A Novel Phase Transfer Catalyzed Synthesis of Dialkyl Phosphorocyanidates from Dialkyl Phosphorochloridates

Article abstract of DOI:10.1081/SCC-120030316

Dialkyl phosphorocyanidates 2a-2d were prepared from dialkyl phosphorochloridates 1a-1d and potassium cyanide in high yield under phase transfer catalyzed conditions.

Full text of DOI:10.1081/SCC-120030316

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A Novel Phase Transfer Catalyzed Synthesis
of Dialkyl Phosphorocyanidates from Dialkyl
Phosphorochloridates
Enxue Shi a & Chengxin Pei a
a Beijing Institute of Pharmaceutical Chemistry, 1044‐401, Beijing, 102205, P.R. China
Published online: 21 Aug 2006.
To cite this article: Enxue Shi & Chengxin Pei (2004) A Novel Phase Transfer Catalyzed Synthesis of Dialkyl
Phosphorocyanidates from Dialkyl Phosphorochloridates, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 34:7, 1285-1288, DOI: 10.1081/SCC-120030316
To link to this article: http://dx.doi.org/10.1081/SCC-120030316
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 7, pp. 1285–1288, 2004
A Novel Phase Transfer Catalyzed Synthesis
of Dialkyl Phosphorocyanidates from
Dialkyl Phosphorochloridates
*
Enxue Shi and Chengxin Pei
Beijing Institute of Pharmaceutical Chemistry, Beijing, P.R. China
ABSTRACT
Dialkyl phosphorocyanidates 2a–2d were prepared from dialkyl phos-
phorochloridates 1a–1d and potassium cyanide in high yield under
phase transfer catalyzed conditions.
Key Words: Dialkyl phosphorocyanidates; Dialkyl phosphorochlori-
dates; Phase transfer catalyst; Cyanide.
INTRODUCTION
As a kind of versatile coupling and phosphorylating reagents,[1] dialkyl
phosphorocyanidates were generally prepared from trialkyl phosphites
*
Correspondence: Enxue Shi, Beijing Institute of Pharmaceutical Chemistry, Beijing
1044-401, 102205, P.R. China; Fax: þ86-10-69767099; E-mail: shienxue@yahoo.
com.cn.
1285
DOI: 10.1081/SCC-120030316
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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1286
Shi and Pei
through Arbuzov reaction.[2,3] Though several attempts[2,4–7] failed in prepar-
ing phosphorocyanidates from phosphorochloridates directly, we recently
reported a convenient synthesis of dialkyl phosphorocyanidates from phos-
phorochloridates and potassium cyanide in acetonitrile.[8] On the other
hand, early in 1974 phase transfer catalyst (PTC) had been employed in the
preparation of benzoyl cyanide from benzoyl chloride and sodium cyanide,[9]
but no preparation of phosphorocyanidates under PTCed conditions was
reported until now.
Herein, we wish to give another novel facile synthesis of dialkyl phos-
phorocyanidates from dialkyl phosphorochloridates and potassium cyanide,
which was carried out in dichloromethane/water by using tetrabutyl
ammonium bromide as PTC (Sch. 1).
It was found that water (Sch. 1) in the system was necessary; otherwise no
cyanidation would be observed. But tetrabutyl ammonium bromide could be
the iodide.
Therefore, dialkyl phosphorocyanidates 2a–2d were prepared from dialkyl
phosphorochloridates 1a–1d in high yield at room temperature (Table 1).
It should be emphasized that the PTC method we established in this
article can be potentially applied to other nucleophilic substitution reactions
on phosphorus chemistry.
EXPERIMENTAL
GC was recorded on a Varian CP-3800 spectrometer, IR on a Bio-Rad
FTS185 spectrometer, 31P NMR on a Varian UNITY500 spectrometer using
85% H3PO4 as external reference, MS on a Finnigan Mat TSQ70 spectrometer.
General Procedure for Dialkyl Phosphorocyanidates 2a–2d
To the solution of dialkyl phosphorochloridate (0.2 mol) and tetrabutyl
ammonium bromide (0.02 mol) in dichloromethane (20 mL), potassium
Scheme 1.

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Synthesis of Dialkyl Phosphorocyanidates
Table 1. Synthesis of dialkyl phosphorocyanidates 2a–2d.
1287
No.
2a
2b
2c
2d
R
Yield (%)
C2H5
83
C3H7
80
C4H9
82
C5H11
85
cyanide (0.4 mol) in water (2 mL) was dropped at room temperature. The
mixture was then stirred for 1 hr. After filtration, the filtrate was dried by
anhydrous MgSO4 for 24 hr and concentrated in vacuo and distillation gave
the target product.
Diethyl phosphorocyanidate 2a. Yield 83%; b.p. 54–55 (0.7 mm); IR
2210 (nC;;N); 31P-NMR (CDCl3) 220.6; MS 164 (M þ 1).
Dipropyl phosphorocyanidate 2b. Yield 80%; b.p. 76–78 (1.0 mm);
IR 2209 (nC;;N); 31P-NMR (CDCl3) 219.9; MS 192 (M þ 1).
Dibutyl phosphorocyanidate 2c. Yield 82%; b.p. 92–94 (0.8 mm); IR
2209 (nC;;N); 31P-NMR (CDCl3) 219.9; MS 220 (M þ 1).
Diamyl phosphorocyanidate 2d. Yield 85%; b.p. 130–131 (1.2 mm);
IR 2209 (nC;;N); 31P-NMR (CDCl3) 219.9; MS 248 (M þ 1).
REFERENCES
1. Kurihara, T.; Harusawa, S.; Yoneda, R. Application of cyanohyrin O-phos-
phates in organic synthesis. Yukai Gaosei Kaganku Kyokaishi 1988,
46 (12), 1164.
2. Saunders, B.C.; Stacey, G.T.; Wild, F.; Wiling, I.G.E. Esters containing phos-
phorus. Part V. Esters of substituted phosphonic and phosphonous acids.
J. Chem. Soc. 1948, 699.
3. Takamizawa, A.; Sato, Y.; Tanaka, S. DEPC: a new regent for organic syn-
thesis. Yakugaku Zasshi 1965, 85, 298.
4. 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.
5. Yoneda, R.; Shioiri, T. Peptide formation with diphenyl phosphorazidate
and analogs. JP Kakai, 76, 67, 202, 1973.
6. 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 trimethylsilyl cyanide with phosphorus and sulfur acid chlorides. Zh.
Obshch. Khim. 1980, 50 (5), 985.
7. Fukuto, T.R.; Vetter, R.S.; Baker, T.C.; Malik, M.S. US Patent 5, 064, 820,
1991.

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Shi and Pei
8. Shi, E.; Pei, C. Synthesis of phosphorocyanidates via phosphorochlori-
dates. Phosphorus and Sulfur 2003, 178 (5), 1093.
9. Koenig, K.E.; Weber, W.P. Synthesis of benzoyl cyanides by phase trans-
fer catalysis. Tetrahedron Lett. 1974, 26, 2275.
Received in Japan July 28, 2003

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