Russian Journal of Organic Chemistry, Vol. 39, No. 11, 2003, pp. 1672 1673. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 11, 2003,
pp. 1741 1742.
Original Russian Text Copyright
2003 Zhutov, Skornyakov, Proskurina, Zefirov.
SHORT
COMMUNICATIONS
p-Bromo(diacetoxyiodo)benzene, an Efficient Oxidant
for Conversion of Oximes into Nitroso Compounds
E. V. Zhutov, Yu. V. Skornyakov, M. V. Proskurina, and N. S. Zefirov
Lomonosov Moscow State University, Moscow, Russia
Received July 11, 2002
Compounds of hypervalence iodine are extensively
studied in the recent years in versatile reactions,
and many among them became common reagents for
organic synthesis. In particular, in 1991 a reaction
was investigated between iodobenzene dichloride and
aromatic or aromatic-aliphatic oximes of carbonyl
compounds in the presence of pyridine [1] which
might be regarded as preparative procedure for di-
oximation under mild conditions. In 1980 Corey [2]
developing a general method for converting oxo
compounds into nitro compounds carried out alicyclic
oximes oxidation with hypochlorites. He stated basing
on quickly arising and rapidly disappearing blue color
of the reaction mixture that in this oxidation process
intermediately formed chloronitroso compounds.
of ether, 50 ml of water was added, ether layer was
separated, and the water layer was extracted with
ether. The ether solution was washed with water
(2 50 ml) and 5% solution of sodium carbonate
(2 50 ml). The ether solution of bright blue color
was dried over Na2SO4, the solvent was evaporated,
and from the semisolid residue the reaction product
was distilled in a high vacuum at room temperature
(or at slight heating) into a receiver cooled with liquid
nitrogen. Thus a crude reaction product was obtained
containing as impurities a little of p-bromoiodobenz-
ene and of decomposition products of gem-acyloxy-
nitroso compound. The residue after distillation was
recrystallized from ethanol to obtain p-bromoiodo-
benzene in quantitative yield. The crude target
product was subjected to repeated distillation in a
high vacuum collecting the distillate in a trap cooled
with liquid nitrogen. Thus we obtained the gem-acyl-
oxynitroso compounds of analytical purity as dark-
blue liquids (20 C).
We demonstrated that reaction of iodo(p-bromo-
benzene) diacetate with oximes of acetone, cyclo-
hexanone, and cyclopentanone afforded in high yields
the corresponding 1-nitrosoacetoxy derivatives.
2-Acetoxy-2-nitrosopropane. From 8.02
g
(0.02 mol) of iodo(p-bromobenzene) diacetate and
1.46 g (0.02 mol) of acetone oxime was obtained
2.3 g (88%) of 2-acetoxy-2-nitrosopropane and 5.4 g
(95%) of p-bromoiodobenzene. IR spectrum,
,
1
1
cm : 1720 (C=O), 1380 (N=O). H NMR spectrum
(DMSO-d6), , ppm: 1.48 s (6H), 2.20 s (3H).
13C NMR spectrum (DMSO-d6), , ppm: 15.034
(2CH3), 20.123 (1CH3), 64.921 (C N), 168.795
(C=O). Published data see in [3].
Therewith the p-bromoiodobenzene can be quanti-
tatively isolated from the reaction mixture and can
serve as initial compound for the synthesis of the cor-
responding diacetate without losses.
1-Acetoxy-1-nitrosocyclohexane. From 8.02 g
(0.02 mol) of iodo(p-bromobenzene) diacetate and
2.26 g (0.02 mol) of cyclohexanone oxime was
obtained 3.2 g (94%) of 1-acetoxy-1-nitrosocyclo-
hexane and 5.5 g (97%) of p-bromoiodobenzene. IR
gem-Acetoxynirtoso compounds. To a stirred
mixture
of
iodo(p-bromobenzene)
diacetate
(0.02 mol) and 10 ml of glacial acetic acid at 15 C
was added dropwise within 5 min a solution of ket-
oxime (0.02 mol) in 5 ml of glacial acetic acid. In
15 min the reaction mixture was diluted with 50 ml
1
spectrum, , cm : 1740 (C=O), 1370 (N=O).
1H NMR spectrum (DMSO-d6), , ppm: 2.20 s (3H),
1.4 1.9 m (10H). Published data see in [3].
1070-4280/03/3911-1672$25.00 2003 MAIK Nauka/Interperiodica