8.4Hz,1H),7.37(t,J＝7.8Hz,1H),7.27(t,J＝7.8Hz,1H),7.12(br,4H),6.97(s,1H),6.81(s,1H),3.95(br,1H),2.41(br,1H),2.24(br,1H),2.06(br,1H),1.94(br,2H),1.85(q,J＝12.6Hz,1H),1.77(br,1H),1.49(br,J＝9.6Hz,2H),1.26(br,1H)。
13C NMR(150MHz,CDCl3/CS2with Cr(acac)3as relaxation reagent)δ156.91,153.68,153.23,148.17,147.21,147.12,146.78,146.11,146.08,145.96,145.91,145.86,145.82,145.75,145.66,145.50,145.19,145.15,145.13,145.05,145.00,144.47,144.38,143.02,143.00,142.56,142.49,142.36,142.29,142.17,142.05,141.98,141.84,141.63,140.97,140.52,140.33,139.38,139.15,137.47,136.42,134.87,134.72,128.80,123.89,123.14,121.02,120.55,119.75,119.27,112.81,83.15,69.38,66.61,61.43,34.96,33.93,26.76,26.48,25.72。
FT-IRν/cm-1(KBr)3392,2924,2850,1599,1500,1448,1306,1255,1146,1116,888,744,690,574,526。
UV-vis(CHCl3)λmax/nm 255,430,702；MALDI-TOF MS m/z calcd for C81H22N2[M]+1022.1778,found 1022.1762。
实施例9
制备[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2i：
反应步骤：
准确称取C60富勒烯(36.0mg,0.05mmol)，碘化铜(1.9mg,0.01mmol)，1i(0.1mmol)和DMAP(3.1mg,0.025mmol)于25mL干燥的Schlenk tube中，再加入6mL溶剂无水氯苯和97wt％的过氧化二叔丁基(0.2mmol)水溶液密闭，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrek tube中的溶剂完全解冻后置于85℃的油浴中反应4h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先准备好的薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用尽可能少的二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物2i，产物2i的相对产率为43％。
2i:1H NMR(400MHz,DMSO-d6/CS2)δ11.71(s,1H),7.74(d,J＝8.0Hz,1H),7.58(d,J＝8.0Hz,1H),7.53(d,J＝7.2Hz,2H),7.28(d,J＝7.2Hz,2H),7.21-7.09(m,7H),7.04(t,J＝7.2Hz,1H),6.17(s,1H),4.96(d,J＝14.4Hz,1H),4.26(d,J＝14.0Hz,1H),4.05(d,J＝14.0Hz,1H),3.77(d,J＝14.4Hz,1H)。
13C NMR(150MHz,CDCl3/CS2with Cr(acac)3as relaxation reagent)δ157.92,154.86,154.20,153.48,147.47,147.28,146.21,146.13,146.08,146.04,145.98,145.91,145.70,145.68,145.64,145.34,145.31,145.27,145.15,145.08,144.67,144.53,144.47,143.09,143.03,142.69,142.60,142.55,142.50,142.42,142.34,142.28,142.11,142.07,141.98,141.86,141.69,140.67,140.34,139.90,139.74,139.56,138.32,137.93,136.41,136.14,135.08,134.74,130.48,129.22,128.66,128.25,128.10,127.26,123.32,123.20,123.07,120.76,119.12,112.45,82.70,71.56,68.68,57.47,52.34。
FT-IRν/cm-1(KBr)3427,1511,1492,1448,1360,1307,1244,1116,1067,964,833,736,696,574,526。
UV-vis(CHCl3)λmax/nm 257,430,703；MALDI-TOF MS m/z calcd for C83H20N2[M]-1044.1632,found 1044.1651。
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 (3)

1.一种[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法，其特征在于具体合成过程为：以碘化铜为催化剂，以无水氯苯为溶剂，[60]富勒烯与C2-取代的吲哚类化合物在4-二甲氨基吡啶和过氧化二叔丁基的作用下，通过在氮气保护下于40～85℃直接氧化脱氢发生自由基加成反应实现C-C键构建合成目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物；
该合成过程中生成[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的反应方程式为：
其中R1为芳基、杂芳基、烯基或取代氨基，R2为H、甲氧基或氯。
2.根据权利要求1所述的[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法，其特征在于具体合成步骤为：将C60富勒烯、碘化铜、C2-取代的吲哚类化合物和4-二甲氨基吡啶置于干燥的Schlenk tube中，再加入溶剂无水氯苯和97wt％的过氧化二叔丁基水溶液密封，超声至溶解，氮气保护条件下，将其冷冻充氮气以防止低沸点溶液被抽走，待Shrektube中的溶剂完全解冻后置于40～85℃的油浴中反应3～5h，反应结束后，体系冷却至室温，先用一根短柱子过滤掉金属盐及其它不溶物，再用水泵将低沸点溶剂旋干，然后用油泵将高沸点溶剂旋干，接着再用事先准备好的薄层层析硅胶与二硫化碳充分混合均匀的液体装一根高度适中的柱子，再用二硫化碳溶解旋干的样品，湿法上样，用二硫化碳作为洗脱剂先回收未反应的C60富勒烯，然后以二硫化碳/二氯甲烷作为洗脱剂进行洗脱得到目标产物[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物，所述的C2-取代的吲哚类化合物为
3.根据权利要求1或2所述的[60]富勒烯并四氢环戊[2,3-b]吲哚衍生物的合成方法，其特征在于：所述[60]富勒烯、碘化铜、C2-取代的吲哚类化合物、4-二甲氨基吡啶与过氧化二叔丁基的投料摩尔比为1:0.2:2.0:0.5:4.0。
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