A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1967, 47, 62
DOI: 10.15227/orgsyn.047.0062
Submitted by R. Breslow and J. Posner1.
Checked by E. J. Corey and M. F. Semmelhack.
1. Procedure
Caution! See (Note 1).
A. α,α'-Dibromodibenzyl ketone. To a solution of 70 g. (0.33 mole) of commercial dibenzyl ketone in 250 ml. of glacial acetic acid in a 2-l. one-necked flask fitted with a magnetic stirrer a solution of 110 g. (0.67 mole) of bromine in 500 ml. of acetic acid is added through a dropping funnel over a 15-minute period. After addition is complete, the mixture is stirred for an additional 5 minutes and is then poured into 1 l. of water. Solid sodium sulfite is added in small portions until the initial yellow color of the solution is discharged, and the mixture is allowed to stand for 1 hour. The slightly yellow dibromoketone is then collected by filtration and air-dried. Recrystallization from 1 l. of ligroin yields 97 g. of white needles, m.p. 79–87°; an additional 11 g., m.p. 79–83°, is obtained by concentrating the mother liquors, and the two crops are combined (Note 1).
B. Diphenylcyclopropenone. A solution of 100 ml. of triethylamine (Note 2) in 250 ml. of methylene chloride is magnetically stirred in a 2-l. one-necked flask while 108 g. (0.29 mole) of the above dibromoketone in 500 ml. of methylene chloride is added dropwise over 1 hour. The mixture is stirred for an additional 30 minutes and then extracted with two 150-ml. portions of 3N hydrochloric acid; the aqueous extracts are discarded. The red organic solution is transferred to a 2-l. Erlenmeyer flask and cooled in an ice bath. While this solution is swirled, a cold solution of 50 ml. of concentrated sulfuric acid in 25 ml. of water is slowly added. A slightly pink precipitate of diphenylcyclopropenone bisulfate gradually separates (Note 3). This is collected on a sintered-glass funnel and washed with two 100-ml. portions of methylene chloride. The solid is then returned to the flask (Note 4) along with 250 ml. of methylene chloride and 500 ml. of water, and 5 g. of solid sodium carbonate is added in small portions. The organic layers is collected and the aqueous solution extracted with two 150-ml. portions of methylene chloride. The combined organic layers are dried over magnesium sulfate and evaporated to dryness. The impure diphenylcyclopropenone is recrystallized by repeated extraction with boiling cyclohexane (total 1.5 l.), the solution being decanted in each case from a reddish oily impurity. On cooling, the solution deposits 29 g. of white crystals, and an additional 1 g. can be obtained by concentrating the mother liquors to 150 ml. The combined 30 g., m.p. 119–120°, represents an overall yield of 44% based on dibenzylketone.
2. Notes
1. Care should be taken to prevent either the dibromoketone or the cyclopropenone from coming into contact with the skin, as allergic reactions have been observed in several cases. The use of gloves is recommended especially for the bromoketone. The latter product has a wide melting range because it is a mixture of the meso- and d,l-compounds.
2. For best results the commercial triethylamine (Matheson, b.p. 89–90°) should be purified to remove primary and secondary amines and water, either by distillation from acetic anhydride and then from barium oxide, or by reaction with phenylisocyanate.2,3
3. If the white solid fails to separate after 15–30 minutes, concentrated sulfuric acid is added in 4-ml. portions to the cooled solution with swirling until the white solid appears.
4. Since some of the white solid adheres to the walls of the flask, it is convenient to use the same flask for the neutralization after rinsing it with methylene chloride.
3. Discussion
Diphenylcyclopropenone has also been prepared by the action of phenylchlorocarbene on phenylketene acetal4 and by the reaction of dihalocarbene with diphenylacetylene.5 The present procedure6 is the most convenient on a preparative scale.
4. Merits of the Preparation
Diphenylcyclopropenone is the first stable molecule prepared which has a carbonyl group in a three-membered ring. In a very real sense the compound has aromatic character and is fairly stable.4 An interesting cycloaddition reaction of enamines with diphenylcyclopropenone has been reported.7
This preparation is referenced from:

References and Notes
  1. Department of Chemistry, Columbia University, New York, New York 10027.
  2. A. Weissberger, "Technique of Organic Chemistry," Vol. VII, 2nd ed., Interscience Publishers Inc., New York, 1955, p. 445.
  3. J. C. Sauer, Org. Syntheses, Coll. Vol. 4, 561 (1963).
  4. R. Breslow, R. Haynie, and J. Mirra, J. Am. Chem. Soc., 81, 247 (1959).
  5. M. E. Volpin, Yu. D. Koreshokov, and D. N. Kursanov, Izv. Akad. Nauk SSSR, 560 (1959).
  6. R. Breslow, J. Posner, and A. Krebs, J. Am. Chem. Soc., 85, 234 (1963).
  7. J. Ciabattoni and G. A. Berchtold, J. Org. Chem., 31, 1336 (1966).

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

sulfuric acid (7664-93-9)

hydrochloric acid (7647-01-0)

acetic acid (64-19-7)

acetic anhydride (108-24-7)

sodium sulfite (7757-83-7)

sodium carbonate (497-19-8)

bromine (7726-95-6)

barium oxide

cyclohexane (110-82-7)

methylene chloride (75-09-2)

phenylisocyanate (103-71-9)

magnesium sulfate (7487-88-9)

dibenzyl ketone,
dibenzylketone (102-04-5)

Diphenylacetylene (501-65-5)

bromoketone (593-95-3)

triethylamine (121-44-8)

Diphenylcyclopropenone (886-38-4)

diphenylcyclopropenone bisulfate

cyclopropenone (2961-80-0)


phenylketene acetal

α,α'-Dibromodibenzyl ketone (958-79-2)