Synthesis of new macrocyclic schiff bases containing pyrazole and triazole as subcyclic units

Article abstract of DOI:10.1002/jhet.1968

The novel macrocyclic Schiff bases upon which were fused triazole and pyrazole units and containing N, O and S inside the macrocyclic ring as donor atoms were synthesized by condensation of appropriate bis (4-amino-1,2,4-triazole-3-yl-sulfanyl)alkanes 2a-

Full text of DOI:10.1002/jhet.1968

Month 2014
Synthesis of New Macrocyclic Schiff Bases Containing Pyrazole and
Triazole as Subcyclic Units
F. Chena and F-M. Liua,b
*
aCollege of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, People’s Republic of China
bCollege of Materials and Chemical Engineering, Hangzhou Normal University, Hang Zhou, 310036 People’s Republic of China
*
E-mail: fmliu859@sohu.com
Received November 6, 2012
DOI 10.1002/jhet.1968
Published online 00 Month 2014 in Wiley Online Library (wileyonlinelibrary.com).
The novel macrocyclic Schiff bases upon which were fused triazole and pyrazole units and containing N,
O and S inside the macrocyclic ring as donor atoms were synthesized by condensation of appropriate bis
(4-amino-1,2,4-triazole-3-yl-sulfanyl)alkanes 2a-r and pyrazoledialdehyde 3 in refluxing glacial acetic
acid. The structural identities of these compounds were confirmed on the basis of spectrum.
J. Heterocylic Chem., 00, 00 (2014).
INTRODUCTION
derivatives were also reported to possess diverse biological
and pharmacological activities such as inhibitors of hepatitis
C virus, feline immunodeficiency virus and HIV proteases,
human cytomegalovirus and ß-secretase [6–9], and other
analogs were exhibited to be anti-inflammatory and anti-
bacterial properties [10,11]. Among them, macrocyclic
Schiff bases formed an important class of macrocyclic host
systems, which was easily obtained by condensation of a
diamine with a diformyl or diketo compounds, and the
presence of the basic imine functionality offered an
additional coordination or hydrogen-bonding site [12–14].
Meanwhile, the derivatives of 1,2,4-triazole also have a
high potential for biological activity because of the high
Macrocycles have received much attention in the areas
of host–guest complexation, molecular self-assembly, and
specific receptor activity. The successful design, synthesis,
and use of macrocyclic ligands capable of the selective
recognition of other species were of great interest to workers
in catalysis, separation, enzyme mimics, and other areas of
involving molecular recognition [1–4]. Macrocycles with
heterocyclic groups incorporated in the macrocyclic ring
provided rigidity and could form strong and selective
interactions with various charged and neutral moleculars
through their soft donor atoms [5]. Moreover, macrocyclic
© 2014 HeteroCorporation

F. Chen and F.-M. Liu
Vol 000
dipolar moment of this heterocycle, which allowed strong
RESULTS AND DISCUSSION
hydrogen-bonding interaction with the biological target
[15]. Literature survey have revealed the importance of
1,2,4-triazole compounds as antimicrobial agents such as
Fluconazole, Itraconazole, Voriconazole, and Ravuconazole
[16,17]. In addition, pyrazole nucleus was as one of the
significant pharmacophore that had anti-inflammatory,
anticoagulants, antibacterial, antitumor cyclin-dependent
kinase inhibitors, cyclooxygenase-2 (Cox-2) inhibitors
[18–21], and other versatile biological activities. Remarkably,
pyrazole motif made up the core structure of some well-
known drugs (e.g., Viagra, Acomplia, and Celebrex) [22,23].
The design and synthesis of novel macrocyclic host
moleculars with the desired functionality, property, size,
and shape have always been the driving force to promote
the major advances in supramolecular chemistry. In con-
tinuation of our interest in synthesizing biologically active
heterocyclic derivatives, we reported herein the synthesis
of a new family of macrocyclic Schiff bases upon which
fused triazole and pyrazole units and containing N, O,
and S as donor atoms in the macrocyclic ring as outlined
in Scheme 1. According to the theoretical studies, the
most stable conformers of the macrocycles were those
in which the lone pair electrons localized on the nitrogen
and sulfur atoms was exo-oriented and those on the
oxygen atoms were endo-oriented with respect to the
cavity [24,25].
Several synthetic methods have been developed for the
synthesis of different types of macrocycles, and the high
dilution technique was the most effective procedure [26].
Our study was extended to investigate the reactivity of the
1,4-di(1-phenyl-3-methyl-4-formylpyrazole-5-yl)Oxybenzene
3 in refluxing acetic acid under the high dilution conditions
towards the bisaminotriazole derivatives 2a–r (prepared by
heating the dibromo alkanes with 4-amino-1,2,4-triazole
derivatives 1 in aqueous ethanol (50%) containing NaOH)
to obtain the corresponding macrocyclic Schiff bases 4a–r.
In infrared (IR) spectra, the final compounds 4a–r
showed a strong stretching vibration at 1605–1608 cm–1
due to the presence of C = N and a strong stretching vibration
at 1168–1176 cm–1 due to the presence of C–O–C. The 1H-
NMR spectrum revealed a singlet at d 3.75–3.81 ppm was
attributed to CH2CH2 for compounds 4a–f; broad peak at
d 3.06–3.48 ppm was attributed to the SCH2, whereas
broad peak at d 2.02–2.41 ppm was attributed to the
SCH2CH2 for compounds 4g–l; broad peak at d 1.72–
1.74 ppm was attributed to the SCH2CH2 for compounds
4m–r, respectively. In mass spectra, molecular ions
(M++1) peaks of all target compounds were attained from
electrospray ionization mass spectrometry (ESI-MS).
CONCLUSION
In summary, the present study described the synthesis of
some novel macrocyclic Schiff bases upon that fused triazole
and pyrazole units and containing N, O, and S as donor atoms
in the macrocyclic ring, which easily obtained desired yield by
condensation of a diamine 2 with a diformyl- compound 3.
Scheme 1. Synthetic process of the title compounds.
EXPERIMENTAL
All reagents were of commercial availability. Reactions were
monitored by thin-layer chromatography. Melting points were
measured on a Mettler FP-5 capillary melting point apparatus
(Maytag, Beijing, China) and were uncorrected. Elemental analyses
were conducted on a Perkin-Elmer 2400 (Perkin-Elmer, Germany)
elemental analyzer. The IR spectra were determined as potassium
bromide pellet on a Bruker Equinox 55 Fourier transform infrared
(FTIR) spectrophotometer (Bruker Optics, Germany). Mass spectra
were recorded on an Agilent 5975 apparatus (electron impact, 70 eV
(Agilent, the USA)). Compounds 1, 2 [27], and 3 [28] were synthe-
sized according to the reported literatures.
General procedure for the synthesis of 4a–r.
To a
solution of 3 (1 mM) in glacial acetic acid (10 cm3) was added a
solution of the appropriate bis(4-amino-1,2,4-triazole-3-yl-
sulfanyl)alkanes 2a–r (1 mM) in glacial acetic acid (30 cm3).
The reaction mixture was then heated under reflux for 2–4 h
(monitored by thin-layer chromatography). The solvent was
then removed in vacuo, and the remaining solid was crystallized
from acetic acid to give gray solids of 4a–r.
3,8,19,24-Tetramethyl-10,17-diphenyl-11,16,28,29-tetrahydrobis
[1,2,4]-triazolo[4,3-f:3,4-j]dipyrazolo[b,n]-[1,18,5,6,13,14,8,11]
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
Synthesis of New Macrocyclic Schiff Bases Containing Pyrazole and Triazole as
Subcyclic Units
1
dioxatetraazadithiacyclopentacosine (4a).
Pale white solid
(C–O–C), 694 (C–S–C) cmÀ1; H-NMR d 8.42 (s, 2H, N = CH),
6.92–7.66 (m, 14H, ArHs), 3.06 (brs, 4H, SCH2), 2.59 (s, 6H,
triazole–CH3), 2.52 (s, 6H, pyrazole–CH3), 2.02 (brs, 2H, SCH2CH2);
MS (ESI): m/z 743 (M++1); Anal. Calcd for C37H34N12O2S2: C,
59.82%; H, 4.61%; N, 22.63%; O, 4.31%; S, 8.63%. Found: C,
(64%); mp 330–332ꢀC; FTIR n 1614 (C = N), 1175 (C–O–C),
1
694 (C–S–C) cmÀ1; H-NMR d 8.42 (s, 2H, N = CH), 6.92–7.66
(m, 14H, ArHs), 3.75 (s, 4H, CH2CH2), 2.59 (s, 6H, triazole–
CH3), 2.50 (s, 6H, pyrazole–CH3); MS (ESI): m/z 729 (M++1);
Anal. Calcd for C36H32N12O2S2: C, 59.32%; H, 4.43%; N,
23.06%; O, 4.39%; S, 8.80%. Found: C, 59.32%; H, 4.43%; N,
59.82%; H, 4.61%; N, 22.62%; O, 4.32%; S, 8.63%.
8,19-Dimethyl-3,24-diethyl-10,17-diphenyl-11,16,28,29,30-
pentahydrobis[1,2,4]-triazolo[4,3-f:3,4-k]dipyrazolo[b,o]-
[1,19,5,6,14,15,8,12]dioxatetraazadithiacyclohexacosine
23.05%; O, 4.40%; S, 8.80%.
8,19-Dimethyl-3,24-diethyl-10,17-diphenyl-11,16,28,29-
(4h).
Pale white solid (66%); mp 159–161ꢀC; FTIR n 1615
tetrahydrobis[1,2,4]-triazolo[4,3-f:3,4-j]dipyrazolo[b,n]-
[1,18,5,6,13,14,8,11]dioxatetraazadithiacyclopentacosine (4b).
Pale white solid (60%); mp 325–327ꢀC; FTIR n 1615 (C = N), 1175
1
(C= N), 1175 (C–O–C), 694 (C–S–C) cmÀ1; H-NMR d 8.21 (s,
2H, N = CH), 6.94–7.57 (m, 14H, ArHs), 3.06 (brs, 4H, SCH2),
2.01 (brs, 2H, SCH2CH2), 2.50 (q, 4H, CH3CH2), 2.53 (s, 6H,
pyrazole–CH3), 1.35 (t, 6H, CH3CH2); MS (ESI): m/z 771
(M++1); Anal. Calcd for C39H38N12O2S2: C, 60.76%; H, 4.97%;
N, 21.80%; O, 4.15%; S, 8.32%. Found: C, 60.75%; H, 4.97%;
(C–O–C), 694 (C–S–C) cmÀ1; H-NMR d 8.42 (s, 2H, N = CH),
1
6.92–7.66 (m, 14H, ArHs), 3.75 (s, 4H, CH2CH2), 2.62 (q, 4H,
CH3CH2), 2.50 (s, 6H, pyrazole–CH3), 1.30 (t, 6H, CH3CH2); MS
(ESI): m/z 757 (M++1); Anal. Calcd for C38H36N12O2S2: C,
60.30%; H, 4.79%; N, 22.21%; O, 4.23%; S, 8.47%. Found: C,
60.30%; H, 4.78%; N, 22.21%; O, 4.24%; S, 8.47%.
N, 21.80%; O, 4.15%; S, 8.33%.
8,19-Dimethyl-3,10,17,24-tetraphenyl-11,16,28,29,30-
8,19-Dimethyl-3,10,17,24-tetraphenyl-11,16,28,29-tetrahydrobis
[1,2,4]-triazolo[4,3-f:3,4-j]dipyrazolo[b,n]-[1,18,5,6,13,14,8,11]
pentahydrobis[1,2,4]-triazolo[4,3-f:3,4-k]dipyrazolo[b,o]-
[1,19,5,6,14,15,8,12]dioxatetraazadithiacyclohexacosine(4i).
Pale white solid (60%); mp 245–246ꢀC; FTIR n 1609 (C = N), 1169
dioxatetraazadithiacyclopentacosine (4c).
Pale white solid
1
(60%); mp 296–297ꢀC; FTIR n 1615 (C = N), 1171 (C–O–C),
(C–O–C), 692 (C–S–C) cmÀ1; H-NMR d 8.44 (s, 2H, N = CH),
1
693 (C–S–C) cmÀ1; H-NMR d 8.34 (s, 2H, N = CH), 6.86–7.94
6.83–7.98 (m, 24H, ArHs), 3.30 (brs, 4H, SCH2), 2.57 (s, 6H,
pyrazole–CH3), 2.33 (brs, 2H, SCH2CH2); MS (ESI): m/z 867
(M++1); Anal. Calcd for C47H38N12O2S2: C, 65.11%; H, 4.42%;
N, 19.39%; O, 3.69%; S, 7.40%. Found: C, 65.11%; H, 4.42%;
N, 19.38%; O, 3.70%; S, 7.40%.
(m, 24H, ArHs), 3.81 (s, 4H, CH2CH2), 2.50 (s, 6H, pyrazole–
CH3); MS (ESI): m/z 853 (M++1); Anal. Calcd for
C46H36N12O2S2: C, 64.77%; H, 4.25%; N, 19.70%; O, 3.75%; S,
7.52%. Found: C, 64.78%; H, 4.25%; N, 19.70%; O, 3.74%; S,
8,19-Dimethyl-3,24-di(p-chlorophenyl)-10,17-diphenyl-
11,16,28,29,30-pentahydrobis[1,2,4]-triazolo[4,3-f:3,4-k]
dipyrazolo[b,o]-[1,19,5,6,14,15,8,12]dioxatetraazadithia
cyclohexacosine (4j). Pale white solid (72%); mp 242–244ꢀC;
7.52%.
8,19-Dimethyl-3,24-di(p-chlorophenyl)-10,17-diphenyl-
11,16,28,29-tetrahydrobis[1,2,4]-triazolo[4,3-f:3,4-j]dipyrazolo
[b,n]-[1,18,5,6,13,14,8,11]dioxatetraazadithiacyclopentacosine
FTIR n 1604 (C = N), 1168 (C–O–C), 689 (C–S–C) cmÀ1
;
(4d).
Pale white solid (70%); mp 203–204ꢀC; FTIR n 1604
(C = N), 1168 (C–O–C), 689 (C–S–C) cmÀ1
;
1H-NMR d 8.34
1H-NMR d 8.44 (s, 2H, N = CH), 6.83–7.97 (m, 22H, ArHs),
3.30 (brs, 4H, SCH2), 2.57 (s, 6H, pyrazole–CH3), 2.34 (brs,
2H, SCH2CH2); MS (ESI): m/z 935 (M++1); Anal. Calcd. for
C47H36Cl2N12O2S2: C, 60.32%; H, 3.88%; Cl, 7.58%; N,
17.96%; O, 3.42%; S, 6.84%. Found: C, 60.32%; H, 3.88%;
Cl, 7.57%; N, 17.95%; O, 3.43%; S, 6.85%.
(s, 2H, N = CH), 6.86–7.92 (m, 22H, ArHs), 3.81 (s, 4H,
CH2CH2), 2.54 (s, 6H, pyrazole–CH3); MS (ESI): m/z 921
(M++1); Anal. Calcd for C46H34Cl2N12O2S2: C, 59.93%; H,
3.72%; Cl, 7.69%; N, 18.23%; O, 3.47%; S, 6.96%. Found: C,
59.93%; H, 3.72%; Cl, 7.68%; N, 18.24%; O, 3.47%; S, 6.96%.
8,19-Dimethyl-3,24-di(p-methoxyphenyl)-10,17-diphenyl-
11,16,28,29-tetrahydrobis[1,2,4]-triazolo[4,3-f:3,4-j]dipyrazolo
[b,n]-[1,18,5,6,13,14,8,11]dioxatetraazadithiacyclopentacosine
8,19-Dimethyl-3,24-di(p-methoxyphenyl)-10,17-diphenyl-
11,16,28,29,30-pentahydrobis[1,2,4]-triazolo[4,3-f:3,4-k]
dipyrazolo[b,o]-[1,19,5,6,14,15,8,12]dioxatetraazadithia
cyclohexacosine (4k). Pale white solid (68%); mp 165–166ꢀC;
(4e).
Pale white solid (70%); mp 165–166ꢀC; FTIR n 1613
(C = N), 1175 (C–O–C), 694 (C–S–C) cmÀ1
;
1H-NMR d 8.34
FTIR n 1613 (C = N), 1175 (C–O–C), 694 (C–S–C) cmÀ1
;
1H-NMR d 8.43 (s, 2H, N = CH), 6.83–7.97 (m, 22H, ArHs),
3.30 (brs, 4H, SCH2), 2.55 (s, 6H, pyrazole–CH3), 2.35 (brs, 2H,
SCH2CH2), 3.80 (s, 6H, OCH3); MS (ESI): m/z 927 (M++1);
Anal. Calcd for C49H42N12O4S2: C, 63.48%; H, 4.57%; N,
18.13%; O, 6.90%; S, 6.92%. Found: C, 63.48%; H, 4.57%; N,
(s, 2H, N = CH), 6.86–7.91 (m, 22H, ArHs), 3.86 (s, 6H,
OCH3), 3.80 (s, 4H, CH2CH2), 2.52 (s, 6H, pyrazole–CH3); MS
(ESI): m/z 913 (M++1); Anal. Calcd for C48H40N12O4S2: C,
63.14%; H, 4.42%; N, 18.41%; O, 7.01%; S, 7.02%. Found: C,
63.14%; H, 4.42%; N, 18.42%; O, 7.01%; S, 7.01%.
8,19-Dimethyl-3,24-diphenoxymethylene-10,17-diphenyl-
11,16,28,29-tetrahydrobis[1,2,4]-triazolo[4,3-f:3,4-j]dipyrazolo[b,n]-
[1,18,5,6,13,14,8,11]dioxatetraazadithiacyclopentacosine (4f).
Pale white solid (64%); mp 165–167ꢀC; FTIR n 1614 (C = N), 1174
18.12%; O, 6.91%; S, 6.92%.
8,19-Dimethyl-3,24-diphenoxymethylene-10,17-diphenyl-
11,16,28,29,30-pentahydrobis[1,2,4]-triazolo[4,3-f:3,4-k]dipyrazolo
[b,o]-[1,19,5,6,14,15,8,12]dioxatetraazadithiacyclohexacosine
1
(C–O–C), 694 (C–S–C) cmÀ1; H-NMR d 8.34 (s, 2H, N = CH),
(4l).
Pale white solid (63%); mp 227–229ꢀC; FTIR n 1613
6.86–7.91 (m, 24H, ArHs), 5.43 (s, 4H, PhOCH2), 3.78 (s, 4H,
CH2CH2), 2.53 (s, 6H, pyrazole–CH3); MS (ESI): m/z 913 (M++1);
Anal. Calcd for C48H40N12O4S2: C, 63.14%; H, 4.42%; N, 18.41%;
O, 7.01%; S, 7.02%. Found: C, 63.14%; H, 4.42%; N, 18.42%; O,
7.01%; S, 7.01%.
3,8,19,24-Tetramethyl-10,17-diphenyl-11,16,28,29,30-
(C = N), 1172 (C–O–C), 694 (C–S–C) cmÀ1; 1H-NMR d 8.30 (s,
2H, N = CH), 6.68–7.58 (m, 24H, ArHs), 5.43 (s, 4H, PhOCH2),
3.48 (brs, 4H, SCH2), 2.51 (s, 6H, pyrazole–CH3), 2.41 (brs, 2H,
SCH2CH2); MS (ESI): m/z 927 (M++1); Anal. Calcd for
C49H42N12O4S2: C, 63.48%; H, 4.57%; N, 18.13%; O, 6.90%;
S, 6.92%. Found: C, 63.48%; H, 4.57%; N, 18.13%; O, 6.90%;
pentahydrobis[1,2,4]-triazolo[4,3-f:3,4-k]dipyrazolo[b,o]-
[1,19,5,6,14,15,8,12]dioxatetraazadithiacyclohexacosine (4g).
Pale white solid (71%); mp 311–313ꢀC; FTIR n 1615 (C = N), 1174
S, 6.92%.
3,8,19,24-Tetramethyl-10,17-diphenyl-11,16,28,29,30,31-
hexahydrobis[1,2,4]-triazolo[4,3-f:3,4-l]dipyrazolo[b,p]-
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

F. Chen and F.-M. Liu
Vol 000
[1,20,5,6,15,16,8,13]dioxatetraazadithiacycloheptacosine (4m).
Acknowledgments. We are grateful to the Key SCI-Tech Innovation
Team of Zhejiang Province (2010R50017) for financial help.
Pale white solid (70%); mp 202–204ꢀC; FTIR n 1615 (C = N), 1174
(C–O–C), 694 (C–S–C) cmÀ1
;
1H-NMR d 8.20 (s, 2H,
N = CH), 6.83–7.88 (m, 14H, ArHs), 3.22 (brs, 4H, SCH2),
2.59 (s, 6H, triazole–CH3), 2.50 (s, 6H, pyrazole–CH3), 1.72
(brs, 4H, SCH2CH2); MS (ESI): m/z 757 (M++1); Anal. Calcd
for C38H36N12O2S2: C, 60.30%; H, 4.79%; N, 22.21%; O,
4.23%; S, 8.47%. Found: C, 60.31%; H, 4.79%; N, 22.22%;
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8,19-Dimethyl-3,24-diethyl-10,17-diphenyl-11,16,28,29,30,31-
hexahydrobis[1,2,4]-triazolo[4,3-f:3,4-l]dipyrazolo[b,p]-
[1,20,5,6,15,16,8,13]dioxatetraazadithiacycloheptacosine (4n).
Pale white solid (68%); mp 174–175C; FTIR n 1615 (C = N), 1173
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6.93–7.67 (m, 14H, ArHs), 3.22 (brs, 4H, SCH2), 2.60 (q, 4H,
CH3CH2), 2.51 (s, 6H, pyrazole–CH3), 1.72 (brs, 4H, SCH2CH2),
1.30 (t, 6H, CH3CH2); MS (ESI): m/z 785 (M++1); Anal. Calcd
for C49H42N12O4S2: C, 61.20%; H, 5.14%; N, 21.41%; O, 4.08%;
S, 8.17%. Found: C, 61.20%; H, 5.14%; N, 21.42%; O, 4.08%; S,
8.16%.
8,19-Dimethyl-3,10,17,24-tetraphenyl-11,16,28,29,30,31-
hexahydrobis[1,2,4]-triazolo[4,3-f:3,4-l]dipyrazolo[b,p]-
[1,20,5,6,15,16,8,13]dioxatetraazadithiacycloheptacosine (4o).
Pale white solid (62%); mp 178–180ꢀC; FTIR n 1614 (C = N), 1175
1
(C–O–C), 693 (C–S–C) cmÀ1; H-NMR d 8.05 (s, 2H, N = CH),
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6.83–7.68 (m, 24H, ArHs), 3.01 (brs, 4H, SCH2), 2.52 (s, 6H,
pyrazole–CH3), 1.73 (brs, 4H, SCH2CH2); MS (ESI): m/z 881
(M++1); Anal. Calcd for C48H40N12O2S2: C, 65.44%; H, 4.58%;
N, 19.08%; O, 3.63%; S, 7.28%. Found: C, 65.44%; H, 4.58%;
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N, 19.08%; O, 3.64%; S, 7.27%.
8,19-Dimethyl-3,24-di(p-chlorophenyl)-11,16,28,29,30,31-
hexahydrobis[1,2,4]-triazolo[4,3-f:3,4-l]dipyrazolo[b,p]-
[1,20,5,6,15,16,8,13]dioxatetraazadithiacycloheptacosine (4p).
Pale white solid (70%); mp 212–213ꢀC; FTIR n 1609 (C = N),
1170 (C–O–C), 691 (C–S–C) cmÀ1 1H-NMR d 8.04 (s, 2H,
;
N = CH), 6.79–7.75 (m, 22H, ArHs), 3.03 (brs, 4H, SCH2), 2.51
(s, 6H, pyrazole–CH3), 1.73 (brs, 4H, SCH2CH2); MS (ESI):
m/z 949 (M++1); Anal. Calcd for C48H38Cl2N12O2S2: C,
60.69%; H, 4.03%; Cl, 7.46%; N, 17.69%; O, 3.37%; S,
6.75%. Found: C, 60.69%; H, 4.03%; Cl, 7.47%; N, 17.68%;
O, 3.37%; S, 6.75%.
8,19-Dimethyl-3,24-di(p-methoxyphenyl)-11,16,28,29,30,31-
hexahydrobis[1,2,4]-triazolo[4,3-f:3,4-l]dipyrazolo[b,p]-
[1,20,5,6,15,16,8,13]dioxatetraazadithiacycloheptacosine (4q).
Pale white solid (68%); mp 162–163ꢀC; FTIR n 1612 (C = N),
1176 (C–O–C), 694 (C–S–C) cmÀ1 1H-NMR d 8.03 (s, 2H,
;
N = CH), 6.74–7.66 (m, 22H, ArHs), 3.75 (s, 6H, OCH3), 3.01
(brs, 4H, SCH2), 2.52 (s, 6H, pyrazole–CH3), 1.73 (brs, 2H,
SCH2CH2); MS (ESI): m/z 941 (M++1); Anal. Calcd for
C50H44N12O4S2: C, 63.81%; H, 4.71%; N, 17.86%; O, 6.80%;
S, 6.81%. Found: C, 63.81%; H, 4.71%; N, 17.86%; O, 6.79%;
S, 6.82%.
8,19-Dimethyl-3,24-diphenoxymethylene-11,16,28,29,30,31-
hexahydrobis[1,2,4]-triazolo[4,3-f:3,4-l]dipyrazolo[b,p]-
[1,20,5,6,15,16,8,13]dioxatetraazadithiacycloheptacosine (4r).
Pale white solid (62%); mp 189–191ꢀC; FT-IR n 1613 (C = N), 1172
(C–O–C), 693 (C–S–C) cmÀ1; 1H-NMR d 8.03 (s, 2H, N = CH),
6.73–7.68 (m, 24H, ArHs), 5.42 (s, 4H, PhOCH2), 3.01 (brs,
4H, SCH2), 2.51 (s, 6H, pyrazole–CH3), 1.74 (brs, 2H,
SCH2CH2); MS (ESI): m/z 941 (M++1); Anal. Calcd for
C50H44N12O4S2: C, 63.81%; H, 4.71%; N, 17.86%; O, 6.80%;
S, 6.81%. Found: C, 63.81%; H, 4.71%; N, 17.85%; O,
6.80%; S, 6.82%.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet