1-tert-Butoxypropan-2-one as direct reaction product of acetone with tert-butyl hydroperoxide

Full text of DOI:10.1134/S1070428008040258

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 4, pp. 617–618. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © I.N. Grebenshchikov, A.S. Dykman, V.V. Pinson, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 4,
pp. 621–622.
SHORT
COMMUNICATIONS
1-tert-Butoxypropan-2-one as Direct Reaction Product
of Acetone with tert-Butyl Hydroperoxide
I. N. Grebenshchikov, A. S. Dykman, and V. V. Pinson
All-Russian Research Institute of Petrochemical Processes, Zheleznodorozhnyi pr. 40, St. Petersburg, 192148 Russia
Received September 26, 2007
DOI: 10.1134/S1070428008040258
Hydroxyacetone is the main by-product impairing
the quality of phenol obtained from cumene. It is now
believed to be well established [1, 2] that this com-
pound is formed mainly at the stage of acid decom-
position of 1-methyl-1-phenylethyl hydroperoxide. Za-
koshanskii et al. [2] presumed that hydroxyacetone
arises from the reaction of acetone with 1-methyl-1-
phenylethyl hydroperoxide; however, no experimental
proofs for the proposed scheme were given in [2]. We
used as a model tert-butyl hydroperoxide instead of
1-methyl-1-phenylethyl hydroperoxide, taking into ac-
count higher stability of the former under acidic condi-
tions. It is well known [3] that reactions of carbonyl
compounds with hydroperoxides derived from alkanes
lead to the formation of peroxy ketals (Scheme 1).
was reported [4]. 1-tert-Butoxypropan-2-one may be
regarded as an ether derived from hydroxyacetone and
tert-butyl alcohol. Such ethers are known to undergo
decomposition to give the corresponding olefin
(2-methylpropene) and primary alcohol (hydroxyace-
tone). In fact, we observed formation of hydroxy-
acetone upon decomposition of 1-tert-butoxypropan-2-
one in acetone in the presence of sulfuric acid at 100°C
(in a sealed ampule).
Scheme 2.
OOBu-t
OOBu-t
–H+
Me
Me
Me
O
CH2
I
II
[1,3]-Sigmatropic shift
Scheme 1.
OBu-t
Me
O
t-BuOOH, H+
HO
Me
OOBu-t
Me
Me
Me
1-tert-Butoxypropan-2-one. A solution of 45 g
(0.5 mol) of tert-butyl hydroperoxide in 50 ml of di-
oxane was added under stirring to a mixture of 58 g
(1 mol) of acetone, 35 g (0.5 mol) of finely ground
B2O3, 0.3 g (0.003 mol) of H2SO4, and 200 ml of diox-
ane, maintaining the temperature below 40°C. When
the addition was complete, the mixture was stirred for
4 h at 55°C. Excess acetone and most part of the sol-
vent were distilled off, the precipitate was filtered off,
and the filtrate was diluted with water and extracted
with chloroform (3×100 ml). The extracts were com-
bined, washed with water until neutral reaction, and
dried over CaCl2, the solvent was distilled off, and the
residue was distilled under reduced pressure, a fraction
with bp 55–60°C (30 mm) being collected. Published
data [5]: bp 54°C (25 mm). Yield 39 g (60%). 1H NMR
OOBu-t
Me
OOBu-t
OOBu-t
H+
–H2O
t-BuOOH
–H+
Me
Me
Me
I
We have found that the reaction of tert-butyl hydro-
peroxide with acetone under certain conditions gives
1-tert-butoxypropan-2-one in a good yield. This com-
pound is formed via rearrangement of 2-tert-butyldi-
oxyprop-1-ene (II) resulting from elimination of pro-
ton from intermediate cation I (Scheme 2). The proc-
ess competes with the substitution reaction leading to
the formation of peroxy ketal.
Alkyl alkenyl peroxides were not isolated as indivi-
dual substances, but their formation as intermediates
617

GREBENSHCHIKOV et al.
618
1
spectrum (CDCl3), δ, ppm: 3.8 s (2H, CH2), 2.0 s
(3H, CH3), 1.0 s [9H, C(CH3)3]. 13C NMR spectrum
(CDCl3), δC, ppm: 208.7 (C=O), 74.4 [C(CH3)3], 68.9
(CH2), 27.6 (CH3), 26.8 (COCH3).
The H and 13C NMR spectra were recorded on
a Bruker DPX-300 spectrometer at 300 and 75 MHz,
respectively.
REFERENCES
1-Hydroxypropan-2-one. A heat-resistant glass
ampule was charged with 1 g (0.008 mol) of 1-tert-
butoxypropan-2-one and 25 g of a 0.025% solution of
sulfuric acid in acetone. The ampule was sealed and
placed in a thermostat heated to 100°C. After 60 min,
the ampule was cooled and opened, and the mixture
was diluted with water and extracted with diethyl ether
(3×20 ml). The extracts were combined, dried over
Na2SO4, and evaporated. Hydroxyacetone was iden-
tified as the corresponding 2,4-dinitrophenylhydra-
zone, mp 136°C; published data [6]: mp 137°C.
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5.6 t (1H, OH), 4.5 d (2H, CH2), 2.3 s (3H, CH3).
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