Unexpected synthesis of 2-(3,8-diaryl-6-oxo-2,7-diazaspiro[4.4]nona-2,8- dien-1-ylidene)malononitrile, a new heterocyclic system

Full text of DOI:10.1007/s10593-011-0833-x

Chemistry of Heterocyclic Compounds, Vol. 47, No. 6, September 2011 (Russian original Vol. 47, No. 6, June, 2011)
LETTERS TO THE EDITOR
UNEXPECTED SYNTHESIS OF 2-(3,8-DIARYL-
6-OXO-2,7-DIAZASPIRO[4.4]NONA-2,8-DIEN-
1-YLIDENE)MALONONITRILE,
A NEW HETEROCYCLIC SYSTEM
V. D. Dyachenko1*
Keywords: 2-amino-1,1,3-tricyano-1-propene, 2-(3,8-diaryl-6-oxo-2,7-diazaspiro[4.4]nona-2,8-dien-
1-ylidene)malononitrile, phenacyl bromides, alkylation.
2-Amino-1,1,3-tricyano-1-propene (1) obtained in the dimerization of malononitrile in an alkaline me-
dium [1] is used in organic synthesis primarily as a CH-acid component in the preparation of functionalized
pyridines [2–5].
We show here for the first time that the alkylation of tricyanopropene 1 using phenacyl bromides 2a and
2b in DMF in an alkaline medium gives previously unreported 2-(3,8-diaryl-6-oxo-2,7-diazaspiro[4.4]nona-
2,8-dien-1-ylidene)malononitriles 3a and 3b.
R
H
N
O
O
N
NH2
Br
NC
CN
+
NC
R
CN
2a,b
1
CN
R
3a,b
2, 3 a R = H, b R = Cl
The mechanism of this reaction, the scope of its applicability, and the chemical and biological properties
of malononitriles 3a and 3b are currently under study. The reaction mechanism presumably is as follows:
_______________
*To whom correspondence should be addressed, e-mail: chem@luguniv.edu.ua.
Taras Shevchenko Lugansk National University, 2 Oboronnaya St., Lugansk 91011, Ukraine.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 939–941, June, 2011. Original
article submitted May 11, 2011.
0009-3122/11/4706-0776©2011 Springer Science+Business Media, Inc.
776
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R
CN
NC
2a,b
NC
1 + 2a,b
NC
O
N
–H2O
NH2
CN
CN
R
O
R
R
Dimroth
rearrargement
CN
O
NH
3a,b
NC
N
NC
N
CN
R
CN
R
The IR spectra were taken on a Perkin-Elmer FIR spectrum One spectrometer for KBr pellets. The
1H NMR spectra were taken on a Bruker DR-500 spectrometer at 500 MHz in DMSO-d6 with TMS as internal
standard. The 13C NMR spectrum of malononitrile 3b was taken on a Varian VXR-300 spectrometer at 75 MHz
in DMSO-d6 with TMS as internal standard. The chemical ionization mass spectra were taken on a Crommass
Hewlett-Packard 5890/5972 GC/MS at 70 eV using an HP-5 MS column in CH2Cl2 solution. The reaction
course and purity of the products were monitored by thin-layer chromatography on Silufol UV-254 plates using
3:5 acetone–hexane as the eluent with iodine vapor and UV light as the developer. The melting points were
determined on a Koefler block.
2-(6-Oxo-3,8-diphenyl-2,7-diazaspiro[4.4]nona-2,8-dien-1-ylidene)malononitrile (3a). 10% Aqueous
KOH (11.2 ml, 20 mmol) and phenacyl bromide (2a) (4.0 g, 20 mmol) were added consecutively under stirring
to a solution of malononitrile dimer 1 (1.32 g, 10 mmol) in DMF (20 ml), stirred for 2 h, and diluted by the
addition of an equal volume of water. The precipitate formed was filtered off and washed with water, ethanol,
and hexane to give 2.63 g (75%) compound 2a; mp 244–246°C (acetic acid). IR spectrum, ꢀ, cm–1: 3332 (NH),
2228 (CꢀN), 1682 (C=O). 1H NMR spectrum, ꢁ, ppm (J, Hz): 4.95 (2H, s, CH2); 7.14 (1H, s, H-9); 7.37 (1H, t,
J = 7.5, H Ph); 7.48 (2H, t, J = 7.5, H Ph); 7.63 (2H, t, J = 8.0, H Ph); 7.75 (3H, m, H Ph); 8.09 (2H, d, J = 7.0,
H Ph); 12.62 (1H, br. s, NH). Mass spectrum, m/z (Irel, %): 349 [M–H]+ (100), 322 [M–H–HCN]+ (18). Found,
%: C 75.33; H 3.98; N 15.81. C22H14N4O. Calculated, % : C 75.42; H 4.03; N 15.99.
2-[3,8-Di(4-chlorophenyl)-6-oxo-2,7-diazaspiro[4.4]nona-2,8-dien-1-ylidene]malononitrile (3b) was
obtained analogously to malononitrile 2a using 4-chlorophenacyl bromide (2b) (4.66 g, 20 mmol). The yield of
compound 3b was 3.31 g (79%); mp 228–230°C (butanol). IR spectrum, ꢀ, cm–1: 3306 (NH), 2226 (CꢀN), 1692
1
(C=O). H NMR spectrum, ꢁ, ppm (J, Hz): 4.96 (2H, s, CH2); 7.21 (1H, s, H-9); 7.58 (2H, d, J = 8.4, H Ar);
13
7.75 (2H, d, J = 8.5, H Ar); 7.81 (2H, d, J = 8.4, H Ar); 8.13 (2H, d, H Ar); 12.76 (1H, br. s, NH). C NMR
spectrum, ꢁ, ppm: 31.67; 44.74; 94.67; 111.96; 113.49, 114.72; 126.20; 127.61; 129.25; 129.46; 129.66; 130.75;
133.28; 133.82; 134.63; 140.05; 192.73. Mass spectrum, m/z (Irel, %): 417 [M–H]+ (100). Found, %: C 62.88;
H 2.74; N 13.15. C22H12Cl2N4O. Calculated, % : C 63.02; H 2.88; N 13.36.
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