1
102
E. Artuso et al.
PAPER
acted 1 was present. The mixture was extracted with CH Cl (2 × 80
presence or absence of a base and, in case, of a catalyst, see:
(a) Sonoda, N.; Mizuno, T.; Murakami, S.; Kondo, K.;
Ogawa, A.; Ryu, I.; Kambe, N. Angew. Chem., Int. Ed. Engl.
1989, 28, 452. (b) Mizuno, T.; Nishiguchi, I.; Sonoda, N.
Tetrahedron 1994, 50, 5669. (c) Mizuno, T.; Kino, T.; Ito,
T.; Miyata, T. Synth. Commun. 2000, 30, 1675. (d)Mizuno,
T.; Takahashi, J.; Ogawa, A. Tetrahedron 2003, 59, 1327.
(e) Mizuno, T.; Iwai, T.; Ito, T. Tetrahedron 2004, 60, 2869.
(f) Mizuno, T.; Iwai, T.; Ishino, Y. Tetrahedron 2005, 61,
9157.
2
2
mL), dried (Na SO ), and evaporated under reduced pressure. The
2
4
crude residue was then column chromatographed. Elution with pe-
troleum ether–Et O (7:3) afforded thiocarbamate 3h (0.60 g, 33%);
2
elution with Et O–MeOH (1:1) afforded urea 6 (0.78 g, 65%), based
2
on benzylamine (2h).
N,N¢-Dibenzylurea (6)
27
Mp 171.0–171.7 °C (CHCl ) (Lit. 172–173 °C).
3
1
H NMR: d = 4.33 (s, 4 H, 2 CH ), 7.22–7.30 (m, 10 H, 2 C H ).
2
6
5
(
11) For some recent examples for the rearrangements of O-alkyl
N-alkylthiocarbamates, see: (a) Tandel, S. K.; Rajappa, S.;
Pansare, S. V. Tetrahedron 1993, 49, 7479. (b) Harayama,
H.; Nagahama, T.; Kozera, T.; Kimura, M.; Fugami, K.;
Tanaka, S.; Tamaru, Y. Bull. Chem. Soc. Jpn. 1997, 70, 445.
Conditions for the other trial reactions (entries 1–9, 11–14) and
yields for the two products 3h and 6 are reported in Table 1.
Acknowledgment
(c) Böhme, A.; Gais, H.-J. Tetrahedron: Asymmetry 1999,
1
0, 2511. (d) Gais, H.-J.; Böhme, A. J. Org. Chem. 2002, 67,
This work was supported by Ministero dell’Università e della Ricer-
ca Scientifica e Tecnologica (MURST) and National Research
Council (CNR), Italy, National Project ‘New synthetic methodolo-
gies for industrial intermediates and products’ and by University of
Turin.
1153. (e) Pallucca, E.; Degani, I.; Serri, A. M.; Fochi, R.;
Gazzetto, S.; Fenoglio, C.; Ornati, C.; Migliaccio, M.;
Cadamuro, S.; Carvoli, G., (Oxon Italia S.p.A., Italy), EP
1,334,965, 2003; Chem. Abstr., 2003, 139, 164529.
(
12) For example, for toxicity of phosgene, see: (a) Sax, N. I. In
Dangerous Properties of Industrial Materials; Van
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Synthesis 2007, No. 7, 1096–1102 © Thieme Stuttgart · New York