Russian Journal of Organic Chemistry, Vol. 40, No. 6, 2004, pp. 912–913. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 6, 2004,
pp. 948–949.
Original Russian Text Copyright © 2004 by Popov, Korchagina, Ushchenko, Gross.
SHORT
COMMUNICATIONS
Synthesis of Ketones Containing a Diphenyl Ether Fragment
Yu. V. Popov, T. K. Korchagina, V. P. Ushchenko, and A. I. Gross
Volgograd State Technical University, pr. Lenina 28, Volgograd, 400131 Russia
Received February 14, 2004
In continuation of studies [1, 2] on the synthesis of
carbonyl compounds having a diphenyl ether fragment,
we effected acylation of m-phenoxytoluene (I) with
carboxylic acid chlorides and obtained ketones II–IX.
The isolated products contained 90–92% of the main
substance. As catalysts we used aluminum chloride,
antimony(V) chloride, and tin(IV) chloride. The reac-
tions were carried out in weakly polar solvents (1,2-di-
chloroethane, methylene chloride), as well as in polar
nitrobenzene. The highest selectivity and the greatest
yield were achieved using aluminum(III) chloride and
methylene chloride.
hydrochloric acid (to decompose the complex formed
between the product and AlCl3) and extracted with
methylene chloride. The extract was washed in suc-
cession with 10% hydrochloric acid, 10% aqueous
Na2CO3, and water until neutral reaction, and dried
over CaCl2. The solvent was distilled off, and the
residue was subjected to fractional distillation under
reduced pressure. Yield 10 g (70%), bp 185–186°C
(3 mm). IR spectrum, ν, cm–1: 1600–700 (Ar), 1676
(C=O), 3100–2900 (CH3). 1H NMR spectrum
(DMSO-d6), δ, ppm: 2.4 s (3H, CH3), 2.5 s (3H,
CH3CO), 6.7–7.95 m (8H, m-C6H5OC6H3). Mass spec-
trum, m/z (Irel, %): 226 (37.1) [M]+, 211 (100), 183
(7.1), 168 (5.88), 155 (14.7), 141 (4.71), 128 (10.6),
115 (8.8), 106 (12.4), 91 (10), 77 (37.7), 65 (10.6), 51
(23.5), 43 (21.8), 39 (11.8), 32 (10), 28 (42.4). Ketones
III–IX were synthesized in a similar way.
O
Me
I
1-(2-Methyl-4-phenoxyphenyl)hexan-1-one (III).
Yield 6 g (33%), bp 220–222°C (3 mm). IR spectrum,
ν, cm–1: 1600–700 (Ar), 1676 (C=O), 3100–2900
(CH3). Mass spectrum, m/z (Irel, %): 282 (11.6) [M]+,
267 (7.3), 253 (9.4), 239 (7.3), 225 (21.7), 211 (52.2),
183 (100), 167 (17.4), 155 (23.9), 141 (21.0), 127
(14.5), 115 (15.9), 107 (10.1), 91 (31.9), 77 (31.9), 65
(25.4), 51 (25.4), 40 (26.1).
O
Me
RCOCl, MCln
COR
II–IX
II, R = CH3; III, R = C5H11; IV, R = C7H15; V, R = C11H23;
VI, R = C15H31; VII, R = C17H35; VIII, R = C6H5; IX, R =
m-NO2C6H4; M = Al, n = 3; Sb, n = 5; Sn, n = 4.
1-(2-Methyl-4-phenoxyphenyl)octan-1-one (IV).
Yield 11 g (59%), bp 228–229°C (3 mm). IR spectrum,
ν, cm–1: 1600–700 (Ar), 1684 (C=O), 3100–2900
(CH3). Mass spectrum, m/z (Irel, %): 310 (14.7) [M]+,
281 (4.7), 267 (5.3), 253 (21.3), 239 (12), 225 (70.7),
211 (100), 183 (58.7), 167 (30.7), 155 (44.7), 141
(31.3), 127 (24.7), 115 (18), 107 (24), 91 (56), 77
(88.7), 65 (57.3), 57 (36.7), 51 (77.3), 40 (80).
Ketones II–V and VIII are colored liquids, while
compounds VI, VII, and IX are crystalline substances.
Their structure was confirmed by the IR, 1H NMR, and
mass spectra.
1-(2-Methyl-4-phenoxyphenyl)ethanone (II).
A suspension of 11 g (0.08 mol) of AlCl3 in 50 ml
of methylene chloride was cooled to 0°C (ice bath),
a mixture of 35 g (0.19 mol) of m-phenoxytoluene (I)
and 5 g (0.06 mol) of acetyl chloride was added
dropwise under stirring and cooling, and the mixture
was stirred for 1.5–2 h at 3–5°C. It was then poured
under stirring into a mixture of ice with concentrated
1-(2-Methyl-4-phenoxyphenyl)dodecan-1-one
(V). Yield 8 g (34%), bp 240–245°C (3 mm). IR spec-
trum, ν, cm–1: 1600–700 (Ar), 1680 (C=O), 3100–2900
(CH3). Mass spectrum, m/z (Irel, %): 366 (5.3) [M]+,
351 (5.9), 337 (5.9), 309 (5.9), 281 (5.3), 267 (7.2),
1070-4280/04/4006-0912 © 2004 MAIK “Nauka/Interperiodica”