Supplementary Information

The Bamberger Rearrangement of N-Arylhydroxylamine to

p-Aminophenol in a CO2-H2O System

Shijuan Liua*, Yuanping Haob, Jingyang Jiangb
a
College of Chemistry, Key Laboratory of Preparation and Application of Environmental Friendly
Materials of Ministry of Education, Jilin Normal University; Siping 136000 China
b
College of Chemical Engineering, State Key Laboratory of Fine Chemicals,
Dalian University of Technology; Dalian 116024 China

Characterisation data for the products

HPLC data for the mixture after the reaction of N-phenylhydroxylamine
Eluent: 70 mN ammonium acetate aqueous solution (solvent A) + methanol (solvent
B), a linear gradient of 30% of B to 100% over 30 min, UV detector: 254 nm, flow
rate: 1.0 mL min-1. Retention time: p-aminophenol, 3.68 min; o-aminophenol, 6.64
min; N-phenylhydroxylamine, 7.92 min; aniline, 9.35 min; nitrosobenzene, 16.36 min;
azoxybenzene, 19.11 min.

Characterisation data for these p-aminophenols

p-aminophenol mps1187-189 oC. 1H NMR (400 MHz, DMSO-d6) s2 4.36 (2 H, s,
NH2), 6.41 (2 H, d, J = 8.4 Hz, Ph-H), 6.47 (2 H, d, J = 8.4 Hz, Ph-H), 8.33 (1 H, s,
OH).

4-amino-3-methylphenol mps3 179-180 oC. 1H NMR (400 MHz, DMSO-d6)s4 1.98 (3

H, s, CH3), 4.14 (2 H, s, NH2), 6.34 (1 H, d, J = 8.4, Ph-H), 6.40 (1 H, s, Ph-H), 6.43
(1 H, d, J = 8.4, Ph-H), 8.26 (1 H, s, OH)

4-amino-3-chlorophenol mpS5 159-160 oC. 1H NMR (400 MHz, DMSO-d6) 4.60 (2

H, s, NH2), 6.51 (1 H, d, J = 8.8, Ph-H), 6.63 (1 H, s, Ph-H), 6.65 (1 H, d, J = 8.8,
Ph-H), 8.75 (1 H, s, OH).

References
S1 Dunn, S. A. Some physical properties of p-aminophenol. J. Am. Chem. Soc., 1954,
762, 6191-6192.
S2 Motoyama, Y.; Kamo, K.; Nagashima, H. Catalysis in polysiloxane gels:
Platinum-catalyzed hydrosilylation of polymethylhydrosiloxane (PMHS) leading to
reusable catalysts for reduction of nitroarenes. Org. Lett., 2009, 11, 1345-1348.
S3 Proskouriakoff, A; Titherington, R. J. Mercury derivatives of acetylaminocresols.
J. Am. Chem. Soc., 1930, 52, 3978-3984.
S4 Malesani, G.; Galiano, F.; Ferlin, M. G.; Masiero, S. Synthesis of 4,7-dimethoxy-
indoles bearing substituents at the C-5 and C-6 positions and Studies on their
demethylation products. J. Heterocyclic Chem., 1980, 17, 563-569.
S5 Badri, R.; Shushizadeh, M. R. Silica sulfuric acid as an efficient reagent for the
Bamberger rearrangement of phenyl hydroxylamine derivatives in solvent-free
conditions. Asian J. Chem., 2007, 19(6), 4661-4664.

VWD1 A, Wavelength=254 nm (LSJ\10032401.D)

19.112
mAU

1000

800
3.676

600
7.917

400

16.357
200
9.354
6.641

0 2.5 5 7.5 10 12.5 15 17.5 min

Fig. S1 HPLC spectrum for the mixture after the reaction of N-phenylhydroxylamine
 8.330

6.485
6.463
6.422
6.401

4.355

3.376

2.497
NH2

OH
1.00

2.05
1.94

1.98

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
ppm (t1)

Fig. S2 1H NMR spectra of p-aminophenol

8.258

6.443
6.422
6.402
6.396
6.351
6.344
6.330
6.323

4.141

3.366

2.497

1.978

NH2
CH3

OH
1.00

2.06
1.02

2.03

3.03

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

ppm (t1)

Fig. S3 1H NMR spectra of 4-amino-3-methylphenol

 8.756

6.658
6.636
6.630
6.624
6.521
6.514
6.499
6.492

4.601

3.300

2.499

-0.000
NH2
Cl

OH
1.00

2.00
1.00

1.99

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0

1
Fig. S4 H NMR spectra of 4-amino-3-chlorophenol