Reaction of 1,8-diaminonaphthalene with some selected π-acceptors; Prospective optically active non-linear cyanovinylated naphthalenes as well as synthesis of novel perimidin and pleiadene derivatives

Article abstract of DOI:10.1016/j.tet.2004.03.017

Reactions of 1,8-diaminonaphthalene with some selected π-acceptors are reported herein. The reaction of the 1,8-diaminonaphthalene with 1,1,2,2-tetracyanoethylene (TCNE) and 7,7′,8,8′- tetracyanoquinodimethane (TCNQ), via different modes of cyanovinylatio

Full text of DOI:10.1016/j.tet.2004.03.017

Tetrahedron 60 (2004) 3797–3802
Reaction of 1,8-diaminonaphthalene with some selected
p-acceptors; prospective optically active non-linear
cyanovinylated naphthalenes as well as synthesis of novel
perimidin and pleiadene derivatives
*
Ashraf A. Aly and Kamal M. El-Shaieb
Department of Chemistry, Faculty of Science, El-Minia University, El-Minia 61519, Egypt
Received 3 December 2003; revised 6 February 2004; accepted 4 March 2004
Abstract—Reactions of 1,8-diaminonaphthalene with some selected p-acceptors are reported herein. The reaction of the 1,8-
diaminonaphthalene with 1,1,2,2-tetracyanoethylene (TCNE) and 7,70,8,80-tetracyanoquinodimethane (TCNQ), via different modes of
cyanovinylation, yielded (2E)-2,3-bis-(8-aminonaphthalen-1-ylamino)-but-2-enedinitrile and 2-[4-(1H,3H-perimidin-2-ylidene)cyclohexa-
2,5-dienylidene]malononitrile, respectively. On the other site, the reaction of the target molecule with 2-dicyanomethyleneindane-1,3-dione
(CNIND), 2-(2,4,7-trinitro-9H-fluoren-9-ylidene)propane-dicarbonitrile (DTF) and 2,3-dichloro-4,5-dicyano(2,3,4,5-tetrachloro)-1,4-
benzoquinones (DDQ and CHL-p) afforded perimidin and pleiadene derivatives.
q 2004 Elsevier Ltd. All rights reserved.
1. Introduction
4-amino[2.2]paracyclophane and its N-methyl derivative
towards TCNE and 2,3-dichloro-5,6-dicyano-1,4-benzo-
quinone (DDQ), that led to unexpected products such as
2-(4-[2.2]paracyclophanyl)-3,3-dicyanoxaziridine, 4-(N-
carbonitrile-N-ethyl)amino-[2.2]paracyclophane as well as
2,3-dichloro-5-cyano-6-([2.2]paracyclophanyl)amino-1,4-
benzoquinone.10 We also isolated tricyanovinylated pro-
ducts during the reaction of TCNE with amines derived by
heterocyclic compounds.11,12 Moreover, we succeeded in
the syntheses of many heterophanes and heterocycles.13–15
We also synthesized 1,4-benzoxazepines by the reaction of
4-arylidene-2-phenyl-5(4H)-1,3-oxazolones with benzyne
via [2pþ2p]cycloaddition.16 Subsequently, we examined
the reaction of N-vinyl-1H-imidazole with 1,2-dehydro-
benzene and some selected p-deficient compounds which
was catalytic under basic conditions,17 and we showed the
effects of microwaves and thermolysis on the cyclization of
thiourea derivatives.18
In spite of 1,8-diaminonaphthalene (1) having bidenate
nucleophilic centers, limited studies have been reported on
the utilization of 1 in the field of heterocyclic synthesis.1–4
On the other site, most of the chemistry of 1 has been
directed towards metal complexes.5 – 7 Reactions of
aromatic amines with 1,1,2,2-tetracyanoethylene (TCNE)
and 7,70,8,80-tetracyanoquinodimethane (TCNQ) afforded
tricyanovinylated products, which are known as second-
order optically active non-linear compounds.8,9 This is
rationalized by the principle that chromophores comprising
electron donor (D) linked to electron acceptor (A) by means
of a conjugated p-electron system have non-linear optical
activities. The utility of non-linear optical (NLO) phenom-
ena underpins many operations performed by devices in
telecommunication systems switching nodes and provide a
means for optical signal processing in general. Therefore,
we examined the reactions of 1 with both TCNE and TCNQ,
on one site. We also investigated the reaction of 1 with other
selected p-acceptors aiming to obtain heterocyclic com-
pounds which might have biological and/or pharmaceutical
applications.
2. Results and discussion
In the light of the aforementioned promising results, our
attention was turned to study the reaction of compound 1
with various p-acceptors (see Fig. 1). The reactivity 1
towards 1,1,2,2-tetracyanoethylene (TCNE, 2), 7,70,8,80-
tetracyanoquinodimethane (TCNQ, 4), 2-dicyano-
methyleneindane-1,3-dione (CNIND, 6), 2-(2,4,7-trinitro-
9H-fluoren-9-ylidene)propane-dicarbonitrile (DTF, 8), 2,3-
dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 10) and
Sometime ago, we reported an anomalous behavior for
Keywords: 1,8-Diaminonaphthalene; p-Acceptors; Cyanovinylation;
Perimidines; Pleiadenes.
*
Corresponding author. Tel.: þ2086346876; fax: þ2086346876;
e-mail address: ashraf160@yahoo.com
0040–4020/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2004.03.017

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A. A. Aly, K. M. El-Shaieb / Tetrahedron 60 (2004) 3797–3802
Figure 1.
2,3,5,6-tetrachloro-1,4-benzoquinone (CHL-p, 12) is out-
lined in Scheme 1. It is interested to note that the
reactions of 1 with the aforementioned p-acceptors were
carried out in dry ethyl acetate at 215 8C under N2
atmosphere. Addition of 1 as an electron donor to electron
acceptors in dichloromethane at 215 8C leads to complex
formation characterized by CT-bands in the visible region
(Table 1). These CT-complexes gradually disappeared to
give the precipitated reaction products. Presumably,
CT-complexes exist as transient steps before chemical
reactions have taken place. The reaction time and the lmax
of the CT-complexes of 1 with the former acceptors are
given in Table 1.
Upon treatment of compound 2 (TCNE, Fig. 1) with 1,
under the reaction conditions mentioned before, the reaction
afforded compound 3 in 85% yield (Scheme 1). The
1
structural proof of 3 was based upon the mass, H NMR,
13C NMR and IR spectra as well as elemental analysis. Mass
spectroscopy and elemental analysis proved the molecular
formula of 3 as C24H18N6. The IR spectrum of 3 revealed
broad absorption bands at nmax 3220–3180 (NH, NH2) and
2218 (CN) cm21. The NH-proton resonated in the 1H NMR
spectrum of 3 at dH 11.80 (2H), whereas the NH2 appeared
at dH 3.90 (4H), which indicated that the cyanovinylation
process occurs on one NH2 in each of molecule of 1. The
symmetrical structure of 3 was confirmed, since its 1H NMR
Scheme 1. Reaction of 1 with some selected p-acceptors.

A. A. Aly, K. M. El-Shaieb / Tetrahedron 60 (2004) 3797–3802
3799
Table 1. Reaction time and absorption maxim for the CT-complexes of 1
towards various p-acceptors in dichloromethane at 215 8C
two double-doublets (4H) and a broad singlet (2H). The 13C
NMR of 5 confirmed its 1H NMR spectral data by the
appearance of thirteen carbon signals, which indicated its
symmetry. The COSY H–H and C–H spectra of 5 showed
most of distinctive d values of 5 as given in Figure 2.
Compound 5 was unequivocally identified as 2-[4-(1H,3H-
perimidin-2-ylidene)cyclohexa-2,5-dienylidene]malono-
nitrile.
Acceptor lmax
(nm)
Reaction time Acceptor lmax
(nm)
Reaction time
(h)
(h)
2
4
6
500
470
440
1
3
2.5
8
10
12
420
520
400
2
4
6
spectrum showed six discernible sets of aromatic protons,
which appeared as multiplets and the others as double-
doublets, each set related to two protons. The 13C NMR
Interestingly, the reaction between 1 and 2-dicyano-
methyleneindane-1,3-dione (CNIND,21 6, Fig. 1) yielded
another class of symmetrical perimidin derivative 7 in 70%
1
1
spectrum proved the H NMR spectroscopic data by the
yield (Scheme 1). Elemental analysis as well as IR, H
NMR, 13C NMR and mass spectra established the structural
proof of 7. Elemental analysis and mass spectra confirmed
the molecular formula of 7 as C20H12N2O2. The IR spectrum
of 7 showed NH and carbonyl absorption bands at nmax 3180
and 1690 cm21, respectively. It was clearly noted in the IR
spectrum of 7 that there is no absorption due to the nitrile-
group. The 1H NMR spectrum of 7 revealed the NH-proton
at dH 11.60 (2H) related to the NH-protons. The symmetri-
cal structure of 7 was elucidated by 13C NMR spectrum,
since only 12 carbon signals were recognized. The COSY
H–H and C–H spectra of 7 demonstrated some distinctive d
values as given in Figure 2. By the help of the obtainable
spectral data, compound 7 was identified as 2-(1H,3H-
perimidin-2-ylidene)-indan-1,3-dione.
appearance of only 12-carbon signals. The COSY H–H and
C–H spectra of 3 indicated some distinctive d values as
given in Figure 2. According to semi-empirical calculations
using the MM2 level of theory,19 the stereoview of
compound 3 (Scheme 1), in the case of minimization the
steric energy value, is in its E-form (DHf¼196.98 kcal/mol)
rather than in the Z-form (DHf¼314.90 kcal/mol). It is
therefore suggested that the structure of 3 was identified
as (2E)-2,3-bis-(8-aminonaphthalen-1-ylamino)-but-2-
enedinitrile.
7,70,8,80-Tetracyanoquinodimethane (TCNQ, 4, Fig. 1) has
attracted interest because its cyanovinylated products have
non-linear optical properties.8,20 Interest in organic light
emitting chromophores has expanded rapidly since the
discovery of efficient electro-luminescence (EL), its use in
light emitting devices and its potential for electrically
pumped solid state lasers.8,20 In an attempt to carry out the
reaction of 1 with 4, under the same reaction conditions as
between 1 and 2, the reaction produced compound 5 in 80%
Surprisingly, the reaction of 1 with 2-(2,4,7-trinitro-9H-
fluoren-9-ylidene)propane-dicarbonitrile (DTF,22 8, Fig. 1)
afforded the spiro-heterocyclic compound 9 in 75% yield
(Scheme 1). The latter reaction occurred by elimination of a
molecule of malononitrile from 8. The IR spectrum of 9 did
not show any absorption due to the nitrile group, whereas a
strong band appeared at nmax 3180 cm21 related to the
1
yield (Scheme 1). The IR, H NMR, 13C NMR and mass
spectra as well as elemental analysis confirmed the
structural feature of 5. The molecular formula of 5 was
elucidated by mass spectroscopy and elemental analysis as
C20H12N4. The 1H NMR spectrum of 5 is in accordance with
the suggested structure and showed three multiplets (6H),
1
amino group. The H NMR spectrum of 9 revealed two
apparent double-doublets at dH 6.00 and 6.30 (J¼8.6,
1.4 Hz), each integrating for one proton, corresponding to
the naphthalene molecule (Fig. 2). Additionally, H-3 and
Figure 2. Distinctive chemical shifts (d s) of compounds 3, 5, 7 and 9.

3800
A. A. Aly, K. M. El-Shaieb / Tetrahedron 60 (2004) 3797–3802
1
H-1 were resonated in the H NMR spectrum of 9 as two
doublets at dH 8.40 and 7.90 (J¼2.0 Hz), respectively.
3. Experimental
1
Moreover, the two NH-protons were appeared in the H
Melting points are uncorrected. IR spectra were obtained on
Shimadzu 470 spectrophotometer using potassium bromide
pellets. 1H NMR (400.134 MHz) and 13C NMR
(100.6 MHz) spectra were measured on Bruker AM 400
with TMS as an internal standard. Coupling constants are
expressed in Hz. Mass spectra were recorded on a Finnigan
MAT 8430 instrument at 70 eV. Elemental analyses were
carried out in the Microanalysis Center of the Institut fu¨r
NMR spectrum of 9 at dH 3.90 and 3.94. The ring-current
effect of the fluorenyl ring was previously studied.23 It was
shown that the fluorenyl ring system seems to be less
aromatic because it contains a 5-membered ring with 4p-
electrons.23 Thus, the presence of the electron-withdrawing
groups on the benzene rings of fluorenyl group will reduce
the electron density on C-9. However, the presence of the
electron-donating groups attached to C-9 will increase the
aromaticity of the fluorenyl rings, as it allows donation of
electron density into the ‘empty’ p-atomic orbital of C-9.23
Thus, the two former factors affect the shielding and/or the
deshielding appearance of C-9. Since, the withdrawing
effect of the nitro-groups is expected to proceed over the
donating effect of the NH– groups, this can explain the
deshielding appearance of C-9 in compound 9 (dC 100.00).
Moreover, COSY H–H and NOE spectra of 9 indicated
some distinctive d values as given in Figure 2 (see also
Section 3).
¨
Anorganische Chemie, Technische Universitat Braunsch-
weig. For preparative thin layer chromatography (PLC),
glass plates (20£48 cm) were covered with slurry of silica
gel Merck PF254 and air-dried using the solvents listed for
development.
3.1. Starting materials
Commercial 1,8-diaminonaphthalene (1) was used 0 from
Fluka. 1,1,2,2-Tetracyanoethylene (TCNE, 2), 7,7 ,8,80-
tetracyanoquinodimethane (TCNQ, 4), 2-dicyano-
methyleneindane-1,3-dione (CNIND, 6), 2,3-dichloro-5,6-
dicyano-1,4-benzoquinone (DDQ, 10) and 2,3,5,6-tetra-
chloro-1,4-benzoquinone (CHL-p, 12) were bought from
Merck. 2-Dicyanomethyleneindane-1,3-dione (CNIND, 6),
The reactions of 1 with p-acceptors (2, 4, 6 and 8, Fig. 1)
proceeded by nucleophilic addition of the NH groups of 1 to
the p-deficient double bonds, followed by elimination. On
reacting 1 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ, 10) and 2,3,5,6-tetrachloro-1,4-benzoquinone
(CHL-p, 12), the reaction performed by elimination to
give 11a,b, which was followed by condensation to afford
products 13a,b (Scheme 1). We found that compounds
13a,b were obtained in higher percentage yields compared
with 11a,b (Scheme 1). The ability to separate side products
of 11a or 11b indicated that addition-elimination sequence
preceded the condensation. The structural proof of com-
pounds 11a,b and 13a,b was made on the basis of elemental
analyses as well as IR, 1H NMR, 13C NMR and mass
spectra. For example mass spectroscopy and elemental
analysis confirmed the molecular formula of 13a as
C18H7ClN4O. The IR spectrum of 13a demonstrated strong
absorption bands at nmax 3180, 1690 and 2218 cm21 related
to the absorptions of amine–NH, carbonyl and cyano
groups, respectively. The 1H NMR spectrum of 13a
revealed a broad singlet at dH 11.82, whereas two double-
doublets (J¼8.0, 1.2 Hz) and two multiplets could be also
distinguished, which were attributed to naphthalene
protons. The 13C NMR spectrum of 13a showed its
unsymmetrical structure, since all carbons in the molecular
formula were accounted. Four remarkable signals were
distinguished in the 13C NMR of 13a at dC 170.00, 155.80,
113.80 and 113.92 corresponding to carbonyl-, azomethine-
and two nitrile-carbons. The proposed structure of 13a and
13b were identified as 11-chloro-10-oxo-10,12,12a,12b-
tetrahydro-7,12-diaza-pleiadene-8,9-dicarbonitrile and
8,10,11-trichloro-6a,12b-dihydro-7H-7,12-diaza-pleiaden-
9-one.
and
2-(2,4,7-trinitro-9H-fluoren-9-ylidene)propane-
dicarbonitrile (DTF, 8) were prepared following the
procedure mentioned in refs. 21 and 22, respectively. 2,3-
Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 10) and
2,3,5,6-tetrachloro-1,4-benzoquinone (CHL-p, 12) were
bought from Aldrich.
3.2. General procedure. Reaction of 1 with 2, 4, 6, and 8.
General procedure
In an ice-salt bath (215 8C), a solution of 1 (0.16 g, 1 mmol)
in dry ethyl acetate (20 mL) was added dropwise to a
solution of the acceptor 2, 4, 6, or 8 (2 mmol) in dry ethyl
acetate (50 mL) under N2 atmosphere over 10 min. The
reaction mixture was further stirred at the former tempera-
ture for 1–3 h (Table 1) until the consumption of the
starting materials was completed (the reaction progress was
monitored by TLC analysis). The solvent was evaporated
under vacuum and the residue was applied on PC using
toluene as eluent. The major zones were recrystallized from
the stated solvents.
3.2.1. (2E)-2,3-Bis-(8-aminonaphthalen-1-ylamino)-but-
2-enedinitrile (3). Compound 3 (0.38 g, 85%) as green
crystals (Rf 0.3, CH2Cl2), mp 160–162 8C (acetonitrile);
[Found: C, 73.70; H, 4.58; N, 21.46 requires C24H18N6
(390.440): C, 73.83; H, 4.65; N, 21.52%]; nmax (KBr)
3220–3180 (NH, NH2), 3030–2985 (Ar-CH), 2218 (CN),
1590 (CvN) cm21; UV (CH3CN) lmax (log 1) 400 (3.90);
dH (DMSO-d6) 3.90 (4H, br s, 2NH2), 6.60 (2H, dd, J¼8.4,
1.6 Hz), 7.20–7.36 (2H, m), 7.40 (2H, dd, J¼8.4, 1.4 Hz),
7.50–7.66 (2H, m), 7.80 (2H, dd, J¼8.4, 1.4 Hz), 8.00–8.18
(2H, m), 11.80 (2H, br s, NH); dC (DMSO-d6) 110.80 (vinyl-
C), 113.60 (CN), 116.00 (naph-C), 127.90, 128.80, 129.20,
131.20, 131.60 (naph-CH), 132.00 (naph-C–NH2), 133.00
(naph-CH), 134.60 (naph-C–NH), 140.80 (naph-C); m/z (%)
390 [Mþ] (100), 232 (46), 206 (18), 180 (22), 168 (20), 154
(24), 140 (16), 106 (22), 92 (24), 78 (16), 50 (12), 24 (14).
In conclusion, our results demonstrated for the first time, a
general, methodology for the construction of a variety of
little investigated types of heterocyclic compounds
(pleiadene and perimidin) due to the difficulties
accompanied their synthesis. We can also utilize by our
target molecule in a promised synthesis of other interest
heterocyclic compounds.

A. A. Aly, K. M. El-Shaieb / Tetrahedron 60 (2004) 3797–3802
3801
3.2.2. 2-[4-(1H,3H-Perimidin-2-ylidene)cyclohexa-2,5-
dienylidene]malononitrile (5). Compound (0.25 g,
1 h and at room temperature for 3–5 h (Table 1). The
solvent was then removed under vacuum and the residue
was applied on PLC using toluene: ethyl acetate as eluent
(5:1). In case of the reaction of 1 with either 10 or 12, the
first migrating zone contained compounds 11a,b, whereas
the second migrating one contained compounds 13a,b.
5
80%) as orange crystals (Rf 0.5, CH2Cl2), mp 180–
182 8C; [Found: C, 77.75; H, 3.90; N, 18.16 requires
C20H12N4 (308.350): C, 77.91; H, 3.92; N, 18.17%]; nmax
(KBr) 3210 (NH), 3045–2990 (Ar-CH), 2220 (CN), 1590
(CvN) cm21; UV (CH3CN) lmax (log 1) 420 (4.00); dH
(CDCl3) 6.40–6.60 (2H, m, naph-H), 6.70 (2H, dd, J¼8.5,
1.4 Hz, quinone-CH), 7.56–7.74 (2H, m, naph-H), 7.80
(2H, dd, J¼8.4, 1.5 Hz, quinone-CH), 7.90–8.08 (2H, m,
naph-H), 11.90 (2H, br s, NH); dC (CDCl3) 75.80
[vC(CN)2], 90.60 (CvC–NH), 115.80 (CN), 118.00
(naph-C), 124.60 (quinone-CH), 126.60, 128.80 (naph-
CH), 129.90 (naph-C), 133.00 (naph-CH), 134.00 (naph-C–
NH), 134.90 (quinone-CH), 136.90 (naph-C), 148.90 (C-3),
175.90 (CvC(CN)2); m/z (%) 308 [Mþ] (100), 282 (20),
256 (24), 244 (32), 168 (18), 132 (16), 104 (20), 92 (18), 78
(20), 50 (16).
3.3.1. 4-(8-Aminonaphthalen-1-ylamino)-5-chloro-3,6-
dioxo-cyclohexa-1,4-diene-1,2-dicarbonitrile
(11a).
Compound 11a (0.04 g, 10%) as pale yellow crystals (Rf
0.6, CH2Cl2), mp .300 8C (ethyl acetate); [Found: C,
61.80; H, 2.55; Cl, 10.00, N, 16.16 requires C18H9ClN4O2
(348.743): C, 61.99; H, 2.60; Cl, 10.17; N, 16.07%]; nmax
(KBr) 3230–3210 (NH,NH2), 3045–2990 (Ar-CH), 2220–
2210 (CN), 1690 (CO), 1585 (CvN) cm21; UV (CH3CN)
lmax (log 1) 340 (3.20); dH (DMSO-d6) 4.00 (2H, br s, NH2),
6.20–6.40 (2H, m, naph-H), 6.70–7.10 (3H, m), 7.92–8.10
(1H, m), 11.40 (1H, br s, NH); dC (DMSO-d6) 114.50,
115.80 (CN), 120.00 (C-5), 122.40 (naph-C), 126.60,
126.80, 128.24, 130.20, 132.00, 132.18 (naph-CH), 134.00
(naph-C–NH2), 135.60, 135.90 (C-1 and C-2), 137.00
(naph-CH), 138.00 (naph-C), 141.80 (naph-C–NH), 170.00,
172.00 (C-3 and C-6); m/z (%) 348 [Mþ] (100), 346 (30),
316 (20), 290 (24) 288 (26), 274 (18), 220 (24), 178 (20),
150 (16), 134 (24), 104 (18), 92 24), 78 (18), 24 (14).
3.2.3. 2-(1H,3H-Perimidin-2-ylidene)-indan-1,3-dione
(7). Compound 7 (0.22 g, 70%) as orange crystals, (Rf 0.4,
CH2Cl2), mp 260–262 8C (ethanol); [Found: C, 76.75; H,
3.90; N, 8.80 requires C20H12N2O2 (312.322): C, 76.91; H,
3.87; N, 8.97%]; nmax (KBr) 3180 (NH), 3045–2990
(Ar-CH), 1690 (CO), 1590 (CvN), 1580 (CvCH) cm21
;
UV (CH3CN) lmax (log 1) 400 (3.90); dH (CDCl3) 6.40–
6.56 (2H, m, naph-H), 6.90 (2H, dd, J¼8.4, 1.4 Hz), 7.40–
7.60 (2H, m, naph-H), 7.80–8.00 (2H, m, Ar-H), 8.10–8.14
(2H, m, naph-H), 11.60 (2H, br s, NH); dC (CDCl3) 90.00
(CvC–CO), 116.00 (naph-C), 126.00 (2C, naph-CH),
128.00 (2C, Ar-CH), 128.90 (2C, naph-CH), 130.86 (2C,
Ar-CH), 132.00 (2C, Ar-C), 133.60 (2C, naph-CH), 134.00
(2C, naph-C–NH), 138.20 (naph-C), 154.00 (C-2), 174.20
(2C, CvO); m/z (%) 312 [Mþ] (100), 282 (54), 258 (18),
220 (18), 180 (22), 156 (34), 144 (24), 126 (26), 78 (16).
3.3.2. 2-(8-Aminonaphthalen-1-ylamino)-3,5,6-trichloro-
1,4-benzoquinone (11b). Compound 11b as pale yellow
crystals (0.06 g, 15%), (Rf 0.5, CH2Cl2), mp .300 8C
(ethanol); [Found: C, 52.40; H, 2.40; Cl, 28.80; N, 7.52
requires C16H9Cl3N2O2 (367.613): C, 52.28; H, 2.47; Cl,
28.93; N, 7.62%]; nmax (KBr) 3225–3210 (NH,NH2),
3045–2990 (Ar-CH), 1690 (CO), 1592 (CvN) cm21; UV
(CH3CN) lmax (log 1) 325 (3.10); dH (DMSO-d6) 3.90 (2H,
br s, NH2), 6.18–6.40 (2H, m, naph-H), 6.58–7.00 (3H, m),
7.80–7.94 (1H, m), 11.60 (1H, br s, NH); dC (DMSO-d6)
113.30, 113.60, 114.20 (C-3, C-5 and C-6), 118.90 (naph-
C), 124.50, 125.90, 128.20, 130.00, 132.20, 132.24 (naph-
CH), 134.10 (naph-C–NH2), 136.00 (naph-CH), 137.20
(naph-C), 140.00 (naph-C–NH), 170.20, 172.60 (C-3 and
C-6); m/z (%) 378 [Mþ] (100), 376 (86), 374 (44), 372 (14),
342 (34), 316 (20), 304 (24), 280 (24), 278 (28), 220 (24),
178 (20), 150 (16), 134 (24), 104 (18), 92 (24), 78 (18), 50
(18), 24 (14).
3.2.4. 2,9-Spiro-[2,4,7-trinitro-fluorene]-1H,3H-peri-
midin-2-ylidene (9). Compound 9 (0.35 g, 75%) as yellow
crystals (Rf 0.2, ethyl acetate), mp .300 8C (acetone);
[Found: C, 60.50; H, 2.80; N, 15.20 requires C23H13N5O6
(455.379): C, 60.66; H, 2.88; N, 15.38%]; nmax (KBr) 3180
(NH), 3060–3010 (Ar-CH), 1590 (CvN), 1568 (CvCH),
1320–1350 (Ar-NO2 stretch) cm21; UV (CH3CN) lmax (log
1) 360 (3.62); dH (DMSO-d6) 3.90 (1H, br s, NH), 3.94 (1H,
br s, NH), 6.00 (1H, dd, J¼8.6, 1.4 Hz, naph-H), 6.30 (1H,
dd, J¼8.6, 1.4 Hz, naph-H), 6.40–6.60 (4H, m, naph-H),
7.40–7.68 (3H, m, Ar-H), 7.90 (1H, d, J¼2.0 Hz, H-1), 8.40
(1H, d, J¼2.0 Hz, H-3); dC (DMSO-d6) 100.00 (C-9),
118.00, 122.30, 124.80, 126.90, 128.60 (naph-CH), 128.80
(naph-C), 128.90 (naph-CH), 130.00, 132.00, 132.40 (naph-
C), 133.00, 133.20, 133.40, 133.60 (Ar-C), 134.00, 134.20,
135.22 (Ar-CH), 136.00 (CH-1), 138.00 (CH-3), 146.80,
147.00, 147.80 (Ar-C–NO2); m/z (%) 456 [Mþ1] (30), 455
[Mþ] (100), 408 (20), 362 (16), 328 (26), 316 (20), 212 (18),
166 (32), 120 (24), 104 (22), 50 (16), 24 (18).
3.3.3. 11-Chloro-10-oxo-10,12,12a,12b-tetrahydro-7,12-
diaza-pleiadene-8,9-dicarbonitrile (13a). Compound 13a
as yellow crystals (0.23 g, 70%), (Rf 0.2, CH2Cl2), mp 286–
288 8C (acetone); [Found: C, 65.55; H, 2.08; N, 16.80
requires C18H7ClN4O (330.727): C, 65.37; H, 2.13; N,
16.94%]; nmax (KBr) 3180 (NH), 3050–2996 (Ar-CH),
2218 (CN), 1690 (CO), 1590 (CvN) cm21; UV (CH3CN)
l
max (log 1) 410 (3.68); dH (DMSO-d6) 6.50 (1H, dd, J¼8.4,
1.4 Hz, naph-H), 7.20–7.50 (3H, m, naph-H), 7.70 (1H, dd,
J¼8.4, 1.4 Hz, naph-H), 8.00–8.12 (1H, m, naph-H), 11.82
(1H, br s, NH); dC (DMSO-d6) 113.00 (C-11), 120.80
(naph-C), 113.80, 113.92 (CN), 126.40, 128.00, 130.14,
130.50, 132.50, 134.00 (naph-CH), 134.60 (naph-C–NH2),
135.20, 135.68 (C-8 and C-9), 137.80 (naph-C–NH),
138.00 (naph-C), 138.60 (naph-C–N), 155.80 (CvN),
170.00 (C-10); m/z (%) 330 [Mþ] (100), 328 (34), 296
(20), 272 (22), 244 (30), 172 (20), 132 (18), 104 (22), 88
(16), 50 (12), 24 (14).
3.3. Reaction of 1 with 10 and 12. General procedure
By applying the same procedure mentioned before, a
solution of either 10 or 12 (2 mmol) in dry ethyl acetate
(50 mL) was added dropwise to 1 (0.16 g, 1 mmol) in dry
ethyl acetate (20 mL) under N2 atmosphere in 30 min. The
reaction mixture was stirred at the former temperature for

3802
A. A. Aly, K. M. El-Shaieb / Tetrahedron 60 (2004) 3797–3802
Meyers, F.; Bredas, J.-L.; Wenseleers, W.; Goovaerts, E. J.
J. Am. Chem. Soc. 1997, 119, 3144–3154.
3.3.4. 8,10,11-Trichloro-6a,12b-dihydro-7H-7,12-diaza-
pleiaden-9-one (13b). Compound 13b as yellow crystals
(0.27 g, 75%), (Rf 0.3, CH2Cl2), mp 260–262 8C (acetone);
[Found: C, 54.80; H, 2.00; N, 8.10 requires C16H7Cl3N2O
(349.598): C, 54.97; H, 2.02; N, 8.01%]; nmax (KBr) 3220
(NH), 3065–3000 (Ar-CH), 1680 (CO), 1590 (CvN)
cm21; UV (CH3CN) lmax (log 1) 350 (3.40); dH (DMSO-
d6) 6.30 (1H, dd, J¼8.4, 1.6 Hz, naph-H), 7.00–7.38 (3H,
m, naph-H), 7.65 (1H, dd, J¼8.6, 1.5 Hz, naph-H), 7.90–
8.00 (1H, m, naph-H), 11.80 (1H, br s, NH); dC (DMSO-d6)
113.00, 113.60, 114.20 (C-8, 10 and 11), 120.40 (naph-C),
126.00, 126.90, 128.26, 130.00, 132.00, 132.90 (naph-CH),
133.80 (quinone-C–NH), 135.80 (naph-C–NH), 136.40
(naph-C), 138.00 (naph-C–N), 155.00 (CvN), 170.20
(C-9); m/z (%) 349 [Mþ] (100), 347 (80), 345 (42), 343
(16), 316 (28), 314 (30), 280 (12), 278 (16), 244 (14), 242
(18), 192 (20), 176 (16), 142 (20), 88 (26), 50 (12), 24 (14).
9. Miller, J. S. Extended linear chain compounds; Plenum: New
York, 1983; Vols. 1–3. pp 981–1001. (b) Ferraro, J. R.;
Williams, J. M. Introduction to synthetic electrical
conductors; Academic: San Diego, CA, 1987.
10. Aly, A. A.; Hassan, A. A.; Mourad, A. E. Can. J. Chem. 1993,
71, 1845–1849.
11. Mourad, A. E.; Hassan, A. A.; Mohamed, N. K.; Aly, A. A.;
Bahaa, A. A. Heterocycl. Commun. 2001, 7, 541–548.
12. Hassan, A. A.; Mohamed, N. K.; Aly, A. A.; Mourad, A. E.
Pharmazie 1997, 52, 23–28.
13. Aly, A. A. Tetrahedron 2003, 59, 1739–1747.
14. Aly, A. A. Org. Biomol. Chem. 2003, 1, 756–761.
15. Aly, A. A.; Mourad, A. E.; Hassan, A. A.; Mohamed, N. K.;
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