Synthesis of new 2-substituted 2,5-dihydrofuranone derivatives and their chemical transformations

Full text of DOI:10.1134/S1070428009120240

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 12, pp. 1871–1872. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.A. Avetisyan, A.G. Alvandzhyan, K.S. Avetisyan, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 12,
pp. 1872–1873.
SHORT
COMMUNICATIONS
Synthesis of New 2-Substituted 2,5-Dihydrofuranone Derivatives
and Their Chemical Transformations
A. A. Avetisyan, A. G. Alvandzhyan, and K. S. Avetisyan
Erevan State University, ul. A. Manukyana 1, Erevan, 375025 Armenia
e-mail: avetisyan_ks@yahoo.com
Received May 28, 2008
DOI: 10.1134/S1070428009120240
2,5-Dihydrofuran-2-ones having functional substit-
uents in the 3-position constitute structural fragments
of many natural and synthetic biologically active com-
pounds [1–5]. One of the most general and convenient
methods of synthesis of functionally substituted furan-
2(5H)-ones is based on reactions of α-hydroxy ketones
with compounds containing an activated methylene
group [6–8].
In continuation of our studies in this field, in the
present communication we report on the synthesis and
chemical transformations of a new class of com-
pounds, 2,5-dihydrofuran-2-imines based on readily
accessible α-hydroxy ketones. We found that, contrary
to published data [9], tertiary α-hydroxy ketones react
with malononitrile to give mixtures of the correspond-
ing 2,5-dihydrofuran-2-imines I and products of their
subsequent reaction with the second malononitrile
molecule, 2-(2,5-dihydrofuran-2-ylidene)malono-
nitriles II, which were formed in good yields. Detailed
examination of this reaction with a view to find op-
timal conditions showed that the process occurs even
in the absence of a catalyst upon mixing of the reac-
tants in alcohol or benzene.
General procedures for the reactions of α-hy-
droxy ketones with malononitrile. a. The corre-
sponding α-hydroxy ketone and malononitrile, 50 mmol
each, were added to a solution of 0.115 g (5 mmol) of
metallic sodium in 25 ml of anhydrous ethanol. The
mixture was kept for 15–20 h at room temperature, the
solvent was distilled off under reduced pressure, the
residue was dissolved in benzene, and the precipitate
was filtered off and recrystallized from ethanol–water
(2:1) to isolate compound IIa or IIb. The benzene
solution was diluted with four volumes of hexane, and
the precipitate was filtered off and recrystallized from
heptane. We thus isolated compound Ia or Ib.
b. A mixture of 50 mmol of α-hydroxy ketone and
50 mmol of malononitrile in 25 ml of anhydrous
ethanol was kept for 15–20 h at room temperature. The
mixture was then treated as described above in a.
c. A mixture of 50 mmol of α-hydroxy ketone and
50 mmol of malononitrile in 25 ml of anhydrous ben-
zene was kept for 15–20 h at room temperature. The
solvent was partially distilled off under reduced pres-
sure, and the mixture was then treated as described
above in a.
Me
CN
O
CN
CN
2-Imino-4,5,5-trimethyl-2,5-dihydrofuran-3-car-
bonitrile (Ia). Yield 43 (a), 25 (b), 55% (c); mp 97–
98°C (oily substance [10]). IR spectrum, ν, cm–1: 2230
(CN), 1665 (C=N), 1075 (C–O–C), 985 (CH), 890
HO
R1
R2
R1
+
Me
NH
O
R2
Ia, Ib
1
(CH). H NMR spectrum, δ, ppm: 1.4 s (6H, CH3),
Me
CN
2.20 s (3H, CH3), 6.45 s (1H, NH). Found, %: C 64.01;
H 6.48; N 19.01. C8H10N2O. Calculated, %: C 63.98;
H 6.71; N 18.65.
R2
R1
+
CN
CN
O
2-Imino-4-methyl-5,5-pentamethylene-2,5-dihy-
drofuran-3-carbonitrile (Ib). Yield 38 (a), 17 (b),
60% (c); mp 89–90°C. IR spectrum, ν, cm–1: 2225
IIa, IIb
R1 = R2 = Me (a), R1R2 = (CH2)5 (b).
1871

AVETISYAN et al.
1872
1
(CN), 1660 (C=N), 1075 (C–O–C), 980 (CH), 885
(CH). H NMR spectrum, δ, ppm: 1.30–1.40 m (2H,
CH2), 1.45–1.68 m (8H, CH2), 2.40 s (3H, CH3), 6.50 s
(1H, NH). Found, %: C 69.51; H 7.41; N 14.42.
C11H14N2O. Calculated, %: C 69.45; H 7.42; N 14.72.
oil. The H NMR spectra were measured on a Varian
1
Mercury-300 instrument at 300 MHz using hexa-
methyldisiloxane as internal reference.
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198°C. IR spectrum, ν, cm–1: 3084, 3056, 2992, 2230
(CN), 1620, 1580, 1560, 1435, 1390, 1345, 1210,
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