M. Shi, S.-C. Cui, W.-P. Yin
FULL PAPER
[2] a) G. A. Olah, R. Malhotra, S. C. Narang, Nitration: Methods
and Mechanism (Ed.: H. Feuer), VCH Publishers, New York,
1989; b) C. K. Ingold, Structure and Mechanism in Organic
Chemistry, 2nd ed., Cornell University Press, Ithaca, New
York, 1969; c) G. A. Olah, S. J. Kuhn, in Friedel–Crafts and
Related Reactions (Ed.: G. A. Olah), Wiley-Interscience, New
York, vol. 2, 1964; d) G. A. Olah, S. C. Narang, J. A. Olah, K.
Lammertsma, Proc. Natl. Acad. Sci. USA 1982, 4487–4491; e)
M. J. Thompson, P. J. Zeeger, Tetrahedron 1991, 47, 8787–8790;
f) S. C. Bisarya, S. K. Joshi, A. G. Holker, Synth. Commun.
1993, 23, 1125–1137; g) J. A. R. Robrgues, A. P. de Oliveira,
P. J. S. Moran, R. Custodio, Tetrahedron 1999, 55, 6733–6738.
[3] a) G. A. Olah, ACS Symp. Series, vol. 22 (Ed.: F. Albright),
Washington DC, 1967, p. 1; b) J. G. Hoggett, R. B. Moodie,
J. R. Penton, K. Schofield, Nitration and Aromatic Reactivity,
Cambridge University Press, London, 1971; c) K. Schofield,
Aromatic Nitration, Cambridge University Press, London,
1980; d) L. V. Malysheva, E. A. Paukshtis, K. G. Ione, Catal.
Rev. Sci. Eng. 1995, 37, 179–226.
Preparation of the Zirconium and Hafnium Oxychloride Complex:
ZrCl4 or HfCl4 (500 mg) was hydrolyzed with distilled water
(2.0 mL) in a glass vessel. The water was then removed under re-
duced pressure by heating at 80 °C. Then, the product was dried at
120 °C for 24 h in an oven to give the zirconium or hafnium oxy-
chloride complex as a white solid.
Zirconium oxychloride complex: M.p. Ͼ 300 °C, 500 mg, yield:
98%. Zr4Cl5O24H24: calcd. Cl 18.65; found Cl 18.88 (X-ray crystal
structure: see A. Clearfield, P. A. Vaughan, Acta Crystallogr. 1956,
9, 555).
Hafnium oxychloride complex: m.p. Ͼ 300 °C, 487 mg, yield: 96%.
Hf4Cl5O24H24: calcd. Cl 13.64; found Cl 14.99.
A single crystal of this complex was obtained by recrystallization
from water. Therefore, this complex contains water in its crystal
structure. Empirical formula: H72Cl5Hf4O48; formula mass:
1731.79; color, cabit: colorless, prismatic; dimensions:
0.366×0.273×0.186 mm; crystal system: tetragonal; lattice type:
primitive; lattice parameters: a = 17.0031(11), b = 17.0031(11), c =
7.6897(7) Å, α = 90°, β = 90°, γ = 90°, V = 2223.1(3) Å3; space
group: P4/mnc; Z = 2; Dcalcd. = 1.909 gcm–3; F000 = 1152; dif-
fractometer: Rigaku AFC7R; residuals: R, Rw: 0.0808, 0.2076. The
crystal data have been deposited at Fachinformationszentrum
(FIZ) Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany, with
deposition number CSD-414059.
[4] a) J. T. Stewart, C. A. Janicki, Anal. Profiles Drug Subst. 1987,
16, 119–123; b) M. N. Desai, Indian J. Appl. Chem. 1970, 33,
277–282; c) M. Mottier, Arch. Sci. Phys. Nat. 1934, 16, 301–
312.
[5] L. Lunar, D. Sicilia, S. Rubio, D. Perez-Bendito, U. Nickel,
Water Res. 2000, 34, 1791–1802.
[6] a) H. Firouzabadi, N. Iranpoor, M. A. Zolfigol, Synth. Com-
mun. 1997, 27, 3301–3311; b) N. Iranpoor, H. Firouzabadi,
M. A. Zolfigol, Synth. Commun. 1993, 23, 2773–2781.
[7] a) F. J. Waller, A. G. M. Barrett, D. C. Braddock, D. Rampra-
sad, Chem. Commun. 1997, 613–614; b) A. G. M. Barrett, D. C.
Braddock, R. Ducray, R. M. McKinnell, F. J. Waller, Synlett
2000, 57–58; c) F. J. Waller, A. G. M. Barrett, D. C. Braddock,
R. M. McKinnell, D. Ramprasad, J. Chem. Soc., Perkin Trans.
1 1999, 867–872; d) F. I. Waller, A. G. M. Barrett, D. C. Brad-
dock, R. M. McKinnell, A. J. P. White, D. J. Williams, R. Duc-
ray, J. Org. Chem. 1999, 64, 2910–2913; e) A. R. Hajipour,
A. E. Ruoho, Phosphorus, Sulfur Silicon Relat. Elem. 2004, 179,
221–226; f) N. Iranpoor, H. Firouzabadi, R. Heydari, Synth.
Commun. 2003, 33, 703–710.
General Procedure for the Nitration of Phenolic Compounds: Mont-
morillonite KSF (500 mg) was put into a glass vessel and then
heated at 120 °C for 0.5 h under reduced pressure (0.1 Torr) to get
rid of the absorbed water. A solution of resorcinol (110 mg,
1.0 mmol) and hafnium compound (20 mg) in THF (or other sol-
vent, 5 mL) was added into the glass vessel. Nitric acid (60%,
0.095 mL, d = 1.3667, 1.2 mmol) was slowly added dropwise and
the mixture was stirred for 16 h at room temperature. The reaction
mixture was extracted with ethyl acetate or dichloromethane. The
solvent was removed under reduced pressure and the residue was
purified by silica gel column chromatography (eluent: petroleum
ether/EtOAc, 10:1) to give the product.
[8] S. Susanta, F. B. Frederick, K. B. Bimal, Tetrahedron 2000, 56,
8017–8020.
[9] For previous reports on the nitration of phenolic compounds
see: a) B. Gigante, A. O. Prozeres, M. J. Marcelo-Curto, A.
Cornelis, P. Laszlo, J. Org. Chem. 1995, 60, 3445–3447; b) A. V.
Joshi, M. Baidoosi, S. Mukhopadhyay, Y. Sasson, Org. Proc.
Res. Dev. 2003, 7, 95–97; c) H. Suzuki, T. Takeuchi, T. Mori,
J. Org. Chem. 1996, 61, 5944–5947; d) J. M. Riego, Z. Sedin,
J. M. Zaldivar, N. C. Marziano, C. Tortato, Tetrahedron Lett.
1996, 37, 513–515; e) Z. Lysenko, L. C. Rand, (Standford) US
Pat. no. 4,982,001; f) R. J. Schmitt, D. S. Ross, J. R. Hardee,
J. F. Wolf, J. Org. Chem. 1988, 53, 5568–5569.
4-Nitroresorcinol (1): Yellow solid, 135 mg, yield 87%. M.p. 117–
119 °C. IR (KCl): ν = 1532, 1397 cm–1 (NO2), 3354, 1255 cm–1
˜
1
(OH). H NMR (CDCl3, 300 MHz, TMS): δ = 6.47 (dd, J = 9.2,
3.4 Hz, 1 H, Ar), 6.52 (d, J = 3.4 Hz, 1 H, Ar), 8.05 (d, J = 9.2 Hz,
1 H, Ar), 10.97 (s, 1 H, ArOH) ppm. MS (EI) m/z = 155 (47.40)
[M+], 125 (100) [M+ – 30], 97 (94.90) [M+ – 58], 77 (6.77) [M+
–
78], 51 (65.02) [M+ – 104]. C6H5NO4: calcd. C 46.46, H 3.25, N
9.03; found C 46.48, H 3.44, N 9.02.
[10] a) M. Shi, S. C. Cui, J. Fluorine Chem. 2002, 113, 207–209; b)
M. Shi, S. C. Cui, Chem. Commun. 2002, 994–995; c) S. C. Cui,
M. Shi, Adv. Synth. Catal. 2003, 345, 1197–1202; d) M. Shi,
S.-C. Cui, Adv. Synth. Catal. 2003, 345, 1329–1333.
Supporting Information Available: 1H NMR spectral and analytical
data for nitrated products, experimental details, and Figure S1
(yields of nitrated p-chlorophenol vs. time).
[11] The catalytic use of inorganic salts such as ZrIV and HfIV salts
is quite practical because of its simplicity and applicability to
large-scale operations. K. Ishihara, S. Ohara, H. Yamamoto,
Science 2000, 290, 1140–1142.
Acknowledgments
[12] a) A. S. Solovkin, S. V. Tsvetkova, Russ. Chem. Rev. (Engl.
Transl.) 1962, 31, 655–662; b) E. M. Larsen, Adv. Inorg. Chem.
Radiochem. 1970, 12, 1–11; c) M. Aberg, J. Glaser, Inorg. Chim.
Acta 1993, 206, 53–61; d) P. K. Mishra, V. Chakravortty, K. C.
Dash, Indian J. Chem. 1989, 28A, 581–584; e) D. Walther, B.
Ritter, H. Gorls, G. Z. Zahn, Z. Anorg. Allg. Chem. 1997, 623,
1125–1129; f) A. Veyland, L. Dupont, J.-C. Pierrard, J. Rim-
bault, M. Aplicourt, Eur. J. Inorg. Chem. 1998, 1765–1770.
[13] P. Laszlo, A. Cornelis, Aldrichimica Acta 1988, 21, 97–103.
Received: December 30, 2004
We thank the State Key Project of Basic Research (Project 973; no.
G2000048007), the Shanghai Municipal Committee of Science and
Technology, the Chinese Academy of Sciences (KGCX2-210-01),
and the National Natural Science Foundation of China for finan-
cial support (20025206, 203900502, and 20272069).
[1] a) J. H. Clark, Green Chem. 1999, 1, 1–8; b) P. T. Anastas, J. C.
Warner, Green Chemistry: Theory and Practice, Oxford, 1999.
2384
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2005, 2379–2384