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3. (a) Moss, R. A.; Gong, P. K. Langmuir 2000, 16, 8551;
(b) Mochida, K.; Matsui, Y.; Ota, Y.; Arakawa, K.;
Date, Y. Bull. Chem. Soc. Jpn. 1976, 49, 3119.
under reduced pressure to give an oil (0.5 g). This oil was
added slowly to an ice-cooled mixture of HNO3 (1 mL)
and H2SO4 (1 mL). The resulting solution was stirred on
ice for 12 min, poured into ice-water (20 mL) and
extracted with ethyl acetate (2×30 mL). The combined
ethyl acetate extracts were washed with brine (2×30 mL)
followed by saturated NaHCO3 solution (2×30 mL),
dried (MgSO4) and evaporated to give a yellow oil.
Chromatography of the oil on silica, eluting with 50%
ethyl acetate/hexane, gave the title compound (8) as a pale
yellow oil (0.36 g, 24%), which was further purified by
bulb to bulb distillation (oven temperature 200°C, 40
mmHg). IH NMR (CDCl3): l 1.25 (s, 9H), 3.82 (d,
4. (a) Mochida, K.; Nakamura, T.; Yamamoto, M.; Yanai,
K.; Shiotsuki, T.; Matsui, Y. Bull. Fac. Agr. Shimane
Univ. 1983, 17, 152; (b) Hu, C.-C.; Chen, W.-H.; Liu,
C.-Y.; Chen, J.-L. J. Inclusion Phenom. Mol. Recognit.
Chem. 1996, 23, 289; (c) Mochida, K.; Ozoe, Y.;
Miyazaki, H.; Matsui, Y. Bull. Fac. Agr. Shimane Univ.
1980, 14, 158; (d) Breslow, R.; Zhang, B. J. Am. Chem.
Soc. 1994, 116, 7893; (e) Akkaya, E. U.; Czarnik, A. W.
J. Phys. Org. Chem. 1992, 5, 540.
5. (a) Eto, M. In Handbook of Organophosphorus Chem-
istry; Engel, R., Ed.; Marcel Dekker: New York, 1992;
pp. 807–873; (b) Holstege, C. P.; Kirk, M.; Sidell, F. R.
Critical Care Clin. 1997, 13, 923.
JP–H=9.6 Hz, 6H), 7.46 (d, J=8.7 Hz, 1H), 7.62 (dd,
J=8.7, 2.4 Hz, 1H), 7.92 (d, J=2.4 Hz, 1H). 13C NMR
(CDCl3): l 30.8, 34.5, 55.1 (d, JP–C=6.5 Hz), 120.2 (d,
6. (a) Grimsley, J. K.; Rastogi, V. K.; Wild, J. R. Bioreme-
diation 1998, 2, 577; (b) Furlong, C. E.; Humbert, R.;
Withington, A. P.; Richter, R. J.; Chadsey, M. S.; McE-
wan, N.; Gray, J.; Lara, J. C.; Staley, J. T.; Li, W.-F.;
Costa, L. G.; Harrington, M. J.; Thomas, L. C.; Herring-
ton, R. T.; Sayles, G. D.; Haines, J. R. Bioremediation
1998, 2, 521.
7. (a) Ketelaar, J. A. A.; Gersmann, H. R.; Beck, M. M.
Nature 1956, 177, 392; (b) Smolen, J. M.; Stone, A. T.
Environ. Sci. Technol. 1997, 31, 1664.
8. (a) Kazankov, G. M.; Sergeeva, V. S.; Efremenko, E. N.;
Alexadrova, L.; Varfolomeev, S. D.; Ryabov, A. D.
Angew. Chem., Int. Ed. 2000, 39, 3117; (b) Kuo, L. Y.;
Perera, N. M. Inorg. Chem. 2000, 39, 2103; (c) Tsao, B.
L.; Pieters, R. J.; Rebek, J. J. Am. Chem. Soc. 1995, 117,
2210; (d) Morrow, J. R.; Trogler, W. C. Inorg. Chem.
1989, 28, 2330; (e) Menger, F. M.; Gan, L. H.; Johnson,
E.; Durst, D. H. J. Am. Chem. Soc. 1987, 109, 2800; (f)
Gellman, S. H.; Petter, R.; Breslow, R. J. Am. Chem.
Soc. 1986, 108, 2388.
J
P–C=6.2 Hz), 121.7 (d, JP–C=2.6 Hz), 125.3, 131.2 (d,
J
P–C=1.4 Hz), 140.6 (d, JP–C=5.7 Hz), 148.8 (d, JP–C
=
1.4 Hz); EI MS (70 eV) m/z: 303 (M+, 15%), 288 (100),
257 (65), 227 (10), 163 (10), 127 (23), 109 (21), 77 (8).
Anal. calcd for C12H18NO6P: C, 47.53; H, 5.98; N, 4.62.
Found: C, 47.25; H, 5.87; N, 4.79.
14. Results obtained from repeating each kinetic experiment
were reproducible to within 10%.
15. The Cu(II) complexes of the cyclodextrins 4–7, 1,2-
diaminoethane and 1,3-diaminopropane were prepared in
situ using equimolar quantities of Cu(II) perchlorate and
amine. Under the conditions used, the Cu(II) is effec-
tively fully complexed since the binary association con-
stants for such complexes are typically >107 M−1. For
example, values of 5.7×109 and 6.9×107 M−1, have been
reported for the cases of 1,3-diaminopropane (du Preez,
J. G. H.; van Brecht, B. J. A. M. J. Chem. Soc., Dalton
Trans. 1989, 253) and the modified cyclodextrin 5,10
respectively.
16. Seguchi, K. Yukagaku 1979, 28, 20.
9. Scrimin, P.; Ghirlanda, G.; Tecilla, P.; Moss, R. A.
17. 4-tert-Butyl-2-nitrophenyl isopropyl methyl phosphate
(10). To a solution of 4-tert-butylphenol (3.0 g, 20 mmol)
in benzene (10 mL) was added triethylamine (3.06 mL, 22
mmol) followed by phosphorus oxychloride (1.87 mL, 20
mmol). As a precipitate formed, further benzene (20 mL)
was added and the mixture was stirred at 90°C for 60
min. 2-Propanol (1.5 mL, 20 mmol) and triethylamine
(3.06 mL, 22 mmol) were added and the resulting solu-
tion was stirred at 90°C for 60 min. Methanol (0.8 mL,
20 mmol) and triethylamine (3.06 mL, 22 mmol) were
then added and the mixture was stirred for a further 60
min at 90°C, then poured into ethyl acetate (150 mL).
The solution was washed with aqueous HCl (1N, 3×100
mL), then saturated NaHCO3 (2×100 mL), dried
(MgSO4) and evaporated to give an oil (4.78 g). Column
chromatography of the oil on silica eluting with a gradi-
ent of hexane and ethyl acetate gave an oil (1.89 g). A
fraction of the oil (0.25 g) was slowly added to an
ice-cooled mixture of HNO3 (1 mL) and H2SO4 (1 mL).
The resulting solution was stirred on ice for 12 min, then
poured into ice-water (20 mL). The mixture was extracted
with ethyl acetate (2×30 mL). The combined ethyl acetate
extracts were washed with brine (2×30 mL), followed by
saturated NaHCO3 solution (2×30 mL), dried (MgSO4)
and evaporated to give a yellow oil. Chromatography of
the oil on silica eluting with a gradient of hexane and
ethyl acetate gave the title compound (10) as a pale yellow
Langmuir 1996, 12, 6235.
10. (a) Brown, S. E.; Coates, J. H.; Easton, C. J.; Lincoln, S.
F. J. Chem. Soc., Faraday Trans. 1994, 90, 739; (b)
Brown, S. E.; Coates, J. H.; Easton, C. J.; van Eyk, S. J.;
Lincoln, S. F.; May, B. L.; Stile, M. A.; Whalland, C. B.;
Williams, M. L. J. Chem. Soc., Chem. Commun. 1994, 47;
(c) Brown, S. E.; Haskard, C. A.; Easton, C. J.; Lincoln,
S. F. J. Chem. Soc., Faraday Trans. 1995, 91, 1013; (d)
Haskard, C. A.; Easton, C. J.; May, B. L.; Lincoln, S. F.
Inorg. Chem. 1996, 35, 1059; (e) May, B. L.; Kean, S. D.;
Easton, C. J.; Lincoln, S. F. J. Chem. Soc., Perkin Trans.
1 1997, 3157; (f) Sandow, M.; Easton, C. J.; Lincoln, S.
F. Aust. J. Chem. 1999, 52, 1151.
11. Matsui, Y.; Nishioka, T.; Fujita, T. Top. Curr. Chem.
1985, 128, 61.
12. Rossi, R. A.; Bunnett, J. F. J. Org. Chem. 1973, 38, 2314.
13. 4-tert-Butyl-2-nitrophenyl dimethyl phosphate (8). 4-tert-
Butylphenol (0.75 g, 5.0 mmol) was dissolved in toluene
(4 mL) and ether (2 mL) cooled to 5–10°C. Sodium
hydroxide solution (25%, 3 mL) and dimethyl phospho-
rochloridate (0.64 mL, 6.0 mmol) were added simulta-
neously over 30 min. The resulting suspension was stirred
for 4 h at room temperature, then poured into ethyl
acetate (40 mL). The organic solution was separated and
washed with 10% sodium hydroxide solution (2×30 mL)
and water (30 mL), then dried (MgSO4) and evaporated