Reactions of 2,2-disubstituted 1,1-dicyanoethenes with β- dimethylaminoacrolein aminal and 3-dimethylamino-1,1,3-trimethoxypropane

Article abstract of DOI:10.1007/s11172-008-0219-0

A reaction of 2,2-disubstituted 1,1-dicyanoethenes with β-dimethylaminoacrolein aminal and 3-dimethylamino-1,1,3-trimethoxypropane leads to substituted 6,6-dicyano-1-dimethyl-aminohexatrienes and an organic salt containing 1,1,9,9-tetracyano-2,8-diphenylnona-2,4,6,8-tetraenide as the anion and (dimethylaminopropenylidene)dimethylammonium as the cation, on the basis of which new cation-anionic polymethine dyes were obtained.

Full text of DOI:10.1007/s11172-008-0219-0

Russian Chemical Bulletin, International Edition, Vol. 57, No. 8, pp. 1671—1675, August, 2008
1671
Reactions of 2,2ꢀdisubstituted 1,1ꢀdicyanoethenes
with βꢀdimethylaminoacrolein aminal and 3ꢀdimethylaminoꢀ
1,1,3ꢀtrimethoxypropane
Zh. A. Krasnaya, E. O. Tret´yakova, V. V. Kachala, and S. G. Zlotin
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: kra@ioc.ac.ru
A reaction of 2,2ꢀdisubstituted 1,1ꢀdicyanoethenes with βꢀdimethylaminoacrolein aminal
and 3ꢀdimethylaminoꢀ1,1,3ꢀtrimethoxypropane leads to substituted 6,6ꢀdicyanoꢀ1ꢀdimethylꢀ
aminohexatrienes and an organic salt containing 1,1,9,9ꢀtetracyanoꢀ2,8ꢀdiphenylnonaꢀ2,4,6,8ꢀ
tetraenide as the anion and (dimethylaminopropenylidene)dimethylammonium as the cation,
on the basis of which new cationꢀanionic polymethine dyes were obtained.
Key words: unsaturated dinitriles, βꢀdimethylaminoacrolein aminal, 3ꢀdimethylaminoꢀ
1,1,3ꢀtrimethoxypropane, polyenes, cationꢀanionic dyes.
Earlier, we have developed methods for the synthesis
of ωꢀdimethylaminoaldehyde aminals and 1ꢀdialkylꢀ
aminoꢀ1,3,3ꢀtrimethoxypropanes, which, being highly
reactive, readily undergo condensation with various
CHꢀacids in the absence of a catalyst (and often of a
solvent), leading to various polyfunctional conjugated
polyenes, many of which possess unusual spectral proꢀ
perties, whereas some of them are polymethine dyes or
intermediate products for their synthesis.1 The reaction is
characteristic, in particular, for the carbonyl compounds,
in which the labile proton is located not only near the
carbonyl group, but also is separated from it by one or two
double bonds or by a heterocycle.2
1,3,3ꢀtrimethoxypropane 2 (see Ref. 12) with unsaturated
dinitriles 3—6 has been studied.
R1
R2
CN
CN
3—6
Comꢀ
pound
3
R1
R2
Comꢀ
pound
5
R1
R2
Me
Et
Ph
Ph
Me
Me
cycloꢀC6H11
cycloꢀC3H5
4
6
Recently, we have studied interaction of these reagents
with CHꢀacids containing dicyanomethylidene group,
including ones with cyclic alkylidenemalononitriles,3
3ꢀcyanoꢀ2ꢀdicyanomethylideneꢀ4,5,5ꢀtrimethylꢀ2,5ꢀdihydroꢀ
furan,4 3ꢀ(dicyanomethylidene)indanꢀ1ꢀone, and 1,3ꢀbisꢀ
(dicyanomethylidene)indane.5 It turned out that the
reactions under study take different directions depending
on the conditions and result in the formation of analogs
of ketocyanine dyes, polycyanopolymethine salts, which
are anionic dyes, ωꢀdimethylaminopolyene dinitriles conꢀ
taining dihydrofuran ring, and other compounds.
The interest to the polyene donorꢀacceptor chroꢀ
mophores, having nitrile groups in the acceptor fragment,
is caused by the fact that some compounds of this type
have nonlinear optical properties, as well as other interꢀ
esting and unusual spectral features.6—10
We assumed that the reaction at the methyl or methylꢀ
ene group in the dinitriles 3—6 will result in the obtaining
the earlier unknown substituted 6,6ꢀdicyanoꢀ1ꢀdimethylꢀ
aminohexatrienes, which are merocyanine dyes.
However, it turned out that when aminal 1 and reagent
2 react with dinitrile 3 in benzene, a cyclodimerization
of the latter takes place to form (dimethylaminoꢀ
propenylidene)ꢀdimethylammonium salt 7 in high yield.
When the reaction of aminal 1 with dinitrile 3 is carried
out solventꢀfree, salt 7 is obtained in low yield (15%),
whereas the earlier undescribed 1,1,9,9ꢀtetracyanoꢀ
2,8ꢀdiphenylnonaꢀ2,4,6,8ꢀtetraenide salt 8, which is an
anionic dye, becomes the major product (46% yield)
(Scheme 1).
A solventꢀfree interaction of dinitrile 3 with reagent 2
takes predominantly another direction, leading to the forꢀ
mation of a mixture of triene ξꢀaminodinitrile 9 and salt 8
in the ratio 3 : 1 (UV spectral data). Dinitrile 9 was isoꢀ
In the present work, a condensation of βꢀdimethylꢀ
aminoacrolein aminal 1 (see Ref. 11) and 3ꢀdimethylaminoꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1639—1643, August, 2008.
1066ꢀ5285/08/5708ꢀ1671 © 2008 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
Krasnaya et al.
Scheme 1
–
CN
Ph
NH
+
NMe2
a
Me2N
CN
CN
Ph
Me
Ph
CN
CN
NMe2
NMe2
+
7, 73%
Me2N
Me
CN
CN
γ
α
3
1
7
5
3
1
–
+
NMe2
8
2
b
9
+
7
NC
CN Me2N
6
4
β
Ph
Ph
15%
8, 46%
a. In benzene, 20 °C, 24 h. b. Solventꢀfree, 20 °C, 24 h.
Scheme 2
Ph
ξ
Ph
CN
CN
δ
β
NMe2 OMe
OMe
α
CN
a
b
7
+
+
8
Me2N
ε
γ
MeO
Me
CN
3
2
9
a. In benzene, 50—55 °C, 2.5 h. b. Solventꢀfree, 55—60 °C, 3 h.
lated from this mixture in pure form by chromatography
on Al2O3 (Scheme 2).
there was no literature reports on the reactions in which
alkylidenemalononitriles would have transferred a dicyanoꢀ
methylene fragment.
On the reaction of dinitrile 4 with reagent 2, substiꢀ
tuted triene ξꢀaminodinitrile 11 was obtained in 34% yield
(see Scheme 3).
Aminal 1 and reagent 2 react otherwise with dinitrile
4, containing no Me group at the double bond. The reacꢀ
tion of dinitrile 4 with aminal 1 at 20—25 °C leads only to
4,4ꢀdicyanoꢀ1ꢀdimethylaminobutadiene 10 (Scheme 3).
We observed similar transformation in the reaction of
aminal 1 with cyclic alkylidenemalononitriles.3 Earlier,
The interaction of dinitriles 5 and 6 with aminal 1 leads
to a mixture of trienes 12 or 13 and diene 10 (Scheme 4).
Scheme 3
Scheme 4
R
Ph
Et
CN
CN
R
CN
CN
CN
1
Me2N
+ 10
Me
CN
4
12, 13
5, 6
1
2
R = cycloꢀC6H11 (5, 12), cycloꢀC3H5 (6, 13)
a
b
Trienes 12 and 13, being the major products in the
reaction of dinitriles 5 and 6 with aminal 1 in anhydrous
benzene (50—60 °C), were isolated in pure form by chroꢀ
matography on Al2O3.
Ph
CN
CN
Me2N
Me2N
The structures of the synthesized substituted 6,6ꢀdiꢀ
cyanoꢀ1ꢀdimethylaminohexatrienes 9, 11—13 were
established on the basis of the singleꢀdimensional and
twoꢀdimensional NMR spectra on the 1H and 13C nuclei,
as well as on the UV and mass spectral data.
CN
Me CN
10, 40%
11, 34%
a. Solventꢀfree 20—25 °C, 24 h. b. In benzene or solventꢀfree,
60 °C, 3 h.

Polyene
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1673
1
Table 1. H and 13C NMR spectral data for triene dinitriles 9, 11—13
Atom
δ (J/Hz)
9
11
12
13
1H
13C
1H
13C
1H
13C
1H
13C
α
β
γ
—
—
59.59
168.20
112.26
—
—
59.53
168.73
128.55;
—
—
68.04
176.24
114.35
—
—
70.42
171.78
115.47
6.38
2.16 (Me)
6.22
6.25
3Jγ,δ = 13.3
15.28 (Me)
3Jγ,δ = 14.4
3Jγ,δ = 14.4
δ
ε
6.71
155.13
102.67
6.56
155.73
7.46
147.54
100.50
7.54
149.02
100.34
3Jδ,ε = 12.8
3Jδ,ε = 12.0
3Jδ,ε = 11.8
3Jδ,ε = 12.0
5.81
5.55
99.26
5.34
5.36
3Jε,ξ = 14.0
3Jε,ξ = 12.0
3Jε,ξ = 12.4
3Jε,ξ = 12.4
ξ
CN
7.50
—
159.81
117.70,
117.08
44.87,
37.55
135.35
128.59
128.39
129.38
7.30
—
159.45
118.89,
117.74
44.87,
37.54
138.32
128.52
128.23
129.36
6.90
—
153.63
116.86,
116.75
40.20
6.91
—
153.99
116.29,
116.02
39.80
Me2N
3.11,
2.98
—
7.27
7.46
7.46
3.11,
3.00
—
7.23
7.45
7.44
3.01
3.09
1*
2
3
2.82
1.85; 1.73
1.88; 1.35
1.79
43.14
30.78
26.59
25.57
1.74
1.10; 0.82
—
13.42
8.15
—
4
—
—
* Positions 1—4 are related to the atoms of substituent in βꢀposition.
Assignment of signals in the 1H and 13C NMR spectra
was performed on the basis of twoꢀdimensional spectra
COSY, HSQC, and HMBC. Configurations of the double
bonds were established on the basis of the NOESY spectra
and the values of the vicinal spinꢀspin coupling constants
of the methine protons Hγ—Hδ, Hδ—Hε, Hξ—Hε. Thus in
the NOESY spectra of compounds 9 and 11, a correlation
of the Nꢀmethyl protons with Hε was recorded, as well as
of orthoꢀ and metaꢀphenyl protons with Hδ, which, along
the UV spectrum: λmax = 312 nm belongs to the cation,
whereas λmax = 680 nm (in EtOH) or 720 nm (in CHCl3)
to tetracyanononamethine anion.
The iminium cation of salt 8 can be easily exchanged
for the cation of a cyanine dye, resulting in the formation
of new cationꢀanionic polymethine dyes 14—16 in 40—45%
yield as the dark violet crystals, in the electron spectrum
of which, the absorption maxima (λmax) correspond to the
λmax of the cationic and anionic components. In dye 16,
3
3
with the values of the constants Jδ−ε and Jε−ξ being
12—14 Hz (Table. 1), indicates the Eꢀconfiguration of
the double bonds and the sꢀtransꢀconformation of the
diene fragment. Similarly, in compounds 12 and 13
the values of the vicinal spinꢀspin coupling constants for
protons Hγ—Hδ, Hδ—Hε, and Hξ—Hε (11.8—14.4 Hz)
also indicate the Eꢀconfiguration of the double bonds,
whereas a correlation between the mentioned protons in
the NOESY spectra, the sꢀtransꢀconformation of the
diene fragment.
Triene dinitriles 9, 11—13 have one absorption maxiꢀ
mum (λmax = 485—490 nm) in the UV spectrum with high
extinction coefficient (ε = 66000—102000). The presence
of intensive signals of molecular ions is characteristic of
the mass spectra of dinitriles 9, 11—13.
CN
CN
7
5
3
1
–
8
2
NC
CN
6
4
Cat+
Ph
Ph
14—16
S
S
S
S
14: Cat1
=
+
N
N
Et
Et
S
15: Cat2
16: Cat3
=
=
+
β
β
N
N
α
γ
γ
The structures of salts 7 and 8 were confirmed by the
1H NMR and UV spectra and elemental analysis data. In
the UV spectrum of salt 7, there is one absorption maxiꢀ
mum (λmax = 312 nm) belonging to the cation, viz.,
(dimethylaminopropenylidene)dimethylammonium. Tetraꢀ
cyanononamethine salt 8 has two absorption maxima in
Et
Et
S
δ
+
N
N
α
ε
Et
Et

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
Krasnaya et al.
only one absorption band is observed, since the λmax
values for its precursors, salts 8 and Cat3OTs, overlap.
Results of photochemical and photophysical study of
the synthesized anionic 8, cationꢀanionic 14—16, and
merocyanine dyes 9, 11—13 will be presented in subseꢀ
quent papers.
NMR spectrum of which agree with those for salt 7 described
above. After salt 7 was separated, H2O (10 mL) was added to the
solution, which was triturated followed by separation of the
precipitate, which in its turn was washed with H2O and dried to
obtain salt 8 (0.2 g, 46%) as green crystals with m.p. 65—70 °C.
Found (%): C, 77.40; H, 6.35; N, 16.72. C32H30N6. Calculated
(%): C, 77.10; H, 6.02; N, 16.86. UV, λ /nm (ε): (EtOH)
max
312 (37026), 680 (40272); (CHCl3) 312 (34477), 720 (68953).
1H NMR (CDCl3), δ: 3.04, 3.25 (both s, 6 H each, NMe2); 5.08
(t, 1 H, Hβ, J = 12 Hz); 6.35—6.50 (m, 2 H, CH); 7.10—7.45
(m, 13 H, Ph, CH); 7.65 (d, 2 H, Hα, Hγ, J = 12 Hz).
Experimental
NMR spectra for compounds 9, 11—13 were recorded on a
Bruker DRXꢀ500 spectrometer (500.13 and 125.76 MHz for H
(5ꢀDimethylaminoꢀ1ꢀphenylpentaꢀ2,4ꢀdienylidene)malonoꢀ
nitrile (9). A mixture of dinitrile 3 (0.9 g, 5.4 mmol) and
3ꢀdimethylaminoꢀ1,1,3ꢀtrimethoxypropane (2) (0.95 g, 5.4 mmol)
was stirred for 3 h at 55—60 °C. After the heating was stopped,
the UV spectral data showed the formation of a mixture of triene
dinitrile 9 (λmax = 480) and salt 8 (λmax = 312 and λmax = 720) in
the ratio 3 : 1 in the reaction. Salt 8, described above, was not
isolated, while dinitrile 9 was isolated from the concentrated
reaction mixture by chromatography on Al2O3 with elution with
CHCl3. A precipitate from chloroform eluate was repeatedly
washed with anhydrous ether to obtained triene dinitrile 9
(0.27 g, 20%) as a brown powder with m.p. 152 °C (decomp.).
Found (%): C, 76.76; H, 6.24; N, 16.64. C16H15N3. Calculated
1
and 13C, respectively) in DMSOꢀd6 (9, 11) and CDCl3 (12, 13)
at 30 °C. Chemical shifts of 13C and 1H nuclei were calibrated
with respect to the signals of carbon atoms and residual protons
of chloroformꢀd (77.0 and 7.27 ppm) and dimethylsulfoxideꢀd6
(39.5 and 2.50 ppm). Twoꢀdimensional spectra were recorded
following the standard Bruker procedures. 1H NMR spectra of
compounds 7, 8, 10, 14—16 were recorded on a Bruker WMꢀ
250 spectrometer (250 MHz). Mass spectra (EI) were recorded
on a Kratos MSꢀ30 instrument (70 eV). Absorption spectra were
recorded on a Specord UVꢀVIS spectrophotometer. Monitoring
of the reaction courses and isolation of compounds by column
chromatography on Al2O3 were conducted by UV spectroscopy.
Starting dinitriles 3 (see Ref. 13), 4 (see Ref. 13), and 6 (see Ref. 14)
were synthesized according to procedures described earlier.
Dinitrile 5 (b.p. 147—150 °C (10 mm), nD20 1.5050) was obtained
similarly to 6. In the UV spectra (EtOH) of starting dinitriles
(%): C, 77.10; H, 6.02; N, 16.86. UV, λ /nm (ε): (CHCl3)
max
480 (70550); (EtOH) 490 (79888). MS, m/z 249 [M]+.
(3ꢀDimethylaminopropꢀ2ꢀenylidene)malononitrile (10).
A mixture of dinitrile 4 (0.3 g, 1.6 mmol) and aminal 1 (0.28 g,
1.6 mmol) was kept for 1 day at 20—25 °C and concentrated
in vacuo. The residue was chromatographed on Al2O3. A precipitate
from the chloroform eluate was washed with cold anhydrous
ether to obtain nitrile 10 (0.1 g, 40%), identical to the authentic
sample in the m.p., UV and NMRꢀspectra.15
(5ꢀDimethylaminoꢀ2ꢀmethylꢀ1ꢀphenylpentaꢀ2,4ꢀdienylidene)ꢀ
malononitrile (11). A mixture of dinitrile 4 (0.9 g, 5 mmol) and
reagent 2 (0.95 g, 5.4 mmol) was heated under stirring for 3 h at
55 °C and concentrated. The residue was chromatographed on
Al2O3. After concentration of the chloroform eluate, an oily
precipitate of dark brown color was obtained (0.8 g) with
λ
max/nm (ε): 230 (8729) and 295 (15482) (3), 230 (9341) and
295 (15139) (4), 240 (15335) (5), 260 (15529) (6).
(Dimethylaminopropenylidene)dimethylammonium 1,5,5ꢀtriꢀ
cyanoꢀ6ꢀiminoꢀ4ꢀmethylꢀ2,4ꢀdiphenylcyclohexꢀ2ꢀenꢀ1ꢀide (7).
A. Aminal 1 (0.64 g, 3.8 mmol) was added dropwise to a solution
of dinitrile 3 (0.6 g, 3.6 mmol) in anhydrous benzene (3 mL)
under stirring. After 1 day, the mixture was concentrated in vacuo,
anhydrous acetone (5—7 mL) was added to the residue, and this
was cooled down to –10 °C, a precipitate of light gray color was
separated and washed with anhydrous acetone to obtain salt 7
(0.6 g, 73%) with m.p. 168—170 °C. Found (%): C, 75.76; H,
6.64; N, 17.92. C29H30N6. Calculated (%): C, 75.32; H, 6.49;
N, 18.18. UV (EtOH), λmax/nm (ε): 312 (42280). 1H NMR
(DMSOꢀd6), δ: 1.55 (s, 3 H, Me); 3.05, 3.20 (both s, 6 H each,
NMe2); 5.20 (s, 1 H, NH); 5.45 (t, 1 H, Hβ, J = 12 Hz); 6.50
(s, 1 H, CH); 7.20—7.45 (m, 10 H, Ph); 7.72 (d, 2 H, Hα, Hγ,
J = 12 Hz).
B. Reagent 2 (0.094 g, 0.54 mmol) was added dropwise to a
solution of dinitrile 3 (0.09 g, 0.54 mmol) in anhydrous benzene
(3 mL). The mixture was heated for 2.5 h at 50—55 °C and kept
at 20—25 °C for 2 days. A precipitate of light gray color was
separated, and washed with anhydrous acetone to obtain salt 7
(0.05 g, 40%) with m.p. 167—169 °C, giving no m.p. depression
with salt 7 isolated above. UV (EtOH), λmax/nm (ε): 312 (41100).
(Dimethylaminopropenylidene)dimethylammonium 1,1,9,9ꢀtetraꢀ
cyanoꢀ2,8ꢀdiphenylnonaꢀ2,4,6,8ꢀtetraenꢀ1ꢀide (8). A mixture of
dinitrile 3 (0.3 g, 1.8 mmol) and aminal 1 (0.32 g, 1.9 mmol) was
kept for 1 day at 20—25 °C and concentrated in vacuo. A thick
dark red oily residue was washed with anhydrous ether, dissolved
in anhydrous acetone, and cooled down to –10 °C. The
precipitate was separated and washed with anhydrous acetone to
obtain salt 7 (0.06 g, 15%), the m.p., UV spectrum, and 1H
λ
= 490 nm in the UV spectrum. After the precipitate was
wmaasxhed with anhydrous ether several times, triene dinitrile 11
was obtained (0.44 g, 34%) as a brown powder with m.p. 138 °C
(decomp.). Found (%): C, 77.42; H, 6.45; N, 15.82. C17H17N3.
Calculated (%): C, 77.56; H, 6.46; N, 15.97. UV, λmax/nm (ε):
(EtOH) 490 (65750)); (CHCl3) 490 (74955). MS, m/z 263 [M]+.
(2ꢀCyclohexylꢀ5ꢀdimethylaminopentaꢀ2,4ꢀdienylidene)malonoꢀ
nitrile (12). Aminal 1 (0.51 g, 3 mmol) was added dropwise to
dinitrile 5 (0.52 g, 3 mmol) in anhydrous benzene (15 mL)
under stirring, the mixture was kept for 1 h at 20—25 °C and
then heated for 3 h at 55—60 °C. After the heating was stopped,
the UV spectrum of the reaction mixture showed the presence
of absorption maxima λ
= 376 and 485 nm, belonging to
max
dinitriles 10 and 12, respectively (ratio 1 : 4). The residue left
after concentration of the reaction mixture in vacuo was
chromatographed on Al2O3 with CHCl3 as the eluent.
A precipitate was isolated from the chloroform eluate, which
was thoroughly washed with anhydrous ether to obtain dinitrile
12 (0.23 g, 30%) as a dark orange powder with m.p. 140—141
°C. Found (%): C, 74.86; H, 8.05; N, 16.46. C16H21N3.
Calculated (%): C, 75.29; H, 8.23; N, 16.47. UV, λmax/nm (ε):
(EtOH) 485 (102000); (CHCl3) 470 (94444). MS, m/z 255 [M]+.

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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1675
According to the UV spectral data, a mixture of dinitriles 10
References
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2 in anhydrous benzene under conditions described above.
(1ꢀCyclopropylꢀ5ꢀdimethylaminopentaꢀ2,4ꢀdienylidene)malonoꢀ
nitrile (13). Aminal 1 (0.52 g, 3 mmol) was added dropwise to
dinitrile 6 (0.4 g, 3 mmol) in anhydrous benzene (15 mL) and
this was stirred for 1 h at 20—25 °C followed by heating for 2 h at
55—60 °C. The UV spectrum of the reaction mixture showed the
formation of a mixture of dinitriles 13 and 10 in the ratio 2.5 : 1.
Dinitrile 13 (0.13 g, 20%) was isolated (as described above for
dinitrile 12) as a brown powder with m.p. 138—139 °C. Found
(%): C, 72.88; H, 6.95; N, 19.56. C13H15N3. Calculated (%):
C, 73.24; H, 7.04; N, 19.72. UV, λmax/nm (ε): (EtOH) 490
(95343); (CHCl3) 480 (79114). MS, m/z 213 [M]+.
Cationꢀanionic dyes (14—16). Equimolar amounts of salt 8
and cyanine dye tosylate ([Cat1]+OTs–, [Cat2]+OTs–, [Cat3]+OTs–)
were separately dissolved in minimum EtOH—CH2Cl2 (10 : 1).
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20 °C. The crystals of dyes 15 and 16 formed were filtered off
and washed with H2O, EtOH, and ether. In the case of dye 14,
the reaction mixture was concentrated, the residue was suspended
in H2O, the precipitate formed was filtered off, washed with
H2O, EtOH and ether.
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3ꢀEthylꢀ2ꢀ[(3ꢀethylꢀ2,3ꢀdihydrobenzothiazolꢀ2ꢀylidene)methyl]ꢀ
benzothiazolium 1,1,9,9ꢀtetracyanoꢀ2,8ꢀdiphenylnonaꢀ2,4,6,8ꢀ
tetraenꢀ1ꢀide (14). M.p. 122—125 °C. UV, λmax/nm (ε): (CHCl3)
430 (74381) 700 (29585); (EtOH) 420 (67620), 680 (26691).
1H NMR (DMSOꢀd6), δ: 1.35 (t, 6 H, CH3CH2N, J = 7.0 Hz);
4.56 (q, 4 H, CH3CH2N, J = 7.0 Hz); 6.65 (s, 1 H, CH);
6.35—6.50 (m, 2 H, CH); 7.10—8.05 (m, 21 H, Ph, CH).
3ꢀEthylꢀ2ꢀ[(3ꢀethylꢀ2,3ꢀdihydrobenzothiazolꢀ2ꢀylidene)propꢀ
1ꢀenꢀ1ꢀyl]benzothiazolium 1,1,9,9ꢀtetracyanoꢀ2,8ꢀdiphenylnonaꢀ
2,4,6,8ꢀtetraenide (15), m.p. 132—136 °C. UV, λmax/nm (ε):
(CHCl3) 565 (142600) 700 (97750); (EtOH) 560 (149500), 680
(101200). 1H NMR (DMSOꢀd6), δ: 1.30 (t, 6 H, CH3CH2N,
J = 7.0 Hz); 4.40 (q, 4 H, CH3CH2N, J = 7.0 Hz); 6.40—6.60
(m, 4 H, Hα, Hγ, CH); 7.10—8.00 (m, 22 H, Ph, Hβ, CH).
3ꢀEthylꢀ2ꢀ[4ꢀ(3ꢀethylꢀ2,3ꢀdihydrobenzothiazolꢀ2ꢀylidene)ꢀ
butaꢀ1,3ꢀdienꢀ1ꢀyl]benzothiazolium 1,1,9,9ꢀtetracyanoꢀ2,8ꢀ
diphenylnonaꢀ2,4,6,8ꢀtetraenide (16), m.p. 217—220 °C. UV,
λ
max/nm (ε): (CHCl3) 670 (255104); (EtOH) 680 (231912). 1H NMR
(DMSOꢀd6), δ: 1.30 (t, 6 H, CH3CH2N, J = 7.0 Hz); 4.40 (q,
4 H, CH CH2N, J = 7.0 Hz); 6.00—6.40 (m, 5 H, Hα, Hγ, Hε,
CH); 7.130—8.05 (m, 23 H, Ph, Hβ, Hδ, CH).
Received December 25, 2007;
in revised form February 26, 2008