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Green Chemistry
DOI: 10.1039/C5GC01869B
COMMUNICATION
Journal Name
Conversely, these species can be easily reduced during the
electrolysis course, till the cathodic solution becomes colorless
again (Scheme 2b). When halogenated compounds are not
7
R. Khanna, N. Singh, S. Charan, S.P. Lonkar, A.S. Reddy, Y.
Patil and A. K. Viswanath, Mater. Chem. Phys., 2006, 97, 288-
2
94.
C. W. Nogueira, G. Zeni and J. B. T. Rocha, Chem. Rev., 2004,
04, 6255-6286.
8
9
1
1
2
-
very reactive, the molecular oxygen slowly reacts with Y
0
giving Y (Scheme 3), which remains in the medium or can
react according to Scheme 2.
1
D. M. Freudendahl, S. Santoro, S. A. Shahzad, C. Santi and T.
Wirth, Angew. Chem., Int. Ed., 2009, 48, 8409-8411.
0 A. L. Braga, D. S. Ludtke and F. Vargas, Curr. Org. Chem.,
2
006, 10, 1921-1938.
1 F. A. Devillanova, Handbook of Chalcogen Chemistry: New
Perspectives in S, Se and Te, Royal Society of Chemistry,
Cambridge, 2006.
-2
0
-
Y
2
(aq) + O2(aq) + 2 H O(l) → Y (s) + 4 HO (aq)
1
2 I. P. Beletskaya and V. P. Ananikov, Chem. Rev., 2011, 111,
1596-1636.
2
Scheme 3. Oxidation of chalcogenide anion (Y ) into the
-
0
corresponding chalcogenide (Y ).
13 V. P. Ananikov, S. S. Zalesskiy and I. P. Beletskaya, Curr. Org.
Synth., 2011, , 2-52.
4 V. P. Reddy, A. V. Kumar, K. Swapna and K. R. Rao, Org. Lett.,
009, 11, 951-953.
8
1
1
1
This behavior explains the increase of dichalcogenide product
in the sequence: Te > Se > S.
2
5 D. Singh, E. E. Alberto, O. E. D. Rodrigues and A. L. Braga,
Green Chem., 2009, 11, 1521-1524.
6 D. Alves, C. G. Santos, M. W. Paixão, L. C. Soares, D. Souza, O.
Conclusions
E. D. Rodrigues and A. L. Braga, Tetrahedron Lett., 2009, 50
635-6638.
7 C. S. Freitas, A. M. Barcellos, V. G. Ricordi, J. M. Pena, G.
Perin, R. G. Jacob, E. J. Lenardão and D. Alves, Green Chem.,
2011, 13, 2931-2938.
,
6
The electrochemical reduction of elemental chalcogens in
aqueous medium showed to be a simple, efficient and clean
procedure for obtaining chalcogenide ions. From the results
1
shown in Tables 1 and 2, high yields were observed when 18 J. S. Jaworski, Electrochemistry of Organic Selenium and
Tellurium Compounds, in: Z. Rappoport (ed.), The Chemistry
benzyl and primary alkyl halides were used as substrate in the
of Organic Selenium and Tellurium Compounds, Ch. 4, John
reaction, conversely, secondary halides gave lower yields and
Wiley & Sons, Chichester, 2012.
9 C. Thobie-Gautier and C. Degrand, J. Org. Chem., 1991, 56
5703-5707.
no reaction were observed when adamantyl and aryl halides
1
,
were used suggesting a S
N
2 type reaction. The reactivity and
nucleophilic character of telluride ion is responsible for 20 C. Degrand and R. J. Prest, J. Electroanal. Chem., 1990, 282
81-286.
,
2
selectivity
and
high
yields
were
observed
in
2
1 P. Jeroschewski, W. Ruth, B. Strubing and H. Berge, J. Prakt.
Chem., 1982, 324, 787-792.
2 R. T. Ribeiro, J. M. M. Dias, G. A. G. Pereira, D. V. Freitas, P. E.
Cabral Filho, R. A. Raele, A. Fontes, M. Navarro and B. S.
Santos, Green Chem. 2013, 15, 1061-1066.
3 D. V. Freitas, J. M. M. Dias, S. G. B. Passos, G. C. S. de Souza,
E. T. Neto and M. Navarro, Green Chem., 2014, 16, 3247-
3
organochalcogenide reactions. The selenide ion is less reactive
and in most cases the reaction presented a mixture of selenide
and diselenide products. The sulfide ion is even less reactive
and only presented good results when reactive halogenated
compounds were used to give the corresponding mono and
disulfide products in lower selectivity for all cases.
2
2
2
254.
4 NTP Toxicology and Carcinogenesis Studies of Acetonitrile
CAS No. 75-05-8) in F344/N Rats and B6C3F1 Mice
(Inhalation Studies), Natl. Toxicol. Program Tech. Rep. Ser.,
996, 447, 1-272.
5 S. D. Ramgren, L. Hie, Y. Ye, and N. K. Garg, Org. Lett. 2013,
, 3950-3953.
573986/2008-8) and FACEPE (APQ-1991-1.06/12) for financial 26 A. Krief and M. Derock, Tetrahedron Lett., 2002, 43, 3083-
(
Acknowledgements
1
We gratefully acknowledge CAPES, CNPq (482299/2013-4,
2
484778/2011-0 and 473499/2011-8), INCT-INAMI/CNPq
1
5
(
3
086.
support. P.H.M and M.N. are also thankful to CNPq for their
fellowships.
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| J. Name., 2012, 00, 1-3
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