Oxidation of N-Benzyl Aziridine by Molecular Iodine
FULL PAPER
[18]
[19]
[20]
R. Faster, Organic Charge Transfer Complexes, Academic Press,
to the following ones, that we ascribe to 12B: 2.26 (3 H, s, p-Me),
3.06 (3 H, s, N–Me), 4.73 (2 H, s, N–CH2–O), 6.79 (2 H, d, J ϭ
8.3 Hz, Hortho), 7.07 (2 H, d, J ϭ 8.3 Hz, Hmeta). The NMR features
of 12B compare well with those quoted for the analogous N-
(ethoxymethyl)-N-methylaniline.[41] The amount of 12B corre-
sponded to the consumption of about 1/3 of the initially added
iodine. When starting from a 2 ϩ 10 mixture, all products 4, 7, 8,
and 12B were analogously obtained.
New York, 1969.
C. D. Schmulbach, D. M. Hart, J. Am. Chem. Soc. 1964, 86,
2347 and references therein.
K. Toyoda, W. B. Pearson, J. Am. Chem. Soc. 1966, 88, 1629
and references therein.
T. Gündüz, M. Tastekin, Anal. Chim. Acta 1994, 286, 247.
E. M. Nour, G. Abdel-Wahed, S. Abdel-Khalik, M. El-Essawi,
Indian J. Chem., Sect. A 1990, 29A, 73.
At the beginning of stage (i), two well-defined absorption max-
ima were observed at 367 (stronger) and 294 nm (weaker); they
remained unshifted throughout the reaction. Both maxima are
highly indicative for the triiodide ion existence.[20–22]
C. Galli, H. Petride, manuscript in preparation.
[21]
[22]
[23]
Acknowledgments
[24]
[25]
`
This work was supported by the Italian Ministero dellЈUniversita
H. Hartmann, A. P. Schmidt, Z. Phys. Chem. (Frankfurt)
1969, 66, 183.
e della Ricerca Scientifica e Tecnologica (MURST; to C. G.), and
by the Romanian Ministerul Cerceta˜rii si Tehnologiei (MCT), con-
tract n. 921/121.
[26]
[27]
See for example C. A. Audeh, J. R. Lindsay Smith, J. Chem.
Soc.(B) 1971, 1741.
If 2 HI and/or 3 HI are formed at this stage, both are converted
into the respective free bases by reaction with excess 1. At the
same time, 1 gives a stoichiometric amount of iodoamine 5 (see
Experimental Section).
Anthracene derivatives, which have oxidation potentials similar
to that of 1,[1] really give the respective radical cations by using
the I2/pyridine oxidation system. See L. M. Tolbert, Z. Li, S.
R. Sirimanne, D. G. VanDerveer, J. Org. Chem. 1997, 62, 3927.
[1]
A. Cuppoletti, C. Dagostin, C. Florea, C. Galli, P. Gentili, O.
Lanzalunga, A. Petride, H. Petride, Chem., Eur. J. 1999, 5,
2993.
[28]
[29]
[2]
[2a] R. Kossai, J. Simonet, G. Dauphin, Tetrahedron Lett. 1980,
[2b]
21, 3575. –
ibid., J. Electroanal. Chem. 1982, 139, 207.
[3]
J. R. Lindsay Smith, L. A. V. Mead, J. Chem. Soc., Perkin
Trans. 2 1973, 206.
[4] [4a]
This can be better visualized for a slower reaction (e.g., at [1]0/
[I2]0 ϭ 4).
T. Hiyama, H. Koide, H. Nozaki, Tetrahedron Lett. 1973,
[4b]
2143. –
L. A. Carpino, R. K. Kirkley, J. Am. Chem. Soc.
[30] [30a]
1970, 92, 1784. – [4c] J. E. Baldwin, A. K. Bhatnagar, S. C. Choi,
R. G. Kostyanovsky, O. A. PanЈshin, Izv. Akad. Nauk
[30b]
[4d]
S.S.S.R. 1964, 1554. –
A. T. Bottini, J. D. Roberts J. Am.
T. J. Shortridge, J. Am. Chem. Soc. 1971, 93, 4082. –
H. W.
[30c]
Chem. Soc. 1958, 80, 5203. –
R. Apfel, R. Kleinstück,
Heine, J. D. Myers, E. T. Peltzer, Angew. Chem. 1970, 82, 674;
Chem. Ber. 1974, 107, 5. – [30d] B. P. Thill, US Patent 3,855,217
[4e]
Int. Ed. Engl. 1970, 8, 374. –
R. K. Müller, D. Felix, J.
(to Dow Chemical Co.), 17 Dec. 1974; Chem. Abstr. 1975, 82,
Schreiber, A. Eschenmoser, Helv. Chim. Acta 1970, 53, 1479.
P. G. Gassman, I. Nishiguchi, H. Yamamoto, J. Am. Chem.
Soc. 1975, 97, 1600.
[30e]
[5]
[6]
111932t. –
W. S. Gump, E. J. Nikawitz, J. Am. Chem. Soc.
[30f] [30g]
1950, 72, 1309. –
J. R. Pfister, Synthesis 1984, 969. –
Y. Langlois, H. P. Hudson, P. Potier, Tetrahedron Lett. 1969,
E. Hasegawa, S. Koshii, T. Horaguchi, T. Shimizu, J. Org.
Chem. 1992, 57, 6342.
[30h]
2085. –
760.
J. Beger, W. Höbold, J. Prakt. Chem. 1969, 311,
[7] [7a]
[7b]
C. R. Dick, J. Org. Chem. 1967, 32, 72. –
35, 3950.
ibid. 1970,
[31] [31a]
H. W. Heine, B. L. Kapur, C. S. Mitch, J. Am. Chem. Soc.
[31b]
1954, 76, 1173. –
H. W. Heine, B. L. Kapur, J. Am. Chem.
[8]
[9]
G. R. Hansen, T. E. Burg, J. Heterocycl. Chem. 1968, 5, 305.
Sh. A. Markaryan, L. A. Saakyan, Arm. Khim. Zh. 1985, 38,
596.
Soc. 1955, 77, 4892.
[32]
[33]
S. Gabriel, K. Stelzner, Ber. Deutsch. Chem. Ges., 1896, 29,
2381.
S. M. McElvain, L. W. Bannister, J. Am. Chem. Soc. 1954,
76, 1126.
[10]
K. Acosta, J. W. Cessac, P. Narasimha Rao, H. K. Kim, J.
Chem. Soc., Chem. Commun. 1994, 1985.
[11] [11a]
N. C. Deno, R. E. Fruit, J. Am. Chem. Soc. 1968, 90,
[34] [34a]
R. Baltzly, J. S. Buck, E. Lorz, W. Schön, J. Am. Chem.
[11b]
3502. –
51, 2546.
D. G. Lee, R. Srinivasan, Can. J. Chem. 1973,
[34b]
Soc. 1944, 66, 263. –
Org. Syn. 1973, Coll. Vol. 5, 88.
H. Uchida, M. Ohta, Bull. Chem. Soc. Jpn. 1973, 46, 3612.
S. R. Aspinall, J. Am. Chem. Soc. 1940, 62, 1202.
[35]
[36]
[37]
[38]
[39]
[40]
[12]
N. S. Isaacs, M. Hodgson, S. O. Tumi, Tetrahedron Lett. 1981,
22, 4139.
[13] [13a]
T. Okawara, K. Harada, Bull. Chem. Soc. Jpn. 1973, 46, 1869.
T. Okawara, Y. Matsuda, M. Furukawa, Chem. Lett. 1981, 185.
M. Barbier, Heterocycles 1985, 23, 345.
G. Bellucci, G. Berti, R. Bianchini, L. Orsini, Tetrahedron
[13b]
Lett. 1982, 23, 3655. –
G. Bellucci, R. Bianchini, R. Am-
brosetti, J. Chem. Soc., Perkin Trans. 2 1987, 39.
Compare with the 1H-NMR spectral features of pure 1, 2, and
3 reported in the Experimental Section.
[14]
[15]
A small quantity of dimer 2 is observed too, due to the high
local concentration of Hϩ (and then of 5) that builds up when
the drop of HI comes into contact with the solution of 1. If
HI is added in [D6]-acetone, followed by 1, no 2 is observed in
D. H. Wadsworth, M. R. Detty, B. J. Murray, Ch. A. Weidner,
N. F. Haley, J. Org. Chem. 1984, 49, 2676.
1
[16] [16a]
the first H NMR spectrum recorded.
G. Cerichelli, L. Luchetti, J. Chem. Soc., Chem. Commun.
[16b]
[41]
C. J. Pouchert, J. Behnke, The Aldrich Library of 13C and 1H
FT NMR Spectra, Aldrich Chemical Company, 1st ed., 1993,
vol. 2, spectrum n. 458A.
1985, 339. –
V. O. Chechick, V. A. Bobylev, Acta Chem.
Scand. 1994, 48, 837.
[17]
This contrasts the claim[7b] that an iodoamine like 5 may exist
only as a transient species whenever a tertiary aziridine is
treated with a small amount of HI.
Received July 20, 1999
[O99448]
Eur. J. Org. Chem. 2000, 1037Ϫ1043
1043