Synthesis of Benzil from Benzoin with Copper(l1) Acetate

In asynthesirui hydrohenmn from bcnmin via benril, ur have develupetl n synrhesis of bcwil from benzoin. Usually,
in our students'experimenti, benzoin is oxidiprd to bcwil by refluxing i w 1 h in thp prrsmcr of nitric acid'; the purified
b e n d , after rccrssLalliratiun i n m ethanol, rhcn is reduced tu the elsud lw wdium horohvdride. In this orocrdure [three
.
stem including the svnthesis of benzoin) the time reauired is a t l e k i two iaboratorv,oeridds.
What r r iavedonei.t<,oxidlze hena,~n~virht~vdc~uivalentr uf cupper(ll,sretnte mnnacpficacid-water miature(151
3 "1%I 15 min at reflux, producing pure henzil in good yield (9U1,.The purity d the sdld 8s determinrd by'1'l.C (SiO?,tolu-
ene aseluant, one spot R. = O.6.l, and by the mclting point (93 94 TI.
Reactlon
A possible reaction mechanism is suggested as shown below:
OH 0-Cut
I
C6HsCO--CH-CsHs + CuZ+ - I
[CBH~CO-CH-CSHS] + Ht - CsHsCO--CO--CsHs + [Cuo]+ H+
+
[Cuo] Cup+ - 2Cut % Cup0 + 2Ht

Procedure
In a 100-mL flask equipped with a reflux condenser, a mixture of 2 g (9.43 mmol) benzoin, 3.75 g (18.8 mmol) cuprie ac-
etate monohydrate, 15 mL acetieacid,and 5 mL water isrefluxedfor 15 minutes and then filtered through afilter paper in
a preheated funnel t o remove the cuprous oxide. The filtrate is allowed to crystallize by cooling. After filtering through a
Buchner funnel, washing with water, and drying the filter cake on a sheet of filter paper, pure henzil (TLC and mp) is
obtained (905%of yield) and then reduced to hydrohenzoin.
Comments
Compared t o the nitric acid method, this procedure offers the advantage that the crude henzil obtained is well
crystallized and of high purity. In the nitric acid method, the yield depends on the quality of the acid used, and in most
eases the product contains benzoin (Rr of benzoin: 0.12) and must therefore be recrvstallized.
A privious experiment2 using cuiric acetate in a catalytic amount required one t o two hours of refluxing, which is
incompatible with this laboratory experiment (three steps in a period of four hours). Our modification considerably
reduces this time.

' Clarke, H. T.; Dreger, E. E. Organic Syntheses 1967,1,87, and references cited.
Weiss, M.; Apple, M. J. Am. Chem. Soc. 1948,70,36663667.
Author to whom correspondence should be addressed.
P. Depreux3, G. Bethegnles, and A. Marclncal-Lefebvre
Laboratoire de Chimie Organique
Facult6 de Pharmacie
3 Rue du Prafesseur Laguesse
59045 Lille Cedex. France

Volume 85 Number 8 June 1988 553