Synthesis of some benzotriazole-substituted perimidines

Article abstract of DOI:10.1080/104265090930191

2-substituted perimidines 3(a-g) were prepared from an acid-catalyzed reaction of 1,8-diaminonaphthalene with carboxylic acids using microwave irradiation. Addition of these perimidines to 1-chloromethyl benzotriazole in the presence of the sodium amide under reflux conditions gave benzotriazole-substituted perimidines 5(a-f). Yields of these products following recrystallization from water were of the order of 60-65%. IR and ¹HNMR spectra and elemental analysis were used for identification of these compounds. Copyright Taylor & Francis Inc.

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Phosphorus, Sulfur, and Silicon
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Synthesis of Some
Benzotriazole-Substituted
Perimidines
a
a
a
A. Mobinikhaledi , N. Foroughifar & R. Goli
a
Department of Chemistry, University of Arak, Arak,
Iran
Published online: 16 Aug 2006.
To cite this article: A. Mobinikhaledi , N. Foroughifar & R. Goli (2005) Synthesis of
Some Benzotriazole-Substituted Perimidines, Phosphorus, Sulfur, and Silicon and the
Related Elements, 180:11, 2549-2554, DOI: 10.1080/104265090930191
To link to this article: http://dx.doi.org/10.1080/104265090930191
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Phosphorus, Sulfur, and Silicon, 180:2549–2554, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090930191
Synthesis of Some Benzotriazole-Substituted
Perimidines
A. Mobinikhaledi
N. Foroughifar
R. Goli
Department of Chemistry, University of Arak, Arak, Iran
2
1
-substituted perimidines 3(a–g) were prepared from an acid-catalyzed reaction of
,8-diaminonaphthalene with carboxylic acids using microwave irradiation. Ad-
dition of these perimidines to 1-chloromethyl benzotriazole in the presence of the
sodium amide under reflux conditions gave benzotriazole-substituted perimidines
5
(a–f). Yields of these products following recrystallization from water were of the
1
order of 60–65%. IR and HNMR spectra and elemental analysis were used for
identification of these compounds.
Keywords Benzotriazole; diaminonaphthalene; perimidine
INTRODUCTION
Perimidines1 and compounds containing a benzotriazole moiety2−4
attached to a heterocyclic system are of wide interest because of
their diverse biological activities. Several classical synthetic meth-
ods have been reported for the synthesis of perimidine derivatives,
5
−7
which need special reagent or vigorous reaction conditions.
ever, prepartion of perimidies from a cyclocondensation reaction of
,8-diaminonaphtalene with carboxylic acids under microwave irra-
How-
1
diation is the more convenient method. Some interesting features of
this method are the rapid reaction rates, simplicity, and cleaner reac-
8
−12
tion conditions.
Many hetrocycles containing a benzotriazole moi-
2
−4,13−15
ety have been reported by several articles.
However, perimi-
dine derivatives that have a benzotriazole moiety are not well known.
The aim of this study is to prepare some perimidines under mi-
crowave irradiation. We further studied the reaction of these perim-
idines with 1-chloromethylbenzotriazole in order to synthesize some
new benzotriazole-substituted perimidines.
Received October 12, 2004; accepted November 30, 2004.
Address correspondence to A. Mobinikhaledi, University of Arak, Department of
Chemistry, Dr. Beheshti Ave., Arak, Iran. E-mail: akbar mobini@yahoo.com
2549

2
550
A. Mobinikhaledi et al.
RESULTS AND DISCUSSION
Symmetrical perimidines 3(a–g) were prepared by treating the acid-
catalyzed cyclization of 1,8-diaminonaphthalene 1 with the appropriate
carboxylic acid 2 under microwave irradiation (Scheme 1). The nucle-
ophilic addition of perimidines 3(a–f) to 1-chloromethylbenzotriazole
4
in the presence of a strong base, NaNH2, under reflux afforded
benzotriazole-substituted perimidines 5(a–f).
1
HNMR spectra of 3(e–g) are simple because the symmetry of their
structures and have two distinct signals in the aromatic and aliphatic
regions. Comounds 3e and 3f show one and two multiplet signals at
2.60 ppm and 1.54–2.22 ppm due to the resonance of the 2 and 4 methy-
lene groups, respectively. Two singlet signals at 6.16 ppm and 10.12
1
ppm in the HNMR spectrum of 3g are atributed to the resonance of
two cis olefinic and two NH protons, respectively. However, in the the
1
HNMR spectra of 3e and 3f, there is no possibility of the NH signal
SCHEME 1

Synthesis of Benzotriazole-Substituted Perimidines
2551
SCHEME 2
resonance presumably because of the fast tautomerism of the NH azoles
5
in the perimidine rings. In the case of 3g (Scheme 2), the steric effect
of two cis bulky perimidines groups hinders the fast tautomerization
1
of two NH azoles and results in their resonance. Also in the HNMR
spectra of 3c and 3d, the NH signal resonance is observed because of
an intramolecular hydrogen bonding between the NH proton and the
16
Cl group on the perimidine ring.
1
In the HNMR spectra of 5(a–f) the protons of the methylene group
with the protons of two perimidine and benzotriazole rings resonate at
downfield. These protons appeared at 6.05–6.50 ppm for benzotriazole-
substituted perimidines with no electron-withdrawing groups. How-
ever, the methylene groups of 5c and 5d containing perimidine ring
with one and three chlorine atoms resonate at 6.70 ppm and 8.35 ppm,
respectively.
EXPERIMENTAL
All chemicals including 1,8-diaminonaphthalene and carboxylic acids
were of reagent-grade quality and were used without further purifi-
cation. 1-chloromethybenzotriazole was prepared by the reaction of
1
7 1
1-hydroxymethylbenotriazole and thionyl chloride.
HNMR spectra
were recorded on a Brucker 500 MHz spectrometer. IR spectra were
performed on a Galaxy FT-IR 500 spectrophotometer. Reaction progress
(
for 5a–f) was routinely monitored by TLC on silica gel plates. Reactions
were performed in a Samsung microwave oven with a 230V-50Hz power
source, a 900 W output, and a 2450 MHz operating frequency.

2
552
A. Mobinikhaledi et al.
General Procedure for Preparation of 2-Arylperimidines
For preparation of 3a–g, 1,8-diaminonaphthalene (1.0 mmol) was
ground with a pestle in a mortar with an equimolar amount of an ap-
propriate carboxylic acid (1.0 and 0.5 mmol for monofunctional and bi-
functional acid, respectively). The mixture was placed in a 25-mL-glass
beaker and two drops of HCl (4 M) were, added. This beaker was put
into a microwave oven and subjected to microwave irradiation at 100%
power level for 1–1.5 min. The beaker then was kept at room tempera-
ture for 2 h and the crude products were recrystallized from a mixture
of ethanol and water (50:50) to give compounds 3a–g. Perimidines 3a–d
are known compounds.
For the preparation of benzotriazole-substituted perimidines 5(a–
f), a mixture of sodium amide (1 mmol) and an appropriate perimi-
dine compound (1 mmol) in dry toluene (5 mL) was refluxed for 4 h.
Chloromethylbenzotriazole (1 mmol) was added to the hot suspension
and refluxed for 9 h. After cooling and collecting on a funnel, the crude
product was recrystallized from water.
2
-[2-(1H-perimidine-2-yl)-ethyl]–1H-perimidrne (3e)
◦
Yield 65%, M.P. 227–229 C
−
1
IR (KBr): ν = 3200, 3060, 2960, 1650, 1525, 1480 cm
1
HNMR (DMSO): δ (ppm) = 2.60 (m, 4H), 7.01 (m, 12H)
Anal. cald. for C24H18N4: C, 79.56; H, 4.97; N, 15.47. Found: C, 79.70;
H, 5.10; N, 15.10%.
2
-[4-(1H-perimidine-2-yl)-butyl]–1H-perimidrne (3f)
◦
Yield 65%, M.P. 265–267 C
−
1
IR (KBr): ν = 3440, 3050, 2950, 1660, 1525, 1475 cm
1
HNMR (DMSO): δ (ppm) = 1.54 (m, 4H), 2.22 (m, 4H), 6.99 (m, 12H)
Anal. cald. for C26H22N4: C, 80.00; H, 5.64; N, 14.36. Found: C, 80.40;
H, 5.23; N, 14.28%.
2
-[(Z)-2-(1H-perimidine-2-yl)-1-ethenyl]–1H-perimidrne (3g)
◦
Yield 75%, M.P. 210–212 C
−
1
IR (KBr): ν = 3380, 3060, 2950, 1660, 1595, 1425 cm
1
HNMR (DMSO): δ (ppm) = 6.16 (s, 1H), 7.21 (m, 12H), 10.12 (s, 2H)
Anal. cald. for C24H16N4: C, 80.00; H, 4.44; N, 15.56. Found: C, 80.34;
H, 4.10; N, 15.51%.
1
-(1H-1,2,3-benzotriazole-1-yl-methyl)-2-methyl-1H-
perimidine (5a)
Yield 60%, decomposed >290 C
◦

Synthesis of Benzotriazole-Substituted Perimidines
2553
−
1
IR (KBr): ν = 3180, 2730, 1650, 1595, 1475 cm
1
HNMR (DMSO): δ (ppm) = 2.30 (s, 3H, CH3), 6.05 (s, 2H, CH2), 7.75
(
m, 10Harom)
Anal. cald. for C19H15N5: C, 72.84; H, 4.79; N, 22.36. Found: C, 72.45;
H, 4.75; N, 22.75%.
1
-(1H-1,2,3-benzotriazole-1-yl-methyl)-2-ethyl-1H-perimidine
(
5b)
◦
Yield 60%, decomposed >240 C
−
1
IR (KBr): ν = 3000, 2900, 1680, 1550, 1430 cm
1
HNMR (DMSO): δ (ppm) = 1.70 (t, J = 7.4 Hz, 3H, CH3), 3.90 (q,
7.4 Hz, 2H, CH2), 6.10 (s, CH2-N), 7.70 (m, 10Harom)
Anal. cald. for C20H17N5: C, 73.39; H, 5.20; N, 21.41. Found: C, 73.02;
H, 5.62; N, 21.29%.
1
-(1H-1,2,3-benzotriazole-1-yl-methyl)-2-chloromethyl-1H-
perimidine (5c)
◦
Yield 65%, decomposed >273 C
−
1
IR (KBr): ν = 3050, 2950, 1600, 1500, 1460 cm
1
HNMR (DMSO): δ (ppm) = 2.30 (s, 2H, CH2Cl), 6.70 (s, 2H, CH2N),
7.72 (m, 10Harom)
Anal. cald. for C19H14N5Cl: C, 65.61; H, 4.03; N, 20.14; Cl, 10.22.
Found: C, 65.98; H, 3.91; N, 20.36; Cl, 9.75%.
1
-(1H-1,2,3-benzotriazole-1-yl-methyl)-2-trichloromethyl-1H-
perimidine (5d)
◦
Yield 65%, decomposed >232 C
−
1
IR (KBr): ν = 3070, 2960, 1690, 1615, 1400 cm
1
HNMR (DMSO): δ (ppm) = 8.35 (s, 2H, CH2N), 7.72 (m, 10Harom)
Anal. cald. for C19H12N5Cl3: C, 54.74; H, 2.88; N, 16.81; Cl, 25.57.
Found: C, 54.9; H, 2.96; N, 16.4; Cl, 25.79%.
1
-(1H-1,2,3-benzotriazole-1-yl-methyl)-2-[2-(1H-perimidine-2-
yl)ethyl]-1H-perimidine (5e)
◦
Yield 60%, decomposed >295 C
−
1
IR (KBr): ν = 3410, 3060, 2860, 1685, 1620, 1490, 1390 cm
1
HNMR (DMSO): δ (ppm) = 2.27 (m, 4H, CH2-CH2), 6.50 (bs, 2H,
CH2N), 7.65 (m, 16Harom), 11.0 (bs, 1H, NH)
Anal. cald. for C31H23N7: C, 75.46; H, 4.67; N, 19.88. Found: C, 75.81;
H, 4.50; N, 19.60%.

2
554
A. Mobinikhaledi et al.
1
-(1H-1,2,3-benzotriazole-1-yl-methyl)-2-[4-(1H-perimidine-2-
yl)butyl]-1H-perimidine (5f)
◦
Yield 65%, decomposed >305 C
−1
1
IR (KBr): ν = 3420, 3150, 2850, 1650, 1550, 1400 cm , HNMR
DMSO): δ (ppm) = 1.75 (m, 8H, 4 x CH2), 6.10 (s, 2H, CH2N), 7.73
m, 16Harom)
(
(
Anal. cald. for C33H27N7: C, 76.01; H, 5.18; N, 18.81. Found: C, 75.64;
H, 5.30; N, 19.13%.
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