Org. Synth. 1943, 23, 93
DOI: 10.15227/orgsyn.023.0093
TETRAPHENYLPHTHALIC ANHYDRIDE
[Phthalic anhydride, tetraphenyl-]
Submitted by Oliver Grummitt
Checked by Nathan L. Drake and Charles M. Eaker.
1. Procedure
An intimate mixture of
35 g. (0.094 mole) of tetraphenylcyclopentadienone (p. 806) and
9.3 g. (0.095 mole) of maleic anhydride is placed in a
200-ml. round-bottomed flask (Note 1), and to it is added
25 ml. of bromobenzene. After the mixture has been refluxed gently for 3.5 hours
(Note 2), it is cooled
(Note 3), a solution of
7 ml. of bromine in
10 ml. of bromobenzene is added through the condenser, and the flask is shaken until the reagents are thoroughly mixed. After the first exothermic reaction has subsided, the mixture is refluxed gently for 3 hours
(Note 4). The flask is then immersed in a
cooling bath and the temperature of the mixture is held at 0–10° for 2–3 hours. The mixture is filtered with suction, and the crystalline product is washed three times with
10-ml. portions of petroleum ether (b.p.
60–68°). After the product has been dried in the air, it weighs
37–38 g. (
87–89%) and melts at
289–290°. It is light brown, but when pulverized it is almost colorless. The filtrate, when diluted with an equal volume of
petroleum ether and cooled to 0–10°, yields an additional
2–3 g. of a less pure product which melts at
285–288°. The impure material may be purified by recrystallization from
benzene, using
8–9 ml. of benzene per gram of solid
(Note 5).
2. Notes
1.
Ground-glass equipment is preferred; corks are attacked by the
bromine used later.
2.
The operation should be carried out in a
hood because of the
carbon monoxide evolved.
3.
The
tetraphenyldihydrophthalic anhydride may be isolated at this point in practically quantitative yields by cooling the mixture, filtering with suction, and washing the solid with three
10-ml. portions of petroleum ether (b.p.
60–68°). The yield is
41–42 g.; the product melts at
235–240°.
4.
This operation should also be performed in a hood, or the top of the condenser should be connected to a suitable
trap.
5.
The crystallized product must be dried at 110° for 1–1.5 hours; otherwise
benzene, possibly
benzene of crystallization, will be retained by the solid indefinitely.
3. Discussion
Tetraphenylphthalic anhydride has been prepared by condensation of
tetraphenylcyclopentadienone and
maleic anhydride in
nitrobenzene,
1 followed by dehydrogenation of the
tetraphenyldihydrophthalic anhydride with
sulfur.
2,3
Tetraphenylphthalic anhydride has also been prepared by condensation of
tetraphenylcyclopentadienone with
chloromaleic anhydride;
4 and by oxidation of
tetraphenylhydrindene with
chromic acid5 or oxidation of
7-carboxy-4,5,6,7-tetraphenyl-3a,4,7,7a-tetrahydroindene with
potassium permanganate.
6
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
petroleum ether
Benzene (71-43-2)
carbon monoxide (630-08-0)
potassium permanganate (7722-64-7)
bromine (7726-95-6)
sulfur (7704-34-9)
chromic acid (7738-94-5)
Nitrobenzene (98-95-3)
bromobenzene (108-86-1)
maleic anhydride (108-31-6)
Tetraphenylcyclopentadienone (479-33-4)
Tetraphenylphthalic anhydride,
Phthalic anhydride, tetraphenyl- (4741-53-1)
tetraphenyldihydrophthalic anhydride
chloromaleic anhydride
tetraphenylhydrindene
7-carboxy-4,5,6,7-tetraphenyl-3a,4,7,7a-tetrahydroindene
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