3
8
Liu, Chen, and Huang
◦
20
◦
bp 64–68 C/10 mmHg, n
1
D
1.5370. (lit: bp 70 C/
1.5391.)
Similarly, compounds 11 and 12 were prepared
from the corresponding thiophosphoryl dichloride
as a diastereomeric mixtures. Data are shown in
Tables 1–3.
1
7
2 mmHg, yield 33.39%, n
D
Di-(2-chloroethyl)-phosphoramidic Dichloride
25]. This compound was obtained by the reaction
[
of bis-(-chloroethyl)-amine hydrochloride [26] with
excess phosphorus oxychloride under reflux for 12 h
REFERENCES
◦
in 78.64% yield, bp 116–120 C/0.4 mmHg. (lit: bp
[
[
[
[
1] Fu, H.; Tu, G. Z.; Li, Z. L.; Zhao, Y. F. Synthesis 1998,
55.
2] Huang, J.-M.; Chen, R.-Y. Heteroat Chem 2000, 11,
80.
3] Gorin, B. I.; Ferguson, C. G.; Thatcher, G. R. J. Tetra-
hedron Lett 1997, 38, 2791.
4] Breuer, E. In the Chemistry of Organophosphorus
Compounds; Hartley, F. R. (Ed.); Wiley: Chichester,
1996, Vol. 4, pp. 653–729.
◦
1
23–125 C/0.6 mmHg, yield 81.2%)
8
4
Preparation of Compounds 1–9
To a solution of L-methionol (0.68 g, 5 mmol) in
1
0 mL of THF, triethylamine (1.01 g, 10 mmol) was
◦
added, and the mixture was cooled to 0 C in an
ice-bath, then a solution of O-methyl thiophospho-
rodichloridate (0.83 g, 5 mmol) in 5 mL of THF was
[
[
[
5] Hirashima, A.; Eto, M. Agric Biol Chem 1983, 47,
2
831.
6] Tawata, S.; Kuwano, E.; Eto, M. Agric Biol Chem
980, 44, 1489.
◦
slowly added dropwise at 0 C. After the addition,
1
the reaction mixture was stirred for 1 h, warmed to
room temperature, and continued to stir for 6–7 h.
After removal of triethylamine hydrochloride by fil-
tration, the filtrate was concentrated under reduced
pressure. The crude product 1 was purified and sepa-
rated by column chromatography (petroleum ether:
ethyl acetate as eluent) to afford diastereomeric mix-
ture: 0.70 g , yield 61.24%.
Similarly, compounds 2–9 were prepared from
the corresponding thiophosphoryl dichloride as a di-
astereomeric mixtures. The only difference was that
the reactive time was prolonged with increasing R
group. Data are shown in Tables 1–3.
7] Yoshikawa, H.; Fughigami, K.; Shono, T. J. Pesticide
Sci 1986, 11, 631. Induce the thioether groups into
the 2-oxo- and 2-thio-1,3,2-oxazaphospholidines.
8] Cooper, D. B.; Hall, C. R.; Harrison, J. M.; Inch, T. D.
J Chem Soc, Perkin Trans 1977, 1, 1969.
[
[
9] Chen, R.-Y.; Wang, H.-L.; Zhou, J. Heteroat Chem
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994, 5, 497.
[10] Ali, H. M.; Mohamed, K. A. Heteroat Chem 1999, 10,
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4
[
11] He, Z.-J.; Chen, W.-B.; Zhou, Z.-H.; Tang, C.-C. Synth
Commun 2000, 30, 3473.
[12] He, Z.-J.; Chen, W.-B.; Zhou, Z.-H.; Tang, C.-C.
Heteroat Chem 2000, 11, 187.
[13] (a) Berdel, W. E.; Fromm, M.; Fink, U.; Pahlke, W.;
Bicker, U.; Reicher, A.; Rasteter, J. Cancer Res 1983,
4
3, 5538; (b) Hermann, D. B. J. In Abstracts of the Sec-
ond International Conference on Platelet-Activating
Factor and Structurally Related Alkyl Ether Lipids;
Gatlinburg, TN, October 26–29, 1986; p. 53.
[14] Morris, N. S.; Surles, J. R.; Daniel, L. W.; Berens,
M. E.; Modest, E. J.; Piantadosi, C. J Med Chem 1986,
29, 2114.
Preparation of Compounds 10–12
To a solution of L-methionol (0.68 g, 5 mmol) in
10 mL of THF, triethylamine (TEA) (1.01 g, 10 mmol)
◦
was added, and the mixture was cooled to −10 C
in an ice-salt bath. Then a solution of thiophos-
phoryl chloride (0.85 g, 5 mmol) in 5 mL of THF
[
[
[
15] Bhatia, S. K.; Hajudu, J. H. J Org Chem 1988, 53,
034.
16] Thompson, C. M.; Frich, J. A.; Green, D. L. J Org Chem
1990, 55(1), 111–116.
17] Bentrude, W. G.; Setzer, W. N.; Sopchik, A. E.; Bajwa,
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Soc 1986, 108, 6669–6672.
5
◦
was slowly added dropwise at −10 C. The reaction
was monitored by TLC for loss of starting material.
3
1
After completion, a sample for P NMR examina-
tion was taken from the reaction mixture. Then the
phenylamine (0.465 g, 5 mmol) was added at room
temperature to a solution of 2-chloro-2-thio-1,3,2-
oxazaphospholidine-4-methyl ethyl thioether in THF
followed by the addition of TEA (100 mol%). The
reaction mixture was stirred at room temperature
overnight. After removal of triethylamine hydrochlo-
ride by filtration, the filtrate was concentrated un-
der reduced pressure to obtain the crude product 1,
which was purified and separated by column chro-
matography (petroleum ether: ethyl acetate as elu-
ent) to afford a diastereomeric mixture 10: 0.55 g,
yield 38.19%.
[
18] Marc, J. M.; Meyers, A. I. J Org Chem 1993, 58, 3568–
3
571.
[19] Booth, H. S. et al. J Am Chem Soc 1948, 70, 2523.
[
[
[
20] (a) Henry, T. J Org Chem 1958,23,1682–1684.; (b) C.A.
959, 53, 2175.
21] Dickey, J. B. et al. U.S., 2, 487859, 1949; Yang, S.-X.
Chin Sci B, 1984, 6496.
1
22] Yang, S.-X. et al. Chem Lett 1963, 29, 153.
[23] (a) Seel, F. Chem Ber 1962, 95, 199; (b) Jensen, W. I.
US 2, 662, 917; (c) C.A. 48: 1954, 13711g.
[
24] Mahabir, P. K.; Ramamoorthy, V. J Org Chem 1980,
5, 2270–2271.
25] Friedman, O. M.; Seligman, A. M. J Am Chem Soc
954, 76, 655–658.
[26] Ward, K. J Am Chem Soc 1935, 57, 914.
4
[
1