Chemistry of 2-methylene-2,3-dihydrofuran-3-ones: XVIII. Reaction of oxalyl chloride with acetophenone and dibenzoylmethane

Article abstract of DOI:10.1023/A:1012393905104

Treatment of acetophenone and dibenzoylmethane with excess oxalyl chloride gave heterocyclization products, 2-(3-oxo-5-phenyl-2,3-dihydrofuran-2-ylidene)-5-phenyl-2,3-dihydrofuran-3-one and a mixture of 4-benzoyl-5-phenyl-2,3-dihydrofuran-2,3-dione with 4-benzoyl-2-dibenzoylmethylene-5-phenyl-2,3-dihydrofuran-3-one.

Full text of DOI:10.1023/A:1012393905104

Russian Journal of Organic Chemistry, Vol. 37, No. 1, 2001, pp. 116 118. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 1, 2001,
pp. 126 128.
Original Russian Text Copyright
2001 by E. Koz’minykh, Trapeznikova, Chupilova, Igidov, V. Koz’minykh
Chemistry of 2-Methylene-2,3-dihydrofuran-3-ones:
*
XVIII. Reaction of Oxalyl Chloride with Acetophenone
and Dibenzoylmethane
E. N. Koz’minykh, N. N. Trapeznikova, E. A. Chupilova,
N. M. Igidov, and V. O. Koz’minykh
Perm State Pharmaceutical Academy, P.O.Box 8519, Perm, 614051 Russia
fax: (3422)663906; e-mail: kvo@pi.ccl.ru
Received March 12, 1999
Abstract Treatment of acetophenone and dibenzoylmethane with excess oxalyl chloride gave heterocycliza-
tion products, 2-(3-oxo-5-phenyl-2,3-dihydrofuran-2-ylidene)-5-phenyl-2,3-dihydrofuran-3-one and a mixture
of 4-benzoyl-5-phenyl-2,3-dihydrofuran-2,3-dione with 4-benzoyl-2-dibenzoylmethylene-5-phenyl-2,3-di-
hydrofuran-3-one.
Trimethylsilyl enol ethers derived from methyl
ketones and some -diketones are known to react with
oxalyl chloride to give substituted 2,3-dihydrofuran-
we observed appearance and increase in intensity of
yellow orange color which could be ascribed to
initially formed compound Ic or Knoevenagel con-
densation product of Ic with acetophenone, 2-benzoyl-
methylene-5-phenyl-2,3-dihydrofuran-3-one (III):
2
,3-diones I [2 6]. Sychev [7] briefly reported on
the synthesis of 5-p-halophenyl-2,3-dihydrofuran-2,3-
diones Ia and Ib in poor yields (22% and 43%) by
keeping a mixture of para-substituted acetophenones
with oxalyl chloride in hexane for several days.
The possibility for Knoevenagel condensation of
compound Ic with acetophenone under the given
conditions follows from the results of heterocycliza-
tion of phenyl benzyl ketone by the action of oxalyl
chloride, which leads to formation of 4,5-diphenyl-2-
[benzoyl(phenyl)methylene]-2,3-dihydrofuran-3-one
(IV) [8, 9] (Scheme 2). However, we previously
found that 5-aryl-2,3-dihydrofuran-2,3-diones readily
react with carbonyl compounds containing an active
methylene group, following the Knoevenagel con-
densation pattern, but the products are stable cyclic
semiacetals, 2-hydroxy-2,3-dihydrofuran-3-ones V,
rather than 2-acylmethylene derivatives of 2,3-di-
hydrofuran-3-ones [10, 11] (Scheme 3).
1
2
I, R = Alk, Ar; R = H, Alk, Ph, COAlk, COPh, COOAlk;
Ia, R = Br; Ib, R = Cl.
We made an attempt to obtain 5-phenyl-2,3-di-
hydrofuran-2,3-dione (Ic) by the action of excess
oxalyl chloride on acetophenone for a long time at
room temperature. Surprisingly, we isolated in poor
yield a dark brown condensation product, 2-(3-oxo-
5
-phenyl-2,3-dihydrofuran-2-ylidene)-5-phenyl-2,3-di-
hydrofuran-3-one (II) (Scheme 1), which can be
regarded as a nonbenzoid oxa analog of Indigo. We
failed to isolate the desired 2,3-furandione Ic from
the reaction mixture, although during the first 24 h
We failed to obtain compound III by independent
synthesis, by the Wittig reaction of 2,3-furandione Ia
with benzoylmethylene(triphenyl)phosphorane (the
_
*
___________
For communication XVII, see [1].
1
070-4280/01/3701-0116$25.00 2001 MAIK Nauka/Interperiodica

CHEMISTRY OF 2-METHYLENE-2,3-DIHYDROFURAN-3-ONES: XVIII.
117
Scheme 1.
Scheme 2.
reaction resulted in complete tarring) [12], although
analogous compounds with a halogen atom in the
para-position of the phenacylidene fragment are
accessible.
a fragment ion peak with m/z 158 corresponding to
+
+
[M/2] . No ion with m/z 272 [M CO ] was detected;
2
therefore, an alternative lactone structure of 2-(2-oxo-
5-phenyl-2,3-dihydrofuran-3-ylidene)-5-phenyl-2,3-di-
hydrofuran-3-one (VI) can be ruled out.
By the action of excess oxalyl chloride on diben-
zoylmethane we obtained known 4-benzoyl-5-phenyl-
Scheme 3.
2
[
,3-dihydrofuran-2,3-dione (Id) (Ziegler’s furandione)
2, 5, 6] and the Knoevenagel condensation product of
Id with dibenzoylmethane, bright yellow 4-benzoyl-
-dibenzoylmethylene-5-phenyl-2,3-dihydrofuran-3-
2
1
one (VII) (Scheme 4). The H NMR spectrum of VII
provides little information on its structure, for only
aromatic proton signals were observed. Like other
R = H, CN, CONH ; X = Ar, OEt.
2
2
-acylmethylene-2,3-dihydrofuran-3-ones [12], com-
The structure of bis-furanone II was proved by
spectral data. In the mass spectrum of II we observed
pounds II and VII give rise to a dark red color on
treatment with 10% alcoholic alkali.
EXPERIMENTAL
The IR spectra were recorded on a Specord M-80
1
spectrometer in mineral oil. The H NMR spectra
were obtained on RYa-2310 (60 MHz) and Varian
VXP-300 (300 MHz) instruments using DMSO-d6
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 1 2001

1
18
KOZ’MINYKH et al.
Scheme 4.
or CDCl as solvent and TMS or HMDS as internal
Compound Id. Yield 5.0 g (67%). mp 133 134 C
(decomp.) [2]. C H O . M 278.26.
3
reference. The mass spectrum of II was measured
on a Kratos MS-30 instrument (direct sample admis-
sion into the ion source, emission current 1000 mA,
energy of ionizing electrons 70 eV, vaporizer tempera-
ture 120 C). The purity of the products was checked
by TLC on Silufol UV-254 plates using benzene di-
ethyl ether acetone (10:9:1) as eluent; development
with iodine vapor. The constants of 4-benzoyl-5-
phenyl-2,3-dihydrofuran-2,3-dione (Id) coincided with
those reported in [2].
1
7
10
4
Compound VII. Yield 10.0 g (77%). mp 139
1
1
40 C. IR spectrum, , cm : 1664, 1638 (C O,
1
C C); 1604, 1576 (C Carom). H NMR spectrum
(
%
CDCl ), , ppm: 7.04 8.02 m (20H, 4C H ). Found,
: C 80.67; H 4.02. C H O . Calculated, %:
32 20 5
3 6 5
C 79.33; H 4.16.
REFERENCES
2
-(3-Oxo-5-phenyl-2,3-dihydrofuran-2-ylidene)-
1. Koz’minykh, E.N., Igidov, N.M., Koz’minykh, V.O.,
Shavkunova, G.A., and Sof’ina, O.A., Russ. J. Org.
Chem., 2000, vol. 36, no. 9, pp. 1341 1345.
2. Ziegler, E., Eder, M., Belegratis, C., and Prewedo-
urakis, E., Monatsh. Chem., 1967, vol. 98, no. 6,
pp. 2249 2251.
5
-phenyl-2,3-dihydrofuran-3-one (II). Oxalyl
chloride, 10 ml (6-fold excess), was carefully added
with stiring to 2.40 g (0.02 mol) of acetophenone,
and the mixture was kept for 20 days at room tem-
perature. The dark brown needles were filtered off and
washed with ether. Yield 0.05 g (1.6%). mp 270 C
3
.
Saalfrank, R.W. and Lutz, Th., Angew. Chem., Int.
Ed. Engl., 1990, vol. 29, no. 9, pp. 1041 1042.
1
3
(
decomp.). IR spectrum, , cm : 1748 (C O), 1698
2
2
1
4. Kappe, C.O., Kollenz, G., and Wentrup, K., Hetero-
cycles, 1994, vol. 38, no. 4, pp. 779 784.
(C
C ). H NMR spectrum (DMSO-d ), , ppm:
6
4
.75 s (2H, 2CH), 7.40 7.95 m (10H, 2C H ). Mass
spectrum, m/z (I , %; peaks with I > 2% are given):
17 (5) [M+1] , 316 (28) [M] , 288 (2) [M CO] ,
70 (2), 260 (2) [M 2CO] , 244 (2), 226 (2), 211 (2),
02 (2), 193 (2), 171 (2), 158 (5) [M/2] , 139 (3),
22 (2), 106 (7), 105 (100) [PhCO] , 87 (3), 77 (65)
6 5
5
.
Shurov, S.N. and Andreichikov, Yu.S., Khimiya
pyatichlennykh 2,3-dioksogeterotsiklov (Chemistry of
Five-Membered 2,3-Dioxo Heterocycles), Perm:
Perm. Gos. Univ., 1994, pp. 5 54.
rel
+
+
+
3
2
2
1
+
+
6
.
Kollenz, G., Khimiya pyatichlennykh 2,3-dioksogete-
rotsiklov (Chemistry of Five-Membered 2,3-Dioxo
Heterocycles), Perm: Perm. Gos. Univ., 1994,
pp. 55 73.
+
+
+
[
C H ] , 69 (2) [OCCHCO] , 51 (18). Found, %:
6 5
C 76.29; H 3.65. C H O . Calculated, %: C 75.94;
2
0
12
4
H 3.82.
7. Sychev, D.I., Zh. Org. Khim., 1990, vol. 26, no. 12,
p. 2636.
Reaction of dibenzoylmethane with oxalyl
chloride. Oxalyl chloride, 20 ml (twofold excess),
was added with stirring at room temperature to a solu-
tion of 18.0 g (0.08 mol) of dibenzoylmethane in
8. Yates, P. and Weisbach, J.A., J. Am. Chem. Soc.,
1
963, vol. 85, no. 19, pp. 2943 2950.
9. Yates, P. and Weisbach, J.A., J. Am. Chem. Soc.,
100 ml of dry diethyl ether. The originally colorless
1963, vol. 85, no. 19, pp. 2950 2955.
mixture gradually turned lemon yellow. The mixture
was kept for 10 15 h, and the yellow precipitate of
10. Koz’minykh, V.O., Igidov, N.M., and Sokolo-
va, E.Yu., Karbonil’nye soedineniya v sinteze getero-
tsiklov (Carbonyl Compounds in the Synthesis of
Heterocycles), Saratov: Saratov. Gos. Univ., 1992,
part 1, p. 42.
11. Kozminykh, V.O., Konshina, L.O., and Igidov, N.M.,
J. Prakt. Chem., 1993, vol. 335, no. 8, pp. 714 716.
12. Koz’minykh, E.N., Doctoral (Pharm.) Dissertation,
4
-benzoyl-5-phenyl-2,3-dihydrofuran-2,3-dione (Id)
was filtered off and washed with dry diethyl ether.
The filtrate was evaporated, and the thick brown
residue was treated with 200 ml of water. We thus
isolated the second yellow crystalline product, 4-ben-
zoyl-2-dibenzoylmethylene-5-phenyl-2,3-dihydro-
furan-3-one (VII).
Perm, 1999.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 1 2001