Pseudohalogenation of Phosphorochloridates
673
(30 mmol) in water (2 mL) was dropped at room temperature. The mixture was
then stirred for 20–30 min. After filtration, the filtrate was dried by anhydrous
MgSO4 for 24 h and concentrated in vacuo and distillation gave the corre-
sponding product.
(II): To the solution of phosphorochloridate (20 mmol) and 18-crown-6
(2 mmol) in ethyl acetate (20 mL), pseudohalide (30 mmol) was added at
room temperature. The mixture was then stirred for 20–30 min. After fil-
tration, the filtrate was concentrated in vacuo and distillation gave the corre-
sponding product.
REFERENCES
1. Paquette, L. A. Encyclopedia of Reagents for Organic Synthesis; Wiley:
New York, 1995; pp. 1–8.
2. Shioiri, T.; Yamada, S. Diphenyl Phosphorazidate. Org. Synth. 1984, 62, 187.
3. (a) Shi, E.; Pei, C. Synthesis of phosporocyaidates via phosphorochloridates. Phos-
phorus, Sulfur & Silicon 2003, 178, 1093; (b) Das, S. K.; Balasubrahmanyam, S. N.
Dialkyl (3-aryl-1,2,4-Oxadiazol-5-yl)phosphonates: Synthesis and thermal
behavior-evidence for monomeric alkyl metaphosphate. J. Org. Chem. 1983, 48,
4232; (c) Lazuking, L. A.; Kukhar, V. P.; Romanov, G. V.; Khaskin, G. I.;
Dubinina, T. N.; Ofitserov, E. N.; Volkova, V. N.; Pudovik, A. N. Reactions of tri-
methylsilyl cyanide with phosphorus and sulfur acid chlorides. Zh. Obshch. Khim.
1980, 50, 985.
´
4. Łopusinski, A.; Łuczak, L.; Michalski, J. Thiocyanation of dialkyl phosphites and
their structure analogues by thiocyanogen (SCN)2: Mechanism and stereo-
chemistry. Tetrahedron 1982 (38), 679.
5. (a) Koenig, K. E.; Weber, W. P. Synthesis of benzoyl cyanides by phase transfer
¨
catalysis. Tetrahedron Lett. 1974, 26, 2275; (b) Brandstrom, A.; Lamm, B.;
Palmertz, I. The Use of tetrabutylammonium azide in the curtius rearrangement.
Acta. Chem. Scand. 1974, B28, 699.
6. Shi, E.; Pei, C. A Novel phase transfer catalyzed synthesis of dialkyl phosporo-
cyaidates from dialkyl phosphorochloridates. Synth. Commun. 2004, 34, 1285.
¨
¨
7. Brandstrom, A.; Gustavii, K. Ion pair extraction in preparative organic chemistry.
Acta. Chem. Scand. 1969, 23, 1215.
8. Dehmlow, E. V.; Dehmlow, S. S. Ion pair and ion pair extraction. In Phase Transfer
Catalysis; Verlag Chemie: Weinheim Deerfield Beach, Florida Basel, 1980; Vol. 11,
p. 6.
9. (a) Gustavii, K.; Schill, G. Determination of amines and quaternary ammonium
ions as complexes with picrate (I). Constants needed in the calculation of extrac-
tion conditions. Acta. Pharm. Suec. 1966, 3, 241; (b) Gustavii, K. Determination of
amines and quaternary ammonium ions as complexes with picrate (III). Relations
between extraction constants and the nature of cation and of the organic phase.
Acta. Pharm. Suec. 1967, 4, 233.
10. (a) Steinberg, G. M. Reactions of dialkyl phosphites. synthesis of dialkyl chloro-
phosphates, tetraalkyl pyrophosphates, and mixed orthophosphate esters. J. Org.
Chem. 1950, 15, 637; (b) Brigl, P.; Muller, H. Phosphoric esters (I). Chem. Ber.
1939, 72, 2121.