Preparation and reactions of 2-azidoquinoline-3-carboxaldehyde with primary amines and active methylene compounds

Article abstract of DOI:10.3184/030823409X435900

Preparation of 2-azidoquinoline-3-carboxaldehyde has been attempted and its tautomerism has been discussed. The reactivity of 2-azidoquinoline-3- carboxaldehyde towards primary amines, hydrazines and active methylene compounds has been investigated. Analy

Full text of DOI:10.3184/030823409X435900

220 RESEARCH PAPER
APRILꢇꢀꢄꢄꢈ±ꢄꢄꢉ
JOURNAL OF CHEMICAL RESEARCH 2009
Preparation and reactions of 2-azidoquinoline-3-carboxaldehyde with
primary amines and active methylene compounds
Nabila M. Ibrahim, Hisham Abdallah A. Yosef and Mohamed Refat H. Mahran*
Dept. of Organometallic and Organometalloid Chemistry, National Research Centre, Dokki, Cairo, 12622, Egypt
Preparation of 2-azidoquinoline-3-carboxaldehyde has been attempted and its tautomerism has been discussed.
The reactivity of 2-azidoquinoline-3-carboxaldehyde towards primary amines, hydrazines and active methylene
compounds has been investigated. Analytical and spectroscopic measurements have assisted the assignment of
appropriate structures to the new reaction products.
Keywords: 2-azidoquinoline-3-carboxaldehyde, tetrazoles, primary amines, hydrazines
Quinolines are
a ubiquitous and important group of
11
N-heterocycles.1-3 Several representatives of this class have
been screened for bacteriocidal,4 antitumor,5ꢀDQWLLQÀDPPDWRU\6
and antimalarial7 activities. In pursuance of our growing
interest in the chemistry of polyfunctional substrates,8-10
we have now attempted the preparation of 2-azidoquinoline-
3-carboxaldehyde (2) to examine its reactivity towards
certain primary amines (3a–c), hydrazines (4a–d) and active
methylene compounds (5, 6) (Scheme 1).
9
N
4
5
6
7
3
2
8
N
N
N
N
10
7
The reaction of (2) with o-phenylenediamine (3b) also
proceeded in ethanol in the cold to give a yellowish-brown
FU\VWDOOLQHꢀ FRPSRXQGꢀ IRUPXODWHGꢀ DVꢀ ꢁꢂꢃꢄꢅ±LPLGD]RO\Oꢆ
tetrazolo[1,5-a]quinoline (8).
The azido-function in ortho-activated azides is known to
suffer attack by anionic reagents to produce N-heterocyclic
systems.11,12 Moreover, azides are very important building
blocks due to their chemical and biological as well as
industrial applications.11-16
We have found that 2-chloroquinoline-3-carboxaldehyde
(1) reacts with sodium azide in DMF at 0°C to give azide
(2) in the form of colourless crystals. Compatible analytical
and molecular weight determination (MS) for compound
2 corresponded to C10H6N4O. (m/z 198, M+, 5%). Its IR
spectrum showed the azide (N3) band at 2120 cm-1 and the
carbonyl band (C=O) at 1700 cm-1 and its 1H NMR spectrum
showed a signal at G 10.40 due to a proton of the aldehydic
group (CHO).
The reaction of compound (2) with aniline (3a) proceeded
in absolute ethanol at ambient temperature to give a pale
yellow crystalline product formulated as 3-phenylamino-
methylenetetrazolo[1,5-a]quinoline (7) for the following
reasons: (a) No absorption bands were recorded in the IR
spectrum of 7 due to the azido-function around 2100 cm-1. (b)
Correct elementary and molecular weight determination (MS)
corresponded to C16H11N5 (m/z 273, M+, 25.3%).
N
C
N
H
N
N
N
N
8
Structural reasons for (8) are: (a) Elementary analyses and
molecular weight determination (MS) corresponded to
C16H10N6 (m/z 286, M+, 41.0%). (b) Its IR spectrum (KBr,
cm-1) revealed the presence of a strong NH absorption band
at 3324 and absence of absorptions around 2100 (N3). (c)
The 1H NMR spectrum of (8) (DMSO, G ppm) showed a
signal at 12.96 (1H, NH, D2O-exchangeable).
Formation of (8) is best explained in terms of molecular
reaction of the initially formed anil (9) to give a transient
O
O
O
9
H
4
5
8
H
H
6
NaN3
3
2
7
1
N
N
N
N
N
DMF
10
N3
Cl
N
1
2
2A
O
O
R
H2C
R
N
H
NH2
Y
NH2
CN
X
6
4 a, R=H
5 a, R=CN
b, R=C(O)OC2H5
3 a, X=Y=H
b, X=NH2, Y=H
c, X=H, Y=NH2
b, R=CH3
c, R=C6H5
d, R=C6H3(NO2)-2,4
Scheme 1
* Correspondent. E-mail: mrh_mahran@yahoo.com

JOURNAL OF CHEMICAL RESEARCH 2009 221
The reaction of compound (2) with hydrazines (4a–d)
proceeded in absolute ethanol at ambient temperature to give
colourless to yellow crystalline products for which structures
(12a–d) were respectively assigned. Their IR spectra revealed
the absence of absorption bands around 2100 cm-1 (N3).
This excludes the alternative structures (13a–d) from further
consideration. Compatible elementary analyses and molecular
weight determinations (MS) were gained for compounds
(12a–d).
N
+
2
3b
N
N
N HN
N
H
9
H
N
H
C
[O]
-H2
N
H
11
8
9
N
N
H
R
N
N
H
R
4
N
N
N
N
5
6
3
2
7
8
1
N
10
N
N
N
N3
N
10
12
13
Scheme 2
12, 13 a, R= H
b, R= CH3
intermediate like (10) which readily undergoes auto-oxidation
\LHOGLQJꢀWKHꢀ¿QDOꢀSURGXFWꢀꢃ8) (Scheme 2). This behaviour is
familiar in the reactions of (3b) with carbonyl compounds.17
The reaction of azide (2) with p-phenylenediamine (3c) in
ethanol yielded an orange crystalline product formulated as
3-(p-aminophenyl)aminomethylenetetrazolo-[1,5-a]quinoline
(11) for the following reasons: (a) Elementary analyses
and molecular weight determination (MS) corresponded to
C16H12N6 (m/z 288, M+, 59.0%). (b) No absorption bands were
recorded in the IR spectrum of (11) around 2100 cm-1 (N3).
c, R= C6H5
d, R= C6H3(NO2)2-2,4
The behaviour of compound (2) towards active methylene
compounds, namely, malononitrile (5a), ethyl cyanoacetate
(5b) and indan-1,3-dione (6) was also investigated. The
reaction of (2) with malononitrile (5a) proceeded in ethanol
to give a yellow product for which structure (14) was
assigned for the following reasons: (a) Elementary analyses
and molecular weight determination (MS) corresponded to
C16H6N6 (m/z 282, M+, 8.6%). (b) Its IR spectrum (KBr, cm-1)
revealed the absence of absorptions around 2100 (N3) and
presence of bands at 3392 (NH), 2208 (CN) and 1627 (C=N).
N
NH2
CN
HN
N
N
N
N
11
CN
CN
N
C
N
On the other hand, the spectrum showed strong bands at 3342,
3209 (NH2). Its H NMR spectrum (DMSO, G ppm) showed
14
1
signals at 5.55 (2H, NH2, D2O-exchangeable) and at 7.32 and
6.65 as two doublets (each with JHH = 10 Hz) due to the AB-
V\VWHPꢀRIꢀWKHꢀ±1±&6H4±1±ꢀULQJꢇꢀLQꢀDGGLWLRQꢀWRꢀWKHꢀH[SHFWHGꢀ
signals due to the quinoline moiety. The structure of (11) was
DOVRꢀFRQ¿UPHGꢀE\ꢀ;ꢂUD\ꢀFU\VWDOORJUDSKLFꢀDQDO\VLVꢊꢀ$Qꢀ257(3ꢀ
diagram of single X-ray diffraction of compound (11) is
shown in Fig. 1. The crystal data and experimental parameters
XVHGꢀIRUꢀWKHꢀLQWHQVLW\ꢀGDWDꢀFROOHFWLRQꢀVWUDWHJ\ꢀDQGꢀ¿QDOꢀUHVXOWVꢀ
of the structure determination, are presented in Table 1
(cf. Experimental).
A possible mechanism for formation of compound (14) is
depicted in Scheme 3.
Condensation of (2) with (5a) would produce the
ethylenic compound (15) which can rearrange to the tricyclic
intermediate (16). Loss of N2 molecule from (16) which is
frequently observed in organic azides18-20 can produce the
nitrene species (17) which adds another molecule of (5a)
to yield the transient (18). The latter undergoes then auto-
R[LGDWLRQꢀWRꢀDIIRUGꢀWKHꢀ¿QDOꢀSURGXFWꢀꢃ14).
Condensation of compound (2) with ethyl cyanoacetate (5b)
in methylene chloride yielded a pale yellow crystalline product
formulated as ethyl tetrazolo[1,5-a]-quinolin-3-(D-cyano)-
acrylate (19) for the following reasons: (a) Elementary analyses
and molecular weight determination (MS) corresponded to
C15H11N5O2 (m/z 293, M+, 19.8%). (b) Its IR spectrum (KBr,
cm-1) revealed a weak band at 2224 (CN) and strong bands at
1721 (C=O, ester) and 1614 (C=N). The 1H NMR spectrum of
(19) (DMSO, G ppm) showed signals of the ethoxy group at
1.36 (t, 3H, CH3) and 4.41 (q, 2H, CH2).
CN
11 12
C
9
4
5
8
O
OC2H5
6
3
2
7
1
N
10
N
N
N
19
Fig. 1 An ORTEP overview of compound (11).

222 JOURNAL OF CHEMICAL RESEARCH 2009
CN
CN
H
C
C
- H2O
2
+
5a
N3
N
15
CN
HN
CN
HN
5a
- N2
N:
N
N3
N
16
17
CN
HN
[O}
- H2
14
CN
CN
N
H
C
H
N
18
Scheme 3
Fourier Transform Infrared Spectrophotometer model FT/IR-3000E.
The 1H NMR spectra were recorded in deuterated dimethylsulfoxide
(DMSO) on JOEL JNM-EX 270 (at 270 MHz) and/or JOEL 500 AS
(at 500 MHz) Spectrometer using tetramethylsilane (TMS) as an
internal reference. 13C NMR spectra were recorded on JOEL 500 AS
(at 125 MHz). Mass spectra (EI-MS) were determined at 70 eV on a
Finnigan MAT SSQ 7000 spectrometer.
When compound (2) was allowed to react with indan-1,3-
dione (6) in ethanol at room temperature, a golden yellow
crystalline product was formed and assigned structure (20) for
the following reasons: (a) Elementary analyses and molecular
weight determination (MS) corresponded to C19H10N4O2 (m/z
326, M+, 10.2%).
X-Ray diffraction: Intensity data collection was performed with
.DSSD±&&'ꢀ (QUDIꢂ1RQLXVꢀ FR 590 Single Crystal Diffractometer.
The structure was solved by direct methods using the SIR92 program30
DQGꢀUH¿QHGꢀXVLQJꢀPDXus.31 The molecular graphics were made with
ORTEP.32 Crystallographic data (CIF) for the structure reported in
this article has been deposited in the Cambridge Crystallographic
Data Centre (CCDC) as supplementary publication No. 706167.
Copies of the data can be obtained, free of charge, on applicaion
to the CCDC, 12 Union Road, Cambridge CB 12EZ, UK(FAX:
+ 44(1223)336-033; E-mail: deposite@ccdc.cam.ac.uk).
O
9
C
4
5
6
3
7
2
8
1
N
O
N
N
10
N
20
2-Chloroquinoline-3-carboxaldehyde (1) was prepared according
to an established method.33
As expected in the mass spectra of cyclic polycarbonyl
compounds,19,20 the molecular ion peak of (20) suffers
successive loss of two neutral CO molecules to give radical
cations at m/z 298, 100% and m/z 270, 24.1%, respectively. (b)
The IR spectrum of (20) (KBr, cm-1) disclosed the presence of
strong absorption bands at 1725 (C=O), 1682 (C=O) and 1613
(C=N).
Preparation of 2-Azidoquinoline-3-carboxaldehyde (2)
To
a solution of 2-chloro-3-formylquinoline(1) (0.05 mole) in
dry dimethylformamide (DMF) (40 mL) was added sodium azide
(0.1 mole) under good stirring and cooling in ice-bath for 30 min.
The mixture was stirred at room temperature for further 5 hours.
The product was treated with ice-cold water. The precipitated material
ZDVꢀ ¿OWHUHGꢇꢀ ZDVKHGꢀ ZLWKꢀ LFHꢂFROGꢀ ZDWHUꢇꢀ GULHGꢀ DQGꢀ UHFU\VWDOOLVHGꢀ
from acetone to give compound (2) as colourless crystals.
2-Azidoquinoline-3-carboxaldehyde (2): Yield 13.8
g (70%).
Conclusion
0ꢊSꢊꢀꢄꢋꢌ±ꢄꢋꢄ°C. (dec.) IR (cm-1): 2120 (N3), 1700 (C=O). MS: m/z
198, M+ (5%). 1H NMR: G 10.40 (s, 1H, CHO), 9.05 (s, 1H, H-4),
8.7 (d, 1H, H-8, J = 8 Hz), 8.5 (d, 1H, H-5, J = 8 Hz), 8.16 (t, 1H, H-
7), 7.92 (t, 1H, H-6), 13C NMR: G 187.5 (CHO), 139.7 (C-N3), 134.4,
131.6, 128.6,116.4 (aromatic carbons). Anal. Calcd for C10H6N4O
(198.18): C, 60.61; H, 3.05; N, 28.27. Found: C, 60.57; H, 3.13; N,
28.22%.
It is evident that azide (2) resulting from the reaction of 2-
chloroquinoline-3-carboxaldehyde (1) with sodium azide,
reacts in the tautomeric tetrazolo-form (2
2A), this
might be attributable to proximity of the azido-function in (2)
to the ring nitrogen atom.21 This phenomenon predominates at
least under the prevailing experimental conditions.
Results of the present study extend to the chemistry of the
important class of tetrazoles22,23ꢀZKLFKꢀ¿QGꢀZLGHꢀDSSOLFDWLRQVꢀ
in medicine,24-26 agriculture27 and industry.28,29
Reaction of 2-azidoquinoline-3-carboxaldehyde (2) with aniline (3a)
A solution of aniline (16 mmole) in ethanol (10 mL) was added to a
stirred solution of compound 2 (10 mmole) in ethanol (20 mL) and
WKHꢀPL[WXUHꢀZDVꢀVWLUUHGꢀIRUꢀꢌꢈꢀKꢊꢀ7KHꢀSUHFLSLWDWHꢀIRUPHGꢀZDVꢀ¿OWHUHGꢇꢀ
washed with ethanol and recrystallised from cyclohexane to give
compound (7) as pale yellow crystals.
Experimental
Melting points were determined on an Electrothermal digital melting
point apparatus and were uncorrected. Elemental analytical data
were obtained at the analytical laboratory of the National Research
Centre. The IR spectra were recorded in KBr disks on a Jasco
4-Phenylaminomethylenetetrazolo[1,5-a]quinoline (7): Yield 1.6 g
ꢃꢍꢈꢎꢆꢊꢀ0ꢊSꢊꢀꢌꢏꢍ±ꢌꢏꢐ°C. IR (cm-1): 1621 (C=N), 1563, 1526 (C=C).
MS: m/z 273, M+ (25.3%).1H NMR: G 9.10 (s, 1H, H-4) 8.90 (s, 1H,
azomethine proton), 8.60 (d, 1H, H-8, J = 7.9 Hz), 8.38 (d, 1H, H-5,

JOURNAL OF CHEMICAL RESEARCH 2009 223
J = 7.9 Hz), 8.02 (t,1H, H-7), 7.85 (t,1H, H–6), 7.55–7.30 (m, 5H,
N-C6H5). 13C NMR (DMSO, G ppm): Signals due to the N-phenyl
carbon atoms (6C) appeared at 146.98 (C-1'), 121.48 (C-2', C-6'),
129.06 (C-3', C-5') and 121.73 (C-4'). The carbon skeleton of the
tetrazoloquinoline nucleus (9C) gave signals at 154.03 (C-2), 151.24
(C-4, C-10), 133.31 (C-7, C-9), 133.11 (C-3), 131.40 (C-5), 130 (C-6)
and 127.62 (C-8). The azo-methine carbon atom (C-11) gave a signal
at 116.83. Anal. Calcd for C16H11N5 (273.30): C, 70.32; H, 4.06; N,
25.63. Found: C, 70.28; H, 4.11; N, 25.80%.
(C-10, C-7), 129.27 (C-3, C-9), 128.68 (C-5), 124.93 (C-6) and
124.35 (C-8). The azomethine carbon atom (CH=N-, C-11) disclosed
a signal at 116.56 ppm. Anal.Calcd for C10H8N6 (212.21): C, 56.60;
H, 3.80; N, 39.60. Found: C, 56.85; H, 3.68; N, 39.77%.
2-Methyl-1-((tetrazolo[1,5-D]quinolin-3-yl)methylene)hydrazine
(12b): Pale yellow crystals (ethanol). Yield 1.69 g (75%). M.p. 228–
230°C. IR (cm-1): 3291 (NH), 1629 (C=N). MS: m/z 226, M+ (85.0%).
1H NMR: G 8.55 (d, 1H, H-8, J = 8.1 Hz), 8.43 (s, 1H, H-4), 8.32 (s,
1H, azomethine proton), 8.22 (d, 1H, H-5, J = 8.1 Hz), 7.87 (t, 1H,
H-7), 7.79 (s, 1H, NH, D2O-exchangeable), 7.75 (t,1H, H-6), 2.98 (d, 3H,
CH3, J = 4 Hz). 13C NMR: G 129.77 (C-2), 129.11 (C-4, C-10), 128.49
(C-7), 128.06 (C-9), 122.49 (C-3, C-5), 122.12 (C-6), 121.04 (C-8),
115.93 (C-11) and 32.94 (CH3). Anal. Calcd for C11H10N6 (226.24): C,
58.40; H, 4.46; N, 37.15. Found: C, 58.33; H, 4.51; N, 36.80%.
2-Phenyl-1-((tetrazolo[1,5-D]quinolin-3-yl)methylene)hydrazine
(12c): Yellow crystals (acetone). Yield 2.7 g (94%). M.p. 277–278°C.
IR (cm-1): 3262 (NH), 1601 (C=N). MS: m/z 288, M+ (100%).
1H NMR: G 11.25 (s, 1H, NH, D2O-exchangeable), 8.58 (d, 1H, H-8,
J = 8.1 Hz), 8.51 (s, 1H, H-4), 8.41 (s, 1H, azomethine proton), 8.26
(d, 1H, H-5, J = 8.1 Hz), 7.92 (t, 1H, H-7), 7.80 (t,1H, H-6), 7.31–
6.88 (m, 5H, N-C6H5). Anal. Calcd for C16H12N6 (288.31): C, 66.66;
H, 4.20; N, 29.15. Found: C, 66.72; H, 4.16; N, 29.40%.
2-(2,4-Dinitrophenyl)-1-((tetrazolo[1,5-D]quinolin-3-yl)methyl-
ene)hydrazine: (12d):Yellow crystals (DMF/H2O). Yield 3 g (80%).
M.p. 278–279°C. IR (cm-1): 3287 (NH), 1615 (C=N). MS: m/z 378,
M+ (86.7%). 1H NMR: G 9.17 (s, 1H, aromatic proton of the
dinitrophenyl ring)), 9.01 (s, 1H, H-4), 8.82 (s, 1H, NH, D2O-
exchangeable), 8.81 (s, 1H, azomethine proton), 8.65 (d, 1H, H-8,
J = 8.4 Hz), 8.37–8.31 (m, 2H, H-5 and 1H, aromatic proton of the
dinitrophenyl group), 8.01 (t, 1H, H-7), 7.86 (t,1H, H-6), 7.67 (d, 1H,
aromatic proton of the dinitrophenyl group, J = 9.9 Hz). Anal.Calcd
for C16H10N8O4 (378.81): C, 50.80; H, 2.66; N, 29.62. Found: C,
50.47; H, 2.44; N, 29.78%.
Reaction of 2-azidoquinoline-3-carboxaldehyde (2) with o- and/or
p-phenylenediamine (3b,c)
General procedure
o-, or p-Phenylenediamine (3b or 3c) (0.66 g, 5 mmole) was added
to a stirred solution of compound (2) (1.98 g, 10 mmole) in ethanol
(20 mL). The mixture was stirred for 5–7 hours (the reaction was
7/&ꢂFRQWUROOHGꢆꢊꢀ7KHꢀSUHFLSLWDWHꢀIRUPHGꢀZDVꢀFROOHFWHGꢀE\ꢀ¿OWUDWLRQꢀ
and recrystallised from ethanol to give compound (10) and/or (11),
respectively.
3-(2'–Imidazolyl)tetrazolo[1,5-a]quinoline (10): Yield 0.7 g (25%).
M.p. 303–305°C. IR (cm-1): 3324 (NH),1607 (C=N). MS: m/z 286,
M+ (41.0%). 1H NMR: G 12.96 (s, 1H, NH, D2O-exchangeable), 9.18
(s, 1H, H-4), 8.69 (d, 1H, H-8, J = 8.1 Hz), 8.44 (d, 1H, H-5, J = 8.1 Hz),
8.05 (t, 1H, H-7), 7.88 (t, 1H, H-6), 7.79–7.29 (m, 4H, imidazole ring-
protons). Anal. Calcd for C16H10N6 (286.3): C, 67.13; H, 3.52; N,
29.35. Found: C, 67.17; H, 3.40; N, 29.52%.
3-(p-Aminophenyl)aminomethylenetetrazolo[1,5-a]quinoline (11):
Yield 2.0 g (70%). M.p. 253–254°C. IR (cm-1): 3342, 3209 (NH2),
1622 (C=N). MS: m/z 288, M+ (59.0%). 1H NMR: G 9.13 (s, 1H,
H-4), 8.82 (s, 1H, azomethine proton), 8.65 (d, 1H, H-8, J = 8.1 Hz),
8.40 (d, 1H, H-5, J = 8.1 Hz), 8.00 (t, 1H, H-7), 7.85 (t, 1H, H-6), 7.32,
6.65 (2d, 2H, AB system of N-C6H4-N moiety, each with J = 10 Hz),
5.55 (s, 2H, NH2, D2O-exchangeable). Anal.Calcd for C16H12N6
(288.31): C, 66.66; H, 4.20; N, 29.15. Found: C, 66.69; H, 4.08; N,
29.50%.
Reaction of 2-azidoquinoline-3-carboxaldehyde (2) with malono-
nitrile (5a)
X-ray crystallographic structural data: Table 1.
To a stirred solution of compound (2) (10 mmole) and malononitrile
(20 mmole) in ethanol (20 mL) was added a solution of piperidine
(0.2 mL) in ethanol (5 mL). The mixture was stirred at room
temperature for 15 hours. The volatile materials were evaporated
under reduced pressure and the residue was chromatographed on
silica gel using petroleum ether (b.p. 60–80°C) and acetone (80:20,
v/v) as an eluent to give compound (14) as yellow crystals.
4-(Dicyanomethyleneamino)-1-imino-1H-cyclopenta[c]quinoline-
2-carbonitrile (14): Yellow crystals (acetone). Yield 1.4 g (50%).
M.p. 213–215°C. IR (cm-1): 3392 (NH), 2208 (CN), 1627 (C=N).
MS: m/z 282, M+ (8.6%). 1H NMR: G 8.65 (d, 1H, H-8, J = 8.1 Hz),
8.38 (s, 1H, methine proton in the cyclopentene ring), 8.28 (d, 1H,
H-5, J = 8.1 Hz), 8.03 (t, 1H, H-7), 7.86 (t,1H, H-6). Anal. Calcd for
C16H6N6 (282.26): C, 68.08; H, 2.14; N, 29.77. Found: C, 68.32; H,
2.03; N, 29.93%.
Reaction of 2-azidoquinoline-3-carboxaldehyde (2) with hydrazine
derivatives (4a–d); general procedure
A solution of compound 2 (10 mmole) in ethanol (30 mL) was
mixed with a solution of the hydrazine derivative (4a, 4b, 4c or 4d)
(10 mmole) in ethanol (10 mL) and stirred at room temperature for
2 hours (for10 hours in the case with (4d). The precipitate formed was
FROOHFWHGꢀE\ꢀ¿OWUDWLRQꢇꢀZDVKHGꢀZLWKꢀHWKDQROꢀDQGꢀUHFU\VWDOOLVHGꢀIURPꢀ
the appropriate solvent to give compounds (12a–d), respectively.
1-((Tetrazolo[1,5-D]quinolin-3-yl)methylene)hydrazine
(12a):
Colourless crystals (ethanol). Yield 1.9 g (90%). M.p. 216–217°C.
IR (cm-1): 3420, 3350 (NH2), 1604 (C=N). MS: m/z 212, M+ (45.0%).
1H NMR: G 8.57 (d, 1H, H-8, J = 8.0 Hz), 8.34 (s, 1H, H-4), 8.24 (s,
1H, azomethine proton), 8.23 (d, 1H, H-5, J = 8.0 Hz), 7.89 (t, 1H,
H-7), 7.78 (t,1H, H-6), 7.76 (s, 2H, NH2, D2O-exchangeable). 13C
NMR (DMSO, G ppm): signals at 147.90 (C-2), 130.71 (C-4), 129.83
Table 1 Crystal data and experimental parameters used for the intenisty data collection strategy and final results of the structure
determination of compound (11)
1-Crystal data:
2- Data collection:
Empirical formula
Formula weight (Fw)
Colour
C16H12N6
288.314
Brown
T max
19.98°
Index ranges( h,k,l)
hmax. = 9
k
max. = 7
Crystal description
Crystal system
Space group
Crystal length (a)
Crystal length (b)
Crystal length (c)
Crystal angle (D)
Crystal angle (E)
Crystal angle (J)
Crystal volume (V)
Cell formula units(Z)
Temperature
Radiation
Cube
l
max. = 16
2419
Monoclinic
P21/c
9.9994(6)Å
8.0975(5)Å
17.7759(11)Å
90.00°
Measured reflections
Independent reflections
Observed reflections
Rint
3- Refinement:
R (all) [I>3V(I)]
R (gt)
1418
846
0.034
0.071
0.036
0.07
0.077
0.07
1.443
1.657
1.448
845
105.466(3)°
90.00°
R
w (ref)
1387(15)Å3
4
Rw (all)
R
w (gt)
298 K
MoKD
S (ref)
S (all)
Wavelength (l)
Ucalc (Dx)
0.71073Å
1.381 Mgm-3
600
S (gt)
Reflections
Parameters
Restrains
F (000)
199
0
P
0.09 mm-1
291 – 19.98°
T range

224 JOURNAL OF CHEMICAL RESEARCH 2009
3
4
M.M. Ali, R.K.C. Tasneem and P.K. Saiprakash, Synlett, 2001, 2, 251.
H.V. Patel, K.V. Vyas and P.S. Fernandes, Indian J. Chem., 1990, 29(B),
836.
Reaction of 2-azidoquinoline-3-carboxaldehyde (2) with ethyl
cyanoacetate (5b)
To an equimolar amount of compound (2) (10 mmole) and ethyl
cyanoacetate (10 mmole) in ice-cold methylene chloride was added
sodium methoxide powder (2 mmole). The cold reaction mixture
was stirred for 30 minutes when a precipitate was formed, stirring
was continued for additional two hours at room temperature.
7KHꢀ SUHFLSLWDWHꢀ ZDVꢀ ¿OWHUHGꢇꢀ ZDVKHGꢀ ZLWKꢀ FROGꢀ PHWK\OHQHꢀ FKORULGHꢀ
and recrystallised from ethyl acetate to give compound (19) as pale
yellow crystals.
5
6
N.K. Sukhova, M. Lidak, A. Zidernane, I.S. Pelevina and S.S. Voronia,
Khim. Farm. Zh., 1989, 23, 1226.
R.D. Dillard, D.E. Pavey and D.N. Benslay, J. Med. Chem., 1973, 16,
251.
7
8
J.C. Craig and P.E. Person, J. Med. Chem., 1971, 14, 1221.
M.S. Mohamed, W.A. Zaghary, T.S. Hafez, N.M. Ibrahim, M.M. Abo
El-Alamin and M.R.H. Mahran, Bull. Fac. Pharm. Cairo Univ., 2003,
40, 1.
9
N.M. Ibrahim, Phosphorus, Sulfur & Silicon, 2006, 181(8), 1773.
Ethyl tetrazolo[1,5-a]quinoline-3-(D-cyano)acrylate (19). Yield
ꢌꢊꢋꢏꢀJꢀꢃꢍꢈꢎꢆꢊꢀ0ꢊSꢊꢀꢌꢐꢑ±ꢌꢑꢈ°C. IR (cm-1): 2224 (CN), 1721 (C=O,
ester), 1614 (C=N). MS: m/z 293, M+ (19.8%). 1H NMR: G 9.07
(s, 1H, H-4), 8.78 (s, 1H, azomethine proton), 8.68 (d, 1H, H-8,
J = 8.1 Hz), 8.42 (d, 1H, H-5, J = 8.1 Hz), 8.13 (t, 1H, H-7), 7.90
(t,1H, H-6), 4.41 (q, 2H, ethoxy-CH2), 1.36 (t, 3H, ethoxy-CH3).
13C NMR (DMSO, G ppm): signals at 160.84 (C=O), 146.41 (C-
2), 145.34 (C-10), 134.67 (C-4), 133.96 (C-7), 131.10 (C-8), 130.8
(C-9), 128.77 (C-5), 123.10 (C-6), 119.14 (C{N), 116.37 (C-11),
114.6 (C-3), 107.27 (C-12), 62.9 (CH3) and 14.20 (CH2). Anal. Calcd
for C15H11N5O2 (293.28): C, 61.43; H, 3.78; N, 23.88. Found: C,
61.52; H, 3.73; N, 23.61%.
10 N.M. Ibrahim, H.A.A. Yosef and M.R.H. Mahran, Phosphorus, Sulfur
and Silicon (Special Issue: M. Mikolajczyk)(2008); in press.
11 D.R. Sutherland and G.J. Tennant, J. Chem. Soc. Perkin Trans. I,
1974, 534.
12 T.C. Porter, R.K. Smally, M. Teguiche and B. Purwono, Synthesis,
1997, 773.
13 E.F.V. Scriven, Azides and nitrenes, reactivity and utility, Academic Press,
Orlando Fla (1984).
14 C. Sander and F.J. Mühbaur, Envir. Exp. Bot., 1977, 17, 43.
15 W. Owaise, J.L. Rosichan, R.C. Roland, A. Kleinhofs and R.N. Nilan,
Mut. Res., 1983, 118, 299.
16 N. Bhanumathi, K.R. Rao, P.B. Sattur, Heterocycles, 1986, 24(6), 1683.
17 T. Saski, K. Kenamatsu and M. Murata, Tetrahedron, 1972, 28, 2382.
18 Th. Kappe, A. Pfanschlager and W. Stadlbauer, Synthesis, 1989, 666.
19 M.R. Mahran, W.M. Abdou and N.M. Abdel Rahmam, Chem. Indy,
1990, 233.
Reaction of 2-Azidoquinoline-3-carboxaldehyde (2) with indan-1,3-
dione (6)
To a stirred solution of compound (2) (10 mmole) and indan-1,3-
dione (6) (10 mmole) in ethanol (20 mL) was added a solution of
piperidine (0.2 mL) in ethanol (5 mL). The mixture was stirred at
URRPꢀWHPSHUDWXUHꢀIRUꢀꢏꢀKRXUVꢊꢀ7KHꢀSUHFLSLWDWHꢀIRUPHGꢀZDVꢀ¿OWHUHGꢇꢀ
washed with ethanol and recrystallised from ethyl acetate to give
compound (20) as yellow crystals.
20 R.Aw. Johnson, Mass spectrometry for organic compounds, Cambridge,
Cambridge University Press,1972, pp.72.
21 W. Stadlbauer and G. Hojas, J. Chem. Soc. Perkin Trans I, 2000, 2085.
22 G.I. Koldobskii, V.A. Ostrovskii and V.S. Poplavskii, Khim. Geterotsikl.
Soedin, 1981, (10), 1299.
23 S.C.S. Bugalho, A.C. Serra, L. Lapiniski, M.L.S. Cristiana and R. Fausto,
Phys. Chem., 2002, 4, 1725.
3-2(1,3-Indanyl)methylenetetrazolo[1,5-a]quinoline (20). Yield
ꢄꢊꢄꢐꢀJꢀꢃꢋꢈꢎꢆꢊꢀ0ꢊSꢊꢀꢄꢑꢏ±ꢄꢑꢍ°C. IR (cm-1): 1725 (C=O, ester), 1682
(C=O, aryl), 1613 (C=N). MS: m/z 326, M+ (10.2%). 1H NMR:
G 9.88 (s, 1H, exocyclic methine proton), 8.70 (d, 1H, H-8, J = 6.6 Hz),
8.43 (d, 1H, H-5, J = 8.1 Hz), 8.39 (s, 1H, H-4), 8.2-7.93 (m, 6H, H-6,
H-7 and four aromatic protons of the indandione moiety). 13C NMR
(DMSO, G ppm): Signals at 161.48 (2C=O), 147.05 (C-2), 145.98
(C-4), 131.42 (C-7, C-10), 129.41 (C-3, C-9), 123.73 (C-5, C-6),
117.76 (-CH=C-C=O), 117.27 (-CH=C-C=O) and 117.00 (C-8).
The carbon skeleton of the aroyl group (D-dicarbonyl group) disclosed
signals at 135.3 (2C, =C-C=O), 134.60 (1C) and 131.74 (3C). Anal.
Calcd for C19H10N4O2 (326.31): C, 69.94; H, 3.03; N, 17.17. Found:
C, 69.71; H, 3.22; N, 16.89%.
24 T. Mavromoustakes, A. Kolocouris, M. Zervou, P. Roumelioti,
J. Matsoukas and R. Weismann, J. Med. Chem., 1999, 42, 1714.
25 Y. Tamura, F. Watanabe, T. Nakatani, K. Yasui, M. Fuji, T. Komurasaki,
H. Tsuzuki, R. Mackawa, T. Yoshioka, K. Kawada, K. Sugita and
M. Ohtani, J. Med. Chem.,1998, 41, 640.
ꢀꢄꢍꢀ 2ꢊ$ꢊꢀ (Oꢂ6D\HGꢇꢀ 7ꢊ0ꢊꢀ $Oꢂ7XUNLꢇꢀ +ꢊ0ꢊꢀ $Oꢂ'DI¿ULꢇꢀ %ꢊ$ꢊꢀ $Oꢂ%DVVDPꢀ DQGꢀ
M.E. Hussein, Boll. Chim. Farm., 2004, 143(6), 227.
27 G. Sandmann, C. Schneider and P. Boger, Z. Naturforsch. C, 1996, 51,
534.
28 G.I. Koklobskii, V.A. Ostraovskii and V.S. Poplavskii, Khim. Geter.
Soeden, 1981, 10, 1299.
29 C. Zhao-Xu and X. Heming, Int. J. Quantum Chem., 2000, 79, 350.
30 A. Altomare, G. Cascarano, C. Giacovazzo and A. Gualiardi, M.C. Burla,
G. Polidori and M. Camalli, J. Appl. Cryst., 1994,27, 435.
31 S. Mackay, C.J. Gilmore, C. Edwards, N. Stewart and K. Shankland,
1999, MaXXVꢀ &RPSXWHUꢀ 3URJUDPꢀ IRUꢀ WKHꢀ 6ROXWLRQꢀ DQGꢀ 5H¿QHPHQWꢀ RIꢀ
Crystal Structures. Bruker Nonius, The Netherlands, MacScience, Japan
and The University of Glasgow.
Received 17 November 2008; accepted 10 January 2009
Paper 08/0299 doi: 10.3184/030823409X435900
Published online: 21 April 2009
32 C.K. Johnson, 1976, ORTEP-I I, A Fortran Thermal-Ellipsoid Program,
Report ORNL-5138. Oak Ridge National Laboratory, Oak Ridge,
Tennessee, USA.
33 O. Meth-Cohn, B. Narine and B.A. Tamowski, J. Chem. Soc. Perkin
Trans I, 1981, 1520.
References
ꢀ ꢌꢀ 5ꢊꢀ(OGHU¿HOG, Heterocyclic Comp., 1952, 4, 7.
2
O. Meth-Gohn and B. Narines, Tetrahedron, 1978, 19, 2045.