A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1950, 30, 93
DOI: 10.15227/orgsyn.030.0093
[4-Cyclohexene-1,2-dicarboxylic anhydride, cis-]
Submitted by Arthur C. Cope and Elbert C. Herrick1.
Checked by Charles C. Price, Kenneth N. Campbell, and Robert P. Kane.
1. Procedure
The apparatus shown in Fig. 16, consisting of a 2-l. three-necked round-bottomed flask fitted with an efficient stirrer (Note 1), a gas-inlet tube, a thermometer, and a reflux condenser, is assembled in a ventilated hood. Bubbler tubes containing benzene are attached to the gas inlet tube and the top of the reflux condenser, and 500 ml. of dry benzene and 196 g. (2 moles) of maleic anhydride (Note 2) are placed in the flask. Stirring is begun, the flask is heated with a pan of hot water, and butadiene is introduced (from a commercial cylinder controlled by a needle valve) at a rapid rate (0.6–0.8 l. per minute). When the temperature of the solution has reached 50° (within 3–5 minutes) the pan of water is removed. The exothermic reaction causes the temperature to reach 70–75° in 15–25 minutes. The rapid stream of butadiene is nearly completely absorbed for 30–40 minutes, after which the rate is decreased until the reaction is completed (equal rates of bubbling in the two bubbler tubes) after 2–2.5 hours. The solution is poured into a 1-l. beaker at once to avoid crystallization of the product in the reaction flask. The beaker is covered and the mixture is kept at 0–5° overnight.
The product is collected on a large Büchner funnel and washed with 250 ml. of 35–60° petroleum ether. A second crop (5–15 g.) obtained by diluting the filtrate with an additional 250 ml. of petroleum ether is separated by filtration, combined with the first crop in a large crystallizing dish, and dried to constant weight (1–2 hours) in an oven at 70–80°. The yield of cis4-tetrahydrophthalic anhydride is 281.5–294.5 g. (93–97%), m.p. 99–102° (Note 3).
Fig. 16. Assembly of apparatus for addition of butadiene to maleic anhydride.
Fig. 16. Assembly of apparatus for addition of butadiene to maleic anhydride.
2. Notes
1. Any stirrer that produces sufficiently vigorous agitation to disperse the gas through the liquid is satisfactory. It was found to be unnecessary to introduce the gas below the surface of the liquid.
2. A good grade of commercial maleic anhydride was used, m.p. 52–54°.
3. The product is analytically pure and suitable for use in preparing diethyl cis4-tetrahydrophthalate (p. 304). Recrystallization from ligroin2 or ether3 raises the m.p. to 103–104°.
3. Discussion
cis4-Tetrahydrophthalic anhydride has been prepared by the reaction of maleic anhydride and butadiene.2,3,4,5,6 The procedure described is adapted from the one used by Kohler and Jansen.5
This preparation is referenced from:

References and Notes
  1. Massachusetts Institute of Technology, Cambridge, Massachusetts.
  2. Diels and Alder, Ann., 460, 113 (1928).
  3. Jenkins and Costello, J. Am. Chem. Soc., 68, 2733 (1946).
  4. Farmer and Warren, J. Chem. Soc., 1929, 903.
  5. Kohler and Jansen, J. Am. Chem. Soc., 60, 2144 (1938); Cope and Herrick, J. Am. Chem. Soc., 72, 983 (1950).
  6. Fieser and Novello, J. Am. Chem. Soc., 64, 806 (1942).

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


petroleum ether

Diethyl cis-Δ4-tetrahydrophthalate

cis-Δ4-Tetrahydrophthalic anhydride

Benzene (71-43-2)

butadiene (106-99-0)

maleic anhydride (108-31-6)

4-Cyclohexene-1,2-dicarboxylic anhydride, cis- (935-79-5)