A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1965, 45, 99
DOI: 10.15227/orgsyn.045.0099
[Phosphonic dichloride, styryl-]
Submitted by R. Schmutzler1
Checked by William G. Dauben and David A. Cox.
1. Procedure
The reaction is conducted in a 500-ml. three-necked flask equipped with a sealed mechanical stirrer, a dropping funnel, and a reflux condenser carrying a drying tube. The flask is flushed with dry nitrogen, and 104 g. (0.50 mole) of phosphorous pentachloride in 150 ml. of dry benzene is added. The mixture is cooled in an ice bath (Note 1) and stirred while a solution of 26 g. (0.25 mole) of styrene in 50 ml. of dry benzene is added through the dropping funnel during a period of 30 minutes. A dense crystalline solid begins to form immediately, and after the addition is completed the mixture is stirred for 30 minutes at room temperature. The dropping funnel is replaced by a gas-inlet tube which is connected to a cylinder of sulfur dioxide through a wash bottle containing concentrated sulfuric acid. Sulfur dioxide is bubbled through the stirred mixture until all the precipitate is dissolved. The mildly exothermic reaction is controlled by occasionally cooling the reactants with an ice bath. The benzene solvent is removed from the clear solution under reduced pressure, and the residue is distilled at reduced pressure from a Claisen flask with Vigreux indentations. The yield of styrylphosphonic dichloride is 49–52 g. (89–94%), b.p. 107–110° (0.2 mm.). The distillate solidifies during or after the distillation, m.p. 71–72°.
2. Notes
1. Care must be taken not to freeze the benzene before the styrene is added.
3. Discussion
Styrylphosphonic dichloride has been prepared by the addition of phosphorus pentachloride to styrene with subsequent reaction of the adduct with phosphorus pentoxide2 or sulfur dioxide.3,4
4. Merits of the Preparation
The addition reaction of phosphorus pentachloride to styrene and its derivatives provides a convenient route to styrylphosphonic acids and their derivatives.2,3,4,5,6,7 The styrene phosphorus pentachloride adduct also can be reduced with phosphorus to give the corresponding dichlorophosphine.4,8
The behavior of phosphorus pentachloride toward carbon-carbon multiple bonds has received considerable attention, and the procedure described represents but one example of a wide variety of derivatives of unsaturated phosphonic acids which are accessible. Indene was the first olefinic compound to be reacted with phosphorus pentachloride,9 and the reaction of phosphorus pentachloride with other unsaturated compounds has been described.2,3,4,5,6,10,11,12,13 More recent examples include the reaction of phosphorus pentachloride with vinyl ethers14,15,16 and vinyl thioethers,17 providing access to β-alkoxy- and β-alkylmercaptovinylphosphonic and phosphonothioic acid derivatives.

References and Notes
  1. Explosives Department, E. I. du Pont de Nemours and Company, Wilmington, Delaware.
  2. W. H. Woodstock, U.S. Patent 2,471,472 [C.A., 43, 7499 (1949)].
  3. K. N. Anisimov, Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.), 693 (1954).
  4. G. K. Fedorova and A. V. Kirsanov, J. Gen. Chem. USSR (Engl. Transl.), 4006 (1960).
  5. E. Bergmann and A. Bondi, Ber., 63, 1158 (1930).
  6. G. M. Kosolapoff and W. F. Huber, J. Am. Chem. Soc., 68, 2540 (1946).
  7. A. D. F. Toy, U.S. Patent 2,425,766 [C.A., 42, 596 (1948)].
  8. E. N. Walsh, T. M. Beck, and W. H. Woodstock, J. Am. Chem. Soc., 77, 929 (1955).
  9. J. Thiele, Chemiker-Ztg., 36, 657 (1912); C. Harnist, Ber., 63, 2307 (1930).
  10. E. Bergmann and A. Bondi, Ber., 64, 1455 (1931); 66, 278, 286 (1933).
  11. L. Anschütz, F. König, F. Otto, and H. Walbrecht, Ann., 525, 297 (1936).
  12. G. B. Bachman and R. E. Hatton, J. Am. Chem. Soc., 66, 1513 (1944).
  13. K. N. Anisimov and N. E. Kolobova, Bull. Acad. Sci. USSR (Engl. Transl.), 943, 947 (1956).
  14. K. N. Anisimov and A. N. Nesmeyanov, Bull. Acad. Sci. USSR (Engl. Transl.), 521 (1954).
  15. K. N. Anisimov, Bull. Acad. Sci. USSR (Engl. Transl.), 693 (1954).
  16. K. N. Anisimov, N. E. Kolobova, and A. N. Nesmeyanov, Bull. Acad. Sci. USSR (Engl. Transl.), 685, 689 (1954).
  17. K. N. Anisimov, N. E. Kolobova, and A. N. Nesmeyanov, Bull. Acad. Sci. USSR (Engl. Transl.), 21 (1956).

Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

sulfuric acid (7664-93-9)

Benzene (71-43-2)

phosphorus pentachloride,
phosphorous pentachloride (10026-13-8)

sulfur dioxide (7446-09-5)

PHOSPHORUS (7723-14-0)

nitrogen (7727-37-9)

styrene (100-42-5)

indene (95-13-6)

vinyl (2669-89-8)

Styrylphosphonic dichloride,
Phosphonic dichloride, styryl- (4708-07-0)

styrene phosphorus pentachloride


phosphorus pentoxide (1314-56-3)