Synthesis and characterization of 1-aryl-5-hepta-Oacetyl-β-D-maltosyl- 2-S-benzyl-2,4-isodithiobiurets

Article abstract of DOI:10.1155/2012/521751

The facile synthesis of 1-aryl-5-hepta-o-acetyl-β-D-maltosyl-2- Sbenzyl-2,4-isodithiobiurets (IIIa-g) has been achieved by the interaction of 1-hepta-O-acetyl-β-D-maltosyl isothiocyanate (I) with various1-aryl-S- benzyl isothiocarbamides (IIa-g). All the newly synthesized N-maltosylated compounds characterized by elemental analysis, IR, NMR and Mass spectral studies.

Full text of DOI:10.1155/2012/521751

ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
2012, 9(1), 330-334
http://www.e-journals.net
Synthesis and Characterization of 1-Aryl-5-hepta-O-
acetyl-
β
-D-maltosyl-2-S-benzyl-2,4-isodithiobiurets
R. D. GHUGE and S. P. DESHMUKH*
P .G. Department of Chemistry, Shri Shivaji College
Akola-4444001(M.S.) India
rdghuge.2011@rediffmail.com
Received 9 June 2011; Accepted 12 August 2011
Abstract: The facile synthesis of 1-aryl-5-hepta-o-acetyl-
benzyl-2,4-isodithiobiurets (IIIa-g) has been achieved by the interaction of
1-hepta-O-acetyl- –D-maltosyl isothiocyanate (I) with various1-aryl-S-benzyl
β-D-maltosyl-2-S-
β
isothiocarbamides (IIa-g). All the newly synthesized N-maltosylated
compounds characterized by elemental analysis, IR, NMR and Mass spectral
studies.
Keywords: Synthesis, Maltosyl isothiocyanate, Aryl isothiocarbamides, isodithiobiurets
Introduction
Glycosylated isothiocyanates1-3 is important class of organic compounds in the field of
carbohydrate chemistry. In the last few years maltosyl isothiocyanate4-6 is used as the key
intermediate in synthetic carbohydrate chemistry. Its derivatives shows various applications
in medical chemistry as an antitumor agent7, antifungal agent8, bacteriostatic agent and also
used against hepatic diseases9.
In view of these applications of N-maltosides we herein reports new route for the
synthesis of 1-aryl-5-hepta-O-acetyl-
β
-D-maltosyl-2-S-benzyl-2,4-isodithiobiurets by the
interaction of hepta-O-acetyl-β-D-maltosyl isothiocyanate with various 1-aryl-S-benzyl
isothiocarbamides.
All the newly synthesized N-maltosylated compounds characterized by elemental
analysis, IR, 1H NMR and mass spectral studies.
Experimental
Melting points were taken in open capillary tubes and are found uncorrected. Specific
rotations [α]D were measured on a Equip Tronics digital polarimeter model no. EQ 800 in
CHCl3 at 300. IR Spectra10-11 were recorded on a Perkin-Elmer Spectra RXI (4000-450 cm-1)

Synthesis and Characterization
331
1
FTIR Spectrometer. H NMR spectra12-13 were obtained on a Bruker DRX-300 (300 MHZ
FT NMR) Spectrometer for a sample in CDCl3 solution with TMS as an internal reference.
The mass spectra14-15were recorded on a Jeol-SX 102 FAB mass spectrometer.
OAc
OAc
O
O
AcO
Xylene
AcO
OAc
AcO
OAc
Pb(SCN)2
AcO
+
OAc
O
OAc
O
O
O
AcO
N=C=S
AcO
OAc
OAc
Br
(I)
Hepta-O-acetyl-α-D-
maltosyl bromide
Lead
thiocyanate
Hepta-O-acetyl-β-D-
maltosyl isothiocyanate(I)
Scheme 1
OAc
O
AcO
OAc
AcO
OAc
O
HN=C-NH-R
S
O
N=C=S
+
AcO
CH2C6H5
(II a-g)
OAc
(I)
Hepta-O-acetyl-
β
-D-maltosyl isothiocyanate
1-Aryl-S-benzyl isothiocarbamide
Reflux
Benzene
OAc
O
AcO
OAc
AcO
OAc
O
O
N
NHR
NH
AcO
OAc
S
S-CH2C6H5
(III a-g)
1-Aryl-5-hepta-O-acetyl-β-D-maltosy-2-S-benzyl-2,4-isodithiobiurets
Where, R= a) phenyl; b) o-Cl-phenyl; c) m-Cl-phenyl; d) p-Cl-phenyl; e) o-Tolyl; f) m-Tolyl;
g) p-Tolyl, Ac =COCH3
Scheme 2
General procedure
Hepta-O-acetyl-β-D-maltosyl isothiocyanate (I)
Hepta-O-acetyl-β
reaction of hepta-O-acetyl-
-D-maltosyl isothiocyanate (I) has been prepared (Scheme 1) by condensation
-D-maltosyl bromide (0.005 M) with lead thiocyanate (0.005 M) in
α
boiling xylene for 3 h, After completion of reaction the xylene solution is filtered and the
excess xylene has been removed by distillation. The sticky residue obtained was triturated
several times with petroleum ether (bp 60-80 0C) to afford a solid. It was then purified from

332
S. P. DESHMUKH et al.
CHCl3. The purity of product checked by TLC. The product (I) was found desulphurisable
when boiled with plumbite solution and also show positive charring test when heated with
conc. H2SO4.
1-Aryl-5-hepta-O-acetyl-β-D-maltosyl-2-S-benzyl-2,4-isodithiobiurets (IIIa-g)
1-Aryl-5-hepta-O-acetyl-
β
prepared by the interaction of hepta-O-acetyl-
-D-maltosyl-2-S-benzyl-2,4-isodithiobiurets (IIIa-g) were
-D-maltosyl isothiocyanate (I),
β
(0.005 M) with various 1-aryl-S-benzyl isothiocarbamides (0.005 M) in boiling benzene
medium for 3 h (Table 1, Scheme 2). Afterwards, solvent was distilled off and a viscous
semi-solid mass was isolated as residue. It was then triturated several times with
0
petroleum ether (bp. 60-80 C) to afford a solid. All products (IIIa-g) were purified
from ethanol water, purity of products checked by TLC. The products were found
desulphurisable when boiled with plumbite solution and also shows positive charring
test when heated with conc. H2SO4. The % yield, M.P. Optical rotation, Rf values and
elemental analysis are shown in Table 1.
Table 1. Characterisation data of the synthesized products (III a-g)
Analysis*
Rf (CCl4:
EtOAc)
(3:2)
31
[α]D
(CHCl3)
S.
No.
Products Yield,
M.P.
°C
Required
%
Found
%
(III a-g)
III a
III b
III c
%
46
95
89
60
41
47
57
91.85
(c,0.3266)
+ 206
N, 4.57
S, 6.96
N, 4.40
S, 6.71
N, 4.40
S, 6.71
N, 4.40
S, 6.71
N, 4.50
S, 6.85
N, 4.50
S, 6.85
N, 4.50
S, 6.85
N, 4.56
S, 6.95
N, 4.38
S, 6.74
N, 4.41
S, 6.70
N, 4.39
S, 6.73
N, 4.52
S, 6.80
N, 4.50
S, 6.87
N, 4.7
0.84
(3 : 2)
0.73
1
2
3
4
5
6
7
130-132
115-118
98-100
106-107
125
(c, 5800)
+150
(3 : 2)
0.81
(c,0.3333)
-73.78
(3 : 2)
0.83
III d
III e
(c,0.4066)
+ 257
(3 : 2)
0.67
(c,0.4667)
+ 123
(3 : 2)
0.65
132-134
105-108
III f
(c,0.4062)
-24.63
(c,0.4071)
(3 : 2)
0.70
(3 : 2)
III g
S, 6.83
*Satisfactory C and H analysis is found in all cases
The required 1-aryl thiocarbamides were prepared by already known method16 i.e.
by interaction of appropriate aryl amine hydrochloride and ammonium thiocyanate. The
required 1-aryl–S-benzyl isothiocarbamides were prepared by already described
procedure17 i.e. benzyl chloride (0.04 M.) was added in ethanolic suspension of aryl
thiocarbamides (0.04 M) and the reaction mixture was refluxed for 90 min. Afterwards,
it was cooled and rendered basic with dilute cold ammonium hydroxide as the sticky
residue was obtained which solidify after 2 h. filtered and washed with petroleum ether
0
(bp 60-80 C).
Results and Discussion
The structures of the newly synthesized compounds were firmly established on the basis of
elemental analysis, IR, 1HNMR and Mass spectral studies.

Synthesis and Characterization
333
Hepta-O-acetyl-β-D-maltosyl isothiocyanate (I)
0
Yield 72%, M.P. 118-120 C, [α]D31+ 300(c,0.3333 m, CHCl3), Rf -0.75 (CCl4;EtOAc,3:2),
IR (KBr): υ 2962 (ali. C-H), 2032 (-N=C=S), 1753 (C=O), 1375 (C-N), 1231 (C-O), 1039.7
1
and 938,900 (characteristic of maltose), 770 cm-1 (C-S) ; HNMR (CDCl3): δ 5.4-3.7
(m,14 H,maltosyl ring protons); 2.2-2.0 (m, 21H,acetyl); Mass (m/z) : 677 (M+), 619, 559,
457, 331, 169, 109. Anal. Calcd. for C27 H35 O17 SN; C, 47.85; H,5.16; N, 3.63; S, 4.15
found C,47.80; H,5.20; N, 3.50, S, 4.02%.
1-Phenyl -5-hepta-O-acetyl-β-D-maltosyl-2-S-benzyl-2,4-isodithiobiuret-(IIIa)
IR (KBr): υ 3468 (N-H), 2960.9 (Ar-H), 1752.4 (C=O), 1567.2 (C=N), 1371.4 (C-N), 1231
(S-CH2), 1136.2 (C=S), 1039.4, 938 and 901 (cha.of maltose ring), 770.2 cm-1 (C-S);
1HNMR (CDCl3): δ 7.46-7.06 (m, 13H, Ar-NH and Ar-H); 6.25-6.23 (d, 1H, maltose NH),
5.4-3.8 (m, 14H, maltose ring), 2.2-2.0 (m, 21H, acetyl H); Mass (m/z): (M+1)+ 920,
828,786,331,169,109. Anal. Cald. For C4lH49O17N3S2; C, 53.33; H,5.33; N,4.57; S, 6.96
found C, 53.35; H, 5.30; N, 4.56; S, 6.95%.
1-p-Cl-Phenyl-5-hepta-O-acetyl-β-D-maltosyl-2-S-benzyl-2,4- isodithiobiuret (IIId)
IR (KBr) : υ 3468.5 (N-H), 2966.8 (Ar-H), 1754.6 (C=O), 1565 (C=N), 1371 (C-N), 1221
1
(S-CH2), 1136.4 (C=S), 1040.1, 938 and 901 (cha.of maltose), 772.1 cm-1(C-S); HNMR
(CDCl3): δ 7.38-7.37 (d,1H,NH); 7.35 - 7.22 (m, 11H, Ar-H); 6.86-6.83 (d,1H, NH
maltose); 5.44 – 3.60 (m, 14H, maltose ring); 2.21 – 2.00 (m, 21 H,acetyl); Mass (m/z) :
(M++1) 954, 862, 842, 619, 559, 457, 331, 169, 109. Anal. Calcd. for C41H48O17 N3S2Cl; C,
51.57; H, 5.03; N, 4.40; S, 6.71 found C, 51.56; H, 5.00, N, 4.39; S, 6.73%
1-o-Tolyl-5-hepta-O-acetyl-β-D-maltosyl-2-S-benzyl-2,4-isodithiobiuret (IIIe)
IR (KBr) : υ 3471.2 (N-H), 2961 (Ar-H), 1752.9 (C=O), 1566 (C=N), 1371.5 (C-N), 1232
(S-CH2), 1138.1 (C=S), 1039.4, 939.9 and 902 (cha. of maltose), 770.2 cm-1 (C-S); 1HNMR
(CDCl3) : δ 7.37 -7.19 (m, 12H, Ar-H); 6.25 – 6.23 (d, 1H, NH maltose); 5.44 – 3.9 (m, 14H
maltose ring); 2.35 (S, 3H, methyl), 2.30-1.99 (m, 21 H, Acetyl); Mass (m/z): (M++1) 934,
842, 619, 559, 331, 169, 109 (not located); Anal. Calcd. for C42H51O17N3S2; C, 54.01 H,
5.46; N, 4.50 S, 6.85 found C, 53.87, H, 5.38, N, 4.52; S 6.80%.
Acknowledgment
Authors are thankful to SAIF, C.D.R.I. Lucknow for providing spectra and also Dr. S.G.
Bhadange, Principal of Shri Shivaji College, Akola for providing necessary facilities.
References
1.
Garcia Fernandez J M and Mellet C O, Adv Carbohydr Chem Biochem., 2000, 55,
35-135.
2.
3.
Fuentes J, Angulo M and Pradera M A, J Org Chem., 2002, 67(8), 2577 -2887.
Fernandez J G, Zafra E, Lopez O, Robina I and Fuentes J, Tetrahedron Assemetry,
1999, 10(15), 3011-3023.
4.
5.
Witczak Z J, Adv Carbohydr Chem Biochem., 1986, 44, 9145.
Ortizmellet C, Balanco J, Jose L, Fernandez G and Fuentes J, J Carbohydr Chem.,
1993, 12, 487-505.
6.
Dustan D and Hough L, Carbohydr Res., 1972, 23, 17-21.

334
7.
S. P. DESHMUKH et al.
Tsujihara K, Ozeki M, Morikawa G, Kawamori M, Akaike Y and Arai Y, J Med
Chem., 1982, 25, 441-446.
8.
9.
Mote S P and Deshmukh S P, Rasayan J Chem., 2011, 4(1) , 29-35.
Mizutani, Kito A (Nagoya J A) and Kyoji (Seto J A), U.S. Patent 1978, 4080442.
10. Segal L, O’conner R T and Eggerton F V, J Chem Soc., 1960, 82, 2807-2810.
11. Varma R, Kulkarni S Y, Jose C I and Pansare V S, Carbohydr Res., 1984, 25, 133.
12. Lemeiux R U and Driguez H, J Am Chem Soc., 1975, 97, 4069.
13. Ong G T, Chang K Y, Wu S H and Wang K T, Carbohydr Res., 1994, 265, 311-318.
14. Pearson M S M, Robin A, Bourgougnon N, Jean Claude Meslin J C and Denial D, J
Org Chem., 2003, 68, 8583.
15. Silverstein R M, Bassler G C and Morill T C, Spectrometric Identification of Organic
Compounds; 5th Ed., John Willey and Sons: Inc. New York 1991.
16. Krall H and Gupta R D, J Indian Chem Soc., 1935, 12, 629.
17. Werner E W, J Chem Soc., 1890, 57, 295-305.

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