Model GCMS-QP5000 spectrometer. High-resolution mass
spectral data were obtained on a JEOL DX-303 mass spec-
trometer. Flash column chromatography (FCC) was performed
using silica gel BW-300 (Fuji Silysia Chemical Co.). Preparative
gel-permeation liquid chromatography (GPLC) was performed
on a JAI (Japan Analytical Industry) LC-908 instrument with
JAIGEL 1H-2H columns and chloroform as eluent. High-
performance liquid chromatography (HPLC) was performed on
a Hitachi instrument with Hitachi L-4200 (UV-VIS Detector),
Hitachi L-6250 (Intelligent pump), Hitachi L-2500 (Chromato-
Integrator), RP-18 GP 150–4.6 Mightysil (reversed-phase col-
umn) and methanol/distilled water as eluent. Analytical thin
layer chromatography (TLC) was performed using EM reagent
0.25 mm silica gel 60-F plates. Visualisation was accomplished
with UV light and ethanolic phosphomolybdic acid solution
followed by heating. Characteristics of all aziridines in this
paper (aziridines from indene,7b allylic alcohols,7a E- and Z-oct-
2-ene,6 2-methylhept-2-ene,6 and the others4c) were found to be
identical to those published previously.
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General procedure for preparation of aziridines
To a mixture of iodine (0.1 mmol, 10 mol%), Chloramine-T
(1.0 mmol), and a quaternary ammonium salt (0.1 mmol,
10 mol%) in distilled water (3.0 mL) was added the appropriate
olefin (2.0 mmol). The mixture was stirred at room temperature
from 1 to 5 hours under an ambient atmosphere. After the
addition of Et2O (40 mL), the organic layer was washed with
brine (60 mL). The aqueous phase was extracted with Et2O
(20 mL × 1). The combined organic extracts were dried over
K2CO3 and concentrated to give the crude product. Purification
by flash column chromatography (silica gel; 10% ethyl acetate in
hexane) gave the corresponding aziridine as a white crystalline
solid or colorless oil.
Larger-scale process of styrene aziridination
To a mixture of iodine (10 mmol, 10 mol%), Chloramine-T
(100 mmol), and Aliquat® 336 (10 mmol, 10 mol%) in distilled
water (300 mL) was added styrene (200 mmol). The mixture
was stirred at room temperature under an ambient atmosphere
for 1.5 hours. After the decantation of water, the crude product
was obtained as a brown solid. The resultant solid was puri-
fied by recrystallisation from methanol (100 mL) to give the
corresponding aziridine 86% yield (purity: >99% by HPLC).
Analytical HPLC was performed using RP-18 GP 150-4.6
Mightysil reversed-phase column on a Hitachi instrument. UV
detection was at 230 nm, and 10% methanol in distilled water
was run at 1.0 mL minϪ1 flow rate.
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and K. B. Sharpless, Org. Lett., 1999, 1, 783.
Acknowledgements
8 (a) K. Sato, M. Aoki, M. Ogawa, T. Hashimoto and R. Noyori,
J. Org. Chem., 1996, 61, 8310; (b) K. Sato, M. Aoki, M. Ogawa,
T. Hashimoto, D. Panyella and R. Noyori, Bull. Chem. Soc. Jpn.,
1997, 70, 905.
9 Only one example of solvent-free aziridination of conjugated
nitroalkenes has been reported. See S. Fioravanti, L. Pellacani,
S. Stabile, P. A. Tardella and R. Ballini, Tetrahedron, 1998, 54, 6169.
This work was supported, in part, by the Sasakawa Scientific
Research Grant from The Japan Science Society and a Grant-
in-Aid for Scientific Research from the Ministry of Education,
Science, Sports and Culture of Japan. We also acknowledge the
Instrumental Analysis Center, Faculty of Engineering, Osaka
University.
3188
J. Chem. Soc., Perkin Trans. 1, 2001, 3186–3188