European Journal of Organic Chemistry
10.1002/ejoc.201601226
COMMUNICATION
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Aniline, phenol, anisole can also be chlorinated in moderate to good
yields by CMOBSA under mild reaction conditions (Table 4, 10a-
10i). With electron-donating (methyl) and electron-withdrawing
(cyano and nitro) as substituent, anilines produced corresponding
products (10a-10e) with good yields. To our delight, 1-
methoxynaphthalene was easily regioselectively transformed into the
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4-chlorinated
product
(10f) in 96% yield.[18] 1,3,5-
trimethoxybenzene, naphthalen-1-ol, 2-methoxyphenol were also
chlorinated under mild conditions with satisfactory yields in 89%,80%
and 62%, respectively.
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In this work, N-chloro-N-methoxybenzene sulfonamide,
a new
chlorinating reagent was conveniently and economically prepared in
high yield. It has properties of high reactivity, easy availability, wide
substrate range and stable storage. It is also of more economic
value in relation to other chlorinating reagents, such as CFBSA and
1-chloro-1,2-benziodoxol-3-one. 1,3-Diketones, β-keto esters,
benzoyl trifluoroacetones, phenols, anisoles, heteroarenes and
aromatic amines could be chloridized by this reagent. Furthermore,
the dichlorination of benzoyl trifluoroacetones with CMOBSA and the
subsequent removal of trifluoroacetyl supplied a way to selectively
synthesize ɑ,ɑ-dichloroketones, avoiding the formation of
monochloro or trichloro ketones. The application of this chlorinating
reagent in other transformations is actively underway.
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We are grateful to the National Natural Science Foundation of
China (NSFC) (grant number 21372077) for financial support.
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Keywords: CMOBSA • chlorination • economic • stability • a,a-
dichlorketones
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