56
S. Nagashima et al. / Applied Catalysis A: General 450 (2013) 50–56
+
[5] S. Nagashima, S. Kamiguchi, S. Ohguchi, T. Chihara, Chem. Eng. J. 161 (2010)
O
C
O
H
H+
Mo
384–387.
H
S
– H+
C6H5
• •
[6] S. Kamiguchi, S. Nishida, I. Takahashi, H. Kurokawa, H. Miura, T. Chihara, J. Mol.
Catal. A 255 (2006) 117–122.
[7] S. Kamiguchi, S. Nagashima, T. Chihara, Chem. Lett. 36 (2007) 1340–1341.
[8] S. Kamiguchi, N. Ikeda, S. Nagashima, H. Kurokawa, H. Miura, T. Chihara, J.
Cluster Sci. 20 (2009) 683–693.
[9] S. Nagashima, S. Kamiguchi, K. Kudo, T. Sasaki, T. Chihara, Chem. Lett. 40 (2011)
78–80.
[10] Kh.I. Areshidze, M.K. Gadzhiev, Soobshch. Akad. Nauk Gruz. SSR 87 (1977)
609–612.
CH3
O
R
CH3
C
O
R
• •
Mo
O
H
O
+
R S C6H5
CH3
C
Scheme 2. S-Alkylation mechanism over a Brønsted acid site and coordinatively
unsaturated site of (H3O)2[(Mo6Cl8)Cl6]·6H2O (2).
[11] A. Onoe, S. Tai, JP Patent 2002-371056A to Sumitomo Seika Chemicals Co., Ltd.
[12] M. Selva, F. Trotta, P. Tundo, J. Chem. Soc. Perkin Trans. 2 (1992) 519–522.
[13] K.I. Areshidze, M.K. Gadzhiev, N.M. Nebieridze, Neftekhimiya 16 (1976)
898–901.
[14] S. Vijaikumar, K. Pitchumani, J. Mol. Catal. A 217 (2004) 117–120.
[15] P.B. Venuto, L.A. Hamilton, P.S. Landis, J.J. Wise, J. Catal. 5 (1966) 81–98.
[16] P. Tundo, F. Trotta, G. Moraglio, F. Ligorati, Ind. Eng. Chem. Res. 27 (1988)
1565–1571.
with basic reagents. Catalytic S-acetylation with acetate esters has
not been reported, as far as we know.
4. Conclusions
[17] F.W. Koknat, J.A. Parsons, A. Vongvusharintra, Inorg. Chem. 13 (1974)
1699–1702.
[18] P. Nannelli, B.P. Block, Inorg. Synth. 12 (1970) 170–178.
[19] V. Kolesnichenko, L. Messerle, Inorg. Chem. 37 (1998) 3660–3663.
[20] S. Kamiguchi, M. Noda, Y. Miyagishi, S. Nishida, M. Kodomari, T. Chihara, J. Mol.
Catal. A 195 (2003) 159–171.
[21] G.F. Froment, Catal. Rev. 50 (2008) 1–18.
[22] M. Kawamura, M. Hatta, N. Koune, N. Kitagishi, US Patent 4 124 646 to Seitetsu
Kagaku Co., Ltd. (1978).
Selective S-alkylations of benzenethiol with various types of
alkylating reagents were applied in the presence of halide clus-
ters as a catalyst in gas-phase reactions at elevated temperatures.
Above 200 ◦C, [(Nb6Cl12)Cl2(H2O)4]·6H2O (1)/SiO2 developed cat-
alytic activity for the S-alkylation with methanol to yield methyl
phenyl sulfide selectively. Halide clusters of molybdenum, tan-
talum and tungsten supported on silica gel also catalyzed the
reaction. Primary alcohols with short alkyl chains afforded the
corresponding sulfides. Ethers, dialkyl carbonates and orthoesters
were active reagents for the reaction at 400 ◦C. Of these, orthoesters
were the most effective reagents for the syntheses of methyl or
ethyl phenyl sulfides. Alkyl halides also selectively afforded the
corresponding alkyl phenyl sulfides. The reactivity of olefins with
benzenethiol was high. The S-alkylation of benzenethiol with 1-
hexene was a spontaneous reaction above 200 ◦C; however, the
alkylation was catalyzed by the halide cluster, selectively yield-
ing n-hexyl phenyl sulfide. For the synthesis of longer unbranched
alkyl phenyl sulfides, 1-olefins were more effective reagents than
1-halogenated alkanes. When alkyl acetates were employed for
the reaction, S-alkylation proceeded on all of the clusters except
for 1. Thus, halide clusters exhibited S-alkylation catalysis of ben-
zenethiol for a wide variety of alkylating reagents.
[23] E.G. Kataev, F.G. Gabdrakhmanov, V.P. Tutubalina, Zh. Org. Khim. 7 (1971)
122–125.
[24] S. Kamiguchi, S. Iketani, M. Kodomari, T. Chihara, J. Cluster Sci. 15 (2004) 19–31.
[25] S. Kamiguchi, T. Mori, M. Watanabe, A. Suzuki, M. Kodomari, M. Nomura, Y.
Iwasawa, T. Chihara, J. Mol. Catal. A 253 (2006) 176–186.
[26] S. Kamiguchi, K. Kondo, M. Kodomari, T. Chihara, J. Catal. 223 (2004) 54–63.
[27] S. Kamiguchi, S. Takaku, M. Kodomari, T. Chihara, J. Mol. Catal. A 260 (2006)
43–48.
[28] S. Kamiguchi, A. Nakamura, A. Suzuki, M. Kodomari, M. Nomura, Y. Iwasawa, T.
Chihara, J. Catal. 230 (2005) 204–213.
[29] S. Kamiguchi, S. Nagashima, K. Komori, M. Kodomari, T. Chihara, J. Cluster Sci.
18 (2007) 414–430.
[30] S. Nagashima, S. Kamiguchi, S. Ohguchi, T. Chihara, J. Cluster Sci. 22 (2011)
647–660.
[31] S. Kamiguchi, I. Takahashi, H. Kurokawa, H. Miura, T. Chihara, J. Mol. Catal. A
309 (2006) 70–75.
[32] S. Kamiguchi, S. Nishida, H. Kurokawa, H. Miura, T. Chihara, J. Mol. Catal. A 226
(2005) 1–9.
[33] S. Nagashima, S. Kamiguchi, S. Ohguchi, T. Chihara, Catal. Today 164 (2011)
135–138.
[34] S. Kamiguchi, M. Watanabe, K. Kondo, M. Kodomari, T. Chihara, J. Mol. Catal. A
203 (2003) 153–163.
[35] E.A. Bartkus, E.B. Hotelling, M.B. Neuworth, J. Org. Chem. 25 (1960)
232–233.
[36] R.J. Laufer, US Patent 3 076 848 to Consolidation Coal Company (1963).
[37] S. Khushvakhtova, E.A. Viktorova, T.A. Danilova, Vestn. Mosk. Univ. Ser. 2: Khim.
11 (1970) 346–349.
[38] C. Goux, P. Lhoste, D. Sinou, Tetrahedron 50 (1994) 10321–10330.
[39] X. Zhang, W. Rao, P.W.H. Chan, Synlett 2008 (2008) 2204–2208.
[40] A. Simon, H.G. Schnering, H. Wöhrle, H. Schäfer, Z. Anorg. Allg. Chem. 339 (1965)
155–170.
References
[1] S.C. Lee, R.H. Holm, Angew. Chem. Int. Ed. Engl. 29 (1990) 840–856.
[2] D.M.P. Mingos, D.J. Wales, Introduction to Cluster Chemistry, Prentice-Hall,
New Jersey, 1990.
[3] N. Prokopuk, D.F. Shriver, Adv. Inorg. Chem. 46 (1999) 1–49.
[4] J.D. Corbett, Pure Appl. Chem. 64 (1992) 1359–1408.