Synlett 2018; 29(09): 1167-1170
DOI: 10.1055/s-0036-1591770
letter
© Georg Thieme Verlag Stuttgart · New York

Selective Synthesis of [60]Fullerene Multiadducts through Dicyclohexylcarbodiimide (DCC) Mediated Reactions

Hao Zhang
a  Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. of China   Email: [email protected]
,
Yanbang Li
a  Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. of China   Email: [email protected]
,
Liangbing Gan*
a  Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. of China   Email: [email protected]
b  State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, P. R. of China
› Author Affiliations
This work is supported by NNSFC (Grant 21672009) and MOST (2015CB856600).
Further Information

Publication History

Received: 03 January 2018

Accepted after revision: 08 February 2018

Publication Date:
27 February 2018 (online)


Abstract

4-Methylpiperidine (MePi) reacts with C60 in the presence of DCC to form C60(MePi)4(DCC). The DCC moiety in the C60 derivative facilitates facile replacement reactions with thiols and phenols to form pentathiolyl derivatives C60(RS)5(H) and benzofuran-containing C60 derivatives such as C60(MePi)2(OC6H4), respectively.

Supporting Information

 
  • References and Notes


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  • 13 Experimental Procedures and Characterization Data for Compound 3aA solution of compound 1 (36.6 mg, 0.028 mmol) in 10 mL of toluene was stirred at 60 °C. Then ethanethiol (0.04 mL, 0.54 mmol) was added into the solution. The resulting mixture was stirred at 60 °C for 5 h. The solution was directly chromatographed on a silica gel column eluting with toluene to give the orange band as compound 3a (22.8 mg, 0.022 mmol, 80%).Characterization Data 1H NMR (400 MHz, CDCl3): δ = 5.12 (s, 1 H), 3.37–3.23 (m, 10 H), 1.48–1.43 (m, 15 H). 13C NMR (126 MHz, CDCl3): δ = 154.25, 153.10, 151.12, 150.22, 148.88, 148.77, 148.61, 148.40, 148.26, 148.23, 148.06, 147.71, 146.96, 146.90, 146.67, 145.29, 145.18, 144.74, 144.50, 144.37, 144.27, 144.21, 144.02, 143.43, 143.37, 143.29, 143.25 (C60), 60.46 (CH), 56.70, 56.06, 54.15, 28.40 (CH2), 27.87 (CH2), 27.73 (CH2), 15.15 (CH3), 15.13 (CH3), 14.51 (CH3).
  • 14 Experimental Procedures and Characterization Data for Compound 4aA solution of compound 1 (224.2 mg, 0.17 mmol) in 50 mL of toluene was stirred at 60 °C. Then phenol (320 mg, 3.3 mmol) was added into the solution. The resulting mixture was stirred at 60 °C for 2 d. The solution was directly chromatographed on a silica gel column eluting with toluene to give the brown band as compound 4a (48.1 mg, 0.048 mmol, 28%), several other minor byproducts could not be separated.Characterization Data 1H NMR (500 MHz, CDCl3): δ = 7.57 (dd J = 0.9, 7.5 Hz, 1 H), 7.44–7.41 (m, 1 H) 7.25 (d, J = 8.1 Hz, 1 H), 7.11–7.08 (m, 1 H), 4.00 (d, J = 11.0 Hz, 1 H), 3.95 (d, J = 10.5 Hz, 1 H), 3.74 (d, J = 10.7 Hz, 1 H), 3.65 (d, J = 10.8 Hz, 1 H), 3.08–3.04 (m, 1 H), 2.93–2.81 (m, 3 H), 1.95–1.93 (m, 1 H), 1.82–1.80 (m, 2 H), 1.68–1.65 (m, 3 H), 1.56–1.54 (m, 2 H), 1.38–1.36 (m, 2 H), 1.04 (d, J = 5.8 Hz, 3 H), 1.00 (d, J = 6.5 Hz, 3 H). 13C NMR (126 MHz, CDCl2CDCl2): δ = 157.91, 153.74, 152.52, 152.30, 151.50, 150.48, 150.04, 149.82, 149.44, 149.20, 149.08, 148.87, 148.77, 147.98, 147.70, 147.63, 147.49, 147.17, 146.94, 146.85, 146.62, 146.58, 146.33, 145.91, 145.79, 145.73, 145.52, 145.38, 145.16, 145.02, 144.97, 144.82, 144.73, 144.69, 144.52, 144.24, 144.08, 144.04, 143.89, 143.85, 143.69, 143.33, 143.14, 143.12, 142.72, 142.59, 142.37, 141.70, 140.96, 139.83, 138.98, 136.73, 134.57, 134.18, 130.60 (CH), 126.81, 124.90 (CH), 121.97 (CH), 111.32 (CH), 100.75, 77.49, 74.65, 71.21, 65.54, 51.52 (NCH2), 51.07 (NCH2), 50.27 (NCH2), 49.28 (NCH2), 35.41 (CH2), 35.27 (CH2), 35.14 (CH2), 35.11 (CH2), 30.86 (CH), 30.77 (CH), 22.14 (CH3), 22.04 (CH3). ESI-FT-ICR-HRMS-Positive: m/z calcd for C78H29N2O [M + H+]: 1009.2255; found: 1009.2274.
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