ChemComm
Page 4 of 4
COMMUNICATION
DOI: 10.1039/C6CC09374D
carbon catalyst for the direct CꢀH arylation of benzene, reductive
hydrogen atom transfer reaction and oxidation reaction, together with
high stability and easy recyclability.
We thank the National Natural Science Foundation of China (Nos.
21125314, 21402208, 21533011).
Notes and references
1 (a) C. J. Hofer, R. N. Grass, M. Zeltner, C. A. Mora, F. Krumeich
and W. J. Stark, Angew. Chem. Int. Ed., 2016, 55, 8761ꢀ8765; (b)
S. A. Miners, G. A. Rance and A. N. Khlobystov, Chem. Soc. Rev.
,
2016, 45, 4727ꢀ4746.
2
L. Wang, H. Liu, R. M. Konik, J. A. Misewich and S. S. Wong,
Chem. Soc. Rev., 2013, 42, 8134ꢀ8156.
A. C. Dillon, Chem. Rev., 2010, 110, 6856ꢀ6872.
Scheme 1. C-H arylation catalyzed by N-CNTs-800. Reaction conditions: 1, 0.4
mmol; benzene or toluene, 4 mL; t-BuOK, 1.2 mmol; N-CNTs-800, 10.0 mg; 120
oC; 24 h. Yields were determined by GC using dodecane as an internal standard.
3
4
D. Tasis, N. Tagmatarchis, A. Bianco and M. Prato, Chem. Rev.
,
2006, 106, 1105ꢀ1136.
F. Hu, M. Patel, F. Luo, C. Flach, R. Mendelsohn, E. Garfunkel, H.
He and M. Szostak, J. Am. Chem. Soc., 2015, 137, 14473ꢀ14480.
H. Yang, X. Cui, X. Dai, Y. Deng and F. Shi, Nat. Commun., 2015, 6,
To explore the catalytic mechanism of NꢀCNTsꢀ800 for the CꢀH
5
6
arylation of benzene with iodobenzene in the presence of
interaction between NꢀCNTsꢀ800 and ꢀBuOK was investigated. As in
the homogeneous systems, coordination and stabilization of ꢀBuOK
with the catalyst was essential to achieve high catalytic efficiency.
Herein, the strong interaction of NꢀCNTsꢀ800 with ꢀBuOK was
tꢀBuOK, the
t
6478.
t
7 (a) S. Yang, L. Peng, P. Huang, X. Wang, Y. Sun, C. Cao and W.
Song, Angew. Chem. Int. Ed., 2016, 55, 4016ꢀ4020; (b) Y. Gao, G.
Hu, J. Zhong, Z. Shi, Y. Zhu, D. S. Su, J. Wang, X. Bao and D. Ma,
Angew. Chem. Int. Ed., 2013, 52, 2109ꢀ2113; (c) S. Pattisson, E.
Nowicka, U. N. Gupta, G. Shaw, R. L. Jenkins, D. J. Morgan, D.
t
obviously reflected by the FTIR spectra (Figure S9, ESI). The
characteristic band for CꢀN vibration in NꢀCNTsꢀ800 (1625 cmꢀ1)
exhibited blueshift to 1670 cmꢀ1 after
the nanotubes, and correspondingly peaks for CꢀO vibration in
(1458 and 1447 cmꢀ1) showed redshifts. Moreover, EDS mapping
during TEM observation revealed that both elements K and O from
t
ꢀBuOK was immobolized onto
W. Knight and G. J. Hutchings, Nat. Commun., 2016, 7, 12855; (d)
M. A. Patel, F. Luo, M. R. Khoshi, E. Rabie, Q. Zhang, C. R.
Flach, R. Mendelsohn, E. Garfunkel, M. Szostak and H. He, ACS
Nano, 2016, 10, 2305ꢀ2315.
Y. Gao, P. Tang, H. Zhou, W. Zhang, H. Yang, N. Yan, G. Hu, D.
Mei, J. Wang and D. Ma, Angew. Chem. Int. Ed., 2016, 55, 3124ꢀ
3128.
tꢀBuOK
tꢀ
8
9
BuOK were uniformly distributed along the tubular backbone of Nꢀ
CNTsꢀ800, suggesting the strong interaction between NꢀCNTsꢀ800 and
C.ꢀL. Sun and Z.ꢀJ. Shi, Chem. Rev., 2014, 114, 9219ꢀ9280.
tꢀBuOK (Figure S10, ESI). This indicates that the resultant NꢀCNTsꢀ
10 J. Zhang, L. Qu, G. Shi, J. Liu, J. Chen and L. Dai, Angew. Chem.
Int. Ed., 2016, 55, 2230ꢀ2234.
11 (a) H. Dai, Acc. Chem. Res., 2002, 35, 1035ꢀ1044; (b) P. M.
Ajayan, Chem. Rev., 1999, 99, 1787ꢀ1800.
800 could activate ꢀBuOK, and their combination may cooperatively
t
catalyze the CꢀH arylation of benzene with iodobenzene (for proposed
reaction mechanism, see Scheme S2, ESI).
Carbon catalysts have been demonstrated to be effective for various
organic reactions. To further explore the applications of the porous Nꢀ
doped CNTs obtained in this work, other reactions were performed
using NꢀCNTsꢀ800 as the catalyst (Scheme S3, ESI). To our delight,
the resultant porous Nꢀdoped CNTs were very effective for all these
reactions. Compared to the oxygenꢀdoped mesoporous carbon (i.e.
catalyst Cꢀ1)6, which was reported to be the best carbocatalyst for the
aniline alkylation with benzyl alcohol to Nꢀbenzylaniline, NꢀCNTsꢀ800
displayed ~5 times higher activity under the same other conditions
(Scheme S3a, ESI). The reduction of nitrobenzene to aniline was also
performed very well over NꢀCNTsꢀ800, much better than that over the
reported catalyst Cꢀ1 (Scheme S3b, ESI). NꢀCNTsꢀ800 showed very
high catalytic efficiency for the selective oxidation of aromatic alkanes
in aqueous solution, comparable to the nitrogen, phosphorus and sulfur
coꢀdoped hollow carbon shells that were the best carbocatalyst for this
kind of reactions to date as reported recently (Scheme S3c, ESI).7a The
superior catalytic activities of the resultant Nꢀdoped CNTs may result
from the N doping together with the unique nanotubular structures and
high BET surface area.
12 (a) J. Zhang, Z.ꢀA. Qiao, S. M. Mahurin, X. Jiang, S.ꢀH. Chai, H.
Lu, K. Nelson and S. Dai, Angew. Chem. Int. Ed., 2015, 54, 4582ꢀ
4586; (b) M.ꢀH. Sun, S.ꢀZ. Huang, L.ꢀH. Chen, Y. Li, X.ꢀY. Yang,
Z.ꢀY. Yuan and B.ꢀL. Su, Chem. Soc. Rev., 2016, 45, 3479ꢀ3563.
13 T. Jin, Y. Xiong, X. Zhu, Z. Tian, D.ꢀJ. Tao, J. Hu, D.ꢀe. Jiang, H.
Wang, H. Liu and S. Dai, Chem. Commun., 2016, 52, 4454ꢀ4457.
14 F. Yang, C. Chi, C. Wang, Y. Wang and Y. Li, Green Chem., 2016,
18, 4254ꢀ4262.
15 J. Long, X. Xie, J. Xu, Q. Gu, L. Chen and X. Wang, ACS Catal.
2012, , 622ꢀ631.
16 P. Zhang, Y. Gong, H. Li, Z. Chen and Y. Wang, Nat Commun
2013, , 1593.
,
2
,
4
17 (a) Y. Wu, S. Fang and Y. Jiang, Solid State Ionics, 1999, 120, 117ꢀ
123; (b) L. T. Weng, C. Poleunis, P. Bertrand, V. Carlier, M.
Sclavons, P. Franquinet and R. Legras, J. Adhes. Sci. Technol.
,
1995, , 859ꢀ871.
9
18 H. Schmiers, J. Friebel, P. Streubel, R. Hesse and R. Köpsel,
Carbon, 1999, 37, 1965ꢀ1978.
19 (a) C.ꢀL. Sun, H. Li, D.ꢀG. Yu, M. Yu, X. Zhou, X.ꢀY. Lu, K.
Huang, S.ꢀF. Zheng, B.ꢀJ. Li and Z.ꢀJ. Shi, Nat. Chem., 2010,
2,
1044ꢀ1049; (b) J. P. Barham, G. Coulthard, R. G. Kane, N.
Delgado, M. P. John and J. A. Murphy, Angew. Chem. Int. Ed.
,
2016, 55, 4492ꢀ4496.
In summary, hierarchically porous Nꢀdoped oneꢀdimensional CNTs
were obtained through a morphologyꢀpreserved thermal transformation
of organic polymer nanotubes. Its remarkable structureꢀdependent
properties render the asꢀprepared NꢀCNTs a superior heterogeneous
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012