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Y. Shigemitsu et al. / Dyes and Pigments 92 (2011) 580e587
5.10. 2-[(4-Dimethylaminophenyl)(methylsulfanyl)methylene]
malononitrile (7j)
1524, 1445, 1206. UV(ethanol)lmax nm(log
320(3.24), 226(4.10). 1H-NMR(CDCl3)
CH2e), 3.71(3H,s,NMe), 6.17(1H,dd,J
3
): 342(3.19), 335(3.21),
3.70e3.82(8H,brs,Ne
d
:
¼
2.7 Hz, 1.8 Hz, 4-H),
This compound was synthesized via the scheme in reference [8].
6.67(1H,dd,2.7 Hz, 0.9 Hz, 3-H), 7.15(1H,dd,0.9 Hz, 1.8 Hz, 5-H).
Mp 97 ꢁC. IR(KBr) nmax cmꢀ1: 2211(CN), 2190(CN), 1604, 1475.
UV(ethanol)lmax nm(log
3): 427(4.29), 322(3.94).
5.17. 2,3-Dicyano-3-(3-indolyl) acrylonitrile (10a)
5.11. 1-(4-Diethylaminophenyl)ethene-1,2,2-tricarbonitrile (8a)
This compound was synthesized via the scheme in reference
[8]. Mp:206e207 ꢁC. IR(KBr) nmax cmꢀ1:3262, 2223(CN), 1481,
This compound was obtained from 0.298 g of N,N-diethylaniline
mixed with 0.256 g of tetracyanoethylene in a similar manner to
that of 7a, giving 0.425 g (85% yield) of purple needles. Mp
133e135 ꢁC. IR(KBr) nmax cmꢀ1: 3275, 2979, 2212(CN), 1604, 1490,
1420, 1231, 1211, 1125. UV(ethanol)lmax nm(log 3): 249(3.73),
284 nm(3.78), 355 nm(3.98), 466 nm(4.21).
5.18. 2-Cyano-3-(3-indolyl)-3-dimethylamino acrylonitrile (10b)
1457, 1424. UV(ethanol)lmax nm(log
3): 526(4.63), 289(3.92),
258(3.93).
A solution of 0.218 g of 10a and 1.0 g of dimethylamine (exces-
sive volume) was gradually heated for 5 min. After cooling, the
precipitate was washed with water and was collected by filtration
and recrystallized from methanol to give 0.168 g (71% yield) of
white needles. Mp: 180 ꢁC. IR(KBr) nmax cmꢀ1: 3304(br,NH),
5.12. 2-{Diethylamino[(4-diethylaminophenyl)methylene]}
malononitrile (8b)
This compound was obtained from 0.250 g of 8a mixed with
0.100 g of dimethylamine in a similar manner to that of 7c, giving
2220(CN), 2182(CN), 1560, 1456, 1336, 1244. 1H-NMR(CDCl3)
d:
9.30(1H,brs,NH), 7.67(1H,d,J ¼ 3.0Hz,7-H), 7.24-7.46(1H,m,4,5,6-H),
0.106
IR(KBr) nmax cmꢀ1: 2971, 2203(CN), 2198(CN), 1603, 1519, 1437,
1195. UV(ethanol)lmax nm(log
): 477(2.23), 358(4.24). 1H-
NMR(CDCl3)
g
(85% yield) of white needles. Mp 119e121 ꢁC.
3.49(3H,brs,N-Me), 3.06(3H,brs,N-Me). UV(ethanol)lmax nm(log 3):
255(3.93), 277(4.07), 303(4.19), 326(4.17).
3
d: 1.20(5H,t,J ¼ 7.1 Hz, eCH2eCH3), 1.53(6H,s,NMe),
5.19. 2-Cyano-3-(3-indolyl)-3-morpholino acrylonitrile (10c)
3.39(5H,q,J ¼ 7.1 Hz, eCH2eCH3), 6.64(2H,d,J ¼ 9.1 Hz, 3,5-H),
7.22(2H,d,J ¼ 9.1 Hz, 2,6-H).
This compound was obtained from 0.218 g of 10a mixed
with excessive amount of morpholine in a similar manner to that
5.13. 2-[(4-Diethylaminophenyl)(morpholino)methylene]
malononitrile (8c)
of 10b, giving 0.267
Mp:198e199. IR(KBr) nmax cmꢀ1: 3649(NH), 2207(CN), 2199(CN),
1517, 1446, 1112, 753. 1H-NMR(CDCl3)
9.19(1H,s,NeH),
7.73(1H,d,J ¼ 3.3 Hz,2-H), 7.42e7.51(2H,m,aromatic-H), 7.27e7.34
(2H,m,aromatic-H), 3.88(8H,w,NeCH2eCH2eO). UV(ethanol)
lmax nm(log ): 256(3.67), 276(3.73), 312(3.96).
g
(96% yield) of white needles.
d
:
This compound was obtained from 0.125 g of 8a mixed with
0.100 g of morpholine in a similar manner to that of 7c, giving
0.123
IR(KBr) nmax cmꢀ1: 2969, 2912, 2856, 2201(CN), 2124(CN), 1603,
1509, 1198. UV(ethanol)lmax nm(log ): 369(4.36), 320(4.15),
224(4.31). 1H-NMR(CDCl3)
g
(80% yield) of yellow needles. Mp 172e174 ꢁC.
3
3
5.20. 2,3-Dicyano-3-(1-methyl-2-phenyl)indol-1-yl-acrylonitrile
(11a)
d
: 1.20(5H,t,J ¼ 7.1 Hz, eCH2eCH3),
3.40(5H,q,J ¼ 7.1 Hz, eCH2eCH3), 3.60e3.84(8H,brs,NeCH2e),
6.65(2H,d,J ¼ 9.1 Hz, 3,5-H), 7.27(2H,d,J ¼ 9.1 Hz, 2,6-H).
This compound was synthesized via the scheme in reference [8].
Mp:208e209 ꢁC. IR(KBr) nmax cmꢀ1: 2217(CN), 1515, 1471, 1394,
5.14. 1-(1-Methyl-1H-pyrrol-2-yl)ethene-1,2,2-tricarbonitrile (9a)
1083, 767, 750. 1H-NMR(CDCl3)
d: 7.40e7.79(10H,m,NH,4,5,6,7-
H,ph-H), 3.79(3H,S,NMe). UV(ethanol)lmax nm(log 3): 286(4.30),
A solution of 0.243 g of 1-methyl-1H-pyrrole and 0.384 g of
tetracyaniethylene in 20 ml of DMF was heated for 15 min at
50e60 ꢁC. After cooling, the precipitate was washed with water and
was collected by filtration and recrystallized from methanol to give
468(4.18).
5.21. 2-Cyano-3-(1-methyl-2-phenyl)indol-3-yl-3-dimethylamino
acrylonitrile (11b)
0.394
IR(KBr) nmax cmꢀ1: 3114, 2217(CN), 1539. UV(ethanol)lmax nm(log
): 389(4.28), 225(4.22).
g
(72% yield) of yellow grains, mp 180e184 ꢁC.
This compound was obtained from 0.308 g of 11a mixed with
excessive amount of dimethylamine in a similar manner to that of
10b, giving 0.302 g (93% yield) of white needles. Mp:178e179 ꢁC.
IR(KBr) nmax cmꢀ1: 2930, 2204(CN), 2195(CN), 1550, 1407, 748. 1H-
3
5.15. 2-{Dimethylamino[(1-methylpyrrol-2-yl)methylene]}
malononitrile (9b)
NMR(CDCl3)d: 2.78(3H,S,N-Me), 3.31(3H,S,N-Me), 3.75(3H,S,N-
Me), 7.28e7.51(9H,m,4,5,6,7-H,ph-H). UV(ethanol)lmax nm(log 3):
This compound was obtained from 0.091 g of 9a mixed with
0.050 g of dimethylamine in a similar manner to that of 7c, giving
0.098 g (82% yield) of transparent needles. Mp 114e116 ꢁC. UV(e-
289(4.12).
5.22. 2-Cyano-3-(1-methyl-2-phenyl)indol-3-yl-3-morpholino
thanol)lmax nm(log
3): 312(4.12), 225(4.21).
acrylonitrile (11c)
5.16. 2-[(1-Methylpyrrol-2-yl)(morpholino)methylene]
malononitrile (9c)
This compound was obtained from 0.161 g of 11a mixed with
excessive amount of morpholine in a similar manner to that of 10b,
giving 0.678 g (92% yield) of white needles. Mp:227e228 ꢁC.
IR(KBr) nmax cmꢀ1: 2958, 2860, 2207(CN), 2189(CN), 1513, 1486,
This compound was obtained from 0.277 g of 9a mixed with
0.150 g of morpholine in a similar manner to that of 7c, giving
0.243 g (67% yield) of transparent needles. Mp 154e158 ꢁC.
IR(KBr) nmax cmꢀ1: 3119, 2979, 2933, 2859, 2197(CN), 2080(CN),
1113,
7.31e7.46(5H,m,animotic-H), 3.76(3H,S,NMe), 2.95e4.00(8H,m,Ne
CH2eCH2eO). UV(ethanol)lmax nm(log ): 290 (4.32).
742.
1H-NMR(CDCl3)
d
:
7.54e7.66(4H,m,animotic-H),
3