Alkylidenemalononitriles
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
685
respectively) in CDCl3, chemical shifts are given relative to Me4Si.
Mass spectra were obtained on Shimadzu GCMSꢀQP2010Plus
spectrometer (capillary column SPBꢀ5 30 m × 0.25 mm, carrier
gas helium, temperature regime from 40 to 300 C at the rate of
8 deg min–1, injector temperature 280 C, source of ions temꢀ
perature 200 C, ionization energy 70 eV). Elemental composiꢀ
tion of the samples was determined on a Karlo Erba 1106 eleꢀ
mental analyzer.
The starting aldehydes, ketones, malononitrile, pyridine, and
morpholine were commercially available from Acros, dichloroꢀ
methane (reagent grade) from ComponentꢀReactant, which were
distilled or recrystallized before use.
Molybdenum hexacarbonyl (Acros) was recrystallized and
dried in a vacuum desiccator before use.
Reactions were carried out in a 10ꢀmL glass tube placed into
a 17ꢀmL stainless steel microautoclave with continuous stirring
and controlled heating or in a flask equipped with a reflux conꢀ
denser with stirring.
Reaction of carbonyl compounds with malononitrile catalyzed
by Mo(CO)6 (general procedure). The compound Mo(CO)6
(0.1—0.3 mmol), the ligand (morpholine or pyridine)
(0.1—0.3 mmol), ketone or aldehyde (10 mmol), malononitrile
(12 mmol), and dichloromethane (2 mL) (for solid ketones or
aldehydes) were placed into a stainless steel microautoclave
(V = 17 mL) or into a glass tube (the results of the parallel
experiments were virtually the same) under argon. The autoꢀ
clave (tube) was sealed and the reaction mixture was heated at
140 C for 5 h for ketones or at 20—40 C for 1—2 h for aldehydes
with stirring. After the reaction reached completion, the autoꢀ
clave (tube) was cooled to room temperature and opened, the
reaction mixture was filtered through a layer of silica gel, washꢀ
ing down with hexane. The solvent was evaporated, the residue
was distilled in vacuo or recrystallized from ethanol. The yields
are given in calculation based on the isolated alkylidenemalonoꢀ
nitrile. The structure of the synthesized compounds was estabꢀ
lished by spectroscopic methods and/or by their comparison with
known samples and literature data.
C(12)); 86.17 (C(13)); 112.09 (C(14), C(15)); 186.58 (C(1)).
Found (%): C, 78.17; H, 9.65; N, 12.18. C15H22N2. Calculatꢀ
ed (%): C, 78.21; H, 9.63; N, 12.16.
(Adamantꢀ2ꢀylidene)malononitrile (4). The yield was 95%,
m.p. 180—181 C (ethanol) (cf. Ref. 7: m.p. 180—182 C). IR,
/cm–1: 1595 (C=C), 2240 (CN). 13C NMR (CDCl3), : 27.02
(C(5), C(7)); 36.15 (C(6), C(10)); 38.92 (C(1), C(3)); 40.18
(C(4), C(8), C(9)); 77.80 (C(11)); 111.98 (C(12), C(13)); 193.7
(C(2)). Found (%): C, 78.75; H, 7.16; N, 14.05. C13H14N2. Calꢀ
culated (%): C, 78.75; H, 7.12; N, 14.13.
(Propꢀ2ꢀylidene)malononitrile (6a). The yield was 98%, b.p.
79—80 C (5 Torr) (cf. Ref. 8: b.p. 75 C (4 Torr)). IR, /cm–1
:
1600 (C=C), 2250 (CN). 13C NMR (CDCl3), : 24.28 (C(1),
C(3)); 80.15 (C(4)); 110.33 (C(5), C(6)); 174.55 (C(3)). Found (%):
C, 67.87; H, 5.69; N, 26.44. C6H6N2. Calculated (%): C, 67.90;
H, 5.70; N, 26.40.
(Heptꢀ2ꢀylidene)malononitrile (6b). The yield was 95%, b.p.
125—126 C (8 Torr) (cf. Ref. 8: b.p. 113—114 C (4 Torr)). IR,
/cm–1: 1600 (C=C), 2250 (CN). 13C NMR (CDCl3), : 13.89
(C(7)); 22.44 (C(6)); 22.52 (C(1)); 26.83 (C(4)); 29.70 (C(5));
37.75 (C(3)); 85.81 (C(8)); 111.76 (C(9)); 111.97 (C(10)); 182.80
(C(2)). Found (%): C, 73.98; H, 8.69; N, 17.33. C10H14N2. Calꢀ
culated (%): C, 74.03; H, 8.70; N, 17.27.
(Decꢀ2ꢀylidene)malononitrile (6c). The yield was 98%, b.p.
180—181 C (4 Torr). 13C NMR (CDCl3), : 14.10 (C(10));
22.70 (C(9)); 24.86 (C(1)); 29.08 (C(7)); 29.27 (C(5)); 29.54
(C(4)); 30.28 (C(6)); 33.08 (C(8)); 37.12 (C(3)); 84.59 (C(11));
111.57 (C(12)); 112.37 (C(13)); 179.15 (C(2)). Found (%):
C, 76.40; H, 9.86; N, 13.74. C13H20N2. Calculated (%): C, 76.42;
H, 9.87; N, 13.71.
(1ꢀCyclopropylethylidene)malononitrile (8). The yield was
98%, b.p. 91—92 C (4 Torr). 13C NMR (CDCl3, : 1.01 (C(4),
C(5)); 16.55 (C(1)); 27.95 (C(3)); 83.47 (C(6)); 112.43 (C(7));
112.49 (C(8)); 182.86 (C(2)). Found (%): C, 72.68; H, 6.07;
N, 21.25. C8H8N2. Calculated (%): C, 72.70; H, 6.10; N, 21.20.
4ꢀ[Nꢀ(2ꢀCyanoacetyl)amino]pentꢀ3ꢀenꢀ2ꢀone (10). The yield
was 98%, m.p. 102—103 C. 13C NMR (CDCl3), : 21.20 (C(5));
26.00 (C(7)); 29.35 (C(1)); 109.01 (C(3)); 110.37 (C(8)); 153.86
(C(4)); 162.68 (C(6)); 206.54 (C(2)). MS, m/z (Irel (%)): 166 [M]+
(100), 164 (70), 133 (35), 131 (58), 129 (65), 98 (8), 96 (20), 94
(32), 82 (10), 59 (15). Found (%): C, 57.78; H, 6.06; N, 16.91.
C8H10N2O2. Calculated (%): C, 57.82; H, 6.07; N, 16.86.
Benzylidenemalononitrile (12a). The yield was 99%, m.p.
81—82 C. 13C NMR (CDCl3), : 82.73 (C(8)); 112.67 (C(9));
113.81 (C(10)); 129.67 (C(3), C(5)); 130.83 (C(2), C(6)); 134.70
(C(4)); 160.13 (C(7)). Found (%): C, 77.88; H, 3.91; N, 18.21.
C10H6N2. Calculated (%): C, 77.91; H, 3.92; N, 18.17.
[4ꢀ(N,NꢀDimethylamino)benzylidene]malononitrile (12b).
The yield was 98%, m.p. 163—164 C. 13C NMR (CDCl3), :
39.90 (C(12), C(13)); 71.76 (C(9)); 111.63 (C(3), C(5)); 113.06
(C(10), C(11)); 116.05 (C(7)); 133.83 (C(2), C(6)); 154.28 (C(4));
158.11 (C(8)). Found (%): C, 73.02; H, 5.60; N, 21.38. C12H11N3.
Calculated (%): C, 73.07; H, 5.62; N, 21.30.
Cyclopentylidenemalononitrile (2a). The yield was 99%, b.p.
120—121 C (7 Torr) (cf. Ref. 8: b.p. 113—114 C (4 Torr)). IR,
/cm–1: 1610 (C=C), 2250 (CN). 13C NMR (CDCl3), : 25.42
(C(3), C(4)); 36.25 (C(2), C(5)); 81.40 (C(6)); 112.04 (C(7),
C(8)); 178.15 (C(1)). Found (%): C, 72.68; H, 6.08; N, 21.24.
C8H8N2. Calculated (%): C, 72.70; H, 6.10; N, 21.20.
Cyclohexylidenemalononitrile (2b). The yield was 98%, b.p.
118—119 C (4 Torr) (cf. Ref. 8: b.p. 137 C (10 Torr)). IR,
/cm–1: 1590 (C=C), 2240 (CN). 13C NMR (CDCl3), : 24.98
(C(4)); 27.83 (C(3), C(5)); 34.61 (C(2), C(6)); 82.09 (C(7));
111.70 (C(8), C(9)); 185.46 (C(1)). MS, m/z (Irel (%)): 146 [M]+
(30), 145 (32), 131 (30), 118 (20), 105 (28), 92 (18), 81 (15),
68 (15), 55 (100), 41 (30). Found (%): C, 73.91; H, 6.85; N, 19.24.
C9H10N2. Calculated (%): C, 73.94; H, 6.89; N, 19.16.
Cyclooctylidenemalononitrile (2c). The yield was 75%, b.p.
100—101 C (2 Torr). IR, /cm–1: 1595 (C=C), 2255 (CN).
13C NMR (CDCl3), : 25.08 (C5)); 25.21 (C(3), C(7)); 25.94
(C(4), C(6)); 37.75 (C(2), C(8)); 84.56 (C(9)); 112.53 (C(10),
C(11)); 182.57 (C(1)). Found (%): C, 75.75; H, 8.09; N, 16.17.
C11H14N2. Calculated (%): C, 75.82; H, 8.10; N, 16.08.
Cyclododecylidenemalononitrile (2d). The yield was 30%, b.p.
215—217 C (10 Torr). IR, /cm–1: 1592 (C=C), 2254 (CN).
13C NMR (CDCl3), : 23.10 (C(6), C(8)); 24.56 (C(5), C(9));
25.29 (C(3), C(11)); 26.78 (C(4), C(7), C(10)); 33.39 (C(2),
(4ꢀMethoxybenzylidene)malononitrile (12c). The yield was
1
99%, m.p. 108—108.5 C. H NMR, : 3.92 (s, 3 H, OCH3);
7.01—7.03 (d, 2 H, H(3) arom., H(5) arom.); 7.67 (s, 1 H, CH=C);
7.90—7.92 (d, 2 H, H(2) arom., H(6) arom.). 13C NMR (CDCl3),
: 55.86 (C(11), CH3); 78.37 (C(8)); 113.44 (C(9)); 114.52
(C(10)); 115.18 (C(3), C(5)); 124.03 (C(1)); 133.50 (C(2), C(6));
159.01 (C(7)); 164.88 (C(4)). Found (%): C, 71.68; H, 4.37;
N, 15.22. C11H8N2O. Calculated (%): C, 71.73; H, 4.38; N, 15.21.