Synthesis of 4-aryl-1,3,4a-triazaphenanthrene-2-selones via three-component condensation of quinolin-2-amine, potassium selenocyanate and an acyl chloride

Article abstract of DOI:10.3184/174751918X15254464184094

A three-component reaction between quinolin-2-amine, potassium selenocyanate and variously substituted benzoyl chlorides in acetone at room temperature provided a simple and efficient one-pot route for the synthesis of six 4-aryl-1,3,4a-triazaphenanthrene

Full text of DOI:10.3184/174751918X15254464184094

JOURNAL OF CHEMICAL RESEARCH 2018
VOL. 42 MAY, 233–234
RESEARCH PAPER 233
Synthesis of 4-aryl-1,3,4a-triazaphenanthrene-2-selones via three-component
condensation of quinolin-2-amine, potassium selenocyanate and an acyl chloride
Sonia Singha, Mohammad H. Mosslemina* and Alireza Hassanabadib
aDepartment of Chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran
bDepartment of Chemistry, Zahedan Branch, Islamic Azad University, Zahedan, Iran
A three-component reaction between quinolin-2-amine, potassium selenocyanate and variously substituted benzoyl chlorides in acetone at room
temperature provided a simple and efficient one-pot route for the synthesis of six 4-aryl-1,3,4a-triazaphenanthrene-2-selones in good yields.
Keywords: quinolin-2-amine, 4-aryl-1,3,4a-triazaphenanthrene-2-selones, benzoyl chlorides, potassium selenocyanate
Many triaza analogues of polycyclic aromatic compounds that
feature a bridgehead nitrogen have a long history of widespread
use as precursors for constructing functional materials such as
antibacterial agents, pesticides, active dyes, encapsulation resins of
integrated circuits and structural adhesives for advanced carbon-
fibre composites in the aerospace industry.1–5 As a result, several
reports of their synthesis have appeared in the literature,6–10 but most
of them require forcing conditions, long reaction times and complex
synthetic pathways.
and potassium selenocyanate (KSeCN). We thought that
a synthesis of some benzo analogues of the 4-aryl-1,3,4a-
triazaphenanthrene-2-selones (4) might be simply achieved by
a similar reaction in which 2-aminopyridine was replaced by
quinolin-2-amine (1) (Scheme 1).
So it proved, and a series of six such compounds were
prepared in good yields using a variety of substituted benzoyl
chlorides (2; Ar = various) in reaction with quinolin-2-amine
(1) and KSeCN (3) (Table 1).
Thus, new routes for the synthesis of these molecules have
attracted considerable attention in a search for rapid access to these
heterocycles. The current interest in selenium-containing organic
compounds stems from their remarkable biological functions.11–15
The first synthesis of acyl isoselenocyanates, which were generated
by the reaction of acyl chlorides and potassium selenocyanate,
was described by Douglas.15 Recently, a few syntheses of
heterocycles from acyl isoselenocyanates have been reported.16–20
Herein, we describe a synthesis of a series of new 4-aryl-1,3,4a-
triazaphenanthrene-2-selones using a reported method.17
The structures of compounds 4a–f were deduced from their
elemental analyses and their IR, 1H NMR and 13C NMR spectra.
The mass spectra of compounds 4a–f are fairly similar and
display molecular ion peaks. For example, the mass spectrum
of 4a showed a molecular ion peak at 370, confirming that it
is a 1:1:1 adduct of quinolin-2-amine, 4-chlorobenzoyl chloride
and potassium selenocyanate. The IR spectrum of 4a exhibited
absorption bands at 1580 cm−1 for the C=N bond and 1279 cm−1
1
for the C=Se groups. The 500 MHz H NMR spectrum of
4a exhibited multiplets at δ 6.77–8.70 ppm for the aromatic
protons, and the 13C NMR spectrum of 4a showed 15 distinct
resonances in agreement with the proposed structure.
A tentative mechanism for this transformation is proposed
in (Scheme 2). The reaction starts with the formation of acyl
isoselenocyanate 5, followed by addition of quinolin-2-amine
Results and discussion
A recent report17 described the synthesis of a series of aryl
triazanaphthalene-selones by the reaction at room temperature
in acetone solvent between 2-aminopyridine, an acyl chloride
Scheme 1
O
O
Ar
N
H
1
4
N
3
2 +
N
C
Se
Ar
Se
5
N
HO
H
Ar
H
6
N
-H2O
Se
N
N
7
Scheme 2
* Correspondent. E-mail: mhmosslemin@iauyazd.ac.ir

234 JOURNAL OF CHEMICAL RESEARCH 2018
Table 1. Yields of a series of 4-aryl-1,3,4a-triazaphenanthrene-2-selones
(4) prepared from quinolin-2-amine (1), an acyl chloride (2) and KSeCN
(3) (Scheme 1)a
123.1, 126.4, 127.8, 128.6, 129.9, 131.6, 133.2, 136.5, 140.6, 148.2, 162.1,
168.5, 172.9; MS (m/z, %): 415 (5); Anal. calcd for C17H10BrN3Se: C, 49.18;
H, 2.43; N, 10.12; found: C, 49.30; H, 2.54; N, 10.26%.
4
a
b
c
d
e
f
Ar
4-ClC6H4
C6H5
4-BrC6H4
3-O2NC6H4
4-O2NC6H4
4-CH3C6H4
% Yieldb
83
80
81
87
85
76
m.p. (°C)
374–376
359–361
251–253
317–319
306–308
235–237
4-(3-Nitrophenyl)-1,3,4a-triaza-phenanthrene-2-selone (4d): Cream-
coloured powder; m.p. 317–319 °C; IR (KBr) (νmax/cm−1): 1724, 1584,
1512, 1476, 1345, 1273 (C=Se); 1H NMR (500 MHz, DMSO-d6): δ (ppm)
6.90–8.61 (10H, m, 10CH aromatic); 13C NMR (125 MHz, DMSO-d6):
δ (ppm) 112.4, 116.9, 122.7, 127.3, 127.8, 128.8, 129.6, 130.8, 132.5, 134.4,
136.5, 140.8, 147.8, 148.3, 155.8, 167.6, 174.2; MS (m/z, %): 381 (9); Anal.
calcd for C17H10N4O2Se: C, 53.56; H, 2.64; N, 14.70; found: C, 53.69; H,
2.81; N, 14.84%.
4-(4-Nitrophenyl)-1,3,4a-triaza-phenanthrene-2-selone (4e): Cream-
coloured powder; m.p. 306–308 °C; IR (KBr) (νmax/cm−1): 1720, 1581,
1507, 1468, 1330, 1280 (C=Se); 1H NMR (500 MHz, DMSO-d6): δ (ppm)
6.87–8.47 (10H, m, 10CH aromatic); 13C NMR (125 MHz, DMSO-d6):
δ (ppm) 112.5, 117.6, 122.9, 127.4, 127.8, 129.5, 130.4, 132.7, 136.8, 140.6,
147.5, 148.1, 156.2, 167.8, 174.3; MS (m/z, %): 381 (6); Anal. calcd for
C17H10N4O2Se: C, 53.56; H, 2.64; N, 14.70; found: C, 53.66; H, 2.79; N,
14.85%.
aReaction conditions: a mixture of an acyl chloride (2) (1 mmol) and KSeCN (3) (1 mmol)
in acetone (6 mL) was stirred at room temperature (r.t.) for 10 min and then quinolin-
2-amine (1), in acetone (4 mL) was added and stirring was continued at r.t. for 6 h.
bIsolated yields.
1 to generate 6, subsequent cyclisation of which generates 7,
which is converted into 4 by elimination of water.
Experimental
4-p-Tolyl-1,3,4a-triaza-phenanthrene-2-selone
(4f):
Cream-
coloured powder; m.p. 235–237 °C; IR (KBr) (νmax/cm−1): 1708, 1592,
1435, 1264 (C=Se); 1H NMR (500 MHz, DMSO-d6): δ (ppm) 2.35 (3H,
s, CH3), 7.05–8.46 (10H, m, 10CH aromatic); 13C NMR (125 MHz,
DMSO-d6): δ (ppm) 22.1 (CH3), 111.6, 116.7, 121.6, 128.7, 129.5, 129.8,
130.3, 132.2, 133.6, 136.4, 140.5, 147.8, 156.4, 167.3, 172.7; MS (m/z,
%): 350 (5); Anal. calcd for C18H13N3Se: C, 61.72; H, 3.74; N, 12.00;
found: C, 61.84; H, 3.88; N, 12.11%.
Melting points were determined with an Electrothermal 9100
apparatus and are uncorrected. Elemental analyses for C and H were
performed using a Heraeus CHN-O-Rapid Analyzer. Mass spectra
were recorded on a Finnigan-MAT 8430 mass spectrometer operating
at an ionisation potential of 70 eV. IR spectra were recorded on a
Shimadzu IR-470 spectrometer. NMR spectra were obtained on a
Brucker DRX 500 Avance spectrometer (1H NMR at 500 MHz,
13C NMR at 125 MHz) in DMSO-d6 using TMS as internal standard.
Chemical shifts (δ) are given in parts per million (ppm). All of the
chemicals used in this study were purchased from Merck or Fluka
(Buchs, Switzerland) and were used without further purification.
Received 14 April 2018; accepted 20 April 2018
Paper 1805376
https://doi.org/10.3184/174751918X15254464184094
Published online: 30 May 2018
CAUTION: All reactions involving selenium-containing compounds
should be carried out in a well-ventilated hood.
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Synthesis of the 4-aryl-1,3,4a-triazaphenanthrene-2-selones: general
procedure
To a solution of potassium selenocyanate (1 mmol) in dry acetone
(3 mL) was added an acyl chloride (1 mmol) in dry acetone (3 mL). The
reaction mixture was stirred at r.t. for 10 min. Then quinolin-2-amine
(1 mmol) in dry acetone (4 mL) was added to the mixture. The progress
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4-(4-Chlorophenyl)-1,3,4a-triaza-phenanthrene-2-selone (4a): Cream-
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coloured powder; m.p. 374–376 °C; IR (KBr) (νmax/cm−1): 1724, 1580, 1543,
1
1452, 1279 (C=Se); H NMR (500 MHz, DMSO-d6): δ (ppm) 6.77–8.70
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4-Phenyl-1,3,4a-triaza-phenanthrene-2-selone
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Cream-
coloured powder; m.p. 359–361 °C; IR (KBr) (νmax/cm−1): 1734,
1
1588, 1490, 1267 (C=Se); H NMR (500 MHz, DMSO-d6): δ (ppm)
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δ (ppm) 111.4, 117.4, 121.5, 126.2, 127.9, 128.4, 129.8, 132.7, 133.4,
136.2, 141.5, 147.6, 150.6, 165.7, 173.8; MS (m/z, %): 336 (7); Anal.
calcd for C17H11N3Se: C, 60.72; H, 3.30; N, 12.50; found: C, 60.88; H,
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4-(4-Bromophenyl)-1,3,4a-triaza-phenanthrene-2-selone (4c): Cream-
coloured powder; m.p. 251–253 °C; IR (KBr) (νmax/cm−1)): 1731, 1583, 1492,
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