Some Reactions with Indane-1,3-dione: A Facile Synthesis of Pentacycline Heterocyclic Analogues

Article abstract of DOI:10.1002/jhet.3572

Indane-1,3-dione 1 reacts with salicylaldehyde 5 and malononitrile 3 to afford 6-amino-7-imino-7H-indeno-[2′,1′:5,6]-pyrano-[3,4-c]-chromene 6, which could be transformed into the corresponding 7-oxo derivative 7. 2-(3-Oxoindan-1-ylidene)-malononitrile 10 couples with the diazonium salts 8, 14, and 15 to afford after cyclization the indeno-[2,1-c]-pyridazine 13 and the indeno-[2′,1′:3,4]-pyridazino-[1,6-a]-quinazoline derivatives 20 and 21, respectively.

Full text of DOI:10.1002/jhet.3572

Month 2019 Some Reactions with Indane-1,3-dione: A Facile Synthesis of Pentacycline
Heterocyclic Analogues
Fathy M. Abdelrazek,a,b
Peter Metz,b and Anne Jaegerb
*
aDepartment of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt
bDepartment of Organic Chemistry, Faculty of Natural Sciences, TU-Dresden, 01069, Dresden, Germany
*E-mail: prof.fmrazek@gmail.com
Received December 21, 2018
DOI 10.1002/jhet.3572
Published online 00 Month 2019 in Wiley Online Library (wileyonlinelibrary.com).
Indane-1,3-dione 1 reacts with salicylaldehyde 5 and malononitrile 3 to afford 6-amino-7-imino-7H-
indeno-[20,10:5,6]-pyrano-[3,4-c]-chromene 6, which could be transformed into the corresponding 7-oxo
derivative 7. 2-(3-Oxoindan-1-ylidene)-malononitrile 10 couples with the diazonium salts 8, 14, and 15 to
afford after cyclization the indeno-[2,1-c]-pyridazine 13 and the indeno-[20,10:3,4]-pyridazino-[1,6-a]-
quinazoline derivatives 20 and 21, respectively.
J. Heterocyclic Chem., 00, 00 (2019).
INTRODUCTION
of some new heterocyclic pentacycline derivatives as a
novel class of tetracycline analogs starting from indane-
1,3-dione.
Tetracycline antibiotics have been heavily utilized for
the treatment of infectious diseases over the past few
decades. However, their excessive use in human and
veterinary medicine led to increasing the resistance of
many microbial strains that were previously susceptible
to tetracycline antibiotics. Therefore, the search for other
more potent alternatives attracts much attention and is
still under consideration as a major target for chemists
and organic chemistry researchers [1–5].
In the past few decades, we were involved in a program
aiming at the synthesis of heterocyclic compounds of
expected biological activity [6–15]. In the context of this
trend and, because of the striking biological activities of
tetracycline derivatives, we report here simple syntheses
RESULTS AND DISCUSSION
Indane-1,3-dione 1 reacts with furanaldehyes 2a,b and
malononitrile 3 in a one-pot reaction to afford the
indeno-[1,2-b]-pyran derivatives 4a,b, respectively (cf.
Scheme 1 and Experimental section). Similarly, 1 reacts
with salicylaldehyde 5 and malononitrile 3 under the
same reaction conditions to afford the indeno-[20,10:5,6]-
pyrano-[3,4-c]-chromene 6. The IR spectrum of 6 showed
absorption bands corresponding to NH, NH2, & C═O
functions (cf. Experimental section). The 1H NMR
© 2019 Wiley Periodicals, Inc.

F. M. Abdelrazek, P. Metz, and A. Jaeger
Vol 000
Scheme 1. Synthesis of compounds 4, 6, 7, 9, 12, and 13. [Color figure can be viewed at wileyonlinelibrary.com]
spectrum showed a singlet at δH = 4.03 ppm attributable to
the pyran-H4, a multiplet at 7.75–8.5 (10H) assignable to
two phenyl rings and the amino group and a singlet at
10.1 (1H) disappeared upon exchange with D2O, which
is attributed to the NH. The MS of 6 showed a molecular
ion peak at m/z = 316. The 13C NMR and elemental
analyses are coinciding with structure 6. Refluxing
compound 6 in acetic acid/HCl mixture for 1 h furnished
the chromene compound 7. The IR spectrum of 7 showed
12. This is apparently due to the presence of the NH in
9B, which is involved in making the N─H … O═C
hydrogen bonds [17], thus blocking the C═O group
against nucleophilic attacks. Therefore, we have followed
the alternative route allowing indane-1,3-dione 1 to
condense firstly with malononitrile 3 according to a
known literature method [18] to afford 2-(3-oxoindan-1-
ylidene)-malononitrile 10. This last compound 10 couples
smoothly with 8 to afford directly compound 12
presumably via the intermediate 11, which undergoes
cyclization under the coupling conditions. Refluxing the
indeno-[2,1-c]-pyridazine-3-imine compound 12 in acetic
acid/HCl mixture (1:1) afforded the pyridazin-3-one
derivative 13. Spectral data and element analyses of 12
and 13 are in full agreement with their suggested structures.
Following the same route 2-(3-oxoindan-1-ylidene)-
malononitrile 10 underwent the coupling reaction with
the diazonium salts 14 and 15 (freshly prepare by
diazotization of ethyl anthranilate and anthranilonitrile,
two carbonyl absorptions at νmax = 1681 & 1676 cmꢀ1
.
The NH signal at 10.1 ppm (which appeared in 6)
1
disappeared in the H NMR spectrum of 7.
On the other hand, coupling of indan-1,3-dione 1 and
pyridine-4-diazonium chloride 8 according to literature
methods [16,17] afforded the azo/hydrazo derivative
9A–9B, which was subjected to react with malononitrile 3
in order to obtain the combined azo/condensation
derivative 11. However, using this route, we could not
obtain the acyclic derivative 11 or its cyclized derivatives
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Scheme 2. Synthesis of compounds 16, 17, 20, and 21. [Color figure can be viewed at wileyonlinelibrary.com]
respectively) to afford the hydrazo derivatives 16 and 17,
respectively (Scheme 2).
upon reflux in acetic acid/HCl mixture (1:1). The identity
was deduced from matching melting points, TLC, and
IR spectra.
On the other hand, ethyl 2-cyan-2-(3-oxo-2,3-dihydro-
1H-inden-1-ylidene)acetate 23 was required for further
reactions. Reacting indanedione 1 with ethyl cyanoacetate
22 according to the reported method [19,20], we could
not obtain the required compound 23 or its alternative
indeno[1,2-b]pyran derivative 24.
Repeating the reaction with different basic catalysts and
under different conditions we obtained always one and the
same product (TLC and mp). Elemental analysis and mass
spectrum showed that this product consists of two
molecules of 1 after elimination of one water molecule.
Thus, the self-condensation structure 25 (Scheme 3) was
assigned to this product. Spectral data are in favor of this
structure (cf. Experimental section). The same product
was also obtained upon refluxing 1 alone in ethanol using
the same catalyst. This structure was further confirmed by
X-ray crystallography [21] as shown in Figure 1, which
showed two molecules of indane-1,3-dione condensed
through the carbonyl group of one molecule with the
active methylene of the other. The X-ray shows two
molecules of the product.
The IR spectra of 16 showed absorption band at
νmax = 3110 & 3067, 2187, 1714, and 1682 cmꢀ1 due to
1
NH, CN, ester C═O, and ring C═O, respectively. The H
NMR spectrum revealed the ester triplet and quartet at
1.4 and 4.5 ppm and a singlet at 15.3 ppm due to the
hydrazone NH beside the other signals at their expected
positions. The IR spectrum of 17 showed absorption
bands at νmax = 3215 & 3164, 2186 & 2205, and
1680 cmꢀ1 assignable to the NH, two CN, and the ring
1
C═O, respectively. The H NMR spectrum revealed the
aromatic multiplet beside the NH singlet at 13.25 ppm.
The C13 NMR data, mass spectra, and elemental analyses
are in complete agreement with the proposed structures
(cf. Experimental section).
Compounds 16 or 17 could be easily cyclized into the
required indeno-[20,10:3,4]-pyridazine-[1,6-a]-quinazoline
derivatives 20 and 21, upon reflux in ethanol presumably
via the intermediates 18 and 19, respectively. The
cyclization was catalyzed by addition of two drops of
piperidine where the color changes promptly from dark
red to yellow to afford 20 and 21, respectively. The IR of
20 showed absorption bands at νmax = 2210, 1676 &
1689 cmꢀ1 corresponding for the cyano group and two
ring carbonyl functions, respectively. The 1H NMR
spectrum revealed only an aromatic multiplet.
EXPERIMENTAL
The IR of 21 showed absorption bands at νmax = 3225 &
3185, 2218, 1680 cmꢀ1 assignable to NH, CN, and C═O,
respectively. The 1H NMR spectrum revealed the
aromatic multiplet 7.30–7.75 and a singlet at 9.38 ppm
assignable to NH. The 13C NMR, MS, and elemental
analyses are in full agreement with the proposed structure.
The 5-imino compound 21 could be smoothly
transformed into the corresponding 5-oxo compound 20
Melting points were measured on an Electrothermal
9100 apparatus (Kleinfeld, Gehrden, Germany) and are
uncorrected. FT-IR spectra (KBr) were obtained on a
Nicolet 205 spectrophotometer (Nicolet, Madison, WI,
1
USA). H NMR and 13C NMR spectra were obtained on
a Bruker AC 300 P (1H: 300 MHz, 13C: 75 MHz; Bruker,
Rheinstetten, Germany) in CDCl3 unless mentioned
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F. M. Abdelrazek, P. Metz, and A. Jaeger
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Scheme 3. Synthesis of [1,2`]biindenylidene-3,1`,3`-trione 25.
Figure 1. X-ray crystallography of 25. [Color figure can be viewed at wileyonlinelibrary.com]
otherwise using TMS as internal reference. Chemical
shifts are expressed in δ (ppm) values. 13C NMR multi-
plicities were determined using DEPT and off resonance
pulse sequences. Spectral and elemental analyses were
carried out in the organic microanalytical laboratory of
the Department of Chemistry, Technical University of
Dresden and the Microanalytical Center at Cairo
University.
brown solids that precipitated were filtered off and
recrystallized from acetonitrile to give 4a,b.
2-Amino-4-furan-2-yl-5-oxo-4,5-dihydro-indeno[1,2-b]
pyran-3-carbonitrile 4a.
Dark brown flakes, mp 197–
198°C (CH3CN); yield (2.26 g; 78%). νmax cmꢀ1: 3152–
3128 (NH2), 2215 (CN), 1681 (C═O). δH: 4.17 (s, 1H,
pyran 4-H), 6.8–7.7 (m, 9H, Ar + NH2). δc: 26.7 (d),
58.2 (s), 102.4 (s), 106.7 (d), 110.5 (d), 118.2 (s), 123.7
(d), 126.1 (d), 128.3 (d), 134.5 (d), 136.7 (s), 137.5 (s),
142.0 (d), 152.3 (s), 159.5 (s), 171.4 (s), 192.4 (s). MS:
m/z = 290. Calcd for C17H10N2O3 (290.28): C, 70.34; H,
3.47; N, 9.65; found: C, 70.50; H, 3.55; N, 9.54.
Synthesis of the 4-furanyl-4,5-dihydroindeno[1,2-b]pyrans
4a,b.
A mixture of indanedione 1 (1.46 g; 0.01 mol)
and each of 2- or 3-furanaldehyde 2a or 2b (0.96 g;
0.01 mol) and malononitrile 3 (0.66 g; 0.01 mol) in
ethanol (25 mL) was heated to reflux. Triethylamine (two
drops) were added, and the reflux was continued for 1 h
and left to cool to overnight. The reaction mixture was
then poured onto ice-cold water and neutralized with
drops of conc. HCl till acid reaction (pH paper). The dark
2-Amino-4-furan-3-yl-5-oxo-4,5-dihydro-indeno[1,2-b]
pyran-3-carbonitrile 4b.
Dark brown flakes, mp 163–
165°C (CH3CN); yield (2.35 g; 81%). νmax cmꢀ1: 3147–
3124 (NH2), 2205 (CN), 1678 (C═O). δH: 4.25 (s, 1H,
pyran-4H), 6.25 (d, 1H, J = 4 Hz, furan-4H), 6.8 (s, 2H,
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NH2), 7.18 (s, 1H, furan-2H), 7.3 (d, 1H, J = 4 Hz, furan-
5H), 7.5–7.68 (m, 4H, ArH). δc: 33.1 (d), 57.5 (s), 102.3
(s), 111.2 (d), 117.2 (s), 118.5 (s), 126.8 (d), 128.2 (d),
129.5 (d), 134.2 (d), 134.5 (s), 135.9 (s), 138.2 (d), 141.5
(d), 160.9 (s), 176.5 (s), 187.2 (s). MS: m/z = 290. Calcd
for C17H10N2O3 (290.28): C, 70.34; H, 3.47; N, 9.65;
found C, 70.55; H, 3.40; N, 9.59.
3-Imino-9-oxo-2-(pyridine-4-yl)-3,9-dihydro-2H-
indeno[2,1-c]pyridazine-4-carbonitrile 12. To a solution of
indan-1-ylidene malononitrile 10 (1.94 g; 0.01 mol)
in ≈30 mL of pyridine was added dropwise a solution of
the diazonium salt 8 (freshly prepared by diazotization
[0.94 g; 0.01 mol] of 4-aminopyridine/conc. hydrochloric
acid with sodium nitrite [0.69 g, 0.01 mol] solution 1:1 in
an ice bath at 0°C). After complete addition of the
diazonium salt solution (≈10 min), a dark brown solid
precipitate appeared. Stirring was continued at room
temperature for further 1 h. The reaction mixture was
diluted with cold water (≈30 mL), filtered off, washed
thoroughly with water, dried, and recrystallized from
ethanol/DMF 1:1. Dark brown crystals, mp 209–210°C
(EtOH/DMF); yield (2.7 g; 76%). νmax cmꢀ1: 3215–3165
(NH), 2228 (CN), 1678 (C═O). δH: 7.1 (d, 2H,
J = 12.5 Hz, pyridine), 7.32–7.75 (m, 4H, Ar), 8.48 (d,
2H, J = 12.5 Hz, pyridine), 8.45 (br s, 1H, NH). MS: m/
z = 299. Calcd for C17H9N5O (299.29): C, 68.22; H,
3.03; N, 23.40; found C, 68.40; H, 3.15; N, 23.62.
Synthesis of the indeno-pyrano-chromenes 6 & 7. To a
mixture of the indanedione 1 (1.46 g; 0.01 mol),
salicylaldehyde 5 (1.22 g; 0.01 mol), and malononitrile 3
(0.66 g; 0.01 mol) in ethanol (25 mL) was added two
drops of triethylamine, and the reaction mixture was
stirred at 60°C for 1 h. The reaction mixture was then
diluted with cold water acidified by conc. HCl where a
yellow precipitate appeared, filtered off, and
recrystallized from the proper solvent to afford the imino-
chromene derivative 6. Refluxing 6 (1.58 g; 0.005 mol)
in AcOH/HCl solution for 1 h furnished the chromene—
compound 7.
6-Amino-7-imino-7H-indeno[20,10:5,6]pyrano[3,4-c]
chromene-13(13bH)-one 6. Yellow powder, mp >300°C
3,9-Dioxo-2-pyridin-4-yl-3,9-dihydro-2H-indeno[2,1-c]
pyridazine-4-carbonitrile 13.
Compound 12 (1.49 g;
(CH3CN); yield (2.53; 80%). νmax cmꢀ1: 3186–3124 (NH
& NH2), 1676 (C═O). δH: 4.03 (s, 1H, pyran-H), 7.75–
8.5 (m, 10H, 8ArH + NH2), 10.1 (s, 1H, NH). δc: 26.7
(d), 73.3 (s), 97.6 (s), 117.0 (d), 122.7 (d), 123.7 (d),
124.0 (s), 126.1 (d), 126.3 (d), 128.2 (d), 129.6 (d), 134.5
(d), 136.5 (s), 137.7 (s), 153.0 (s), 154.3 (s), 160.5 (s),
191.9 (s), 198.3 (s). MS: m/z = 316. Calcd for
C19H12N2O3 (316.31): C, 72.15; H, 3.82; N, 8.86; found
C, 72.32; H, 3.48; N, 8.65.
0.005 mol) was refluxed in acetic acid/HCl (1:1) for 1 h,
then cooled and neutralized with ammonia solution. The
solid precipitate that appeared was filtered off, washed
thoroughly with water, dried, and recrystallized from
dioxane to afford reddish brown crystals, mp 269–270°C
(dioxane); yield (1.29 g; 86%). νmax cmꢀ1: 2224 (CN),
1672 & 1686 (2C═O). δH: 7.05 (d, 2H, J = 12.5 Hz,
pyridine-3, 5H), 7.32–7.42 (m, 3H, Ph), 7.78 (t, 1H, Ph),
8.47 (d, 2H, J = 12.5 Hz, pyridine-2, 6H). δc: 109.1
(d), 115.5 (s), 123.3 (s), 126.24 (d), 127.12 (d),
128.45 (d), 131.92 (d), 136.7 (s), 137.75 (s), 137.72
(s), 150.32 (d), 155.5 (s), 161.1 (s), 162.25 (s), 162.32 (s),
MS: m/z = 300. Calcd for C17H8N4O2 (300.27): C, 68.00;
H, 2.69; N, 18.66; found C, 68.25; H, 2.62; N, 18.55.
6-Amino-7H-indeno[20,10:5,6]pyrano[3,4-c]chromene-
7,13(13bH)-dione 7.
Yellow crystals, mp >300°C
(dioxane); yield (1.3 g; 82%). νmax cmꢀ1: 3175–3125
(NH2), 1681 & 1676 (2C═O). δH: 4.1 (s, 1H, pyran-H),
7.72–8.42 (m, 10H, 8ArH + NH2). δc: 34.3 (d), 76.8 (s),
105.9 (s), 117.2 (d), 122.8 (d), 123.6 (d), 124.1 (s), 126.2
(d), 126.4 (d), 128.3 (d), 129.7 (d), 134.5 (d), 136.5 (s),
137.7 (s), 154.1 (s), 162.8 (s), 164.1 (s), 164.3 (s), 192.0
(s). MS: m/z = 317. Calcd for C19H11NO4 (317.29):
C, 71.92; H, 3.49; N, 4.41; found C, 72.62; H, 3.47; N, 4.62.
Preparation of the hydrazo derivatives 16 & 17. To a
solution of indan-1-ylidene malononitrile 10 (1.94 g;
0.01 mol) in ≈30 mL of pyridine was added dropwise a
solution of the diazonium salts 14 or 15 (freshly prepared
by diazotization [1.65 g; 0.01 mol] of ethyl anthranilate
or [1.18 g; 0.01 mol] anthranilonitrile/conc. hydrochloric
acid with sodium nitrite solution 1:1 in an ice bath at
0°C). After complete addition of the diazonium salt
solution (≈10 min), dark red solid precipitates appeared,
respectively. Stirring was continued at room temperature
for further 1 h. The reaction mixture was diluted with
cold water (≈30 mL), filtered off, washed thoroughly
with water, dried, and recrystallized from ethanol/DMF
1:1 to afford 16 and 17, respectively.
2-(2-(Pyridin-4-yl)hydrazono)-1H-indene-1,3(2H)-dione
9. These were prepared according to the reported method
[16,17]. Dark brown crystals, mp 276–277°C (dioxane);
yield (1.91 g; 76%). νmax cmꢀ1: 3114 & 3069 (NH),
1695 (ring C═O). δH: 6.95 (d, 2H, J = 12.6 Hz,
pyridine), 7.62 (d, 2H, Ph), 7.74 (m, 2H, Ph), 8.45 (d,
2H,
J
=
12.6 Hz, pyridine), 11.85 (s, 1H-D2O
251. Calcd for
exchangeable, NH). MS: m/z
=
C14H9N3O2 (251.25): C, 66.93; H, 3.61; N, 16.73; found
C, 66.73; H, 3.85; N, 16.80.
Ethyl 2-(2-(1-(dicyanomethylene)-3-oxo-1,3-dihydro-2H-
inden-2-ylidene)hydrazinyl)-benzoate 16.
Red crystals,
2-(3-Oxoindan-1-ylidene)-malononitrile 10.
Prepared
mp 310–312°C (EtOH/DMF); yield (3.14 g; 85%). νmax
according to literature method; mp 228°C (lit. mp 232°C
[18]).
cmꢀ1: 3110 & 3067 (NH), 2187 (CN), 1714 (ester C═O),
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F. M. Abdelrazek, P. Metz, and A. Jaeger
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1682 (ring C═O). δH: 1.4 (t, 3H, J = 7.5 Hz, CH3), 4.5 (q,
2H, J = 7.5 Hz, CH2), 7.6–7.8 (m, 4H, Ph), 7.9 (d, 1H,
j = 8.1 Hz, Ph), 8.05 (dd, 1H, Ph), 8.28 (d, 1H,
J = 8.1 Hz, Ph), 8.59 (d, 1H, J = 8.1 Hz, Ph), 15.3 (s, 1H,
NH). δc: 14.32 (q), 61.93 (t), 69.90 (s), 114.05 (s), 114.38
(s), 115.78 (s), 116.88 (d), 124.39 (d), 125.18 (d), 125.59
(d), 131.08 (d), 131.54 (s), 134.72 (d), 135.16 (d), 135.64
(d), 138.91 (s), 143.70 (s), 156.09 (s), 167.01 (s), 184.55
(s). MS: m/z = 370. Calcd for C21H14N4O3 (370.37): C,
68.10; H, 3.81; N, 15.13; found C, 68.29; H, 3.65; N, 15.25.
Transformation of 21 into 20. Compound 21 (1.615 g;
0.005 mol) refluxed in AcOH/HCl (1:1) for 1 h, then
cooled and neutralized with ammonia solution. The solid
precipitate that appeared was filtered off, washed
thoroughly with water, dried, and recrystallized from
dioxane and found to be 20 (1.46 g; 90%) (identical mp,
TLC, and IR).
[1,20]Biindenylidene-3,10,30-trione 25.
Compound 1
(1.46 g; 0.01 mol) was refluxed for 30 min in ethanol
(25 mL) catalyzed by one drop of triethylamine. After
cooling to room temperature, the flask contents were
poured on ice-cold water and neutralized with drops of
HCl. The precipitated solid was filtered off and
recrystallized from dioxane.
2-(2-(2-(2-Cyanophenyl)hydrazono)-3-oxo-2,3-dihydro-1H-
inden-1-ylidene)malononitrile 17. Red crystals, mp 298–
301°C (EtOH/DMF); yield (2.78 g; 86%). νmax cmꢀ1
:
3215 & 3164 (NH), 2186 & 2205 (2CN), 1680 (ring
C═O). δH: 7.32–7.36 (m, 3H, Ph), 7.62–7.74 (m, 3H,
Ph), 7.91–7.93 (m, 2H, Ph), 13.25 (s, 1H, NH). δc: 69.95
(s), 101.05 (s), 115.75 (s; CN), 115.28 (d), 117.76 (s; Ph-
CN), 119.39 (d), 126.18 (d), 126.88 (d), 128.38 (d),
131.74 (d), 132.95 (d), 133.76 (d), 136.54 (s), 137.58 (s),
137.73 (s), 144.30 (s), 162.36 (s), 170.65 (s). MS: m/
z = 323. Calcd for C19H9N5O (323.32): C, 70.58; H,
2.81; N, 21.66; found C, 70.65; H, 2.65; N, 21.45.
Cyclization of compounds 16 and 17. Compounds 16
(1.85 g) or 17 (1.615 g) (0.005 mol of each) in ethanol
(25 mL) was heated to reflux, and two drops of
piperidine was added where the color changes promptly
from dark red to yellow. The reaction mixture was left to
cool overnight where a yellow precipitate appeared in
each case, filtered off, and washed thoroughly with
ethanol and recrystallized from dioxane to afford 20 and
21, respectively.
Yellow crystals turn into dark blue in acetone and to rose
red on contact with water, mp 212–213°C (dioxane); yield
(1.23 g; 90%). νmax cmꢀ1: 1713.5, 1681 & 1654 (3C═O).
δH: 3.25 (s, 2H, CH2), 7.47 (d, 1H, J = 8 Hz), 7.56 (t,
1H, J = 8 Hz), 7.70–7.73 (m, 4H), 7.77 (t, 1H, J = 8 Hz),
7.95 (d, 1H, J = 8 Hz). δc: 43.41 (t), 124.62 (d), 125.85
(d), 126.82 (s), 131.66 (d), 133.05 (d), 135.32 (d), 135.58
(d), 140.39 (s), 141.24 (s), 145.88 (s), 159.26 (s), 190.35
(s), 196.45 (s). MS: m/z = 274. Calcd for C18H10O3
(274.26): C, 78.83; H, 3.68; found C, 78.69; H, 3.63.
X-ray crystallographic data: yellow crystals, C18H10O3
(Mr
=
274.26 g*molꢀ1), crystal dimensions
=
0.28*0.26*0.17 mm. Molecules per unit cell Z = 32,
Dcalcd = 1.482 g*cmꢀ3. F(000) = 4544e, crystal system:
orthorhombic, space group Fdd2 (No. 43), cell constants
with standard deviations: a = 18.003 (2) Ǻ, b = 20.933 (2)
Ǻ, c = 26.101 (3) Ǻ, α[°] = 90.00, β[°] = 90.00 (1),
γ[°] = 90.00; V[Ǻ3] = 9836.2 (18). Data were collected
using a Bruker Nonius area detector at T [K] = 100 (2),
with graphite monochromator multi-layer with Mo Kα
radiation (λ = 0.71073 Ǻ) using the CCD data collection
and SADABS absorption correction method; absorption
coefficient μ = 0.101 cmꢀ1; the final difference Fourier
5,12-Dioxo-5,12-dihydroindeno[20,10:3,4]pyridazino[1,6-a]
quinazoline-7-carbonitrile 20. Yellow crystals, mp 318–
320°C (dioxane); yield (1.38 g; 85%). νmax cmꢀ1: 2210
(CN), 1676 & 1689 (two ring C═O). δH: 7.70–8.20 (m,
3H), 8.18–8.21 (d, 1H, J = 8 Hz), 8.24–8.32 (t, 1H,
J = 8 Hz), 8.35–8.63 (m, 2H), 8.87–8.93 (d, 1H, J = 8 Hz).
δc: 114.75 (d), 115.78 (s), 122.82 (s), 126.12 (s), 126.22
(d), 126.85 (d), 127.18 (d), 128.04 (d), 128.50 (d), 131.76
(d), 136.64 (s), 137.70 (s), 137.73 (s), 138.89 (d), 146.18
(s), 157.55 (s), 158.93 (s), 162.36 (s), 167.75 (s). MS: m/
z = 324. Calcd for C19H8N4O2 (324.29): C, 70.37; H,
2.49; N, 17.28; found C, 70.29; H, 2.63; N, 17.35.
ρ = 0.44 (ꢀ0.34)e Ǻꢀ3. Max. resolution [sin θ/λ]max
=
0.70 Ǻꢀ1/99.9%. Absorption correction min. 97.2%; max.
98.3%. Total number of reflections collected and counted
were 143,426, number of independent reflections 7522,
and number of observed reflections 7110. Rav = 0.160.
The final R and R2W = 0.042 and 0.114, respectively.
5-Imino-12-oxo-5,12-dihydroindeno[20,10:3,4]
pyridazino[1,6-a]quinazoline-7-carbonitrile 21.
Yellow
Acknowledgments. We are thankful to the Alexander von
Humboldt Foundation (Germany) for financing a research fellow-
ship to F. M. Abdelrazek from June to August 2018; during this
time, a considerable part of the syntheses and spectra of this work
has been carried out.
crystals, mp 312–314°C (dioxane); yield (1.4 g; 87%).
νmax cmꢀ1: 3225–3185 (NH), 2218 (CN), 1680 (C═O).
δH: 7.30–7.75 (m, 8H, Ar), 9.38 (s, 1H, NH). δc: 114.65
(d), 115.75 (s), 117.84 (s), 126.14 (s), 126.25 (d), 126.88
(d), 130.16 (d), 118.74 (d), 128.56 (d), 131.76 (d),
136.55 (s), 137.68 (s), 137.71 (s), 135.85 (d), 145.38 (s),
157.48 (s), 158.83 (s). 162.39 (s), 164.25 (s). MS: m/
z = 323. Calcd for C19H9N5O (323.31): C, 70.58; H,
2.81; N, 21.66; found C, 70.49; H, 2.95; N 21.60.
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