A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1932, 12, 66
DOI: 10.15227/orgsyn.012.0066
Submitted by Louis F. Fieser and E. L. Martin.
Checked by C. R. Noller
1. Procedure
In a 1-l. round-bottomed flask, fitted with a reflux condenser attached to a gas trap, are placed 118 g. (1 mole) of succinic acid and 215 cc. (235 g., 3 moles) of acetyl chloride. The mixture is gently refluxed on the steam bath until all the acid dissolves; this requires one and a half to two hours. The solution is allowed to cool undisturbed and is finally chilled in an ice bath. The succinic anhydride, which separates in beautiful crystals, is collected on a Büchner funnel, washed with two 75-cc. portions of ether, and dried in a vacuum desiccator. The yield of material melting at 118–119° is 93–95 g. (93–95 per cent of the theoretical amount).
Submitted by R. L. Shriner and H. C. Struck.
Checked by C. R. Noller, F. B. Hilmer, and J. D. Pickens.
1. Procedure
Two hundred thirty-six grams (2 moles) of succinic acid (Note 1) and 153.5 g. (1 mole) of phosphorus oxychloride are placed in a 1-l. Claisen flask. One neck of the flask is equipped with a reflux condenser connected to a gas trap; the other neck and the side arm of the flask are closed with corks. The mixture is heated (Note 2) with a free flame for about fifty minutes until no more hydrogen chloride is evolved. The condenser is removed and the flask is arranged for distillation, with a tube leading from the side arm of the receiver to the drain in order to carry off the vapors. A few cubic centimeters of distillate is collected below 255°, at which temperature the receiver is changed and succinic anhydride is collected from 255–260° (Note 3). The product melts at 118–120° and weighs 164–192 g. (82–96 per cent of the theoretical amount).
The succinic anhydride may be purified by dissolving 50 g. of the crude material in 35 cc. of acetic anhydride. The hot solution is cooled in an ice bath. The crystals are filtered with suction, washed with two 20-cc. portions of cold, absolute ether, and air-dried quickly at 40°. The yield of the pure anhydride, which melts at 119–120°, is 43.5 g.
2. Notes
1. Succinic acid having a melting point of 189–190° was used. Less pure material gives a lower-melting product.
2. The reaction foams considerably at the start, hence slow and careful heating is necessary. It is best to heat the flask directly with the flame, making certain that all parts of the mixture are heated about equally.
3. The tarry mass left in the distilling flask may be easily removed by warm dilute sodium hydroxide.
3. Discussion
Succinic anhydride has been prepared from succinic acid with phosphorus pentachloride,1, 2 phosphorus oxychloride,2, 3 phosphorus pentoxide,4 thionyl chloride,5 acetyl chloride,3, 6, 7 or succinyl chloride;8 from barium or sodium succinate with benzoyl chloride,1 acetyl chloride,9 acetic anhydride,10 or benzophenone dichloride;11 from succinyl chloride and oxalic acid6 or sodium acetate;9 and from ethyl succinate and benzoyl chloride.12
The procedure in Org. Syn. Coll. Vol. I, 1941, 91, for preparing benzoic anhydride when applied to succinic acid and acetic anhydride gives a 72 per cent yield of succinic anhydride. Procedure I above has the advantage of convenience; Procedure II is more economical.
This preparation is referenced from:

References and Notes
  1. Gerhardt and Chiozza, Ann. 87, 292 (1853).
  2. Volhard, ibid. 242, 150 (1887).
  3. Verkade and Hartman, Rec. trav. chim. 52, 947 (1933).
  4. d'Arcet, Ann. chim. phys. (2) 58, 288 (1835).
  5. Meyer, Monatsh. 22, 420 (1901).
  6. Anschütz, Ann. 226, 8 (1884).
  7. Schulz, Ber. 18, 2459 (1885).
  8. Anschütz, ibid. 10, 1883 (1877).
  9. Heintz, Jahresb. 1859, 279.
  10. Oddo and Manuelli, Gazz. chim. ital. 26 (II) 482 (1896).
  11. Evlampiev, J. Gen. Chem. (U.S.S.R.) 7, 2934 (1937) [C. A. 32, 5377 (1938)].
  12. Kraut, Ann. 137, 254 (1866).

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

barium or sodium succinate

hydrogen chloride (7647-01-0)

ether (60-29-7)

acetic anhydride (108-24-7)

sodium acetate (127-09-3)

sodium hydroxide (1310-73-2)

phosphorus pentachloride (10026-13-8)

acetyl chloride (75-36-5)

thionyl chloride (7719-09-7)

ethyl succinate

Oxalic acid (144-62-7)

Succinic acid (110-15-6)

benzoyl chloride (98-88-4)

Benzoic anhydride (93-97-0)

Phosphorus Oxychloride (21295-50-1)

benzophenone dichloride

Succinic anhydride (108-30-5)

succinyl chloride (543-20-4)

phosphorus pentoxide (1314-56-3)