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The Journal of Organic Chemistry
4-Bromo-2,6-dinitrophenol (9a): 1H NMR (400 MHz, CDCl3):
REFERENCES
δ (ppm) = 8.44 (s, 2 H), 11.3 (s, 1 H). 13C NMR (151 MHz,
DMSO-d6): δ (ppm) = 124.2 (Cq), 125.2 (2×CH), 141.9 (Cq), 160.9
(Cq). HRMS (ESI): calcd. for C6H2O5N279Br [M-]: 260.9153,
found: 260.9154. The analytical data is in agreement with those of
an authentic sample prepared according to the general procedure
for authentic samples (see below).
1
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2-Bromo-4,6-dinitrophenol (9b): 1H NMR (400 MHz, CDCl3):
δ (ppm) = 8.76 (d, J = 2.7 Hz, 1 H), 9.90 (d, J = 2.7 Hz, 1 H),
11.62 (s, 1 H). 13C NMR (101 MHz, DMSO-d6): δ (ppm) = 121.2
(Cq), 123.9 (CH), 126.8 (Cq), 129.3 (CH), 135.5 (Cq), 164.4 (Cq).
HRMS (ESI): calcd. for C6H2O5N279Br [M-]: 260.9153, found:
260.9149. The analytical data is in agreement with those of an au-
thentic sample prepared according to the general procedure for au-
thentic samples (see below).
General Procedure for the preparation of authentic samples for
the nitrohydroxylation of bromobenzene (1c): In a 50 mL flask
2-bromophenol (0.5 mmol, 57.9 µL) or 4-bromophenol (0.5 mmol,
59 mg) was dissolved in ethanol (1 mL) and H2SO4 (2 mL, 18M).
HNO3 (1 mL, 14.4M) was added. The resulting solution was stirred
for 4 hours at room temperature. Afterwards the mixture was ex-
tracted with ethyl acetate (3×5 mL), the combined organic phases
were dried over Na2SO4 and the solvent was removed under re-
duced pressure.
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Experiments under re-use of HNO3 (Scheme 3): In a closed air-
filled reaction tube with pressure equilibration benzene (1) (30
mL), DDQ (1.50 mmol, 341 mg) and nitric acid (7.2 M, 20 mL)
were combined to form the biphasic reaction mixture. The mixture
was irradiated with an 8W LED lamp for 24 h under vigorous stir-
ring. Afterwards, the aqueous phase was separated from the organic
layer and used for the same reaction again. This step was repeated
twice. The organic layer was diluted with H2O (100 mL), extracted
with CH2Cl2 (3×150 mL) and dried over sodium sulfate. The sol-
vent was concentrated slowly under reduced pressure (to 10 mbar)
and the crude product was obtained as a yellow-orange liquid.
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1
Analysis of the product distribution was performed by H NMR
spectroscopy in CDCl3 using dimethyl terephthalate as internal
standard.
ASSOCIATED CONTENT
(12) For catalytic oxidations with oxygen, see: (a) Niwa, S.;
Eswaramoorthy, M.; Nair, J.; Raj, A.; Ito, N.; Shoji, H.; Namba,
T.; Mizukami, F. Science 2002, 295, 105. (b) Dong, T.; Li, J.;
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Sabagh, A. M.; Yehia, F. Z.; Eshaq, G.; ElMetwally, A. E. ACS
Sustainable Chem. Eng. 2017, 5, 4811. (c) Borah, P.; Datta, A.;
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7779.
Supporting Information
Optimization experiments, control experiments, NMR spectra and
pictures of experimental setup. The Supporting Information is
available free of charge on the ACS Publications website.
AUTHOR INFORMATION
Corresponding Author
*Markus.Heinrich@fau.de; Tel.: +49-9131-85-24115; Fax: +49-
9131-85-22585.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
We are grateful to the Deutsche Bundesstiftung Umwelt (DBU) for
the support of our research (grant No. 80014/189 and 30388-31).
(14) For catalytic oxidations with dinitrogen oxide, see: (a) Koekkoek,
A. J. J.; Kim, W.; Degirmenci, V.; Xin, H.; Ryoo, R.; Hensen, E. J.
M. J. Catal. 2013, 299, 81. (b) Meng, L.; Zhu, X.; Hensen, E. J. M.
ACS Catal. 2017, 7, 2709.
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