Synthesis and characterization of N-glucosylated dithiadiazepine derivatives through carbon-sulfur bond formation

Article abstract of DOI:10.1515/hc-2015-0093

New 4,7-bis(arylamino)-2-tetra-O-acetyl-β-d-glucopyranosylimino-1,3,5,6-dithiadiazepines were synthesized via reaction of N-tetra-O-acetyl-β-d-glucopyranosyl isocyanodichloride with 1,6-diaryl-2,5-dithio-bis-ureas without using any catalyst. Thus, the syn

Full text of DOI:10.1515/hc-2015-0093

Heterocycl. Commun. 2015; aop
SSnyehnaltAh. Cehasvains*,aAvnindashcGh. UalhreaancdtBealririazmaNt. Bioerand of N-glucosylated
dithiadiazepine derivatives through carbon-sulfur
bond formation
DOI 10.1515/hc-2015-0093
Received May 22, 2015; accepted June 8, 2015
various thiadiazepines [16–18], to our best knowledge,
not much work has been reported for the synthesis of
1,3,5,6-dithiadiazepines.
Carbohydrates play a vital role in numerous biologi-
Abstract: New 4,7-bis(arylamino)-2-tetra-O-acetyl-β-d- cal processes including modification of proteins, molecu-
glucopyranosylimino-1,3,5,6-dithiadiazepines were synthe- lar recognition, and immune response [19]. Carbohydrates
sized via reaction of N-tetra-O-acetyl-β-d-glucopyranosyl are an important moiety in many natural antibiotics
isocyanodichloride with 1,6-diaryl-2,5-dithio-bis-ureas including bleomycin, neocarzinostatin, and other DNA-
without using any catalyst. Thus, the synthesis of 7-mem- targeting drugs [20]. Introduction of carbohydrates into
bered heterocycles containing two sulfur and two nitrogen synthetic drugs leads to new hybrid molecules of consid-
atoms through carbon-sulfur bond formation was explored. erable interest. For example, high levels of glucosylation
The chemical structures of these new compounds were elu- imparts molecular changes that accompany malignant
cidated by IR, 1H NMR, 13C NMR, mass spectral, and elemen- transformations, which is characteristic of cancer cells
tal analyses.
[21]. The carbohydrate moiety can be expected to act as
drug carrier and improve the selectivity of compounds for
Keywords: carbon-sulfur bond; dithiadiazepine; dithio- cancerous cell lines.
bis-urea; glucopyranosyl isocyanodichloride.
In view of the biological importance of diazepine
derivatives [22–24] and in continuation of our work on
the synthesis of N-glucosylated heterocyclic compounds
[25–28], N-glucosylated dithiadiazepine derivatives have
been synthesized through the formation of carbon-sulfur
bonds. The current study aims at the synthesis of new
N-glucosylated dithiadiazepine derivatives, which are
uncommon 7-membered heterocycles.
Introduction
Heterocyclic ring systems that contain nitrogen and sulfur
atoms are important scaffolds in medicinal chemistry
[1–7]. Diazepines are seven-membered heterocyclic com-
pounds with two nitrogen atoms. Such molecules possess
a wide range of medicinal properties [8]. Substitution of
the diazepine segment in the bioactive molecule often
leads to improvement of pharmacological activities [9].
Some of 1,2-diazepine derivatives are used in the treat-
ment of epilepsy, malignant gliomas, and amyotrophic
lateral sclerosis [10–12]. Synthesis, ESR, and X-ray diffrac-
tion studies of 1,4,5,7-dithiadiazepine and 1,6,2,4-dithiadi-
azepine derivatives have been reported [13–15]. Although
extensive synthetic studies have been published for
Results and discussion
1,6-Diaryl-2,5-dithio-bis-ureas 2a–e have been synthesized
by reacting two equivalents of aryl isothiocyanates 1a–e
with one equivalent of hydrazine hydrate at ambient tem-
perature [29, 30]. The IR spectrum of 2c shows an absorp-
tion band at 3210 cm-1, which indicates the presence of the
NH functional group. The absence of an absorption band
at 2800 cm-1 and presence of an absorption band at 628 cm-1
for Cꢀ=ꢀS indicated that the symmetric dithio-bis-ureas 2a–e
exist in the thione tautomeric form. Further support for
*Corresponding author: Snehal A. Chavan, Department of
Chemistry, Mahatma Jyotiba Phule Educational Campus,
Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur 440033,
India, e-mail: i_snehal123@yahoo.com
Avinash G. Ulhe and Baliram N. Berad: Department of Chemistry,
Mahatma Jyotiba Phule Educational Campus, Rashtrasant Tukadoji
Maharaj Nagpur University, Nagpur 440033, India
1
this structural feature comes from analysis of the H NMR
spectrum of 2c, which does not show a peak attributable
to the SH group [31] but shows a peak in the low field
region at δ 9.60 for four NH protons [32]. Three signals
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ꢀꢀꢀꢁ
2ꢀ ꢀS.A. Chavan et al.: N-Glucosylated dithiadiazepine derivatives
at δ 7.37, 7.20, and 6.96 belong to eight aromatic protons. product 6a in a very low yield. The optimized solvent was
The signal in the upfield region at δ 2.33 is attributed to used for the conversion of 2b–e to 6b–e.
1
the methyl protons.
Detailed analyses of IR, H NMR, 13C NMR, and mass
The symmetrical dithio-bis-ureas 2a–e were then spectra of compounds 6a–e were fully consistent with
allowed to react with N-tetra-O-acetyl-β-d-glucopyranosyl the given structures. The IR spectra of compounds 6a–e
isocyanodichloride(4)inamixtureofCHCl3-DMF(1:1)under show two strong bands in the ranges of 3300–3100 cm-1 and
reflux conditions to yield hydrochloride salts of 4,7-bis(aryl- 1742–1753 cm-1 due to the N-H and ester carbonyl stretching,
1
amino)-2-tetra-O-acetyl-β-d-glucopyranosylimino-1,3,5,6- respectively. The H NMR spectra show a multiplet due to
dithiadiazepines 5a–e, as depicted in Scheme 1. During the glucosyl ring protons in the range of δ 5.35–3.83 ppm
the intermolecular cyclocondensation reaction, evolution and a characteristic triplet or doublet for anomeric proton
of the hydrogen chloride gas was clearly noticed by testing (H1) of the glucose moiety within the region of δ 5.30–5.40.
with moist blue litmus paper. The final compounds 5a–e Coupling constant (J) of H1/H2 within the range of 12.3–
were found to be in the salt forms, which, upon treatment 9.3 Hz indicates that the glucosyl moiety exists as the β
with saturated solution of sodium bicarbonate, were trans- anomer [33]. The acetyl protons of the glucosyl moiety
formed into free bases 6a–e. Formation of these products resonate as a multiplet within δ 2.06–1.83. In addition,
1
may be rationalized by the mechanism shown in Scheme 2. the H NMR spectra of compounds 6a–e exhibit a broad
For optimization of the cyclocondensation reaction, singlet centered at δ 9.70 for the NH-aryl functionality. The
the preparation of 6a was carried out in different solvents aromatic protons also appear in the expected region as are
including CHCl3, DCM, a mixture of CHCl3-DMF, and DMF other protons of the substituents. The 13C NMR spectra of
under reflux condition. The time needed for completion compounds 6a–e show numbers of signals that are fully
of the reaction varied from 5 to 10 h. The effect of solvent consistent with the number of carbon atoms in the mole-
on the reaction time and product yield was observed. The cules. The signal for β anomeric carbon is observed within
yield of 6a was found to increase significantly when the the range of δ 83.50–84.06. The mass spectra of compounds
+
reaction was carried out in the 1:1 CHCl3-DMF mixture. 6a–e show ion peaks [M+1] and the characteristic frag-
The reaction conducted in other solvents gave the desired ment ion peaks at 169, 331, and 413 for the glucosyl moiety.
S
C
SH
C
H
N
H
N
H
N
CHCl3
N
2 Ar
N
C
S
H2N NH2
H2O
HN
Ar
N
H
C
S
Ar
N
N
C
Ar
H
rt, 15 min.
Ar
SH
1a-e
2a-e
OAc
OAc
Cl
Cl
O
O
Excess Cl2
AcO
AcO
AcO
AcO
1:1 CHCl3-DMF
∆, 5 h
N C
N C
S
AcO
AcO
3
4
NHAr
NHAr
a: Ar = Ph
Saturated solution
OAc
OAc
S
S
S
b
: Ar = 4-Me-C6H4
of NaHCO3
N
N
N
O
O
x HCl
AcO
AcO
AcO
AcO
c: Ar = 3-Me-C6H4
d: Ar = 4-OMe-C6H4
N
N
N
S
AcO
AcO
e
: Ar = 2-Cl-C6H4
NHAr
NHAr
6a-e
5a-e
Scheme 1ꢀSynthetic route for the synthesis of compounds 6a–e from symmetrical dithio-bis-ureas (2a–e).
Ar
HS
N
Ar
NH
NH
N
OAc
OAc
C
N
Cl
Cl
NaHCO3
S
C
AcO
AcO
O
O
AcO
AcO
x HCl
5
6
N C
N C
N
H
N
- HCl
AcO
AcO
Cl
C
Ar
HS
C
HS
HN Ar
4
2
Scheme 2ꢀPlausible mechanism for the formation of compound 6 through C-S bond formation.
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ꢁꢀꢀꢀ
S.A. Chavan et al.: N-Glucosylated dithiadiazepine derivativesꢂ ꢂ3
4,7-Bis(4-methylphenylamino)-2-tetra-O-acetyl-β-d -
glucopyranosylimino-1,3,5,6-dithiadiazepine (6b)ꢁThe free base
was obtained in 79% yield; mp 110°C; [α]D25 +150° (c 0.1, EtOH); Rf 0.52
(50% EtOAc-hexane); IR: νmax 3460 (N-H), 1742 (Oꢀ=ꢀC-O), 1607 (Cꢀ=ꢀN),
1380 (C-N), 746 cm-1 (C-S); 1H NMR (DMSO-d6): δ 9.64 (s, 2H, NH), 7.47–
7.04 (m, 8H, ArH), 5.36 (d, J ꢀ=ꢀ 9.3 Hz, 1H, H1), 5.00–3.98 (m, 6H, H2–7),
2.26 (s, 6H, 2ꢀ×ꢀCH3), 2.11–1.83 (12H, m, 4ꢀ×ꢀCH3CO); 13C NMR (CDCl3):
δ 169.7, 169.3, 169.0, 155.6, 138.8, 130.1, 129.6, 129.3, 129.1, 125.5, 117.6,
116.8, 89.0, 79.0, 78.7, 78.4, 72.6, 70.8, 21.1, 20.9, 20.4, 20.4, 20.3; MS:
Conclusions
We achieved the synthesis of 1,3,5,6-dithiadiazepine deriv-
atives 6a–e having glucosyl residue through a C-S bond
formation in an efficient manner. The overall conversion
was carried out in three steps in good yields.
+
m/z 686 [M+1] . Anal. Calcd for C31H35N5O9S2: C, 54.29; H, 5.14; N, 10.21;
Experimental
S, 9.35. Found: C, 54.15; H, 5.28; N, 10.09; S, 9.22.
4,7-Bis( 3-methylphenylamino)-2-tetra-O-acetyl-β-d -
glucopyranosylimino-1,3,5,6-dithiadiazepine (6c)ꢁThe free base
Melting points were measured using an electro-thermal apparatus
and are not corrected. FT-IR spectra were recorded using KBr disks
was obtained in 73% yield; [α]D25 +50° (c 0.1, EtOH); mp 100°C; H
1
1
on a Perkin Elmer FT-IR spectrophotometer. H NMR (400 MHz) and
13C NMR (400 MHz) spectra were recorded on a Brucker Avance II 400
NMR spectrometer. Electron-impact mass spectra were obtained at
an ionizing potential of 70eV. Optical rotations were measured using
an Equip-Tronics Digital Polarimeter EQ-801. Purity of compounds
was checked by thin layer chromatography, which was performed on
aluminum sheet Silica Gel 60 F254 (Merck). The spots were visualized
by exposure to UV light and iodine vapor.
1,6-Diaryl-2,5-dithio-bis-ureas 2a–e were synthesized by the pre-
viously described method and exhibited virtually identical physical
properties as reported in the literature [29–31]. N-Tetra-O-acetyl-β-d-
glucopyranosyl isocyanodichloride (4) was synthesized by excessive
chlorination of N-tetra-O-acetyl-β-d-glucopyranosyl isothiocyanate
(3) using the previously reported method [25, 26].
NMR (DMSO-d6): δ 9.70 (bs, 2H, 2ꢀ×ꢀNH),7.43–6.73 (m, 8H, ArH), 5.38
(d, J ꢀ=ꢀ 9.28 Hz, 1H, H1), 5.33–3.99 (m, 6H, H2–7), 2.38 (s, 6H, 2ꢀ×ꢀCH3),
2.15–1.97 (12H, m, 4ꢀ×ꢀCH3CO); 13C NMR (DMSO-d6) δ: 169.7, 169.2, 169.0,
155.7, 141.1, 138.0, 128.5, 122.6, 121.6, 117.8, 117.3, 114.0, 79.1, 78.8, 78.5,
21.3, 20.4, 20.39, 20.28; Anal. Calcd for C31H35N5O9S2: C, 54.29; H, 5.14;
N, 10.21; S, 9.35. Found: C, 54.40; H, 4.98; N, 9.91; S, 9.55; IR νmax cm-1:
3462 (N-H), 1742 (Oꢀ=ꢀC-O), 1594 (Cꢀ=ꢀN), 1380 (C-N), 774 (C-S); MS (m/z):
+
686 [M+1] ; Rf 0.52 (50% EtOAc-hexane).
4,7-Bis(4-methoxyphenylamino)-2-tetra-O-acetyl-β-d-
glucopyranosylimino-1,3,5,6-dithiadiazepine (6d)ꢁThe free base
was obtained in 75% yield; mp 115°C; [α]D25 +100° (c 0.1, EtOH); Rf 0.56
(30% EtOAc-hexane); IR: νmax 3393 (N-H), 1751 (Oꢀ=ꢀC-O), 1604 (Cꢀ=ꢀN),
1
1370 (C-N), 668 cm-1 (C-S); H NMR (DMSO-d6) δ: 9.46 (s, 2H, 2ꢀ×ꢀNH),
7.52–6.80 (m, 8H, ArH), 5.35–3.83 (m, 7H, H1–7), 3.73 (s, 6H, 2ꢀ×ꢀOCH3),
2.06–1.93 (12H, m, 4ꢀ×ꢀCH3CO); 13C NMR (CDCl3): δ 174.9, 174.4, 174.2,
161.8, 161.1, 159.0, 140.0, 137.1, 131.3, 124.3, 124.1, 123.6, 119.0, 118.6,
84.1, 83.7, 83.4, 78.3, 73.1, 60.2, 25.6, 25.5; MS: m/z 169, 331, 413. Anal.
Calcd for C31H35N5O10S2: C, 51.87; H, 4.91; N, 9.76; S, 8.93. Found: C,
51.99; H, 4.66; N, 9.50; S, 9.08.
Synthesis of 4,7-bis(arylamino)-2-tetra-O-acetyl-β-d-
glucopyranosylimino-1,3,5,6-dithiadiazepines 6a–e
N-Tetra-O-acetyl-β-d-glucopyranosyl isocyanodichloride (4, 0.43 g,
1.0 mmol) was added to a stirred solution of 2a–e (1.0 mmol) in a mixed
solvent of CHCl3-DMF (1:1) and the mixture was heated under reflux for
5 h. The evolution of hydrogen chloride gas was observed with moist
blue litmus paper. Progress of the reaction was monitored by TLC
analysis. The mixture was cooled and diluted with dichloromethane.
The organic layer was washed with water and dried with anhydrous
sodium sulfate. The organic layer was evaporated under reduced pres-
sure to afford a salt form of the product 5a–e. The crude product 5a–e
was triturated with aqueous saturated solution of sodium bicarbonate
for 10 min. The free base 6a–e was extracted with ethyl acetate. The
extract was dried with anhydrous sodium sulfate and concentrated
under reduced pressure to afford a free base 6a–e as a creamy solid,
which was crystallized from CHCl3-petroleum ether.
4,7-Bis(2- chlorophenylamino)-2-tetra-O-acetyl-β-d -
glucopyranosylimino-1,3,5,6-dithiadiazepine (6e)ꢁThe free base
was obtained in 95% yield; mp 83°C; [α]D25 +50° (c 0.1, EtOH); Rf 0.55
(50% EtOAc-hexane); IR: νmax 3461 (N-H), 1742 (Oꢀ=ꢀC-O), 1592 (Cꢀ=ꢀN),
1
1381 (C-N), 747 cm-1 (C-S); H NMR (CDCl3): δ 7.96–6.98 (m, 8H, ArH),
5.35 (t, J ꢀ=ꢀ 9.5 Hz, 1H, H1), 5.14–3.85 (m, 6H, H2–7), 2.12–1.95 (12H, m,
4ꢀ×ꢀCH3CO); 13C NMR (DMSO-d6): δ169.7, 169.23, 169.0, 155.7, 141.1, 128.7,
128.3, 120.8, 116.7, 83.5, 78.5, 78.3, 70.5, 60.2, 20.4, 20.3, 20.2; MS: m/z
+
726 [M+1] . Anal. Calcd for C29H29N5O9S2Cl2: C, 47.94; H, 4.02; N, 9.64; S,
8.83. Found: C, 47.59; H, 4.20; N, 9.86; S, 8.60.
Acknowledgments: The authors are thankful to Prof. H.
D. Juneja, head, Post-Graduate Department of Chemistry,
Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur,
for providing necessary laboratory facilities. The authors are
also grateful to the director of the Sophisticated Analytical
Instrumentation Facility (SAIF), Panjab University, Chandi-
garh, for spectral analysis. S.A.C. is thankful to the Council of
Scientific and Industrial Research [CSIR; 09/128(0086)/2012-
EMR-I, June 22, 2012], New Delhi, and A.G.U. is thankful to
the University Grants Commission (UGC), Delhi, for the
financial support in the form of research fellowship.
4,7-Bis(phenylamino)-2-tetra-O-acetyl-β-d-glucopyranosylimino-
1,3,5,6-dithiadiazepine (6a)ꢁThe free base was obtained in 81%
yield; mp 140°C; [α]D25 +200° (c 0.1, EtOH); Rf 0.50 (50% EtOAc-hexane);
IR: νmax 3462 (N-H), 1743 (Oꢀ=ꢀC-O), 1601 (Cꢀ=ꢀN), 1380 (C-N), 744 cm-1 (C-
1
S); H NMR (DMSO-d6): δ 9.73 (s, 2H, 2ꢀ×ꢀNH), 7.62–6.89 (m, 10H, ArH),
5.33 (t, J ꢀ=ꢀ 12.3 Hz, 1H, H1), 5.38–3.97 (m, 7H, H1–7), 2.07–1.93 (m, 12H,
acetyl protons); 13C NMR (CDCl3): δ 170.9, 170.7, 170.0, 169.6, 137.1, 134.2,
130.1, 129.5, 129.3, 128.1, 128.0, 127.6, 127.4, 123.5, 123.3, 122.1, 83.9, 73.2,
+
72.8, 70.8, 7.18, 69.7, 20.7, 20.6; MS: m/z 658 [M+1] . Anal. Calcd for
C29H31N5O9S2: C, 52.96; H, 4.75; N, 10.65; S, 9.75. Found: C, 52.72; H, 4.45;
N, 10.54; S, 9.80.
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4ꢀ ꢀS.A. Chavan et al.: N-Glucosylated dithiadiazepine derivatives
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