RSC Advances
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14 Dibromomethane condensation with thiols is oen
problematic, see: E. W. Della and S. D. Graney, J. Org.
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Valencia, J. L. Gazquez and A. Vela, J. Phys. Chem. A, 2017,
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62–66; (b) R. C. Desai, R. P. Farrell, G.-H. Kuo and 30 Selected works by Krief and others cite an unpublished
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18 We believe that our simple isolation procedure is key for 31 Formation of thiomethylmanganese organometallics have
optimal performance, since adopting aqueous workups
gave us inconsistent results (variable amounts of
dithioacetal products).
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19 G. Bashiardes and S. G. Davies, Tetrahedron Lett., 1987, 28, 32 For alternative methods for the generation of sulfenyl-
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´
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25 A 13C-NMR signal at 68.9 was assigned to bis(bromomethyl)
ether as judged by a HSQC experiment.
26 Integrals of signals at 5.6 and 5.0 ppm are congruent with
compound identity (2 : 1 ratio). 5.6 ppm signal correlates
to a 13C signal at 69.0 ppm and signal at 5.0 correlates
with a 13C signal at 90.6 ppm.
27 As judged by its chemical shi compared to the other species
´
(more unshielded protons). No acetyl signals besides AcOH 37 (a) J. Y. Gauthier, T. Henien, L. Lo, M. Therien and
related were found. Aer extended times 5–24 h in CDCl3,
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28 Following a strict measurement of the reagents, we couldn't
nd evidence of formation of bis(bromomethyl)ether by 1H-
NMR (see ref. 17). However, extremely caution is mandatory
as bis(halomethyl)ethers are highly toxic and carcinogenic:
R. T. Drew, S. Laskin, M. Kuschner and N. Nelson, Arch. 38 (a) B. Roy, D. Sengupta and B. Basu, Tetrahedron Lett., 2014,
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29 Formaldehyde and p-nitrobenzaldehyde are well-known to
55, 6596–6600; (b) X. Ling, S. Zhang, P. Shao, P. Wang, X. Ma
and M. Bai, Tetrahedron Lett., 2015, 56, 5242–5244.
be superior electrophiles experimentally: (a) M. Regitz and 39 Although sulfenylation by electrophilic quench of anionic
G. Maas in, Diazo Compounds Properties and Synthesis,
Academic Press, Inc., Orlando, 1986, ch. 14, p. 472S; and
methylene groups using disuldes is well stablished, this
is the rst time that methylsulde organometallics are
24658 | RSC Adv., 2018, 8, 24654–24659
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