SHORT PAPER
Novel Conversion of Amines into Isothiocyanates
2685
IR (neat): 2088 cm–1 (N=C=S).
(5) Wadsworth, W. S.; Emmons, W. D. J. Org. Chem. 1964, 29,
1
2816.
H NMR (250 MHz, CDCl ): d = 1.69 (d, J = 6.8 Hz, 3 H), 4.92 (q,
3
(
(
6) Dyer, E.; Johnson, T. B. J. Am. Chem. Soc. 1932, 54, 777.
7) (a) Shibanuma, T.; Shiono, M.; Mukaiyama, T. Chem. Lett.
1977, 573. (b) Adam, W.; Bargon, R. M.; Bosio, S. G.;
Schenk, W. A.; Stalke, D. J. Org. Chem. 2002, 67, 7037.
8) (a) Rathke, A. Ber. Dtsch. Chem. Ges. 1872, 5, 799.
J = 6.8 Hz, 1 H), 7.26–7.63 (m, 5 H).
1
3
C NMR (62.9 MHz, CDCl ): d = 25.0, 57.0, 125.4, 128.2, 128.9,
3
1
40.1.
(
Diethyl Phenylamidophosphate (3a)
This compound was prepared using known methods.
White solid; mp 95–96 °C [Lit.15 96–97 °C].
1
(b) Dyson, G. M.; George, H. J. J. Chem. Soc. 1924, 125,
1
5
1702. (c) Kim, S.; Yi, K. Y. Tetrahedron Lett. 1985, 26,
1661.
(
9) Molina, P.; Alajarin, M.; Tamaiki, H. Synthesis 1982, 596.
H NMR (250 MHz, CDCl ): d = 1.30 (t, J = 7.0 Hz, 6 H), 3.95–
3
(
10) (a) Jochims, J. C.; Seeliger, A. Angew. Chem. 1967, 79, 151.
b) Wong, R.; Dolman, S. J. J. Org. Chem. 2007, 72, 3969.
4
1
.30 (m, 4 H), 6.80–7.35 (m, 5 H + NH).
(
3
C NMR (62.9 MHz, CDCl ): d = 16.1 (d, JPC = 6.9 Hz), 62.6 (d,
(11) (a) Boas, U.; Pederson, M. H. J. Chem. Soc., Chem.
Commun. 1995, 1995. (b) Boas, U.; Pederson, B.;
Christensen, J. B. Synth. Commun. 1998, 28, 1223.
3
JPC = 5.0 Hz), 117.2 (d, JPC = 7.5 Hz), 121.3, 129.2, 139.8.
3
1
P NMR (101.2 MHz, CDCl , H PO ): d = 2.88.
3
3
4
(c) Boas, U.; Gertz, H.; Christensen, J. B.; Heegaard, P. M. H.
Tetrahedron Lett. 2004, 45, 269.
Phenyl Isothiocyanate (2a) from 3a
Diethyl phenylamidophosphate (3a, 5 mmol) was added to a stirred
(
12) Yarovenko, V. N.; Shirokov, A. V.; Zavarzin, I. V.;
Krupinova, O. N.; Ignatenko, A. V.; Krayushhkin, M.
Synthesis 2004, 17.
mixture of CS (10 mmol) and NaOH (0.4 g, 10 mmol) in toluene
2
(10 mL) at reflux. The mixture was stirred for 3–5 h at reflux. The
(
13) (a) Sardarian, A. R.; Kaboudin, B. Tetrahedron Lett. 1997,
resultant soln was cooled at r.t. and then filtered. Evaporation under
reduced pressure gave an oily mixture. This residue was extracted
with hexane (2 × 50 mL) and the extract was filtered, washed with
H O (2 × 50 mL), dried (MgSO ), and filtered. The filtrate was con-
38, 2543. (b) Kaboudin, B. Chem. Lett. 2001, 880.
(
c) Kaboudin, B.; Nazari, R. Tetrahedron Lett. 2001, 42,
8211. (d) Kaboudin, B.; Nazari, R. Synth. Commun. 2001,
2
4
31, 2245. (e) Kaboudin, B.; Balakrishna, M. S. Synth.
centrated in vacuo to give an oil that was passed through a silica
plug (hexane). Evaporation of the solvent under reduced pressure
gave pure 2a (45% yield).
Commun. 2001, 31, 2773. (f) Kaboudin, B. Tetrahedron
Lett. 2002, 43, 8713. (g) Kaboudin, B. Tetrahedron Lett.
2
2
1
2
003, 44, 1051. (h) Kaboudin, B.; Rahmani, A. Synthesis
003, 2705. (i) Kaboudin, B.; Saadati, F. Synthesis 2004,
249. (j) Kaboudin, B.; Rahmani, A. Org. Prep. Proced. Int.
004, 36, 82. (k) Kaboudin, B.; Moradi, K. Tetrahedron
Acknowledgment
The Institute for Advanced Studies in Basic Sciences (IASBS) is
thanked for supporting this work.
Lett. 2005, 46, 2989. (l) Kaboudin, B.; As-habei, N.
Tetrahedron Lett. 2003, 44, 4243. (m) Kaboudin, B.;
Karimi, M. Bioorg. Med. Chem. Lett. 2006, 16, 5324.
(
2
n) Kaboudin, B.; Farjadian, F. Beilstein J. Org. Chem. 2006,
, 4. (o) Kaboudin, B.; Moradi, K. Synthesis 2006, 2339.
References
(
(
(
p) Kaboudin, B.; Jafari, E. Synthesis 2006, 3063.
q) Kaboudin, B.; Elahamifar, D. Synthesis 2006, 224.
r) Kaboudin, B.; Sorbiun, M. Tetrahedron Lett. 2007, 48,
(
1) (a) The Chemistry of Cyanates and their Thio Derivatives;
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(
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(
1
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Synthesis 2008, No. 17, 2683–2685 © Thieme Stuttgart · New York