Please do not adjust margins
Green Chemistry
Page 3 of 5
DOI: 10.1039/C5GC01505G
Journal Name
COMMUNICATION
Table 2 Yields for compound 2a, depending on the time and reagents ratio.a
1
2
T. Ogoshi, S. Kanai, S. Fujinami, T.-A. Yamagishi, Y.
Nakamoto, J. Am. Chem. Soc. 2008, 130, 5022.
D. Cao, Y. Kou, J. Liang, Z. Chen, L. Wang, H. Meier, Angew.
Entry
Amount of PF
(equiv.)
Amount of
Time
(min)
Yields
(%)b
H2SO4,
mol %
5
Chem. 2009, 121, 9901; Angew. Chem. Int. Ed. 2009, 48
9721.
T. Ogoshi, T. Yamagishi, Eur. J. Org. Chem., 2013, 2961.
,
3
4
1
2
1
1.5
2
10
10
10
10
10
10
10
10
20
30
10
10
10
30
32%
38%
45%
52%
65%
84%
75%
58%
82%
80%
45%
68%
76%
-
(a) W. Si, L. Chen, X.-B. Hu, G. Tang, Z. Chen, J.-L. Hou, Z.-T.
Li, Angew. Chem. 2011, 123, 12772; Angew. Chem. Int. Ed.,
2011, 50, 12564; (b) H. Zhang, K. T. Nguyen, X. Ma, H. Yan, J.
Guo, L. Zhu, Y. Zho, Org. Biomol. Chem. 2013, 11, 2070; (c) X.
Yan, P. Wei, Z. Li, B. Zheng, S. Dong, F. Huang, Q. Zhou,
Chem. Commun. 2013, 49, 2512; (d) N. L. Strutt, H. Zhang, M.
5
3
5
4
2.5
3
5
5
5
6
3
10
15
20
10
10
10
10
10
-
7
3
A. Giesener, J. Lei, J. A. Stoddart, Chem. Commun., 2012, 48
5
,
1647; (e) S. Dong, J. Yuan, F. Huang, Chem. Sci., 2014, , 247.
8
3
For pillararene-based MOFs see: (f) N. L. Strutt, D. Fairen-
Jimenez, J. Iehl, M. B. Lalonde, R. Q. Snurr, O. K. Farha, J. T.
Hupp, J. F. Stoddart, J. Am. Chem. Soc., 2012, 134. For
reviews see: (g) P. J. Cragg; K. Sharma, Chem. Soc. Rev., 2012,
41, 597; (h) T. Ogoshi, T. Yamagishi, Chem. Commun., 2014,
50, 4776; (i) T. Ogoshi, T. Yamagishi, Bull. Chem. Soc. Jpn.,
2013, 86, 312; (j) D. Cao; H. Meier, Asian J. Org. Chem., 2014,
9
3
10
11
12
13
14
3
1
2
5
3
a
b
3
, 244.
All reactions are carried out in 5 mmol scale. Yields after washing with water
5
(a) I. Nierengarten, S. Guerra, M. Holler, J.-F. Nierengarten,
R. Deschenaux, Chem. Commun., 2012, 48, 8072; (b) I.
Nierengarten, S. Guerra, M. Holler, L. Karmazin-Brelot, J.
Barberá, R. Deschenaux, J.-F. Nierengarten, Eur. J. Org.
Chem., 2013, 3675.
and ethyl alcohol. PF = Paraformaldehyde.
Conclusions
6
7
H. Yamamoto, H. Kudo, T. Kozawa,Proc. SPIE 9051, Advances
in Patterning Materials and Processes XXXI, 2014, 90511Z,
doi: 10.1117/12.2046595.
(a) R. R. Kothur, J. Hall, B. A. Patel, C. L. Leong, M. G.
Boutelle, P. J. Cragg, Chem. Commun., 2014, 50, 852; (b) Q.
Zhao, J. W. C. Dunlop, X. Qiu, F. Huang, Z. Zhang, J. Heyda,J.
Dzubiella, M. Antonietti, J. Yuan, Nature Communications,
In conclusion, we have demonstrated a simple, solvent-free,
energy efficient, clean and high yield pathway for the synthesis
of pillar[6]arenes. This method also demonstrates a suitable
and cost-effective alternative to commercially available
products and solvents for the reaction media. This protocol is
also applicable on a gram-scale synthesis. Clean reaction, high
yields, ease of product isolation, short reaction time, low
catalyst loading and avoidance of toxic solvents are the
notable advantages of the present methodology and these
features make this procedure to be a green synthetic protocol.
We believe that our novel procedure will open up a new
practical and convenient route for the synthesis of
pillar[6]arenes.
2014, 5, Article number: 4293, doi:10.1038/ncomms5293.
8
9
(a) L.-L. Tan, H. Li, Y. Tao, S. X.-A. Zhang, B. Wang, Y.-W. Yang,
Adv. Mater., 2014, 26, 7027; (b) T. Ogoshi, R. Sueto, K.
Yoshikoshi, T. Yamagishi, Chem. Commun., 2014, 50, 15209.
(a) X. B. Hu, Z. Chen, G. Tang, J. L. Hou, Z. T. Li, J. Am. Chem.
Soc. 2012, 134, 8384; (b) M. Barboiu, Angew. Chem. Int. Ed.,
2012, 51, 11674.
10 (a) J. Fan, H. Deng, J. Li, X. Ji, C. Li, Chem. Commun., 2013, 49
,
6343; (b) W. Xia, X. Hu, Y. Chen, C. Lin, L. Wang, Chem.
Commun., 2013, 49, 5085.
11 (a) C. Li, J. Ma, L. Zhao, Y. Zhang, Y. Yu, X. Shu,J. Li and X. Jia,
Chem. Commun., 2013, 49, 1924; (b) D.-D. Zheng, D.-Y. Fu, Y.
Wu, Y.-L. Sun, L.-L. Tan, T. Zhou, S.-Q. Ma, X. Zha, Y.-W. Yang,
Chem. Commun., 2014, 50, 3201.
12 (a) T. Ogoshi, T. Aoki, K. Kitajima, S. Fujinami, T.-A.
Yamagishi, Y. Nakamoto, J. Org. Chem., 2011, 76, 328; (b) T.
Boinski, A. Szumna, Tetrahedron, 2012, 68, 9419; (c) H. Tao,
D. Cao, L. Liu, Y. Kou, L. Wang, H. Meier, Sci. China Chem.,
2012, 55, 223.
13 (a) M. Holler, N. Allenbach, J. Sonet, J.-F. Nierengarten,
Chem. Commun., 2012, 48, 2576; (b) Y. Ma, Z. Zhang, X. Ji, C.
Han, J. He, Z. Abliz, W. Chen, F. Huang, Eur. J. Org. Chem.,
2011, 5331.
14 (a) K. Wang, L.-L. Tan, D.-X. Chen, N. Song, G. Xi, S. X.-A.
Zhang, C. Li, Y.-W. Yang, Org. Biomol. Chem., 2012, 10, 9405;
(b) Y. Kou, H. Tao, D. Cao, Z. Fu, D. Schollmeyer, H. Meier,
Eur. J. Org. Chem., 2010, 6464.
Acknowledgements
This work was supported by the Russian Science Foundation
(Ref. # 15-13-10033) and, for A.M, by BRNS–DAE (Ref. No.
37(2)/14/35/2014-BRNS/563, June 10, 2014).
Notes and references
‡Representative synthetic procedure of pillar[6]arenes 2:
A
mixture of the appropriate 1,4-dialkoxy benzene (5 mmol),
paraformaldehyde (0.46 g, 15 mmol) and 98% H2SO4 (30 µL, 10
mol%) was ground by means of porcelain mortar and pestle at
room temperature. After the continuous grinding for 10 minutes
by hand a deep green gummy mass of a crude product was
observed. The reaction mixture was then poured into 5 mL of
ethanol and 0.5 mL of water. The resulting precipitate was
filtered off, washed two-three times with ethyl alcohol and dried
15 X. B. Hu, Z. Chen, L. Chen, L. Zhang, J. L. Hou, Z. T. Li, Chem.
Commun., 2012, 48, 10999.
16 For the template solvent effects and pillar[n]arenes
interconversions see: (a) T. Ogoshi, N. Ueshima, T. Akutsu, D.
Yamafuji, T. Furuta, F. Sakakibaraa, T. Yamagishi, Chem.
Commun., 2014, 50, 5774; (b) T. Ogoshi, N. Ueshima, F.
Sakakibara, T. Yamagishi, T. Haino, Org. Lett., 2014, 16, 2896;
in order to get the pure per-alkylated pillar[6]arenes 2 without
any other purification by column chromatography or
recrystallization.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins