Synthesis of 1-(3-Phenoxyphenyl)butane-1,3-dione from ethyl acetoacetate

Full text of DOI:10.1134/S1070363213100253

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 10, pp. 1949–1951. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © Yu.V. Popov, T.K. Korchagina, G.V. Kalmykova, L.A. Losevskaya, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83,
No. 10, pp. 1743–1745.
LETTERS
TO THE EDITOR
Synthesis of 1-(3-Phenoxyphenyl)butane-1,3-dione
from Ethyl Acetoacetate
Yu. V. Popov, T. K. Korchagina, G. V. Kalmykova, and L. A. Losevskaya
Volgograd State Technical University, ul. Lenina 28, Volgograd, 400131 Russia
e-mail: galinakalmykova@yandex.ru
Received March 28, 2013
DOI: 10.1134/S1070363213100253
1,3-Diketones occupy an important place among
various diphenyl oxide derivatives [1]. The presence of
two reaction sites in the molecule makes them
indispensable synthons for obtaining the new sub-
stances possessing a high biological activity. For ex-
ample, 1,3-diketones can be used for the synthesis of
3-hydroxyketones, pyrazolo[5,1-c]-1,2,4-triazines [2],
N-substituted aminopyridones [3], flavones, isoxazoles
[4] and also as ligands in metal-polymer compounds
[5], in polymer chemistry to improve dispersion of
thermostabilizers in the compositions of halogenated
polymers [6].
Currently, the synthesis of 1,3-dicarbonyl com-
pounds containing diphenyloxide fragment is promising
for obtaining new biologically active substances.
_
O
O
C
O
C
O
C
Na+
Cl
H3C
OC2H5
+
C
H
I
II
O
O
C
O
C
CH3
OC2H5
CH
C
_NaCl
O
III
Acylation of sodium enolate of ethyl acetoacetate
with 3-phenoxybenzoyl chloride was used for con-
struction of the dicarbonyl system.
reactivity. Therefore C-derivatives are formed.
Subsequent ketone cleavage of the product of C-
acylation results in the desired 1-(3-phenoxyphenyl)-
butane-1,3-dione.
O
C
O
C
The reaction of sodium enolate of ethyl aceto-
acetate I with 3-phenoxybenzoyl chloride II was
carried out at room temperature at vigorous stirring for
5 h. The hydrolysis of the resulting ethyl 3-oxo-2-(3-
phenoxybenzoyl)butanoate III was performed at 100°C
for 2 h.
O
H2O
CH3
C
III
H2
IV
Although the excess electron density is located
predominantly at the oxygen atoms, which are more
electronegative compared with the carbon atoms, the
central carbon atom possesses the most nucleophilic
The obtained dione IV is pale yellow finely
dispersed crystalline solid melting at 125–130°C. The
yield was 65%.
1949

1950
POPOV et al.
1-(3-Phenoxyphenyl)butane-1,3-dione IV exist as
data which is due to intramolecular transfer of the proton
with the simultaneous shift of the bonding electrons.
both diketone and keto-enol forms as show the spectral
H
O
O
O
C
O
C
C
C
O
O
CH3
C
C
CH3
H
H2
VA
V
H
O
C
O
C
O
CH3
C
H
VC
The presence of conjugated bonds and the
formation of intramolecular hydrogen bond make the
enol form more stable, therefore the enolization degree
increases significantly.
anhydrous ether. The mixture was stirred for 5 h, then
poured into 150 mL of water, and the organic layer
was separated. The aqueous layer was extracted with
diethyl ether (2×50 mL). The organic layers were
combined, washed until pH 7, dried over Na2SO4 and
concentrated. Yield 7.3 g (90%), oily liquid, nD20
1.5785. IR spectrum, ν, cm–1: 2962–3058 (C–H), 1750
(C=O, ether), 1680 (C=O, diketone), 1298 (С–С, CH2),
The structure of the synthesized 1,3-diketone was
confirmed by IR, 1H NMR spectroscopy and gas
chromatography-mass spectrometry.
1
The IR spectrum of the product obtained contains
the absorption bands characteristic of the keto group
(1714 cm–1) and C=O involved into an intramolecular
hydrogen bond (1612–1661 cm–1) and the absorption
band corresponding to the stretching vibrations of the
1258 (C–O–C). H NMR spectrum, δ, ppm: 0.8–1.32
m (3Н, СН3), 1.8–2.25 m (3Н, СН3), 4.2–4.25 m (2Н,
СН2), 4.69 s (Н, СН), 6.94–7.76 m (9Н, С6Н5ОС6Н4).
Mass spectrum, m/z (Irel, %): 326 (2) [M]+, 197.2 (100),
140 (5).
1
OH groups (3058–3100 cm–1). In the H NMR spec-
trum of 1-(3-phenoxyphenyl)butane-1,3-dione there
were signals of ketone and enol forms. The signals of
protons of CH3 and CH2 groups of the keto form were
registered at 0.8–2.25 and 4.3 ppm, respectively. A
signal of vinyl CH group at 6.3 ppm indicates the
presence of keto-enol tautomers. The protons of OH
groups resonate in a very weak field (16 ppm). The
high value of the chemical shift of the proton of the
enol hydroxy group is caused by intramolecular
hydrogen bond between this hydroxyl and a carbonyl
group.
1-(3-Phenoxyphenyl)butane-1,3-dione (IV). A mix-
ture of 2-ethoxy-1-(3-phenoxyphenyl)butane-1,3-dione
(III) and water was refluxed for 2 h. The precipitate
formed was filtered off and washed with cyclohexane.
The final product was recrystallized from methanol.
Yield 4.2 g (65%), yellow crystals, mp 125–130°C. IR
spectrum, ν, cm–1: 2740–2890 (OH), 2900–3300 (C–H),
1780, 1696 (C=O), 1546 (C=C), 1294 (CH3). 1H NMR
spectrum, δ, ppm: 0.8–2.25 m (3Н, СН3), 16.0 s (Н,
ОН), 4.2–4.25 m (2Н, СН2), 6.03 s (Н, =СН), 6.94–
7.76 m (9Н, С6Н5ОС6Н4). Mass spectrum, m/z (Irel,
%): 254 (100) [M]+, 255 (66) [M + Н]+, 253 (26), 197
(5), 161 (3).
Ethyl 3-oxo-2-(3-phenoxybenzoyl)butanoate (III).
To a mixture of 100 mL of absolute diethyl ether and
0.6 g (25 mmol) of sodium was added dropwise under
cooling while stirring 3.5 g (27 mmol) of ethyl aceto-
acetate. Then the reaction mixture was incubated over-
night. To the obtained sodium enolate of ethyl aceto-
acetate I was added with stirring a solution of 5.8 g
(25 mmol) of 3-phenoxybenzoyl chloride in 50 mL of
The IR spectra were recorded on a Specord M 82
1
spectrometer. The H NMR spectra were registered on
a Varian Mercury 300 BB instrument in CDCl3,
internal reference hexamethyldisiloxane. Mass spectra
were taken on a MAT-11 Variant (70 eV).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013

SYNTHESIS OF 1-(3-PHENOXYPHENYL)BUTANE-1,3-DIONE
1951
2003, vol. 33, no. 12, p. 2087.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 10 2013