One-pot multi-component synthesis of mono- and bis-indolylimidazole derivatives using Zn2+@KSF and their antibacterial activity

Article abstract of DOI:10.5560/ZNB.2014-4026

The preparation of mono- and bis-indolylimidazole derivatives using Zn ²⁺ supported on montmorillonite KSF (Zn²⁺@KSF) as an efficient heterogeneous catalyst is described. The structures of these compounds were characterized by IR,

Full text of DOI:10.5560/ZNB.2014-4026

One-pot Multi-component Synthesis of Mono- and Bis-indolylimidazole
Derivatives Using Zn2+@KSF and Their Antibacterial Activity
Nosrat O. Mahmoodia, Iraj Nikokarb, Marzieh Farhadia, and Atefeh Ghavidasta
a
Department of Chemistry, Faculty of Science, University of Guilan, P. O. Box 41335-1914,
Rasht, I. R. Iran
b
Laboratory of Microbiology and Immunology of Infectious Diseases, Paramedicine Faculty,
Guilan University of Medical Sciences, P. O. Box 44715-1361, Guilan, I. R. Iran
Reprint requests to Prof. Nosrat O. Mahmoodi. Fax: +98-131-3233262.
E-mail: mahmoodi@guilan.ac.ir and nosmahmoodi@gmail.com
Z. Naturforsch. 2014, 69b, 715 – 720 / DOI: 10.5560/ZNB.2014-4026
Received February 2, 2014
The preparation of mono- and bis-indolylimidazole derivatives using Zn2+ supported on mont-
morillonite KSF (Zn2+@KSF) as an efficient heterogeneous catalyst is described. The structures of
these compounds were characterized by IR, 1H NMR and 13C NMR spectroscopy. The antibacterial
activity of the selected products was examined. Some products exhibit promising activities.
Key words: Zn2+@KSF, Clay Catalyst, Bis-indole, Indolylimidazole, Multicomponent Reaction
(MCR)
Introduction
The most common synthetic routes to the N-
substituted imidazole ring system involves the cyclo-
Click chemistry was first presented by Sharpless and condensation of a diketone, an aldehyde and ammo-
depicts a set of powerful, highly reliable, and selective nia in the presence of an acid catalyst, known as the
reactions for the rapid synthesis of valuable new com- Debus-Radziszewski imidazole synthesis [11]. It is an
pounds and MCRs via heteroatom links, and also refers example of a multicomponent reaction (MCR). In this
to a group of reactions that are simple to achieve, high- reaction, typically homogeneous acids are used as cat-
yielding, regiospecific, wide in scope, versatile, with alysts, which pose problems of separation and reuse of
safe by-products that can be removed by nonchromato- the acids or treatment of acidic waste material. Solid
graphic methods [1]. One such reaction is the synthe- acids are being used as substitutes for liquid acids for
sis of various mono- and bis-indolylimidazole deriva- a number of superior chemical processes [12]. Several
tives using Zn2+ supported on montmorillonite KSF inorganic oxides, mixed oxides, including alumina, sil-
(Zn2+@KSF). Indoles and imidazoles are two fami- ica, titania, zirconia, and zeolites and clays have been
lies of compounds which have been widely investi- used as both supports and solid acid catalysts [13].
gated due to their significant biological activities. In- Clay minerals have a different and interesting set of
dole and its derivatives have been termed as ‘priv- properties. They are very effective catalysts for a wide
ileged pharmacologic structures’ since they bind to variety of organic reactions, often displaying highly
many biological receptors with high affinity [2 – 4]. In sought product-, regio- or shape-selectivity [14 – 18].
addition, imidazole derivatives are fluorescent, show
numerous pharmacological properties and participate Results and Discussion
in several vital biochemical processes [5 – 7]. Several
substituted imidazoles have been used as inhibitors of
P38αMAP kinase, as herbicides, fungicides and thera- synthesis of bis-heterocyclic compounds [19 – 26], we
peutic agents [8 – 10]. report an efficient method for the synthesis of mono-
Following our prior efforts in the design and click
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N. O. Mahmoodi et al. · One-pot Multi-component Synthesis of Mono- and Bis-indolylimidazole Derivatives
Scheme 1. MCRs for the synthesis of 1–4.
and bis-indolylimidazoles via an MCR by using Zn2+
As shown in Table 1, entry 1, in the absence of cata-
supported on montmorillonite KSF as a mild and het- lyst this MCR was very slow, and only 15% of the de-
erogeneous catalyst (Scheme 1). In this effort, the re- sired product was isolated. When this reaction was car-
action of both one equivalent of indole-3-carbaldehyde ried out over various acid catalysts the yield and rate of
derivatives 6a–c or half-equivalent of bis-aldehydes the reaction were increased. Using Zn2+ supported on
7a–c together with one equivalent of aniline deriva- montmorillonite-KSF as catalyst led to higher yields
tives 5a–d, benzil and NH4OAc in the presence of and shorter reaction time (entry 7). Several solvents
Zn2+@KSF afforded the desired compounds 1–4 in such as MeOH, CHCl3 and DMF were examined, but
good yields. Bis-aldehydes 7a–c were prepared ac- longer reaction times and low yields were observed
cording to the literature [27]. The reports claiming that with CHCl3 and DMF (entries 9, 10).
a combination of two or more different heterocyclic
In other efforts, the effect of the amount of catalyst
moieties in a single molecule would enhance signif- on the yield and the rate of the reaction was examined.
icantly the biological activity, prompted us to pursue It was found that 0.03 g of Zn2+@KSF per 1 mmole
our efforts.
of substrates was sufficient. An increase in the amount
Initially, we attempted to find a click synthetic route of Zn2+@KSF to 0.05 mg showed no substantial im-
for the preparation of mono- and bis-indolylimidazoles provement in the yield, while the yield of the reaction
1–4. For this reason, the reaction of indole-3- was reduced by decreasing the amount of Zn2+@KSF
carbaldehyde 6a and aniline 5a was selected under the to 0.01 g.
aspects of catalyst, temperature, solvent and reaction
time. The conditions were optimized, and the results thesized by using Zn2+@KSF in EtOH at 70 ◦C. All
are shown in Table 1.
products were fully characterized by IR, 1H NMR, 13
The mono- and bis-indolylimidazoles 1–4 were syn-
C
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N. O. Mahmoodi et al. · One-pot Multi-component Synthesis of Mono- and Bis-indolylimidazole Derivatives
717
Table 1. Variation of reaction conditions for the synthesis of Table 2. Mono- and bis-indolylimidazoles 1–4, reaction
4a.
times and yields.
Entry
R1
R2
R3
R4
Time Product Yield
Entry
Catalyst
Solvent Temperature Time
Yield
(%)
(◦C)
(min)
(min)
(%)
1
2
3
4
5
6
7
8
9
–
EtOH
EtOH
EtOH
70
70
70
70
70
70
70
65
50
100
240
100
80
45
40
45
40
40
60
15
43
50
68
72
70
77
72
25
48
1
2
3
4
5
6
7
8
H
H
H
H
H
Br
H
Me
Me
–
H
H
H
H
Br
Br
Br
H
H
–
H
OMe
OEt
H
H
H
40
35
35
35
80
50
50
20
16
45
50
60
1a
1b
1c
1d
1e
1f
1g
1h
1i
2
77
78
80
78
57
65
67
80
88
87
95
91
p-TsOH
KSF
p-TsOH@KSF EtOH
OMe OMe
H+@KSF
Fe3+@KSF
Zn2+@KSF
EtOH
EtOH
EtOH
H
OMe
OEt
H
OEt
–
H
H
H
H
H
–
Zn2+@KSF MeOH
Zn2+@KSF CHCl3
9
10
Zn2+@KSF
DMF
45
10
11
12
–
–
–
–
–
–
–
–
3
4
NMR spectroscopic and elemental analyses. The re-
sults are summarized in Table 2.
The proposed mechanism for the formation of 1–4 and Gram-negative bacteria using the cultures of
in the presence of Zn2+@KSF initially involves forma- four different standard microorganisms: Pseudomonas
tion of diamine 6 via nucleophilic addition of aniline aeruginosa (PS) and Salmonella enteritis (SE) as
to the in situ-prepared imine 5. Diamine 6, in the pres- Gram-negative models and Bacillus subtilis (BS and
ence of catalyst, undergoes double condensation reac- Bacillus subtilis (BS) and Micrococcus luteus (ML) as
tions with benzil to produce the target imidazoles 1–3 a Gram-positive model. The priorities for antibacterial
(Scheme 2).
activity against Micrococcus luteus are: 1a > 1b > 1i
The in vitro antibacterial activities of compounds > 1e > 1g > 1h = 1c > 2 > 1f. All of them indi-
1a–i and 2–4 were evaluated against Gram-positive cate a good activity. However, mono-indolylimidazoles
Scheme 2. Proposed mech-
anism for the formation
of indoles 1 catalyzed by
Zn2+@KSF.
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N. O. Mahmoodi et al. · One-pot Multi-component Synthesis of Mono- and Bis-indolylimidazole Derivatives
Table 3. Antimicrobial activity
of compounds 1a–i and 2–4.
Entry
Compound
Conc. in
DMSO (µg Pseudomonas
per 0.1 mL)
Antimicrobial activity (zone of inhibition in mm)
Salmonella
enteritis
Bacillus
subtilis
Micrococcus
luteus
aeruginosa
1
2
3
4
5
6
7
8
1a
1b
1c
1d
1e
1f
1g
1h
1i
2
3
4
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
–
–
–
–
–
–
–
–
–
–
–
–
10
18
–
–
13
–
–
–
–
–
–
–
11
–
–
8
7
10
11
–
12
13
9
11
11
16
10
–
25
21
14
–
17
11
15
14
18
13
–
9
10
11
12
13
14
15
9
–
Erythromycin
Tetracycline
DMSO
12
14
–
10
16
–
–
in comparison to bis-indolylimidazoles indicate higher (0.5 mmol) instead of indole-3-carbaldehyde derivatives
(1 mmol).
activity. The results are shown in Table 3.
Compounds 1–4 were inactive against Pseu-
domonas aeruginosa. The range of activities against
Bacillus subtilis are good to moderate: 1i > 1e > 1d
> 1b = 1g = 1h > 1c > 2 = 1d > 1f. Compounds 2
and 1b showed superior activities against Salmonella
enteritis.
3-(1,4,5-Triphenyl-1H-imidazol-2-yl)-1H-indole (1a)
Yield 77%. Colorless solid, m. p. 234 – 236 ◦C. – IR
(KBr): v = 3400, 3050, 1580, 1560, 1490, 1480, 760, 740,
690 cm−1. – 1H NMR (400 MHz, CDCl3): δ = 6.32 (d,
J = 2.4 Hz, 1H), 7.36 – 7.15 (m, 16H), 7.73 (dd, J = 1.2,
8 Hz, 2H), 8.49 – 8.47 (m, 2H) ppm. – 13C NMR (100 MHz,
CDCl3): δ = 106.7, 110.9, 120.7, 122.0, 122.7, 123.9,
126.4, 126.4, 127.2, 127.8, 128.1, 128.3, 128.5, 128.8, 129.2,
129.5, 130.8, 131.1, 134.6, 135.5, 137.3, 137.4, 143.6 ppm.
– HRMS ((+)-ESI): m/z = 411.1741 (calcd. 411.1735 for
C29H21N3).
Experimental Section
Zn2+@KSF was prepared according to the literature pro-
cedure [28]. The 1H NMR spectra were obtained on a Bruker
Avance 400-MHz spectrometer. 13C NMR spectra were
recorded on a Bruker 100 MHz instrument using the sol-
vent as an internal standard. IR spectra were measured with
a Shimadzu IR-470 spectrophotometer. Mass spectra were
recorded with a Termo-LCQ Deca mass spectrometer oper-
ating at an ionization potential of 70 eV or lower. Melting
points are uncorrected and were determined using a Mettler
Fp5 apparatus.
3-(1-(4-Methoxyphenyl)-4,5-diphenyl-1H-imidazol-2-yl)-
1H-indole (1b)
Yield 78%. Colorless solid, m. p. 240 – 242 ◦C. – IR
(KBr): v = 3400, 3050, 2850, 2950, 2980, 1600, 1580,
1570, 1510, 1490, 1440, 1385, 1250, 1025, 840, 778, 740,
690 cm−1. – 1H NMR (400 MHz, CDCl3): δ = 3.80 (s, 1H),
6.32 (d, J = 2.4 Hz, 1H), 6.81 (d, J = 9.2 Hz, 2H), 7.07
(d, J = 8.8 Hz, 2H), 7.31 – 7.19 (m, 11H), Hd, 7.73 (dd,
J = 1.2, 7.6 Hz, 2H), 8.45 (brs, 1H), 8.57 (t, J = 4.2 Hz,
1H) ppm. – 13C NMR (100 MHz, CDCl3): δ = 55.4, 106.8,
110.8, 114.3, 120.6, 122.2, 122.7, 123.8, 126.3, 126.5, 127.2,
127.8, 128.1, 128.3, 129.7, 129.8, 130.0, 130.9, 131.2, 134.7,
135.5, 137.3, 143.8, 159.3 ppm. – HRMS ((+)-ESI): m/z =
441.1844 (calcd. 441.1841 for C30H23N3O).
General procedure for the synthesis of mono- and
bis-indolylimidazoles
Benzil (1 mmol, 0.21 g), aldehyde (1 mmol), aniline
(1 mmol, 0.09 g), ammonium acetate (1 mmol, 0.07 g), and
Zn2+@KSF were dissolved in EtOH. The mixture was
stirred at 70 ◦C for 40 min. The progress of the reaction
was monitored by TLC (EtOAc : petroleum ether 6 : 3). Af-
ter completion of the reaction, the mixture was cooled to
0 ◦C, and the resulting precipitate was filtered off, washed
with cold EtOH and recrystallized from EtOH to yield the
3-(1-(4-Ethoxyphenyl)-4,5-diphenyl-1H-imidazol-2-yl)-
1H-indole (1c)
Yield 81%. Colorless solid, m. p. 206 – 208 ◦C. – IR
desired mono-indolylimidazoles. Bis-indolylimidazoles 2–4 (KBr): v = 3400, 3100, 3050, 2870, 2930, 2980, 1600,
were prepared by a similar procedure using di-aldehydes 1570, 1510, 1465, 1440, 1390, 1250, 1040, 840, 778, 740,
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N. O. Mahmoodi et al. · One-pot Multi-component Synthesis of Mono- and Bis-indolylimidazole Derivatives
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690 cm−1. – 1H NMR (400 MHz, CDCl3): δ = 1.44 (t, 5-Bromo-3-(1-(4-ethoxyphenyl)-4,5-diphenyl-1H-imidazol-
J = 6.8 Hz, 3H), 4.04 – 3.96 (m, 2H), 6.31 (d, J = 8 Hz, 1H), 2-yl)-1H-indole (1g)
6.82 – 6.78 (m, 2H), 7.07 (d, J = 8.4 Hz, 2H), 7.29 – 7.17
Yield 66%. Colorless solid, m. p. 162 – 164 ◦C. – IR
(m, 11H), 7.73 (d, J = 7.6 Hz, 2H), 8.41 (brs, 1H), 8.58 (s,
(KBr): v = 3150, 3050, 2980, 2900, 2850, 1600, 1570, 1510,
1H) ppm. – 13C NMR (100 MHz, CDCl3): δ = 14.7, 63.6,
1470, 1440, 1390, 1250, 1040, 790, 780, 760, 690 cm−1. –
110.8, 114.8, 120.7, 122.2, 122.7, 123.7, 126.3, 126.5, 127.2,
127.7, 128.1, 128.3, 129.7, 131.0, 131.2, 135.9, 137.3, 143.8,
158.8 ppm. – HRMS ((+)-ESI): m/z = 455.2005 (calcd.
455.1998 for C31H25N3O).
1H NMR (400 MHz, CDCl3): δ = 1.42 (t, J = 7 Hz, 3H),
3.98 (q, J = 7.12 Hz, 2H), 6.29 (d, J = 1.6 Hz, 1H), 6.78
(d, J = 9.2 Hz, 2H), 7.02 (d, J = 8.8 Hz, 2H), 7.06 (d,
J = 8.8 Hz, 1H), 7.29 – 7.19 (m, 9H), 7.67 (dd, J = 1.2 Hz,
7.6 Hz, 2H), 8.52 (s, 1H), 9.07 (brs, 1H) ppm. – 13C NMR
3-(1-(3,4-Dimethoxyphenyl)-4,5-diphenyl-1H-imidazol-
(100 MHz, CDCl3): δ = 14.7, 63.7, 112.5, 113.9, 114.8,
124.3, 125.2, 125.43, 126.5, 127.3, 127.8, 128.0, 128.1,
128.3, 129.4, 129.6, 130.0, 130.6, 131.1, 134.2, 134.4, 137.3,
143.3, 158.8 ppm. – HRMS ((+)-ESI): m/z = 533.1120
(calcd. 533.1103 for C31H24BrN3O).
2-yl)-1H-indole (1d)
Yield 78%. Colorless solid, m. p. 243 – 245 ◦C. – IR
(KBr): v = 3380, 3050, 2980, 2930, 1590, 1560, 1500, 1490,
1435, 1390, 1250, 1220, 1020, 780, 760, 740, 693 cm−1
.
–
1H NMR (400 MHz, CDCl3): δ = 3.63 (s, 3H), 3.86 (s,
2-Methyl-3-(1,4,5-triphenyl-1H-imidazol-2-yl)-1H-indole
(1h)
3H), 6.35 (d, J = 2.8 Hz, 1H), 6.61 (s, 1H), 6.73 (s, 2H),
7.18 – 7.31 (m, 11H), 7.73 (dd, J = 3.4, 9.2 Hz, 2H), 8.55 (d,
J = 8 Hz, 1H), 8.66 (brs, 1H) ppm. – 13C NMR (100 MHz,
CDCl3): δ = 55.9 , 56.0, 106.7, 110.7, 110.9, 112.0, 120.6,
121.1, 122.1, 122.6, 123.9, 126.4, 126.5, 127.2, 127.8, 128.1,
128.3, 129.7, 130.0, 131.0, 131.1, 134.7, 135.5, 137.3, 143.8,
148.8, 149.0 ppm. – HRMS ((+)-ESI): m/z = 471.1953
(calcd. 471.1947 for C31H25N3O2).
Yield 80%. Colorless solid, m. p. 266 – 268 ◦C. – IR
(KBr): v = 3150, 3050, 2980, 2900, 2850, 1590, 1570, 1490,
1450, 1390, 740, 690 cm−1. – 1H NMR (400 MHz, CDCl3):
δ = 2.00 (s, 3H), 7.32 – 6.91 (m, 16 H), 7.46 (d, J = 8 Hz,
1H), 7.65 (dd, J = 1.2, 7.8 Hz, 2H), 8.74 (brs, 1H) ppm.
–
13C NMR (100 MHz, CDCl3): δ = 12.6, 110.3, 119.1,
119.9, 121.3, 126.5, 127.4, 127.6, 127.9, 128.1, 128.4, 128.5,
129.0, 129.1, 130.8, 131.1, 135.2, 136.1, 136.7, 143.2 ppm.
– HRMS ((+)-ESI): m/z = 425.1898 (calcd. 425.1892 for
C30H23N3).
5-Bromo-3-(1,4,5-triphenyl-1H-imidazol-2-yl)-1H-indole
(1e)
Yield 57%. Colorless solid, m. p. 246 – 248 ◦C. – IR
(KBr): v = 3450, 3050, 1590, 1570, 1559, 1540, 1490, 790,
760, 695 cm−1. – 1H NMR (400 MHz, CDCl3): δ = 6.29
(s, 1H), 7.46 – 7.12 (m, 15H), 7.68 (d, J = 7.2 Hz, 2H),
8.51 (s, 1H), 8.88 (brs, 1H) ppm. – 13C NMR (100 MHz,
CDCl3): δ = 112.5, 114.0, 124.2, 125.1, 125.6, 126.6, 127.3,
127.9, 128.2, 128.3, 128.7, 128.7, 129.2, 129.7, 130.4, 131.1,
134.0, 134.1, 136.9, 137.5, 142.9 ppm. – HRMS ((+)-ESI):
m/z = 489.0846 (calcd. 489.0841 for C29H20BrN3).
3-(1-(4-Ethoxyphenyl)-4,5-diphenyl-1H-imidazol-2-yl)-
2-methyl-1H-indole (1i)
Yield 84%. Colorless solid, m. p. 278 – 280 ◦C. – IR
(KBr): v = 3400, 3050, 2980, 2930, 2850, 1570, 1510, 1455,
1440, 1390, 1240, 1040, 820, 780, 730, 690 cm−1. – 1H
NMR (400 MHz, CDCl3): δ = 1.35 (t, J = 6.8 Hz, 3H), 2.05
(s, 3H), 3.89 (q, J = 7 Hz, 14 Hz, 2H), 6.59 (d, J = 8.8 Hz,
2H), 6.81 (d, J = 8.8 Hz, 2H), 7.30 – 6.93 (m, 15H), 7.46 (d,
J = 7.2 Hz, 1H), 7.66 (d, J = 7.2 Hz, 2H), 8.75 (brs, 1H)
ppm. – HRMS ((+)-ESI): m/z = 469.2157 (calcd. 469.2154
for C32H27N3O).
2,5-Dibromo-3-(1-(4-methoxyphenyl)-4,5-diphenyl-
1H-imidazol-2-yl)-1H-indole (1f)
Yield 66%. Colorless solid, m. p. 238 – 240 ◦C. – IR
(KBr): v = 3400, 3050, 2980, 2950, 2880, 1650, 1600, 1510,
1,4-Bis(3-(1,4,5-triphenyl-1H-imidazol-2-yl)-1H-indol-
1-yl)butane (2)
1470, 1440, 1390, 1240, 1040, 840, 790, 770, 690 cm−1
.
–
1H NMR (400 MHz, CDCl3): δ = 3.79 (s, 3H), 6.29 (s,
1H), 6.80 (d, J = 8.8 Hz, 2H), 7.04 (d, J = 8.8 Hz, 2H), 7.09
Yield 87%. Colorless solid, m. p. 307 – 309 ◦C. – IR
(d, J = 8.4 Hz, 1H), 7.30 – 7.19 (m, 9H), 7.67 (dd, J = 1.6, (KBr): v = 3050, 2950, 2850, 1610, 1590, 1560, 1490, 1470,
7.6 Hz, 2H), 8.51 (s, 1H), 9.05 (brs, 1H) ppm. – 13C NMR 1440, 760, 740, 690 cm−1 1H NMR (400 MHz, CDCl3):
.
(100 MHz, CDCl3): δ = 55.4, 112.5, 113.9, 114.4, 124.2, δ = 1.43 (s, 2H), 3.81 (s, 2H), 6.10 (s, 1H), 7.39 – 7.10
125.2, 125.4, 126.6, 127.3, 127.9, 128.0, 128.1, 128.3, 129.6, (m, 16H), 7.74 (dd, J = 1.2, 7.8 Hz, 2H), 8.63 – 8.62 (m,
129.7, 130.0, 130.6, 131.1, 134.2, 137.3, 143.3, 159.4 ppm. 1H) ppm. – 13C NMR (100 MHz, CDCl3): δ = 27.1,45.7,
– HRMS ((+)-ESI): m/z = 597.0054 (calcd. 597.0051 for 106.0, 108.9, 120.6, 122.5, 122.8, 126.3, 126.7, 127.1, 127.3,
C30H21Br2N3O).
127.8, 128.1, 128.3, 128.5, 128.9, 129.1, 129.4, 130.9, 131.1,
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N. O. Mahmoodi et al. · One-pot Multi-component Synthesis of Mono- and Bis-indolylimidazole Derivatives
134.9, 135.6, 137.4, 137.7, 143.4 ppm. – HRMS ((+)-ESI): 1,6-Bis(3-(1,4,5-triphenyl-1H-imidazol-2-yl)-1H-indol-
m/z = 876.3947 (calcd. 876.3940 for C62H48N6).
1-yl)hexane (4)
Yield 91%. Colorless solid, m. p. 299 – 301 ◦C. – IR
1,5-Bis(3-(1,4,5-triphenyl-1H-imidazol-2-yl)-1H-indol-
1-yl)pentane (3)
(KBr): v = 3050, 2900, 2850, 1600, 1580, 1560, 1490, 1470,
1
1450, 760, 740, 690 cm−1. – H NMR (400 MHz, CDCl3):
Yield 93%. Colorless solid, m. p. 273 – 275 ◦C. – IR
δ = 1.04 (s, 2H), 1.58 (s, 2H), 3.86 – 3.88 (m, 2H), 6.25 (brs,
1H) 7.38 – 7.17 (m, 16H), 7.73 (d, J = 6.8 Hz, 2H), 8.52 (brs,
1H) ppm. – 13C NMR (100 MHz, CDCl3): δ = 26.3, 29.6,
46.1, 120.0, 120.5, 122.3, 122.6, 127.1, 127.2, 127.8, 127.9,
128.0, 128.3, 128.4, 128.9, 129.1, 129.3, 130.4, 131.1, 135.7,
136.4, 143.4 ppm. – HRMS ((+)-ESI): m/z = 904.4258
(calcd. 904.4253 for C64H52N6).
(KBr): v = 3050, 2900, 2850, 1600, 1580, 1560, 1490,
1
1440, 760, 735, 690 cm−1. – H NMR (400 MHz, CDCl3):
δ = 1.03 – 0.99 (m, 1H), 1.63 – 1.56 (m, 2H), 3.85 (t, J =
6.6 Hz, 2H), 6.25 (brs, 1H), 7.32 – 7.14 (m, 16H), 7.74
(dd, J = 1.6 Hz, 8 Hz, 2H), 8.52 (brs, 1H) ppm. – 13C
NMR (100 MHz, CDCl3): δ = 23.9, 29.3, 46.0, 109.0,
120.6, 122.4, 122.6, 126.4, 127.1, 127.8, 128.1, 128.3, 128.5,
128.9, 129.1, 129.4, 130.8, 131.2, 135.7, 137.4, 143.5 ppm.
– HRMS ((+)-ESI): m/z = 890.4103 (calcd. 890.4097 for
C63H50N6).
Acknowledgement
This study was supported in part by the Research Com-
mittee of University of Guilan.
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