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New Journal of Chemistry
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COMMUNICATION
Journal Name
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RuII(bpy)3Cl2 (1 mol%),
OH
OH
1999, 201.
Br
CCl3Br (2 equiv.), DMSO
3
4
(a) I. Ekladious, Y. L. Colson, M. W. GriDnOstI:a1f0f,.1N03a9t/.CR9eNvJ.0D34ru22gF.
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P. Klingelhoefer, G. Schnabel, R. Pelzer, W. Spiegler, U.S.
Patent, 0277101, January 11, 2012.
O
O
Blue LED ( = 445 nm),
[Air] or [Ar], 5h
Br
6
, No formation
5
6'
, 84% or 77%
Scheme 8. Formation of 2,4-dibromo-6-ethylphenol 6’ from 2-ethylphenol
5
6
D. L. Casinelli, U.S. Patent, 4286968, September 01, 1981.
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To check the reactivity of diols a representative 1,3-propane
diol was treated under the same photochemical condition with
DMSO. It readily afforded the corresponding cyclic acetal 1,3-
dioxane 8 in 64% yield.
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RuII(bpy)3Cl2 (1 mol%),
CCl3Br (2 equiv.), DMSO
O
O
HO
OH
Blue LED ( = 445 nm),
[Air], 6.5h
7
8
, 64%
8
9
V. Cogliano, Y. Grosse, R. Baan, K. Straif, B. Secretan, F. El
Ghissassi, Lancet Oncol., 2004, 5, 528.
Scheme 9. Formation of 1,3-dioxane 6 from 1,3-propane diol
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Further studies on thiols, amines, detailed energy calculations of
the reaction intermediates to shade more light on the mechanism
are in process.
Conclusions
In conclusion, an unprecedented photocatalytic route to the
acetals using DMSO as a “methylene” source was developed
under aerial condition. The reactions proceed under mild
conditions leading to the smooth conversion of alcohols to
acetals in high yields. Moreover this described methodology
uses mild conditions to give smooth conversion of alcohols to
acetals.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The author would like to thank DST-SERB, India (grant number
PDF/2018/000072/CS) for financial support.
Notes and references
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