2086
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 11, November, 2012
Dotsenko et al.
N, 11.87. C10H7ClN2OS (M = 238.70). Calculated (%): C, 50.32;
H, 2.96; N, 11.74. IR, /cm–1: 3310 (NH), 2215 (CN).
1H NMR (200 MHz, DMSOꢀd6), : 7.63 and 7.85 (both d,
2 H each, 4ꢀClC6H4, 3J = 8.2 Hz); 8.11 (s, 1 H, ArCH=); 8.83*
(br.s, 2 H, H2N+=).
(E)ꢀ3ꢀ(2ꢀChlorophenyl)ꢀ2ꢀcyanoꢀ1ꢀiminiopropꢀ2ꢀeneꢀ1ꢀsulfꢀ
enate (4b). Yield 70%, bright red crystals, m.p. 165—168 C
(decomp., EtOH—Me2CO (1 : 2) or AcOH). Found (%): C, 50.44;
H, 2.99; N, 11.83. C10H7ClN2OS (M = 238.70). Calculated (%):
C, 50.32; H, 2.96; N, 11.74. IR, /cm–1: 3310 (NH), 2215 (CN).
1H NMR (200 MHz, DMSOꢀd6), : 7.49—7.66 (m, 3 H, Ar);
7.91 (m, 1 H, Ar); 8.28 (s, 1 H, ArCH=); 8.98* (br.s, 2 H,
H2N+=).
(E)ꢀ2ꢀCyanoꢀ3ꢀ(4ꢀhydroxyꢀ3ꢀmethoxyphenyl)ꢀ1ꢀiminiopropꢀ
2ꢀeneꢀ1ꢀsulfenate (4c). Yield 73%, bright red fine crystalline powꢀ
der, m.p. 188—190 C (decomp., Me2CO). Found (%): C, 52.62;
H, 4.07; N, 11.33. C11H10N2O3S (M = 250.28). Calculated (%):
C, 52.79; H, 4.03; N, 11.19. IR, /cm–1: 3330, 3185 (NH), 2220
(CN). 1H NMR (200 MHz, DMSOꢀd6), : 3.79 (s, 3 H, MeO);
6.93 (d, 1 H, Ar, 3J = 8.2 Hz); 7.36 (d, 1 H, Ar, 3J = 8.2 Hz), 7.56
(s, 1 H, Ar); 7.98 (s, 1 H, ArCH=); 8.74** (br.s, 2 H, H2N+=);
10.32 (s, 1 H, OH).
pound 7a is identical with a sample obtained from aniline, triꢀ
ethyl orthoformate, and malononitrile12 (TLC data).
[(4ꢀEthylphenyl)aminomethylidene]malononitrile (7b). Yield
56%, creamꢀcolored fine crystalline powder, m.p. 248—250 C
(EtOH—acetone). Found (%): C, 72.91; H, 5.66; N, 21.51.
C12H11N3 (M = 197.24). Calculated (%): C, 73.07; H, 5.62;
N, 21.30. IR, /cm–1: 3200—3160 (NH), 2207 and 2223 (2 CN),
1
1665 (C=C). H NMR (500 MHz, CCl4—DMSOꢀd6), : 1.21
(t, 3 H, CH2CH3, 3J = 7.6 Hz); 2.60 (q, 2 H, CH2CH3, 3J = 7.6 Hz);
7.11 and 7.26 (both d, 2 H each, Ar, 3J = 8.3 Hz); 8.25 (d, 1 H,
HC=, 3J = 13.5 Hz); 10.87 (d, 1 H, NH, 3J = 13.5 Hz). 13C NMR
(125 MHz, CCl4—DMSOꢀd6), : 15.226 (CH2CH3); 27.652
(CH2CH3); 52.178 (C=C(CN)2); 113.578 (CN); 115.730 (CN);
117.662 (CAr); 128.183 (CAr); 136.980 (CAr); 140.192 (CAr);
154.460 (C=C(CN)2).
For an Xꢀray diffraction experiment, the crystals of (E)ꢀ3ꢀ
(2ꢀchlorophenyl)ꢀ2ꢀcyanoꢀ1ꢀiminiopropꢀ2ꢀeneꢀ1ꢀsulfenate (4b)
were obtained by its recrystallization from EtOH—Me2CO (1 : 2).
The crystals are monoclinic, C10H7N2OSCl; at 20 C, a =
= 15.0992(8) Å, b = 9.0095(5) Å, c = 7.7519(5) Å, = 101.878(6),
3
V = 1032.0(1) Å , Mr = 238.69, Z = 4, space group P21/c, dcalc
=
= 1.536 g cm–3, (MoꢀK) = 0.543 mm–1, F(000) = 488. The
intensities of 6253 reflections (2351 independent reflections,
Rint = 0.024) were measured on an Xcaliburꢀ3 diffractometer
(MoꢀK radiation, a CCD detector, graphite monochromator,
scan mode, 2max= 55). The unit cell parameters were calcuꢀ
lated from the collected data. The structure was solved by the
direct methods with the SHELXTL program package.35 The
hydrogen atoms were located in the difference electronꢀdensity
maps and refined isotropically. The structure was refined on F2
by the fullꢀmatrix leastꢀsquares method in the anisotropic apꢀ
proximation for the nonꢀhydrogen atoms. Final residuals are
wR2 = 0.103 for 2308 reflections and R1 = 0.037 for 1699 reflecꢀ
tions with F > 4(F) (S = 0.980). Comprehensive data for strucꢀ
ture 4b have been deposited with the Cambridge Crystallographic
Data Centre (CCDC No. 842953).
(E)ꢀ2ꢀCyanoꢀ3ꢀ(2ꢀfuryl)ꢀ1ꢀiminiopropꢀ2ꢀeneꢀ1ꢀsulfenate
(4d). Yield 88%, cherryꢀred bright needles, decomp. >140 C.
Found (%): C, 49.20; H, 3.07; N, 14.53. C8H6N2O2S (M = 194.21).
Calculated (%): C, 49.48; H, 3.11; N, 14.42. IR, /cm–1: 3310
1
(NH), 2220 (CN). H NMR (200 MHz, DMSOꢀd6), : 6.81,
7.27, and 8.12 (all m, 1 H each, 2ꢀfuryl); 7.95 (s, 1 H, ArCH=);
8.73* (br.s, 2 H, H2N+=).
Synthesis of (arylaminomethylidene)malononitriles 7a,b (genꢀ
eral procedure). A 10% aqueous solution of KOH (3.0 mL,
5.4 mmol) was added to a suspension of an appropriate 3ꢀaminoꢀ
thioacrylamide 2a,b (5 mmol) in EtOH (10 mL). The reaction
mixture was heated with stirring to homogenization. The resultꢀ
ing red solution was filtered through a paper filter. The mother
liquor was cooled and an excess of 32% H2O2 (5.0 mL, ~51.7 mmol)
was added dropwise. This initiated a vigorous exothermic reacꢀ
tion accompanied by oxygen evolution and rapid formation of
a light yellow precipitate. The mixture was stirred at 20 C for 2 h
and the precipitate was filtered off. To remove inorganic impuriꢀ
ties, it was washed with water and dissolved in acetone—EtOH
(1 : 1). The resulting solution was filtered through a paper filter.
After 3—4 days, product 7a,b was isolated from the mother liquor.
(Anilinomethylidene)malononitrile (7a). Yield 80%, light yelꢀ
low crystals, m.p. 250—252 C (EtOH—acetone) (subl., transꢀ
formed into large colorless needles; cf. Refs: m.p. 240—242 C,12
253—255 C,31,32 254—256 C,33 and 245—247 C34). Found (%):
C, 70.80; H, 4.16; N, 24.80. C10H7N3 (M = 169.19). Calculatꢀ
ed (%): C, 70.99; H, 4.17; N, 24.84. IR, /cm–1: 3200—3180 (NH),
2210 and 2224 (2 CN), 1650 (C=C). 1H NMR (200 MHz,
References
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3
DMSOꢀd6), : 7.11 (t, 1 H, C(4)HPh, J = 7.2 Hz); 7.42—7.27
3
5. E. N. Zil´berman, Reaktsii nitrilov [Reactions of Nitriles],
Khimiya, Moscow, 1972, p. 74 (in Russian).
(m, 4 H, Ar); 8.42 (d, 1 H, HC=, J = 13.7 Hz); 10.98 (d, 1 H,
NH, 3J = 13.7 Hz). MS (EI, 70 eV), m/z (Irel (%)): 170 [M + H]+
(11.2), 169 [M]+ (97.7), 168 [M – H]+ (11.5), 142 [M – HCN]+
(12.9), 104 [M – 65]+ (32.2), 77 [M – 92]+ (100), 66 [M – 103]+
(16.7), 65 [M – 104]+ (56.1), 64 [M – 105]+ (16.7), 52 [M – 117]+
(19.0), 51 [M – 118]+ (80.4), 50 [M – 119]+ (19.2). Comꢀ
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2749; (b) J. B. Payne, J. H. Deming, P. H. Williams, J. Org.
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26, 663; (d) V. V. Dotsenko, S. G. Krivokolysko, V. P. Litviꢀ
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Nauk, Ser. Khim., 2005, 2319]; (e) V. V. Dotsenko, S. G.
Krivokolysko, V. P. Litvinov, A. V. Gutov, Dokl. Akad. Nauk,
2007, 412, 4, 494 [Dokl. Chem. (Engl. Transl.), 2007, 412, 2, 29].
* The integral intensity of the signal is lowered because of partial
deuterium exchange.