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Org. Synth. 1954, 34, 44
DOI: 10.15227/orgsyn.034.0044
DIPHENYL SUCCINATE
[Succinic acid, diphenyl ester]
Submitted by Guido H. Daub and William S. Johnson1.
Checked by James Cason, Robert A. Wessman, and William G. Dauben.
1. Procedure
A mixture of 118 g. (1 mole) of succinic acid, 188 g. (2 moles) of phenol, and 138 g. (83 ml., 0.9 mole) of phosphorus oxychloride (Note 1) is placed in a 2-l. round-bottomed flask fitted with an efficient reflux condenser capped with a calcium chloride tube (Note 2) and (Note 3). The mixture is heated on a steam bath in a hood (Note 3) for 1.25 hours, 500 ml. of benzene is added, and the refluxing is continued for an additional hour. The hot benzene solution is decanted from the red syrupy residue of phosphoric acid and filtered by gravity into a 1-l. Erlenmeyer flask. The syrupy residue is extracted with two 100-ml. portions of hot benzene, which are also filtered into the Erlenmeyer flask. The combined benzene solutions are concentrated to a volume of about 600 ml. (Note 4), and the pale yellow solution is allowed to cool, whereupon the diphenyl succinate separates as colorless crystals. It is filtered with suction on a Büchner funnel, washed with three 50-ml. portions of ether, and dried on a porous plate at 40°. The yield of diphenyl succinate, m.p. 120–121°, is 167–181 g. (62–67%) (Note 5).
2. Notes
1. The use of a larger proportion of phosphorus oxychloride failed to improve the yield and in general gave an inferior product.
2. Ground-glass joints are preferred; however, burnt-cork stoppers may be used.
3. Provision should be made to dispose of the hydrogen chloride which is evolved during the reaction.
4. If the mother liquor is concentrated further before removal of phenol and phosphorus oxychloride a dark, impure product is obtained.
5. If desired, a second crop may be obtained by the following procedure: The mother liquor is extracted in a 1-l. separatory funnel with eight 50-ml. portions of 5% potassium hydroxide solution. Each extract is extracted in turn with a 50-ml. portion of benzene. The two benzene solutions are washed in turn with a 50-ml. portion of water and two 50-ml. portions of saturated sodium chloride solution. All the benzene solutions are combined, dried over anhydrous sodium sulfate, filtered, and concentrated to a volume of 150 ml. Cooling yields a second crop of diphenyl succinate, which is collected, washed, and dried as described for the first crop. The yield is 13–27 g. (5–10%), m.p. 118–120°.
3. Discussion
The above procedure is a modification of that described by Rasinski.2 Diphenyl succinate has also been prepared by the reaction of phenol and succinic acid in the presence of phosphorus pentoxide in toluene3 and by the treatment of phenol with succinyl chloride.4

References and Notes
  1. University of Wisconsin, Madison, Wisconsin.
  2. Rasinski, J. prakt. Chem., 26, 63 (1882). Bischoff and Hedenstrom, Ber., 35, 4073 (1902).
  3. Bakunin, Gazz. chim. ital., 30, 358 (1900).
  4. Weselsky, Ber., 2, 519 (1869).

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

hydrogen chloride (7647-01-0)

Benzene (71-43-2)

ether (60-29-7)

phenol (108-95-2)

sodium chloride (7647-14-5)

sodium sulfate (7757-82-6)

Succinic acid (110-15-6)

Phosphorus Oxychloride (21295-50-1)

potassium hydroxide (1310-58-3)

toluene (108-88-3)

phosphoric acid (7664-38-2)

succinyl chloride (543-20-4)

Diphenyl succinate,
Succinic acid, diphenyl ester (621-14-7)

phosphorus pentoxide (1314-56-3)