LETTER
Selective Nitration of Aromatic Olefins
1999
Table 3 Selective Nitration of Aromatic Olefinsa (continued)
A. T., Eds.; VCH: Weinheim, 1990, Chap. 1, 1–135.
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Claycop (1.5 equiv)
R2
R2
TEMPO (20 mol%)
R3
NO2
R1
E only
1,4-dioxane (5 mL)
air, 80 °C, 1 h
R1
R3
R1 = aromatic, aliphatic
R2, R3 = H
Entry Alkene
Productb
Yieldc
(%)
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A. S. Egit. Arast. 2008, 32, 145.
NO2
NO2
15
65
16
80
82
Cl
Cl
NO2
17
O2N
O2N
a The reactions were performed on a 1-mmol scale.
b All the products were characterized by 1H and 13C NMR spectrosco-
py and by GC/MS.
c Yield of pure product after column chromatography.
Claycop
heat
TEMPO TEMPOH
R2
R2
R2
O
NO2
NO2
NO2
R3
R1
R1
R1
R3
R3
H
Scheme 2 A plausible mechanism for TEMPO-catalyzed nitration of
aromatic olefins
(6) (a) Preparative Chemistry Using Supported Reagents;
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(b) McKillop, A.; Young, D. W. Synthesis 1979, 401.
(c) McKillop, A.; Young, D. W. Synthesis 1979, 481.
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1992.
(8) Laszlo, P.; Pennetreau, P. J. Org. Chem. 1987, 52, 2407.
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Acknowledgment
E.B. thanks DST New Delhi for an INSPIRE Fellowship (IFA12-
CH-29). C.R.S. and U.N.R thank OSDD and UGC, New Delhi, re-
spectively, for research fellowships. The authors thank CSIR, New
Delhi for financial support as part of the XII Five-Year Plan under
the title ORIGIN (CSC0108).
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