872 Chem. Mater., Vol. 23, No. 3, 2011
Massin et al.
(m, 6H), 1.22 (t, J = 7 Hz, 3H). 13C NMR (CD2Cl2): δ (ppm)
146.1, 128, 115.2, 111, 48.3, 47.8, 44.1, 10.7. IR (KCl, cm-1) 2103
(νN3). Anal. Calcd for C10H14N4: C, 63.13; H, 7.42; N, 29.45.
Found: C, 63.02; H, 7.47; N, 28.14. HR-MS (ESþ): [M þ H]þ
190.1293 (calcd. 190.1297).
protocol B from 4-diethylaminobenzaldehyde (1.77 g, 10 mmol)
and 4 (1.86 g, 10 mmol). After concentration, the resulting oil
was dissolved in water (50 mL) and extracted with dichloro-
methane (3 ꢀ 50 mL). The combined organic phases were dried
with Na2SO4, filtered and evaporated. The black solid was
crystallized from toluene. Yield 2 g (57%), dark solid. 1H
N,N-Bis(2-azidoethyl)aniline (3f). 3f was synthesized accord-
ingly starting from N-Phenyldiethanolamine (5.5 g, 30.2 mmol,
1 equiv) Et3N (4.6 mL, 33.3 mmol, 1.1 equiv) and methanesul-
fonyl chloride (5.2 mL, 66.6 mmol, 2.2 equiv) in Et2O (250 mL),
then sodium azide (7.8 g, 121 mmol, 4 equiv) in DMSO (100
mL). (6.6 g, 94%). 1H NMR (Acetone-d6): δ(ppm) 7.22 (t, J =
8 Hz, 2H), 6.83 (d, J = 8 Hz, 2H), 6.68 (t, J = 8 Hz, 1H), 3.59
(m, 8H). 13C NMR (Acetone-d6): δ(ppm) 147.7, 130.16, 118,
113.5, 51, 49.5. IR (KCl, cm-1) 2100 (νN3). Anal. Calcd for
NMR (CDCl3): δ 7.38 (d, 2H, J = 8.96 Hz), 7.01 (d, 1H, Jtrans
=
16 Hz), 6.76 (d, 1H, Jtrans = 16 Hz), 6.73 (s, 1H), 6.64 (d, 2H, J =
8.96 Hz), 3.41 (q, 4H, 7.02 Hz), 2.56 (s, 2H), 2.44 (s, 2H) 1.20 (t,
6H, J = 7.02 Hz), 1.06 (s, 6H). 13C NMR (CDCl3): δ 169.1,
155.4, 149.1, 138.3, 129.7, 123.7, 122.7, 121.0, 114.3, 113.5,
111.5, 77.2, 44.5, 42.9, 39.2, 31.9, 28.0, 12.6. IR (KCl, cm-1
)
2223 (νCN). Anal. Calcd for C23H27N3: C, 79.96; H, 7.88; N,
12.16. Found: C, 80.01; H, 7.85; N, 12.04. mp (toluene):
169-171 °C.
C
10H13N7: C, 51.94; H, 5.67; N, 42.40. Found: C, 51.34; H,
5.65; N, 42.39. HR-MS (ESþ): [M þ H]þ 232.1304 (calcd
(S,E)-2-(3-(4-(Ethyl(1-phenylethyl)amino)styryl)-5,5-dimethyl-
cyclohex-2-enylidene)malononitrile (1b). 1b was obtained accord-
ing to general protocol B from 2b (150 mg, 0.5 mmol.) and 4 (93
mg, 0.5 mmol.). The product is purified by chromatography on
silica, eluting withchloroform. Yield 60 mg (24%), deep red solid.
1H NMR (CDCl3): δ 7.39 (d, J = 9 Hz, 2H), 7.33 (t, J = 9 Hz,
2H), 7.27 (m, 3H), 7 (d, J = 16 Hz, 1H), 6.78 (m, 3H), 6.74(s, 1H),
5.19 (q, J = 7 Hz, 1H), 3.31 (m, 2H), 2.57 (s, 2H), 2.44 (s, 2H), 1.65
(d, J = 7 Hz, 3H), 1.11 (t, J = 7 Hz, 3H), 1.06 (s, 6H). 13C NMR
(CDCl3): δ 169.3, 155.4, 150.015, 142.1, 138.2, 129.7, 128.7, 127.3,
127, 124.4, 123.7, 121.5, 114.4, 113.6, 112.9, 75.8, 56.3, 43.2, 40.5,
32.4, 39.4, 32.1, 31, 28.2, 17.9. IR (KCl, cm-1) 2215 (νCN). Anal.
Calcd for C29H31N3: C, 82.62; H, 7.41; N, 9.97. Found: C, 81.44; H,
7.35; N, 9.81. m.p.: 133-135 °C.
((,E)-2-(3-(4-(Hexyl(1-phenylethyl)amino)styryl)-5,5-dimethyl-
cyclohex-2-enylidene)malononitrile (1c). Obtained according to
general protocol B from 2c (154 mg, 0.5 mmol.), 4 (93 mg, 0.5
mmol.). The product is purified by chromatography on silica,
eluting with chloroform. Yield 125 mg (52%). 1H NMR (CDCl3):
δ 7.38 (d, J = 9 Hz, 2H), 7.33 (t, J = 9 Hz, 2H), 7.27 (m, 3H), 7 (d,
J = 16 Hz, 1H), 6.79 (d, J = 16 Hz, 1H), 6.73 (m, 3H), 5.18 (q, J =
7 Hz, 1H), 3.17 (m, 2H), 2.56 (s, 2H), 2.44 (s, 2H), 1.64 (d, J = 7
Hz, 3H), 1.5 (m, 2H), 1.23 (m, 6H), 1.06 (s, 6H), 0.86 (t, J = 7 Hz,
3H). δ(ppm) 170.5, 169.3, 159.8, 155.4, 150.3, 142, 138.2, 129.7,
128.7, 127.3, 127.1, 124.3, 123.7, 121.5, 120.7, 114.4, 113.6, 113.1,
75.8, 56.6, 45.8, 46.6, 43.2, 42.8, 39.4, 32.1, 28.2, 27.9, 27.1, 26.9,
25.4, 22.7, 17.9, 14.1. IR (KCl, cm-1) 2223 (νCN). Anal. Calcd for
C23H27N3: C, 82.97; H, 8.23; N, 8.80. Found: C, 81.18; H, 8.11; N,
9.81.
232.1311).
4-((2-Azidoethyl)(ethyl)amino)benzaldehyde (2e). 2e was ob-
tained according to general protocol A from 3e (5 g, 26.3
mmol.), POCl3 (4.9 mL, 52.6 mmol.) and DMF (20 mL). Yield:
9 g (85%). 1H NMR (C2D2Cl4): δ(ppm) 10.4 (s, 1H), 8.42 (d, J =
8.8 Hz, 2H), 7.43 (d, J = 8.8 Hz, 2H), 4.2 (m, 6H), 1.9 (t, J = 6.9
Hz, 3H). 13C NMR (C2D2Cl4): δ(ppm) 189.8, 151.8, 132, 125.1,
110.9, 49, 48.6, 45.4, 11.9. IR (KCl, cm-1) 2102 (νN3), 1666. HR-
MS (ESþ): [M þ H]þ 219.1241 (calcd 219.1246).
4-(Bis(2-azidoethyl)amino)benzaldehyde (2f). 2f obtained ac-
cording to general protocol A from 3f (6.1 g, 26.3 mmol), POCl3
(4.9 mL, 52.6 mmol) and DMF (20 mL). Yield: 5.7 g (83%). 1H
NMR (CDCl3): δ(ppm) 9.76 (s, 1H), 7.75 (d, J = 8 Hz, 2H), 7 (d,
J = 8 Hz, 2H), 3.75 (m, 8H). 13C NMR (CDCl3): δ(ppm) 190.2,
151.3, 132.3, 126.6, 111.5, 50.6, 48.7. IR (KCl, cm-1) 2102 (νN3),
1673. Anal. Calcd for C11H13N7O: C, 50.96; H, 5.05; N, 37.82.
Found: C, 51.30; H, 5.42; N, 35.40. HR-MS (ESþ): [M þ H]þ
260.1266 (calcd 260.1260).
4-((2-Chloroethyl)(ethyl)amino)benzaldehyde (2g). Under argon,
N-Ethyl-N-hydroxyethylaniline (4.2 mL, 26.3 mmol, 1 equiv.)
was dissolved in dry DMF (20 mL, 0.26 mol, 10 equiv.), and the
solution was cooled to 0 °C with an ice bath. POCl3 (4.9 mL, 52.6
mmol, 2 equiv) was added slowly. After stirring at 40 °C for 8 h, the
green solution was added in ice water and neutralized with solid
K2CO3. The aqueous layer was extracted three times with CH2Cl2
(3 ꢀ 10 mL) and the combined organic phases were washed three
times with water (3 ꢀ 10 mL), once with brine(10 mL), dried over
sodium sulfate and concentrated under reduced pressure to afford
pure yellow oil. Yield: 5.5 g (98%). 1H NMR (CDCl3): δ(ppm) 9.88
(s, 1H), 7.88 (d, J = 9 Hz, 2H), 6.9 (d, J = 9 Hz, 2H), 3.86 (m, 4H),
3.68 (q, J = 7.1 Hz, 2H), 1.38 (t, J = 7.1 Hz, 3H). 13C NMR
(CDCl3): δ(ppm) 189.6, 151.4, 131.8, 125.3, 110.6, 51.6, 45.3, 39.8,
11.9. IR (KCl, cm-1) 1666, 1240. Anal. Calcd for C11H14NClO: C,
62.41; H, 6.67; N, 6.62. Found: C, 62.14; H, 6.79; N, 6.64. HR-MS
(ESþ): [M þ Na]þ 234.0659 (calcd 234.0662).
(E)-2-(3-(4-(Diphenylamino)styryl)-5,5-dimethylcyclohex-2-eny-
lidene)malononitrile (1d). Obtained according to general protocol B
starting from 3d (3.77 g, 13.8 mmol) and 4 (2.6 g, 13.8 mmol). After
removal of the solvents, the product was purified by chromatog-
raphy eluting with CH2Cl2 to give a red solid. Yield: 4.7 g (77%).
1H NMR (Acetone-d6): δ 7.59 (d, 2H, J = 10 Hz), 7.25 (m, 12H),
6.97 (d, 2H, J = 10 Hz), 6.82 (s, 1H), 2.65 (s, 2H), 2.61 (s, 2H), 1.1
(s, 6H). 13C NMR (Acetone-d6): δ(ppm) 170.4, 162.9, 156.4, 150.1,
147.8, 138.1, 130.5, 129.9, 128.1, 126.2, 125, 123, 122.5, 43.4, 39.4,
32.5, 28. IR (KCl, cm-1) 2215 (νCN). Anal. Calcd for C31H27N3: C,
84.32; H, 6.16; N, 9.52. Found: C, 82.08; H, 6.31; N, 11.63. HR-MS
(ESþ): Mþ° 441.2212 (calcd. 441.2205). m.p.(dichloromethane-
cyclohexane): 128 °C.
4-(Bis(2-chloroethyl)amino)benzaldehyde (2h). was synthesized
accordingly starting from N-Phenyldiethanolamine (4.7 g, 26.3
mmol, 1 equiv.), dry DMF (20 mL, 0.26 mol, 10 equiv.) and
POCl3((7.4 mL, 78.9 mmol, 3 equiv.). Brown solid 6.28 g (97%).
1H NMR (CDCl3): δ(ppm) 9.88 (s, 1H), 7.87 (d, J = 8.9 Hz, 2H),
6.85 (d, J = 8.9 Hz, 2H), 3.87 (m, 8H). 13C NMR (CDCl3): δ(ppm)
190.1, 132.2, 111.6, 102.2, 98.2, 54.2, 40.5. IR (KCl, cm-1) 1668,
1240. Anal. Calcd for (C11H13NCl2O): C, 53.68; H, 5.32; N, 5.69.
Found: C, 53.62; H, 5.44; N, 5.72. HRSM (ESþ): [M þ Na]þ
246.0445 (calcd 246.0452). m.p.(heptane): 87 °C.
(E)-2-(3-(4-((2-Azidoethyl)(ethyl)amino)styryl)-5,5-dimethylcy-
clohex-2-enylidene)malononitrile (1e). 1e was obtained accord-
ing to general protocol B from 3e (3 g, 13.8 mmol) and 4 (2.6 g,
13.8 mmol). The mixture was crystallized at -20 °C from a
toluene/pentane (1/1, v/v) mixture, filtered, and dried under a
(E)-2-(3-(4-(Diethylamino)styryl)-5,5-dimethylcyclohex-2-en-
ylidene)malononitrile (1a). 1a was obtained according to general
1
vacuum to afford pure red solid. Yield: 4.9 g (92%). H NMR