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DIPHENYL PHOSPHONATE

Diphenyl Phosphonate
O
O P O
H

Amide and Ester Coupling. In the presence of tertiary


amines, preferably Pyridine or Imidazole, the ester acts as an efficient coupling agent in the formation of peptides (eq 1).1,3 Ureas
and thioureas may be similarly prepared from Carbon Dioxide or
Carbon Disulfide (eq 2).4
ZHN

CO2H

CO2Y (PhO)2P(O)H

H2N

R1

[4712-55-4]
C12 H11 O3 P
(MW 234.20)
InChI = 1/C12H11O3P/c13-16(14-11-7-3-1-4-8-11)15-12-95-2-6-10-12/h1-10,16H
InChIKey = OGBPILLJZSJJRC-UHFFFAOYAA

R2

py, rt

R2

O
ZHN
R1

(phosphonylating agent; used in the synthesis of H-phosphonate


monoesters, H-phosphonothioate monoesters, phosphate analogs,
cyclic phosphates, PC bond formation, aminoalkylphosphonates,
and enamines, mild coupling agent for synthesis of esters and
amides)
Alternate Name: diphenyl H-phosphonate; diphenyl phosphite,
DPHP.
Physical Data: mp 12 C (25 C);1a, bp 100 C/0.008 mmHg,
31 P 1.9 (1 J
218219 C/26 mmHg; n25
PH
D 1.55641.5570;
756 Hz).
Solubility: soluble in most aprotic organic solvents. In protic solvents under basic conditions, it undergoes decomposition (transesterification). Readily hydrolyzes in the presence of
bases to a monoester.
Form Supplied in: colourless liquid, purity ca. 90%, widely available. Contains variable amounts of phenol (1015%) and sometimes triphenyl phosphite.
Analysis of Reagent Purity: 31 P NMR [in acetonitrile, P = 2.1
ppm, 1 JPH = 741 Hz (d)]. Possible contaminations: triphenyl
phosphite (P = 129.7 ppm) and phenyl H-phosphonate monoester [P = 0.95 ppm, 1 JPH = 633 Hz (d)].
Purity: vacuum distillation, although for most synthetic applications the reagent can be used as supplied. The amount of phenol
contaminant (based on 1 H NMR analysis) can be significantly
decreased (if so desired) by heating the reagent at 130 C at 20
mm Hg.2
Handling, Storage, and Precautions: store in a cool, dry place.
Keep tightly closed. Upon frequent contacts with atmospheric
moisture the reagent slowly hydrolyzes. The bottles are usually
labeled with precautionary notes: stench, highly toxic, vesicant,
readily absorbed through skin, etc. It may affect liver, kidneys,
nerves, although no toxicological data are available.

CX2 + RNH2

N
H

CO2Y

(1)

(PhO)2P(O)H

(2)
py, 40 C

RHN

NHR

X = O, S

The diester undergoes easy transesterification in two distinct


stages, allowing the preparation of unsymmetrical diesters (eq 3).5
R1OH

(PhO)2P(O)H

(PhO)(R1O)P(O)H

R2OH

py, rt

(R1O)(R2O)P(O)H (3)
R1 = primary, secondary, tertiary; R2 = primary, secondary

The use of stronger bases than pyridine, e.g. Triethylamine,


causes rapid disproportionation to (PhO)3 P and PhOPHO2 .2c,5

1.
2.

Stelzel, P., Methoden Org. Chem. (Houben-Weyl) 1974, 15/2, 246.


(a) Houalla, D.; Wolf, R., Chem. Rev. 1958, 247, 482. (b) Walsh, E. N.,
J. Am. Chem. Soc. 1959, 81, 3023. (c) Yamazaki, N.; Iguchi, T.; Higashi,
F., Chem. Lett. 1977, 185.
3. (a) Yamazaki, N.; Higushi, F., Tetrahedron Lett. 1972, 5047. (b) Yamazaki,
N.; Higashi, F., Tetrahedron Lett. 1974, 1323.
4. Yamazaki, N.; Higashi, F.; Iguchi, T., Tetrahedron Lett. 1974, 1191.
5. Gallagher, M. J.; Garbutt, R.; Liu Yuan Hua; Gum Hee Lee, Phosphorus
Sulfur 1993, 201.

Michael J. Gallagher
University of New South Wales, Kensington,
New South Wales, Australia