Synthesis of substituted cyclobutane and aniline derivatives by condensation of aliphatic aldehydes with malonodinitrile [6]

Full text of DOI:10.1023/B:RUGC.0000045882.03578.cf

Russian Journal of General Chemistry, Vol. 74, No. 7, 2004, pp. 1135 1136. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 7, 2004,
pp. 1227 1228.
Original Russian Text Copyright
2004 by Dyachenko.
LETTERS
TO THE EDITOR
Synthesis of Substituted Cyclobutane and Aniline Derivatives
by Condensation of Aliphatic Aldehydes with Malonodinitrile
V. D. Dyachenko
Shevchenko National Pedagogical University, Lugansk, Ukraine
Received September 18, 2003
Condensation of aliphatic carbonyl compounds
with malonodinitrile yields unstable alkenes which
dimerize to form mainly linear products and cyclo-
hexadienes [1 3].
In this work we found new unusual products of
such reaction. Condensation of isobutyraldehyde I
with malonodinitrile II in ethanol at 20 C yields sub-
stituted cyclobutane VII via intermediates III VI:
III
NC
NC
EtOH, O
NH
CN
CN
<
+
CN
NC
CHO
H2O
CN
+
NH
CN
O
2
I
II
III
IV
NC
NC
NC
EtO C
NC
EtO
EtOH
H O
2
NH3
2
NC CN
NC CN
NH NC CN
VII
VI
V
Condensation of malonodinitrile II with propion-
aldehyde VIII under the same conditions yields previ-
ously unknown substituted aniline XIII, presumably
via intermediates IX XII. The pathways of condensa-
tion of other aliphatic aldehydes with malonodinitrile
and cyanoacetic acid ester are under investigation.
II, O
NH
CN
IX
CN
C N CN
^
CHO
+
NH
CN
CN
O
2
VIII
IX
X
CN
NH
CN
CN
NH
CN
HCN
NH2
CN
XII
CN
XI
CN
XIII
1
070-3632/04/7407-1135 2004 MAIK Nauka/Interperiodica

1136
DYACHENKO
+
The structures of VII and XIII were proved by
single crystal X-ray diffraction; the results will be
published later.
(23) [M 1] , 170 (86), 156 (44), 143 (15), 129 (8),
116 (23), 102 (9), 89 (13), 77 (12), 63 (8), 51 (13), 39
(14). Found, %: C 71.18; H 6.08; N 22.74. C H N .
1
1
11
3
Calculated, %: C 71.33; H 5.99; N 22.68.
4
-Isopropyl-3,3-dimethyl-2-[(cyanoethoxycarbo-
nyl)methyl]-1,1-dicyanocyclobutane VII. Yield 77%,
1
The IR spectra were recorded on an IKS-40 spec-
trophotometer (mulls in mineral oil). The H NMR
spectra of VII and XIII were taken on Varian
Mercury-400 (400.397 MHz) and Bruker DR-500
(500.13 MHz) spectrometers, respectively, in DMSO-
d6 with TMS as internal reference. The mass spec-
trum of XIII was taken on a Kratos MS-890 device
mp 118 119 C (from EtOH). IR spectrum, , cm :
1
1
1
718 (C=O), 2255 sh (C N)]. H NMR spectrum, ,
3
ppm: 0.92 d and 1.03 d (3H each, 2Me, J 6.84 Hz),
.06 s (3H, Me), 1.27 s (3H, Me), 1.39 t (3H,
CH CH O, J 6.14 Hz), 2.03 m [1H, CHMe ], 2.43 d
1H, C H, J 6.80 Hz), 3.39 d (1H, C H, J 7.22 Hz),
.30 m (3H, CH and C H). Found, %: C 66.72; H
1
3
3
2
2
4
3
2
3
(
4
7
1
2
(
70 eV) with direct sample inlet.
.25; N 14.54. C H N O . Calculated, %: C 66.88;
1
6
21
3
2
H 7.37; N 14.62.
-Methyl-2,6-dicyano-3-ethylaniline XIII. Yield
7%, mp 122 123 C (from EtOH), fluoresces under
REFERENCES
4
6
1. Freeman, F., Chem. Rev., 1969, vol. 69, no. 5, p. 591.
. Freeman, F., Chem. Rev., 1980, vol. 80, no. 4, p. 329.
1
UV irradiation. IR spectrum, , cm : 1643 [ (NH )],
2
2
2
210, 2222 [ (C N)], 3275, 3360, 3451 [ (NH )].
2
1
H NMR spectrum, , ppm: 1.16 t (3H, CH CH ),
2
br.s (2H, NH ), 7.38 s (1H, C H). Mass spectrum,
m/z (I , %): 186 (15) [M + 1] , 185 (100) [M] , 184
3. Sharanin, Yu.A., Promonenkov, V.K., and Litvi-
nov, V.P., Malononitril (Malononitrile), Ser.: Organi-
cheskaya khimiya (Organic Chemistry), Moscow:
VINITI, 1991, vol. 20, part 1.
3
2
3
.17 s (3H, Me), 2.73 q (2H, CH , J 7.62 Hz), 6.09
2
5
2
+
+
rel
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 7 2004