Org. Synth. 1950, 30, 93
DOI: 10.15227/orgsyn.030.0093
cis-Δ4-TETRAHYDROPHTHALIC ANHYDRIDE
[4-Cyclohexene-1,2-dicarboxylic anhydride, cis-]
Submitted by Arthur C. Cope and Elbert C. Herrick
1.
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 cis-Δ4-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.
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 cis-Δ4-tetrahydrophthalate (
p. 304). Recrystallization from
ligroin2 or ether
3 raises the m.p. to 103–104°.
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3. Discussion
cis-Δ4-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:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
ligroin
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)
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