CN115572217B - 一种钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法 - Google Patents
一种钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法 Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims description 13
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 13
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000005580 one pot reaction Methods 0.000 claims abstract description 4
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
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- 238000004809 thin layer chromatography Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- -1 carbonate compound Chemical class 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 12
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
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- 238000006722 reduction reaction Methods 0.000 abstract description 2
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- 238000002604 ultrasonography Methods 0.000 description 9
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- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 8
- 238000003818 flash chromatography Methods 0.000 description 8
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 8
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/90—Ring systems containing bridged rings containing more than four rings
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
本发明公开了一种钯催化脱羧的[60]富勒烯并环戊‑4‑酮类衍生物的合成方法，其具体过程为：以[60]富勒烯和碳酸酯类化合物为反应原料，在四三苯基膦钯的催化作用下于50℃一锅反应制得目标产物[60]富勒烯并环戊‑4‑酮类衍生物。本发明操作简单、官能团兼容性强且底物适用范围广，同时还能完成克级制备和还原反应。本发明合成过程脱羧的副产物是无毒的二氧化碳，合成工艺绿色环保。
Description
技术领域
本发明属于富勒烯衍生物的合成技术领域，具体涉及一种钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法。
背景技术
自实现富勒烯的制备以来，富勒烯的化学修饰备受关注。功能化的富勒烯在纳米材料、生物医药、太阳能电池等领域具有广泛的应用。其中富勒烯全碳化合物作为电子受体材料、传输层材料、界面层材料和添加剂等被广泛应用于有机合成与钙钛矿太阳能电池。因此，构建新型富勒烯碳环衍生物，对于拓展富勒烯碳环化合物在不同领域的应用具有重要意义。
发明内容
本发明解决的技术问题是提供了一种操作简单、官能团兼容性强且底物适用范围广的钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，该方法在过渡金属钯催化作用下，以便宜易得的碳酸酯类化合物为反应原料，与富勒烯发生反应，一锅合成了羰基与富勒烯非直接键连的[60]富勒烯并环戊-4-酮类衍生物。
本发明为解决上述技术问题采用如下技术方案，一种钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，其特征在于具体过程为：以[60]富勒烯和碳酸酯类化合物为反应原料，在四三苯基膦钯的催化作用下于50℃一锅反应制得目标产物[60]富勒烯并环戊-4-酮类衍生物，合成过程中的反应方程式为：
其中R为苯基、萘基或取代苯基，该取代苯基苯环上的取代基为-OMe、-F、-Cl、 -Br、-CF3、-CN或-Ph。
进一步限定，所述钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，其特征在于具体步骤为：将[60]富勒烯、碳酸酯类化合物和四三苯基膦钯加入到干燥的史莱克管中，再加入干燥的氯苯和干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，再转移至50℃的油浴中进行反应，TLC监测反应完全，冷却至室温，将反应液经柱层析滤去不溶物，再于50℃减压除去氯苯，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]富勒烯并环戊-4-酮类衍生物。
进一步限定，所述[60]富勒烯、碳酸酯类化合物与四三苯基膦钯的投料摩尔比为1.0:2.0:0.1。
进一步限定，所述钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，其特征在于：所述碳酸酯类化合物为
进一步优选，所述的钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，其特征在于：所述[60]富勒烯并环戊-4-酮类衍生物为
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、官能团兼容性强且底物适用范围广，同时还能完成克级制备和还原反应。本发明合成过程脱羧的副产物是无毒的二氧化碳，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。
实施例1
实施例1
制备[60]富勒烯并环戊-4-酮类衍生物3a：
反应步骤：
将准确称取的[60]富勒烯(36.0mg，0.05mmol)、底物碳酸酯2a(0.10mmol) 和四三苯基膦钯(5.8mg，0.005mmol)加入到25mL干燥的史莱克管中，再加入6mL干燥的氯苯和1mL干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，转移至50℃的油浴中进行反应，TLC监测反应完全后冷却至室温，将上述反应液经快速柱层析滤去不溶物，于50℃减压除去氯苯，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]富勒烯并环戊-4-酮类衍生物3a，产物3a的产率为58％。
3a:1H NMR(600MHz,CDCl3/CS2)δ7.75(dd,J＝17.4,10.8Hz,1H),7.67(d,J＝7.2Hz,2H),7.33(t,J＝7.8Hz,2H),7.24-7.22(m,1H),5.90(d,J＝10.2Hz,1H),5.70(d,J＝17.4Hz,1H),4.91(d,J＝17.4Hz,1H),4.26(d,J＝17.4Hz,1H)；13C{1H}NMR(150MHz, CDCl3/CS2 with Cr(acac)3as relaxation reagent)δ207.8,156.6,155.3,153.5,151.9,147.64,147.59,146.41,146.37,146.31,146.29,146.26,146.12,146.07,146.01,145.97,145.7,145.61,145.58,145.5,145.4,145.3,145.2,144.8,144.6,144.5,144.4,143.9,143.2,142.70, 142.66,142.5,142.13,142.10,142.0,141.99,141.98,141.82,141.79,141.7,141.5,141.4,141.1,140.5,140.1,139.6,139.2,139.1,137.1,135.6,134.7,134.1,131.0,128.1,127.7, 122.0,76.3,68.5,61.5,49.4；FT-IRν/cm-1 1744,1509,1259,1092,1014,793,688,524； UV-vis(CHCl3)λmax/nm 255,315,434,701；MALDI-TOF MS m/z calcdfor C71H10O[M]-878.0737,found 878.0736。
实施例2
制备[60]富勒烯并环戊-4-酮类衍生物3b：
反应步骤：
将[60]富勒烯(36.0mg,0.05mmol)、底物碳酸酯2b(0.10mmol)和四三苯基膦钯(5.8mg,0.005mmol)加入到25mL干燥的史莱克管中，再加入6mL干燥的氯苯和 1mL干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，转移至50℃的油浴中进行反应，TLC监测反应完全后冷却至室温，将上述反应液经快速柱层析滤去不溶物，于50℃减压除去氯苯。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]富勒烯并环戊-4-酮类衍生物3b，产物3b的产率为40％。
3b:1H NMR(600MHz,CDCl3/CS2)δ7.72(dd,J＝17.4,10.2Hz,1H),7.58(d,J＝6.6,1.8Hz,2H),6.84(d,J＝7.2,1.8Hz,2H),5.87(d,J＝10.8Hz,1H),5.68(d,J＝17.4Hz, 1H),4.89(d,J＝17.4Hz,1H),4.25(d,J＝17.4Hz,1H),3.76(s,3H)；13C{1H}NMR(150 MHz,CDCl3/CS2 with Cr(acac)3as relaxation reagent)208.4,158.6,156.7,155.1,153.6, 152.0,147.6,147.5,146.31,146.28,146.22,146.20,146.18,146.02,145.98,145.9,145.6,145.58,145.57,145.5,145.32,145.28,145.22,145.18,145.1,144.7,144.5,144.40,144.36, 143.8,143.1,142.6,142.58,142.56,142.4,142.04,142.02,141.92,141.89,141.7,141.69,141.66,141.4,141.3,141.1,140.4,140.0,139.8,139.6,139.1,137.0,135.5,134.5,134.1, 132.1,131.0,121.8,113.4,76.5,68.1,61.3,55.0,49.3；FT-IRν/cm-1 1736,1508,1247,1179, 1005,791,523；UV-vis(CHCl3)λmax/nm 257,315,435,702；MALDI-TOF MS m/z calcd for C72H12O2[M]-908.0843,found 908.0840。
实施例3
制备[60]富勒烯并环戊-4-酮类衍生物3c：
反应步骤：
将[60]富勒烯(36.0mg,0.05mmol)、底物碳酸酯2c(0.10mmol)和四三苯基膦钯(5.8mg,0.005mmol)加入到25mL干燥的史莱克管中，再加入6mL干燥的氯苯和1mL 干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，转移至50℃的油浴中进行反应，TLC监测反应完全后冷却至室温，将上述反应液经快速柱层析滤去不溶物，于 50℃减压除去氯苯。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]富勒烯并环戊-4-酮类衍生物3c，产物3c的产率为57％。
3c:1H NMR(600MHz,CDCl3/CS2)δ7.77(dd,J＝17.4,10.2Hz,1H),7.68(dd,J＝9.0,5.4Hz,2H),7.03(t,J＝9.0Hz,2H),5.92(d,J＝10.2Hz,1H),5.69(d,J＝17.4Hz,1H), 4.91(d,J＝17.4Hz,1H),4.26(d,J＝17.4Hz,1H)；13C{1H}NMR(150MHz,CDCl3/CS2with Cr(acac)3as relaxation reagent)δ207.0,161.7(JC-F＝248.0Hz),156.3,154.9,153.0, 151.5,147.52,147.46,146.3,146.23,146.2,146.16,146.15,146.0,145.9,145.8,145.7,145.6,145.5,145.4,145.33,145.25,145.22,145.20,145.15,144.6,144.4,144.34,144.28,143.6,143.1,142.58,142.57,142.5,142.4,142.0,141.9,141.88,141.86,141.8,141.7,141.6,141.32,141.28,141.0,140.4,140.1,139.6,139.5,139.1,137.1,135.4,134.8,134.6,133.9, 132.7,132.6,122.2,115.0,114.8,76.0,67.7,61.2,49.1；FT-IRν/cm-11742,1506,1221,1163, 979,932,801,764,524；UV-vis(CHCl3)λmax/nm 258,315,434,700；MALDI-TOF MS m/z calcd for C71H9OF[M]-896.0643,found 896.0641。
实施例4
制备[60]富勒烯并环戊-4-酮类衍生物3d：
反应步骤：
将[60]富勒烯(36.0mg,0.05mmol)、底物碳酸酯2d(0.10mmol)和四三苯基膦钯(5.8mg,0.005mmol)加入到25mL干燥的史莱克管中，再加入6mL干燥的氯苯和1mL 干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，转移至50℃的油浴中进行反应，TLC监测反应完全后冷却至室温，将上述反应液经快速柱层析滤去不溶物，于 50℃减压除去氯苯。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]富勒烯并环戊-4-酮类衍生物3d，产物3d的产率为54％。
3d:1H NMR(400MHz,CDCl3/CS2)δ7.75(dd,J＝17.2,10.4Hz,1H),7.63(d,J＝8.8Hz,2H),7.31(d,J＝8.8Hz,2H),5.91(d,J＝10.4Hz,1H),5.68(d,J＝17.2Hz,1H),4.90 (d,J＝17.6Hz,1H),4.25(d,J＝17.6Hz,1H)；13C{1H}NMR(150MHz,CDCl3/CS2 with Cr(acac)3asrelaxation reagent)δ207.4,156.2,154.8,152.8,151.4,147.5,147.4,146.24, 146.20,146.17,146.1,146.0,145.9,145.7,145.6,145.5,145.44,145.39,145.3,145.23,145.20,145.16,145.1,114.6,144.4,144.3,144.2,143.6,143.1,142.54,142.53,142.5,142.4,141.94,141.9,141.84,141.81,141.78,141.63,141.61,141.26,141.25,140.9,140.4,140.0,139.5,139.3,139.1,137.5,137.1,135.3,134.6,133.8,132.2,128.1,122.3,75.9,67.8,61.3, 49.1；FT-IRν/cm-1 1745,1489,1400,1186,1092,1014,989,935,796,525；UV-vis(CHCl3) λmax/nm 259,316,434,700；MALDI-TOF MS m/z calcd for C71H9OCl[M]-912.0347,found 912.0342。
实施例5
制备[60]富勒烯并环戊-4-酮类衍生物3e：
反应步骤：
将[60]富勒烯(36.0mg,0.05mmol)、底物碳酸酯2e(0.10mmol)和四三苯基膦钯(5.8mg,0.005mmol)加入到25mL干燥的史莱克管中，再加入6mL干燥的氯苯和 1mL干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，转移至50℃的油浴中进行反应，TLC监测反应完全后冷却至室温，将上述反应液经快速柱层析滤去不溶物，于50℃减压除去氯苯。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]富勒烯并环戊-4-酮类衍生物3e，产物3e的产率为50％。
3e:1H NMR(400MHz,CDCl3/CS2)7.85(d,J＝7.6Hz,2H),7.81(dd,J＝17.2,10.4Hz,1H),7.61(d,J＝8.0Hz,2H),5.96(d,J＝10.4Hz,1H),5.68(d,J＝17.2Hz,1H),4.94 (d,J＝17.6Hz,1H),4.29(d,J＝17.6Hz,1H)；13C{1H}NMR(150MHz,CDCl3/CS2 with Cr(acac)3asrelaxation reagent)δ207.6,156.2,154.9,152.6,151.2,147.7,147.6,146.40, 146.36,146.34,146.31,146.13,146.11,145.8,145.7,145.6,145.54,145.49,145.4,145.37,145.35,145.29,145.26,145.1,144.8,144.54,144.48,144.3,143.7,143.24,143.22,143.17, 142.72,142.69,142.68,142.5,142.10,142.07,142.04,142.01,141.96,141.9,141.8,141.78,141.75,141.41,141.38,141.0,140.5,140.2,139.7,139.3,139.2,137.3,135.5,134.9,133.9, 131.5,129.7(JC-F＝32.6Hz),124.91,124.89,124.7,122.9,122.8,75.8,68.1,61.6,49.3； FT-IRν/cm-1 1745,1512,1323,1162,1118,1069,812,525；UV-vis(CHCl3)λmax/nm 256, 316,434,699；MALDI-TOF MS m/z calcd for C72H9OF3[M]-946.0611,found 962.0617。
实施例6
制备[60]富勒烯并环戊-4-酮类衍生物3f：
反应步骤：
将[60]富勒烯(36.0mg,0.05mmol)、底物碳酸酯2f(0.10mmol)和四三苯基膦钯(5.8mg,0.005mmol)加入到25mL干燥的史莱克管中，再加入6mL干燥的氯苯和1mL 干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，转移至50℃的油浴中进行反应，TLC监测反应完全后冷却至室温，将上述反应液经快速柱层析滤去不溶物，于 50℃减压除去氯苯。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]富勒烯并环戊-4-酮类衍生物3f，产物3f的产率为52％。
3f:1H NMR(600MHz,CDCl3/CS2)δ7.86(d,J＝8.4Hz,2H),7.80(dd,J＝17.4,10.8Hz 1H),7.66(d,J＝8.4Hz,2H),5.97(d,J＝10.8Hz,1H),5.68(d,J＝17.4Hz,1H),4.94(d,J＝17.4Hz,1H),4.29(d,J＝17.4Hz,1H)；13C{1H}NMR(150MHz,CDCl3/CS2 with Cr(acac)3asrelaxation reagent)δ206.7,155.9,154.6,152.1,150.8,147.6,147.5,146.33, 146.28,146.25,146.1,146.0,145.7,145.6,145.44,145.43,145.36,145.34,145.31,145.30,145.27,145.23,145.21,144.8,144.7,144.43,144.40,144.3,144.2,143.6,143.2,142.7,142.65,142.62,142.5,142.03,141.98,141.94,141.93,141.9,141.8,141.74,141.68,141.66,141.4,141.3,140.9,140.5,140.2,139.7,139.1,138.9,137.3,135.3,134.9,133.7,131.7, 131.6,123.0,118.0,111.7,75.5,67.9,61.4,49.2；FT-IRν/cm-1 1742,1501,1261,1093,1004, 935,806,524；UV-vis(CHCl3)λmax/nm 256,316,433,605,699；MALDI-TOF MS m/z calcd for C72H9ON[M]-903.0690,found 903.0684。
实施例7
制备[60]富勒烯并环戊-4-酮类衍生物3g：
将[60]富勒烯(36.0mg,0.05mmol)、底物碳酸酯2g(0.10mmol)和四三苯基膦钯(5.8mg,0.005mmol)加入到25mL干燥的史莱克管中，再加入6mL干燥的氯苯和1mL 干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，转移至50℃的油浴中进行反应，TLC监测反应完全后冷却至室温，将上述反应液经快速柱层析滤去不溶物，于 50℃减压除去氯苯。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]富勒烯并环戊-4-酮类衍生物3g，产物3g的产率为58％。
3g:1H NMR(600MHz,CDCl3/CS2)δ7.78(dd,J＝17.4,10.8Hz,1H),7.74(d,J＝8.4Hz,2H),7.56(d,J＝8.4Hz,2H),7.52(dd,J＝8.4,1.2Hz,2H),7.36(t,J＝7.8Hz,2H), 7.27(t,J＝7.8Hz,1H),5.92(d,J＝10.8Hz,1H),5.72(d,J＝17.4Hz,1H),4.92(d,J＝17.4 Hz,1H),4.28(d,J＝17.4Hz,1H)；13C{1H}NMR(150MHz,CDCl3/CS2 with Cr(acac)3asrelaxation reagent)δ208.1,156.5,155.1,153.3,151.8,147.53,147.48,146.29,146.26,146.19,146.17,146.1,145.99,145.96,145.8,145.54,145.51,145.49,145.3,145.20,145.15, 145.13,144.6,144.5,144.4,144.3,143.8,143.11,143.09,142.6,142.5,142.4,141.99, 141.97,141.90,141.87,141.7,141.67,141.66,141.4,141.3,141.0,140.4,140.1,140.03,140.02,139.6,139.5,139.1,138.1,137.0,135.5,134.7,134.0,131.3,128.7,127.4,126.9, 126.6,122.0,76.3,68.2,61.4,49.3；FT-IRν/cm-11742,1484,1181,1142,934,901,812,759, 724,693,524；UV-vis(CHCl3)λmax/nm 259,315,435,701；MALDI-TOF MS m/z calcd for C77H14O[M]-954.1050,found 954.1048。
实施例8
制备[60]富勒烯并环戊-4-酮类衍生物3h：
反应步骤：
将[60]富勒烯(36.0mg,0.05mmol)、底物碳酸酯2h(0.10mmol)和四三苯基膦钯(5.8mg,0.005mmol)加入到25mL干燥的史莱克管中，再加入6mL干燥的氯苯和1mL 干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，转移至50℃的油浴中进行反应，TLC监测反应完全后冷却至室温，将上述反应液经快速柱层析滤去不溶物，于 50℃减压除去氯苯。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]富勒烯并环戊-4-酮类衍生物3h，产物3h的产率为57％。
3h:1H NMR(400MHz,CDCl3/CS2)δ8.21(s,1H),7.89-7.75(m,5H),7.46-7.42(m,2H),5.96(d,J＝10.4Hz,1H),5.73(d,J＝17.2Hz,1H),4.98(d,J＝17.6Hz,1H),4.35(d,J＝17.6Hz,1H)；13C{1H}NMR(150MHz,CDCl3/CS2 with Cr(acac)3as relaxation reagent)δ208.4,156.5,155.3,153.3,152.0,147.61,147.56,146.37,146.35,146.27,146.25,146.2,146.1,146.03,145.97,145.9,145.64,145.61,145.6,145.5,145.4,145.34,145.31,145.26, 145.2,144.7,144.6,144.5,144.3,143.9,143.20,143.16,142.7,142.63,142.60,142.5,142.1,142.04,141.99,141.95,141.8,141.7,141.4,141.3,141.1,140.5,140.1,139.7,139.6,139.1, 137.1,136.6,135.5,134.8,134.1,132.7,132.3,130.5,128.6,128.4,127.6,127.5,126.6,126.1,122.2,76.4,68.6,61.6,49.5；FT-IRν/cm-1 1742,1501,1143,933,798,735,525； UV-vis(CHCl3)λmax/nm 254,315,434,702；MALDI-TOF MS m/z calcd for C75H12O[M]-928.0894,found 928.0895。
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 (5)
1.一种钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，其特征在于具体过程为：以[60]富勒烯和碳酸酯类化合物为反应原料，以氯苯和二氯甲烷为溶剂，在四三苯基膦钯的催化作用下于50℃一锅反应制得目标产物[60]富勒烯并环戊-4-酮类衍生物，合成过程中的反应方程式为：
其中R为苯基、萘基或取代苯基，该取代苯基苯环上的取代基为-OMe、-F、-Cl、-Br、-CF3、-CN或-Ph。
2.根据权利要求1所述的钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，其特征在于具体步骤为：将[60]富勒烯、碳酸酯类化合物和四三苯基膦钯加入到干燥的史莱克管中，再加入干燥的氯苯和干燥的二氯甲烷，将其密封并置于超声中使固体完全溶解，再转移至50℃的油浴中进行反应，TLC监测反应完全，冷却至室温，将反应液经柱层析滤去不溶物，再于50℃减压除去氯苯，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]富勒烯并环戊-4-酮类衍生物。
3.根据权利要求1或2所述的钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，其特征在于：所述[60]富勒烯、碳酸酯类化合物与四三苯基膦钯的投料摩尔比为1.0:2.0:0.1。
4.根据权利要求1或2所述的钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，其特征在于：所述碳酸酯类化合物为
5.根据权利要求1或2所述的钯催化脱羧的[60]富勒烯并环戊-4-酮类衍生物的合成方法，其特征在于：所述[60]富勒烯并环戊-4-酮类衍生物为
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