Synthesis, antifungal activities, and potential detoxification of N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)thiocarbamates

Article abstract of DOI:10.1016/j.carres.2009.05.008

A series of N-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)thiocarbamates were synthesized by the reaction of glucosyl isothiocyanates with monohydric and dihydric alcohols, and acetone oxime, using methods of both normal reaction and microwave-assisted syn

Full text of DOI:10.1016/j.carres.2009.05.008

Carbohydrate Research 344 (2009) 1289–1296
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Synthesis, antifungal activities, and potential detoxification
of N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)thiocarbamates
Yaling Zhou a, Li Wang a, Lixia Han a, Fangui Meng a,b, Chunlong Yang a,b,
*
a Department of Chemistry, College of Science, Nanjing Agricultural University, Nanjing 210095, China
b Key Laboratory of Monitoring and Management of Crop Diseases and Pest Insects, Ministry of Agriculture, Nanjing Agricultural University, Nanjing 210095, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)thiocarbamates were synthesized by the reac-
Received 25 January 2009
Received in revised form 28 April 2009
Accepted 6 May 2009
tion of glucosyl isothiocyanates with monohydric and dihydric alcohols, and acetone oxime, using meth-
ods of both normal reaction and microwave-assisted synthesis. Antifungal activities of the title
compounds were determined with three kinds of plant pathogenic fungi, Fusarium graminearum,
Rhizoctoria cerealis, and Colletotrichum orbiculare. The synthesized glucosyl thiocarbamates easily reacted
Available online 10 May 2009
with HgCl2 to give novel metal–organic compounds, bis[O-alkyl N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyr-
Keywords:
anosyl)thiocarbamato]mercury, in yields of 80%. This strong affinity of thiocarbamates for mercury
showed their potential utility in medical or marine environmental detoxification.
Ó 2009 Elsevier Ltd. All rights reserved.
Glucosyl thiocarbamates
Antifungal activities
Detoxification
Mercury
1. Introduction
thiocarbamates can be used as reagents in ore flotation, since their
strong affinity and good selectivity for certain ions.22 For example,
Thiocarbamates are remarkable for their biological activities
and are widely used as bactericides,1–3 pesticides,4,5 and herbi-
cides.6–9 Many of the thiocarbamates that have been reported are
N-alkyl10 and N-phenyl or benzyl11 compounds, few of which are
N-glucosyl.12,13 The linkage between the hydrophobic tail and the
sugar head in N-glucosyl thiocarbamates appears to modify the
physicochemical properties of non-ionic surfactants by changing
their water solubility.13 As was reported, many biologically impor-
tant products have a sugar unit joined through an atom (O, S, N, or
C) or a group of atoms.14 Glucosyl isothiocyanates, proven to be
excellent intermediates, have been used for the preparation of a
variety of carbohydrate derivatives of synthetic, biological, and
pharmaceutical interest,15,16 since they easily undergo many
important reactions, such as cycloadditions and nucleophilic
additions.17
O-isopropyl-N-ethylthiocarbamate is more selective for copper sul-
fide against gangue iron sulfides; thus, it can perform copper/iron
separation.23
The reports about
infrequent, and only a few of them have been described in de-
tail.12,13 In this study, 20 different N-(2,3,4,6-tetra-O-acetyl-b-
glucopyranosyl)thiocarbamates were synthesized by the reaction
of 2,3,4,6-tetra- O-acetyl-b- -glucopyranosyl isothiocyanate with
D-glucopyranosyl thiocarbamates are quite
D-
D
the compounds linking with one or two hydroxyl groups, respec-
tively (Scheme 1). Their antifungal activities against three plant
pathogenic fungi were evaluated. Furthermore, the potential utility
of these glucosyl thiocarbamates for detoxification was investi-
gated by reacting with HgCl2.
2. Results and discussion
Furthermore, thiocarbamates and some metal atoms (such as
rhodium, iridium, palladium, platinum, and gold) could form the
metal complexes.18 Some thiocarbamates can be used as sulfhydryl
group antidotes, and these compounds may have potential utility
in medical or marine environmental fields,19 owing to their high
affinity to heavy metal cations,20 for example, Hg2+ and Pb2+. Hg-
related health risks do exist for consumers of bivalves.21 Also some
2.1. The synthesis of glucosyl thiocarbamates
Glucosyl isothiocyanates were synthesized in moderate yield by
the reaction of an acylated glucosyl bromide with lead thiocyanate
according to the literature,24–28 and the acylated glucosyl bromide
was prepared by methods described in the literature.29,30 Glucosyl
isothiocyanates reacted with the acyclic and heterocyclic monohy-
dric alcohols to give the thiocarbamates 2a–2j and 2m, for the
most part, in yields of over 80%, except for 2n and 2o, which were
obtained by the reaction of glucosyl isothiocyanates with 1-
(hydroxymethyl)-1H-1,2,4-triazole and acetoxime, respectively.
* Corresponding author. Address: Key Laboratory of Monitoring and Management
of Crop Diseases and Pest Insects, Ministry of Agriculture, Nanjing Agricultural
University, Nanjing 210095, China. Tel./fax: +86 025 84395255.
E-mail address: chunlongyang@yahoo.com.cn (C. Yang).
0008-6215/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2009.05.008

1290
Y. Zhou et al. / Carbohydrate Research 344 (2009) 1289–1296
OAc
H
N
O
ROH
AcO
AcO
O
C
S
R
OAc
2a - 2n
2a: R = CH3, 2b: R = CH2CH3, 2c: R = n-C3H7, 2d: R = i-C3H7
2e 2f 2g 2h
: R = cyc-C6H11
: R = n-C4H9, : R = n-C5H11
,
: R = n-C6H13
2k
,
2i
: R = n-C8H17
2j
2l
: R = CH2CH=CH2, : R = Ph, : R = CH2Ph
,
2m: R = CH2THF, 2n: R = CH2Tr
OAc
O
OAc
AcO
AcO
NCS
H
N
O
HON CMe2
AcO
AcO
O
O
C
OAc
1
C
S
N
OAc
2o
OAc
R
H
N
O
AcO
AcO
diol
C
S
OH
OAc
2p - 2r
2p
2q
2r
: R = H, : R = CH2CH3, : R = n-C3H7
OAc
S
C
R
H
N
O
AcO
diol
AcO
AcO
O
O
C
S
O
N
H
OAc
OAc
AcO
OAc
2s 2t
,
2s: R = H, 2t: R = CH3
THF = tetrahydrofuran-2-yl, Tr = 1H-1,2,4-triazole-1-yl
Scheme 1. Preparation of the title compounds.
However, phenol and benzyl alcohol were more difficult to react
with the glucosyl isothiocyanates owing to their easy oxidation
at high reaction temperatures (100 °C) and long reaction times
(5 h). To limit the oxidation, microwave-assisted synthesis was
used, and compounds 2k and 2l were obtained. In the reaction of
glucosyl isothiocyanates with dihydric alcohols, monothiocarba-
mates 2p–2r, which are linked with only one glucosyl group, with
the other hydroxyl group left open, as well as the bridged bisthioc-
arbamates 2s and 2t, which are linked with two glucosyl groups,
were prepared (Scheme 1). In preparation of monothiocarbamates
IR spectrum an absorbance at about 3300 cmꢀ1 showed the pres-
ence of an NH group, and the absorbance at about 1520 cmꢀ1 indi-
cated the NH(C@S) group. In the 1H NMR spectra the NH of
monothiocarbamates appeared as doublet at d 6.16–7.03 , while
the NH of bisthiocarbamates appeared as broad peak at d 7.08.
H-1, H-2, H-3, and H-4 appeared as doublet of doublets (over-
lapped to appear as three-line patterns), respectively, while H-6a
and H-6b appeared as two-line patterns. As a result of the complex
coupling with H-4, H-6a and H-6b, H-5 appeared as a multiplet. In
the 13C NMR spectra, the C@S of N-(2,3,4,6-tetra-O-acetyl-b-
D-glu-
2p–2r, the molar ratio of diols and N-(2,3,4,6-tetra-O-acetyl-b-
D
-
copyranosyl)thiocarbamates appeared at about d 191–192, and
four acetyl C@O groups on the glucosyl ring appeared at about d
169–171. C-1 appeared at about d 83, C-2–C-6 appeared at about
d 61–73. The elemental analysis data were in accord with the
structure of compounds 2.
glucopyranosyl)isothiocyanates was 2:1, while in preparation of
the bisthiocarbamates 2s and 2t, the ratio of two reactants was just
the opposite.
Compounds with the general structure 2 were characterized by
IR, 1H, and 13C NMR spectroscopy and by elemental analysis. In the
2.2. Antifungal activities of glucosyl thiocarbamates
OAc
Antifungal activities of compounds 2 against three kinds of
plant pathogenic fungi (Fusarium graminearum, Rhizoctoria cerealis,
and Colletotrichum orbiculare) were evaluated by a radial growth
inhibition technique with three repeats for each sample according
to the literature procedure.31 As shown in Table 1, most of com-
H
N
O
AcO
AcO
O
Et3N,DMF
HgCl2
C
S
R
OAc
2
R
O
R
pounds 2 showed weak antifungal activities at 500 l
g mLꢀ1, but
OAc
AcO
O
some of the compounds, such as 2c, 2f, 2s, and 2t exhibited some-
what stronger antifungal activities. It is interesting that there
might be certain relationship between antifungal activities and
the number of carbon atoms in the alcohol position of compounds
2 synthesized by straight-chain fatty alcohols, that is, compounds
2a, 2c, and 2f with odd-numbered carbon atoms have stronger
antifungal activities than compounds 2b, 2e, and 2g with
even-numbered carbon atoms. By comparing 2s and 2t with 2p,
OAc
O
O
N
C
C
N
AcO
AcO
AcO
S Hg
S
OAc
OAc
3
3a
3b
3c
3d
: R = CH3, : R = CH2CH3, : R = n-C3H7, : R = i-C3H7, 3e: R = n-C4H9
3f: R = n-C5H11, 3g: R = n-C6H13, 3h: R = cyc-C6H11, 3i: R = n-C8H17
Scheme 2. Reaction of the thiocarbamates with HgCl2.

Y. Zhou et al. / Carbohydrate Research 344 (2009) 1289–1296
1291
13C NMR spectra (Bruker DRX-500) were recorded using tetra-
methylsilane (TMS, d 0.00) and chloroform (CDCl3, d 77.30) as
internal standards, respectively. Optical rotations were measured
on an ATAGO Automatic Polarimeter (AP-100) at room tempera-
ture (20 °C). Microwave-assisted synthesis was carried out in a
microwave reactor (MAS-I). Elemental analyses were carried out
on an elemental analyzer (Vario EL III). The concentration of mer-
cury was determined with a cold-vapor atomic absorption spec-
trometer (HG-3000). Thin-layer chromatography (TLC) was
performed on precoated plates (GF254) in 0.6% carboxymethyl cel-
lulose sodium (CMC) with subsequent heating and detection by UV
light. Column chromatography was conducted on silica gel C-300.
Table 1
Antifungal activities of compounds 2 against three kinds of plant pathogenic fungi
Compd
Inhibition % (500
l
gꢁmLꢀ1
)
F. graminearum
R. cerealis
C. orbiculare
2a
2b
2c
2d
2e
2f
2g
2h
2i
22.4
13.8
41.6
23.3
18.1
46.6
31.0
32.8
17.0
34.5
29.7
23.7
38.5
30.8
31.0
15.4
37.9
31.4
38.5
39.0
100
13.3
10.2
15.4
0
15.6
41.7
0
23.1
20.0
58.3
37.5
10.7
43.5
25.4
40.0
17.9
15.4
12.2
43.5
45.0
100
43.3
31.0
41.4
36.7
25.5
46.1
20.6
48.3
22.0
23.3
35.5
40.0
16.5
10.0
38.6
12.0
33.3
30.0
45.5
43.0
100
2j
2k
2l
3.2. General procedure for the synthesis of N-(2,3,4,6-tetra-O-
acetyl-b-
D
-glucopyranosyl)thiocarbamates
2m
2n
2o
2p
2q
2r
2s
2t
2,3,4,6-Tetra-O-acetyl-b-
D
-glucopyranosyl isothiocyanate (1,
0.4 g, 1 mmol), which was prepared according to reported proce-
dures,26 was added to a monohydric or dihydric alcohol (20 mL),
respectively, warmed at 90–100 °C (reflux temperature for 2a–
2d) and stirred for 2–4 h, until the starting material 1 disappeared
on TLC. Then the excess reactant was evaporated, and the residue
was recrystallized from EtOH. The clear filtrate was left at room
temperature, and a white solid powder was obtained by filtration.
Some solids of the compounds (2n–2t) could not be obtained di-
rectly by recrystallization, and then the crude products were puri-
fied by column chromatography on silica gel eluting with 1:1
EtOAc–petroleum ether. Fractions containing the product were
combined, and the solvent was removed to afford 2n–2t as white
solids.
p
p = propiconazole.
2q, and 2r, it was also revealed that the antifungal activities of
bisthiocarbamates are
monothiocarbamates.
a
bit stronger than those of the
2.3. The reaction of glucosyl thiocarbamates with HgCl2
3.2.1. O-Methyl N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiocarbamate (2a)
In an attempt to further study the affinity of glucosyl thiocarba-
mates with HgCl2, nine corresponding compounds 3 were synthe-
sized (Scheme 2). The reaction was obviously influenced by the
length of the carbon chain in the alcohol position. Taking com-
pounds 2a and 2i as examples, 2a reacted with HgCl2 for at least
5.5 h, and the reaction temperature was increased to 35 °C to give
3a in a yield of 80%, while 2i reacted with HgCl2 for only 2 h at a
lower temperature of 0 °C to obtain 3i in a yield of 84% (Scheme 2).
Compounds with the general structure 3 were characterized by
IR, 1H, and 13C NMR spectroscopy, elemental analysis and addi-
tional concentration analysis of the mercury atom. In the IR spec-
trum, the absorption at about 3300 cmꢀ1 disappeared, which
indicated the absence of an NH group in compounds 3, while the
absorption at about 1620 cmꢀ1 showed the presence of a C@N
group; furthermore, disappearance of the absorption at about
1520 cmꢀ1 showed the absence of the NH(C@S) group in com-
pounds 3. In the 1H NMR spectra, the NH proton at d 6.16–7.03 dis-
appeared, which was in agreement with their IR spectra. In the 13C
NMR spectra, the four acetyl C@O groups on the glucosyl ring
appeared at about d 169–171, while the C–S of bis[O-alkyl
White powder; yield 95%; mp 188.8–189.5 °C; [
a] +11.62 (c
D
2.0, CHCl3); IR (KBr)
m
/cmꢀ1: 3303 (m, NH), 1745 (s, C@O), 1532
(m, NH(C@S)), 1254 and 1070 (s, C–O–C); 1H NMR (CDCl3,
500 MHz): d 6.90 (d, 1H, J 8.5 Hz, NH), 5.57 (t, 1H, J 8.5, 9.0 Hz,
H-1), 5.37 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.08 (t, 1H, J 9.5, 10.0 Hz, H-
3), 5.00 (t, 1H, J 9.5, 9.5 Hz, H-4), 4.32 (dd, 1H, J 4.0, 4.5 Hz, H-
6a), 4.11 (t, 1H, J 11.0, 12.5 Hz, H-6b), 4.03 (s, 3H, OCH3), 3.86
(m, 1H, H-5), 2.19, 2.18, 2.16, 2.14 (4s, 12H, 4CH3CO); 13C NMR
(300 MHz, CDCl3): d 193.22 (C@S), 171.37, 170.88, 170.10, and
169.81 (4C, 4COCH3), 83.50 (C-1), 73.81 (C-5), 72.87 (C-3), 70.63
(C-2), 68.40 (C-4), 61.82 (C-6), 57.95 (OCH3), 20.97, 20.93, and
20.81 (4C, 4COCH3). Anal. Calcd for C16H23NO10S (421.42): C,
45.60; H, 5.50; N, 3.32; S, 7.61. Found: C, 45.54; H, 5.45; N, 3.28;
S, 7.67.
3.2.2. Preparation of O-ethyl N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiocarbamate (2b)
White crystals; yield 92%; mp 156.2–156.8 °C; lit.32 156–
158 °C; [
a]
+10.75 (c 2.0, CHCl3); IR (KBr) m
/cmꢀ1 : 3318 (m,
N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)thiocarbamato] mer-
D
cury appeared at about d 162–163. By determining the concentra-
tion of mercury, it could be concluded that one mercury atom was
linked with two glucosyl thiocarbamates as shown in Scheme 2.
Moreover, the structures of compounds 3 were confirmed by ele-
mental analysis.
NH), 1744 (s, C@O), 1524 (m, NH(C@S)), 1217 and 1038 (s, C–O–
C); 1H NMR (CDCl3, 500 MHz): d 6.82 (d, 1H, J 8.0 Hz, NH), 5.57
(t, 1H, J 9.5, 9.0 Hz, H-1), 5.34 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.06 (t,
1H, J 10.0, 9.0 Hz, H-3), 4.97 (t, 1H, J 9.5, 9.5 Hz, H-4), 4.48 (q, 2H,
J 1.5, 7.5, 7.0 Hz, OCH2), 4.31 (d, 1H, J 12.5 Hz, H-6a), 4.10 (d, 1H, J
12.5 Hz, H-6b), 3.84 (t, 1H, J 1.5, 8.0 Hz, H-5), 2.07, 2.06, 2.04, 2.03
(4s, 12H, 4CH3CO), 1.30 (t, 3H, J 4.5, 6.5 Hz, CH2CH3); 13C NMR
(300 MHz, CDCl3): d 192.39 (C@S), 171.13, 170.81, 170.05, and
169.76 (4C, 4COCH3), 83.22 (C-1), 73.73 (C-5), 72.98 (C-3), 70.60
(C-2), 68.39 (C-4), 67.41 (OCH2), 61.84 (C-6), 20.86, 20.87, and
3. Experimental
3.1. General methods
20.75 (4C, 4COCH3), 14.17 (CH3). Anal. Calcd for C17H25NO10
(435.45): C, 46.89; H, 5.79; N, 3.22; S, 7.36. Found: C, 46.83; H,
5.81; N, 3.18; S, 7.31.
S
Melting points were determined with a digital melting point
apparatus (WRS-1B) without correction. IR spectra (Bruker Ten-
sor27 FTIR) were recorded for samples on KBr plates. The 1H and

1292
Y. Zhou et al. / Carbohydrate Research 344 (2009) 1289–1296
3.2.3. O-Propyl N-(2,3,4,6-tetra-O-acetyl-b-
glucopyranosyl)thiocarbamate (2c)
D
-
73.87 (C-5), 72.93 (C-3), 71.85 (C-2), 70.68 (C-4), 68.46 (OCH2),
61.81 (C-6), 28.26, 28.13, and 22.50 (3C, CH2), 20.96, 20.87, and
20.81 (4C, 4COCH3), 14.14 (CH3). Anal. Calcd for C20H31NO10S
(477.53): C, 50.31; H, 6.54; N, 2.93; S, 6.71. Found: C, 50.36; H,
6.50; N, 2.99; S, 6.65.
White powder; yield 91%; mp 108.2–108.9 °C; [
a]
D +9.87 (c 2.0,
CHCl3); IR (KBr)
m
/cmꢀ1: 3325 (m, NH), 1749 (s, C@O), 1534 (m,
NH(C@S)), 1232 and 1042 (s, C–O–C); 1H NMR (CDCl3, 500 MHz):
d 6.83 (d, 1H, J 9.5 Hz, NH), 5.60 (t, 1H, J 9.0, 9.0 Hz, H-1), 5.37 (t,
1H, J 9.5, 9.5 Hz, H-2), 5.08 (t, 1H, J 9.5, 9.5 Hz, H-3), 5.00 (t, 1H, J
9.5, 9.5 Hz, H-4), 4.38 (m, 2H, OCH2), 4.33 (dd, 1H, J 5.0, 5.0 Hz,
H-6a), 4.11 (d, 1H, J 12.0 Hz, H-6b), 3.86 (m, 1H, H-5), 2.11, 2.09,
2.06, 2.05 (4s, 12H, 4CH3CO), 1.70 (m, 2H, CH2CH3), 0.97 (t, 3H, J
7.5, 7.5 Hz, CH2CH3); 13C NMR (300 MHz, CDCl3): d 192.54 (C@S),
171.32, 170.87, 170.09, and 169.80 (4C, 4COCH3), 83.32 (C-1),
73.80 (C-5), 73.19 (C-3), 72.90 (C-2), 70.62 (C-4), 68.39 (OCH2),
61.80 (C-6), 21.96 (CH2), 20.97, 20.91, and 20.81 (4C, 4COCH3),
10.51 (CH3). Anal. Calcd for C18H27NO10S (449.47): C, 48.10; H,
6.05; N, 3.12; S, 7.13. Found: C, 48.16; H, 6.09; N, 3.10; S, 7.07.
3.2.7. O-Hexyl N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiocarbamate (2g)
White powder; yield 86%; mp 114.1–114.7 °C; [
a]D +8.35 (c 2.0,
CHCl3); IR (KBr)
m
/cmꢀ1: 3311 (m, NH), 1742 (s, C@O), 1531 (m,
NH(C@S)), 1218 and 1041 (s, C–O–C); 1H NMR (CDCl3, 500 MHz):
d 6.82 (d, 1H, J 9.0 Hz, NH), 5.60 (t, 1H, J 9.0, 9.0 Hz, H-1), 5.36 (t,
1H, J 9.5, 9.5 Hz, H-2), 5.08 (t, 1H, J 10.0, 9.5 Hz, H-3), 5.00 (t, 1H,
J 9.5, 9.5 Hz, H-4), 4.42 (m, 2H, OCH2), 4.33 (dd, 1H, J 4.5, 4.5 Hz,
H-6a), 4.13 (d, 1H, J 12.0 Hz, H-6b), 3.86 (m, 1H, H-5), 2.18, 2.16,
2.13, 2.12 (4s, 12H, 4CH3CO), 1.69 (t, 2H,
J 7.0, 7.0 Hz,
CH2(CH2)3CH3), 1.33 (m, 6H, CH2(CH2)3CH3), 0.90 (t, 3H, J 7.0,
6.0 Hz, CH2(CH2)3CH3); 13C NMR (300 MHz, CDCl3): d 192.52
(C@S), 171.16, 170.84, 170.07, and 169.78 (4C, 4COCH3), 83.25
(C-1), 73.73 (C-5), 72.93 (C-3), 71.71 (C-2), 70.57 (C-4), 68.32
(OCH2), 61.80 (C-6), 31.56, 28.48, 25.61, and 22.70 (4C, 4CH2),
20.93, 20.88, and 20.78 (4C, 4COCH3), 14.20 (CH3). Anal. Calcd for
C21H33NO10S (491.55): C, 51.31; H, 6.77; N, 2.85; S, 6.52. Found:
C, 51.36; H, 6.72; N, 2.89; S, 6.45.
3.2.4. O-2-Propyl N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiocarbamate (2d)
White powder; yield 90%; mp 148.1–148.8 °C; [
a]D +9.71 (c 2.0,
CHCl3); IR (KBr)
m
/cmꢀ1: 3338 (m, NH), 1746 (s, C@O), 1524 (m,
NH(C@S)), 1239 and 1047 (s, C–O–C); 1H NMR (CDCl3, 500 MHz):
d 6.73 (d, 1H, J 8.5 Hz, NH), 5.62 (t, 1H, J 9.5, 9.5 Hz, H-1), 5.54
(m, 1H, CH(CH3)2), 5.40 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.09 (t, 1H, J
9.5, 10.0 Hz, H-3), 4.99 (t, 1H, J 9.5, 9.0 Hz, H-4), 4.33 (dd, 1H, J
8.0, 7.5 Hz, H-6a), 4.11 (d, 1H, J 10.0 Hz, H-6b), 3.84 (m, 1H, H-5),
2.15, 2.14, 2.11, 2.07 (4s, 12H, 4CH3CO), 1.36 (m, 6H, CH(CH3)2);
13C NMR (300 MHz, CDCl3): d 191.59 (C@S), 171.26, 170.87,
170.09, and 169.80 (4C, 4COCH3), 83.23 (C-1), 75.36 (C-5), 73.80
(C-3), 72.92 (C-2), 70.67 (C-4), 68.38 (OCH), 61.78 (C-6), 21.75
and 21.71 (2C, CH3), 20.96, 20.87, and 20.81 (4C, 4COCH3). Anal.
Calcd for C18H27NO10S (449.47): C, 48.10; H, 6.05; N, 3.12; S,
7.13. Found: C, 48.16; H, 6.11; N, 3.07; S, 7.19.
3.2.8. O-Cyclohexyl N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiocarbamate (2h)
White powder; yield 92%; mp 119.0–119.9 °C; [
a]D +6.63 (c 2.0,
CHCl3); IR (KBr)
m
/cmꢀ1: 3301 (m, NH), 1752 (s, C@O), 1536 (m,
NH(C@S)), 1227 and 1049 (s, C–O–C); 1H NMR (CDCl3, 500 MHz):
d 6.75 (d, 1H, J 9.0 Hz, NH), 5.62 (t, 1H, J 9.5, 9.0 Hz, H-1), 5.36 (t,
1H, J 9.5, 9.5 Hz, H-2), 5.27 (m, 1H, OCH(CH2)5), 5.08 (t, 1H, J 9.5,
9.5 Hz, H-3), 5.00 (t, 1H, J 9.5, 10.0 Hz, H-4), 4.34 (dd, 1H, J 9.5,
9.5 Hz, H-6a), 4.10 (d, 1H, J 12.5 Hz, H-6b), 3.86 (m, 1H, H-5),
2.11, 2.08, 2.06, 2.05 (4s, 12H, 4CH3CO), 1.73, 1.55, 1.46, 1.36,
1.26 (5 m, 10H, (CH2)5); 13C NMR (300 MHz, CDCl3): d 191.52
(C@S), 171.28, 170.90, 170.11, and 169.83 (4C, 4COCH3), 83.25
(C-1), 80.06 (OCH), 73.80 (C-5), 72.90 (C-3), 70.67 (C-2), 68.34
(C-4), 61.80 (C-6), 31.44, 25.43, 23.89, and 23.86 (5C, 5CH2),
3.2.5. O-Butyl N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiocarbamate (2e)
Slightly yellow powder; yield 85%; mp 89.2–89.9 °C; [
a]D +8.01
(c 2.0, CHCl3); IR (KBr)
m
/cmꢀ1: 3385 (m, NH), 1744 (s, C@O), 1515
(m, NH(C@S)), 1229 and 1048 (s, C–O–C); 1H NMR (CDCl3,
500 MHz): d 6.83 (d, 1H, J 9.0 Hz, NH), 5.60 (t, 1H, J 9.0, 9.0 Hz,
H-1), 5.37 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.08 (t, 1H, J 9.5, 10.0 Hz, H-
3), 5.00 (t, 1H, J 9.5, 9.5 Hz, H-4), 4.46 (m, 2H, OCH2), 4.33 (dd,
1H, J 4.0, 4.0 Hz, H-6a), 4.13 (d, 1H, J 12.5 Hz, H-6b), 3.86 (m, 1H,
H-5), 1.98, 1.96, 1.93, 1.92 (4s, 12H, 4CH3CO), 1.71 (m, 2H,
CH2CH2CH3), 1.41 (m, 2H, CH2CH2CH3), 0.94 (t, 3H, J 7.0, 7.5 Hz,
CH2CH2CH3); 13C NMR (300 MHz, CDCl3): d 192.56 (C@S), 171.34,
170.84, 170.06, and 169.78 (4C, 4COCH3), 83.34 (C-1), 73.87 (C-
5), 72.92 (C-3), 71.58 (C-2), 70.69 (C-4), 68.47 (OCH2), 61.82 (C-
6), 30.61 (CH2), 20.94, 20.87, and 20.78 (4C, 4COCH3), 19.25
(CH2), 13.92 (CH3). Anal. Calcd for C19H29NO10S (463.50): C,
49.24; H, 6.31; N, 3.02; S, 6.92. Found: C, 49.20; H, 6.25; N, 3.07;
S, 6.96.
20.93, 20.88, and 20.78 (4C, 4COCH3). Anal. Calcd for C21H31NO10
S
(489.54): C, 51.52; H, 6.38; N, 2.86; S, 6.55. Found: C, 51.57; H,
6.32; N, 2.81; S, 6.60.
3.2.9. O-Octyl N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiocarbamate (2i)
White powder; yield 83%; mp 75.0–76.1 °C; [
a] +6.19 (c 2.0,
D
CHCl3); IR (KBr)
m
/cmꢀ1: 3329 (m, NH), 1744 (s, C@O), 1517 (m,
NH(C@S)), 1228 and 1035 (s, C–O–C); 1H NMR (CDCl3, 500 MHz):
d 6.82 (d, 1H, J 9.0 Hz, NH), 5.60 (t, 1H, J 8.5 9.0 Hz, H-1), 5.36 (t,
1H, J 9.5, 9.5 Hz, H-2), 5.08 (t, 1H, J 9.5, 10.0 Hz, H-3), 5.00 (t, 1H,
J 9.5, 9.5 Hz, H-4), 4.41 (m, 2H, OCH2), 4.33 (dd, 1H, J 4.5, 4.0 Hz,
H-6a), 4.09 (d, 1H, J 7.5 Hz, H-6b), 3.86 (m, 1H, H-5), 2.11, 2.09,
2.06, 2.05 (4s, 12H, 4CH3CO), 1.69 (t, 2H,
J 7.0, 6.5 Hz,
3.2.6. O-Amyl N-(2,3,4,6-tetra-O-acetyl-b-
glucopyranosyl)thiocarbamate (2f)
D
-
CH2(CH2)5CH3), 1.30 (m, 10H, CH2(CH2)5CH3), 0.91 (t, 3H, J 7.0,
5.5 Hz, CH2(CH2)5CH3); 13C NMR (300 MHz, CDCl3): d 192.55
(C@S), 171.41, 170.92, 170.13, and 169.84 (4C, 4COCH3), 83.37
(C-1), 73.82 (C-5), 72.87 (C-3), 71.93 (C-2), 70.61 (C-4), 68.37
(OCH2), 61.77 (C-6), 32.00, 29.43, 29.40, 28.58, 26.02, and 22.88
(6C, 6CH2), 21.05, 20.96, and 20.85 (4C, 4COCH3), 14.36 (CH3). Anal.
Calcd for C23H37NO10S (519.61): C, 53.17; H, 7.18; N, 2.70; S, 6.17.
Found: C, 53.13; H, 7.12; N, 2.78; S, 6.12.
White powder; yield 84%; mp 106.2–106.7 °C; [
a]D +8.87 (c 2.0,
CHCl3); IR (KBr)
m
/cmꢀ1: 3323 (m, NH), 1744 (s, C@O), 1523 (m,
NH(C@S)), 1218 and 1039 (s, C–O–C); 1H NMR (CDCl3, 500 MHz):
d 6.83 (d, 1H, J 9.0 Hz, NH), 5.60 (t, 1H, J 9.0, 9.0 Hz, H-1), 5.36 (t,
1H, J 9.5, 9.5 Hz, H-2), 5.08 (t, 1H, J 9.5, 9.5 Hz, H-3), 5.00 (t, 1H, J
9.5, 9.5 Hz, H-4), 4.42 (m, 2H, OCH2), 4.33 (dd, 1H, J 4.5, 4.5 Hz,
H-6a), 4.13 (d, 1H, J 7.5 Hz, H-6b), 3.86 (m, 1H, H-5), 2.17, 2.16,
1.98, 1.92 (4s, 12H, 4CH3CO), 1.72 (t, 2H,
CH2(CH2)2CH3), 1.36 (m, 4H, CH2(CH2)2CH3), 0.94 (m, 3H,
CH2(CH2)2CH3); 13C NMR (300 MHz, CDCl3):
192.55 (C@S),
171.32, 170.83, 170.05, and 169.77 (4C, 4COCH3), 83.37 (C-1),
J
6.5, 6.5 Hz,
3.2.10. O-Allyl N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiocarbamate (2j)
d
White powder; yield 89%; mp 122.4–123.1 °C; [
a]D +1.63 (c 2.0,
CHCl3); IR (KBr)
m
/cmꢀ1: 3399 (m, NH), 1743 and 1701 (s, C@O),

Y. Zhou et al. / Carbohydrate Research 344 (2009) 1289–1296
1293
1511 (m, NH(C@S)), 1230 and 1037 (s, C–O–C); 1H NMR (CDCl3,
500 MHz): d 6.15 (d, 1H, J 9.0 Hz, NH), 5.82 (m, 1H, CH@), 5.29 (t,
1H, J 9.5, 9.5 Hz, H-1), 5.24 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.11 (m, 2H,
@CH2), 5.07 (t, 1H, J 9.5, 10.0 Hz, H-3), 4.91 (t, 1H, J 9.5, 9.5 Hz,
H-4), 4.32 (dd, 1H, J 4.0, 4.0 Hz, H-6a), 4.10 (d, 1H, J 12.5 Hz, H-
6b), 3.81 (m, 1H, H-5), 3.56 (d, 2H, J 6.5 Hz, OCH2), 2.08, 2.05,
2.04, 2.01 (4s, 12H, 4CH3CO); 13C NMR (300 MHz, CDCl3): d
192.50 (C@S), 171.17, 170.89, 170.15, and 169.75 (4C, 4COCH3),
133.44 (CH@), 118.31 (@CH2), 83.35 (C-1), 73.74 (C-5), 72.79 (C-
3), 70.53 (C-2), 68.21 (C-4), 61.74 (C-6), 33.07 (OCH2), 20.98,
6b), 3.91 (m, 2H, H-50), 3.82 (m, 1H, H-5), 2.11, 2.08, 2.06, 2.04
(4s, 12H, 4CH3CO), 1.93 (m, 2H, H-30), 1.65 (m, 2H, H-40); 13C
NMR (300 MHz, CDCl3): d 192.34 (C@S), 171.13, 170.91, 170.15,
and 169.80 (4C, 4COCH3), 83.37 (C-1), 76.42 (OCH2), 73.83 (C-5),
73.28 (C-20), 73.02 (C-3), 70.50 (C-2), 68.68 (C-50), 68.34 (C-4),
61.77 (C-6), 28.20 (C-40), 25.80 (C-30), 21.00, 20.95, and 20.83
(4C, 4COCH3). Anal. Calcd for C20H29NO11S (491.51): C, 48.87; H,
5.95; N, 2.85; S, 6.52. Found: C, 48.82; H, 5.92; N, 2.91; S, 6.56.
3.2.14. Preparation of O-(1H-1,2,4-triazole-1-ylmethyl) N-
20.88, and 20.83 (4C, 4COCH3). Anal. Calcd for C18H25NO10
S
(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)thiocarbamate (2n)
(447.46): C, 48.32; H, 5.63; N, 3.13; S, 7.16. Found: C, 48.38; H,
5.59; N, 3.17; S, 7.21.
The preparation of 1-(hydroxymethyl)-1H-1,2,4-triazole fol-
lowed the literature procedure.33 1-(Hydroxymethyl)-1H-1,2,4-tri-
azole (2 g, 10 mmol) was added to acetone (15 mL), and Et3N
(0.15 g, 1.5 mmol) was dripped to the solution. Then 2,3,4,6-tet-
3.2.11. O-Phenyl N-(2,3,4,6-tetra-O-acetyl-b-D-
glucopyranosyl)thiocarbamate (2k)
ra-O-acetyl-b-D-glucosyl isothiocyanate (1, 2 g, 5 mmol) was added
2,3,4,6-Tetra-O-acetyl-b-
D
-glucopyranosyl isothiocyanate (2 g,
to the solution, and the mixture was stirred until the TLC showed
that the glucosyl isothiocyanate disappeared. After removing the
solvent, the product was separated from the excess 1-(hydroxy-
methyl)-1H-1,2,4-triazole by silica gel column chromatography.
Recrystallization from ether yielded 87% of a white solid. Mp
0.005 mol), phenol (1 g, 0.01 mol), and toluene (20 mL) were added
to a flask. Then the flask was put into a microwave reactor. The
solution was heated to 80 °C and stirred for 0.5 h. A white solid
was obtained after removal of the solvent. Recrystallization from
1:2 toluene–EtOAc gave a pure white solid. Yield 91%; mp 107.1–
61.2–62.5 °C; [
a]
+11.99 (c 2.0, CHCl3); IR (KBr) m
/cmꢀ1: 3499
D
107.9 °C; [
a
]
D
+2.87 (c 2.0, CHCl3); IR (KBr)
m
/cmꢀ1: 3316 (m,
(m, NH of triazole), 3312 (m, NH), 1741 (s, C@O), 1646 (s, C@N of
triazole), 1530 (m, NH(C@S)), 1240 and 1034 (s, C–O–C); 1H NMR
(CDCl3, 500 MHz): d 8.65 (s, 1H, Tr-H), 8.07 (s, 1H, Tr-H), 6.91 (d,
1H, J 9.0 Hz NH), 5.57 (t, 1H, J 9.0, 9.5 Hz, H-1), 5.37 (t, 1H, J 9.5,
9.5 Hz, H-2), 5.12 (t, 1H, J 10.0, 9.5 Hz, H-3), 5.02 (t, 1H, J 9.5,
9.5 Hz, H-4), 4.32 (dd, 1H, J 4.5, 4.0 Hz, H-6a), 4.10 (d, 1H, J
12.5 Hz, H-6b), 4.01 (s, 2H, OCH2), 3.86 (m, 1H, H-5), 2.11, 2.09,
2.06, 2.05 (4s, 12H, 4CH3CO); 13C NMR (300 MHz, CDCl3): d
190.01 (C@S), 170.77, 170.08, and 169.75 (4C, 4COCH3), 152.83,
146.05 (2C, Tr), 83.53 (C-1), 74.05 (OCH2), 73.50 (C-5), 72.96 (C-
3), 70.61 (C-2), 68.19 (C-4), 61.73 (C-6), 20.88 and 20.74 (4C,
4COCH3). Anal. Calcd for C18H24N4O10S (488.47): C, 44.26; H,
4.95; N, 11.47; S, 6.56. Found: C, 44.22; H, 4.89; N, 11.51; S, 6.58.
NH), 1752 and 1727 (s, C@O), 1529 (m, NH(C@S)), 1209 and
1046 (s, C–O–C); 1H NMR (CDCl3, 500 MHz): d 7.28–7.08 (m, 5H,
aromatics), 6.85 (d, 1H, J 8.0 Hz, NH), 5.60 (t, 1H, J 9.0, 9.0 Hz, H-
1), 5.40 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.12 (t, 1H, J 11.5, 9.5 Hz, H-3),
5.06 (t, 1H, J 9.5, 9.5 Hz, H-4), 4.37 (dd, 1H, J 4.5, 4.5 Hz, H-6a),
4.16 (d, 1H, J 11.0 Hz, H-6b), 3.88 (ddd, 1H, J 2.0, 2.5, 2.5 Hz, H-
5), 2.13, 2.10, 2.09, 2.07 (4s, 12H, 4CH3CO); 13C NMR (300 MHz,
CDCl3): d 191.52 (C@S), 171.42, 170.89, 170.10, 169.81 (4C,
4COCH3), 153.03, 129.85, 129.52, 129.25, 128.44, 126.71, 125.51,
122.72, and 122.85 (Ph), 83.91 (C-1), 74.08 (C-5), 72.88 (C-3),
70.88 (C-2), 68.42 (C-4), 61.80 (C-6), 20.79, 20.92, and 20.96 (4C,
4COCH3). Anal. Calcd for C21H25NO10S (483.49): C, 52.17; H, 5.21;
N, 2.90; S, 6.63. Found: C, 52.12; H, 5.25; N, 2.85; S, 6.59.
3.2.15. O-2-Propylimino N-(2,3,4,6-tetra-O-acetyl-b-D-
3.2.12. O-Benzyl N-(2,3,4,6-tetra-O-acetyl-b-
D
-
glucopyranosyl)thiocarbamate (2o)
glucopyranosyl)thiocarbamate (2l)
Compound 2l was prepared in a similar manner to that used for
2k, replacing phenol with benzyl alcohol. White powder; yield
The preparation of acetoxime followed the literature proce-
dure.34 Compound 2o was prepared in a similar manner of 2n,
replacing 1-(hydroxymethyl)-1H-1,2,4-triazole with acetoxime.
77%; mp 158.9–159.6 °C; [
a
]
+3.19 (c 2.0, CHCl3); IR (KBr)
m
/
White powder; yield 40%; mp 78.2–79.1 °C; [
a
]
+8.87 (c 2.0,
D
D
cmꢀ1: 3311 (m, NH), 1739 (s, C@O), 1520 (m, NH(C@S)), 1243
and 1036 (s, C–O–C); 1H NMR (CDCl3, 500 MHz): d 7.38–7.28 (m,
5H, aromatics), 6.93 (d, 1H, J 8.5 Hz, NH), 5.58 (t, 1H, J 9.0,
9.0 Hz, H-1), 5.39 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.22 (s, 2H, OCH2),
5.11 (t, 1H, J 7.0, 7.5 Hz, H-3), 5.03 (t, 1H, J 6.5. 6.5 Hz, H-4), 4.33
(dd, 1H, J 5.5, 5.0 Hz, H-6a), 4.13 (d, 1H, J 11.5 Hz, H-6b), 3.86 (m,
1H, H-5), 2.13, 2.10, 2.05, 2.04 (4s, 12H, 4CH3CO); 13C NMR
(300 MHz, CDCl3): d 192.05 (C@S), 171.20, 170.81, 170.11, 169.70
(4C, 4COCH3), 155.62, 137.65, 135.89, 135.21, 129.07, 128.77,
128.63, 126.59, 128.39, and 127.60 (Ph), 83.51 (C-1), 73.61 (C-5),
73.02 (C-3), 70.48 (C-2), 68.36 (C-4), 61.81 (C-6), 34.47 (OCH2),
CHCl3); IR (KBr)
m
/cmꢀ1: 3342 (m, NH), 1752 (s, C@O), 1611 (s,
C@N), 1546 (m, NH(C@S)), 1279 and 1037 (s, C–O–C); 1H NMR
(CDCl3, 500 MHz): d 6.30 (d, 1H, J 7.5 Hz, NH), 5.85 (t, 1H, J 9.5,
7.0 Hz, H-1), 5.39 (t, 1H, J 9.5, 9.0 Hz, H-2), 5.09 (t, 1H, J 9.5,
9.5 Hz, H-3), 5.02 (t, 1H, J 9.5, 9.5 Hz, H-4), 4.35 (dd, 1H, J 4.0,
4.0 Hz, H-6a), 4.13 (d, 1H, J 12.5 Hz, H-6b), 3.88 (m, 1H, H-5),
2.09, 2.07, 2.06, 2.05 (4s, 12H, 4CH3CO), 1.23 (m, 6H, C(CH3)2);
13C NMR (300 MHz, CDCl3): d 189.41 (C@S), 170.94, 170.13,
169.85, and 169.03 (4C, 4COCH3), 162.98 (C@N), 83.52 (C-1),
74.09 (C-5), 72.81 (C-3), 70.59 (C-2), 68.35 (C-4), 61.80 (C-6),
22.05, 21.01, and 20.85 (4C, 4COCH3), 17.92 (2C, 2CCH3). Anal.
Calcd for C18H26N2O10S (462.47): C, 46.75; H, 5.67; N, 6.06; S,
6.93. Found: C, 46.79; H, 5.60; N, 6.08; S, 6.97.
20.91 and 20.77 (4C, 4COCH3). Anal. Calcd for C22H27NO10
(497.52): C, 53.11; H, 5.47; N, 2.82; S, 6.44. Found: C, 53.16; H,
5.42; N, 2.79; S, 6.41.
S
3.2.16. O-(20-Hydroxylethyl) N-(2,3,4,6-tetra-O-acetyl-b-
D-
glucopyranosyl)thiocarbamate (2p)
3.2.13. O-(Tetrahydrofurfuryl-20-ylmethyl) N-(2,3,4,6-tetra-O-
acetyl-b-
White powder; yield 79%; mp 132.2–133.4 °C; [
2.0, CHCl3); IR (KBr)
/cmꢀ1: 3379 (m, NH), 1742 (s, C@O), 1516
D
-glucopyranosyl)thiocarbamate (2m)
White powder; yield 87%; mp 158.9–159.8 °C; [a]D +9.44 (c 2.0,
a
]
D
+12.37 (c
CHCl3); IR (KBr) m
/cmꢀ1: 3503 (m, OH), 3319 (m, NH), 1742 (s,
m
C@O), 1523 (m, NH(C@S)), 1241 and 1037 (s, C–O–C); 1H NMR
(CDCl3, 500 MHz): d 7.03 (d, 1H, J 9.0 Hz, NH), 5.60 (t, 1H, J 8.5,
8.5 Hz, H-1), 5.40 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.11 (t, 1H, J 9.0,
(m, NH(C@S)), 1226 and 1049 (s, C–O–C); 1H NMR (CDCl3,
500 MHz): d 6.92 (d, 1H, J 9.0 Hz, NH), 5.59 (t, 1H, J 9.5, 9.0 Hz,
H-1), 5.35 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.08 (t, 1H, J 9.5, 9.5 Hz, H-3),
5.00 (t, 1H, J 9.5, 9.0 Hz, H-4), 4.53 (m, 2H, OCH2), 4.36 (dd, 1H, J
3.5, 3.0 Hz, H-6a), 4.19 (m, 1H, H-20), 4.13 (d, 1H, J 12.0 Hz, H-
9.5 Hz, H-3), 5.03 (t, 1H,
J 9.0, 9.0 Hz, H-4), 4.60 (m, 2H,
CH2CH2OH), 4.35 (dd, 1H, J 5.0, 5.0 Hz, H-6a), 4.14 (d, 1H, J
11.5 Hz, H-6b), 3.92 (m, 2H, CH2OH), 3.87 (m, 1H, H-5), 2.12.

1294
Y. Zhou et al. / Carbohydrate Research 344 (2009) 1289–1296
2.10, 2.08, 2.07 (4s, 12H, 4CH3CO), 1.73 (s, 1H, OH); 13C NMR
(300 MHz, CDCl3): d 191.51 (C@S), 171.04, 170.20, 169.93, and
169.79 (4C, 4COCH3), 83.24 (C-1), 73.70 (C-5), 73.16 (C-3), 72.42
(C-2), 70.62 (C-4), 68.28 (C-10), 63.67 (C-20), 61.78 (C-6), 21.75,
NH(C@S)), 1226 and 1038 (s, C–O–C); 1H NMR (CDCl3, 500 MHz):
d 7.08 (br, 2H, 2NH), 5.65 (t, 2H, J 8.5, 8.5 Hz, 2H-1), 5.37 (t, 2H, J
9.0, 9.5 Hz, 2H-2), 5.13 (t, 2H, J 9.0, 9.0 Hz, 2H-3), 4.99 (t, 2H, J
9.5, 9.5 Hz, 2H-4), 4.33 (dd, 2H, J 8.0, 12.0 Hz, 2H-6a), 4.14 (d,
2H, J 12.0 Hz, 2H-6b), 3.92 (m, 3H, CH2CH), 3.87 (m, 2H, 2H-5),
2.04–2.26 (m, 24H, 8CH3CO), 1.28 (m, 3H, CH2CHCH3); 13C NMR
(300 MHz, CDCl3): d 185.50 (2C, C@S), 171.83, 170.80, 170.08,
and 169.85 (8C, 8COCH3), 82.82 (2C, 2C-1), 73.52 (2C, 2C-5),
72.79 (2C, 2C-3), 71.06 (2C, 2C-2), 68.50 (2C, 2C-4), 61.93 (2C,
2C-6), 60.64 (2C, 2OCH2), 21.04, 20.98, 20.81, and 20.78 (8C,
8COCH3), 14.41 (CH3). Anal. Calcd for C33H46N2O20S2 (854.85): C,
46.37; H, 5.42; N, 3.28; S, 7.50. Found: C, 46.33; H, 5.46; N, 3.24;
S, 7.55.
20.96, 20.87, and 20.81 (4C, 4COCH3). Anal. Calcd for C17H25NO11
S
(451.45): C, 45.23; H, 5.58; N, 3.10; S, 7.10. Found: C, 45.19; H,
5.62; N, 3.06; S, 7.07.
3.2.17. O-(20-Hydroxylbutyl) N-(2,3,4,6-tetra-O-acetyl-b-
D-
glucopyranosyl)thiocarbamate (2q)
White powder; yield 50%; mp 206.6–207.5 °C; [
a]D +7.56 (c 2.0,
CHCl3); IR (KBr)
m
/cmꢀ1: 3541 (m, OH), 3331 (m, NH), 1744 (s, C@O),
1519 (m, NH(C@S)), 1226 and 1036 (s, C–O–C); 1H NMR (CDCl3,
500 MHz): d 6.90 (d, 1H, J 8.0 Hz, NH), 5.60 (t, 1H, J 9.0, 9.0 Hz, H-1),
5.38 (t, 1H, J 9.5, 9.0 Hz, H-2), 5.10 (t, 1H, J 9.0, 9.5 Hz, H-3), 5.01 (t,
1H, J 9.5, 9.5 Hz, H-4), 4.44 (m, 2H, OCH2CHOH), 4.33 (dd, 1H, J 4.5,
4.0 Hz, H-6a), 4.13 (d, 1H, J 11.5 Hz, H-6b), 3.86 (m, 1H, H-5), 3.70
(m, 1H, CHOH), 2.11, 2.10, 2.06, 2.05 (4s, 12H, 4CH3CO), 1.83 (m, 2H,
CH2CH3), 1.66 (t, 3H, J 7.5, 6.5 Hz, CH2CH3), 1.55 (s, 1H, OH); 13C
NMR (300 MHz, CDCl3): d 192.51 (C@S), 171.07, 170.95, 170.15, and
169.88 (4C, 4COCH3), 83.20 (C-1), 73.67 (C-5), 73.05 (C-3), 71.24 (C-
2), 70.61 (C-4), 68.31 (C-10), 62.05 (C-20), 61.87 (C-6), 29.00 (C-30),
25.03 (C-40), 20.91, 20.88 and 20.78 (4C, 4COCH3). Anal. Calcd for
C19H29NO11S (479.50): C, 47.59; H, 6.10; N, 2.92; S, 6.69. Found: C,
47.54; H, 6.16; N, 2.88; S, 6.62.
3.3. General reaction of glucosyl thiocarbamates with HgCl2
Glucosyl thiocarbamates 2a–2i (1 mmol) were dissolved in DMF
(20 mL) at room temperature, Et3N (0.15 g, 1.5 mmol) was dripped
into the solution, and the mixture was stirred for 20 min. Then to
the reaction mixture HgCl2 (0.14 g, 0.5 mmol) was slowly added
with stirring for 2–5 h at 0–35 °C. After purification by silica gel
column chromatography and crystallization from ethanol, com-
pounds 3a–3i were obtained.
3.3.1. Bis[O-methyl N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyr-
anosyl)thiocarbamato]mercury (3a)
3.2.18. O-(20-Hydroxylamyl) N-(2,3,4,6-tetra-O-acetyl-b-
glucopyranosyl)thiocarbamate (2r)
D
-
White powder; yield 90%; decomposition temperature (dt)
202.5 °C; [ +53.45 (c 2.0, CHCl3); IR (KBr)
a
]
D
m
/cmꢀ1: 1746 (s,
White powder; yield 44%; mp 192.5–193.7 °C; [
a
]
D +7.03 (c 2.0,
C@O), 1647 (m, C@N), 1225 and 1037 (s, C–O–C); 1H NMR (CDCl3,
500 MHz): d 5.30 (t, 2H, J 9.5, 9.5 Hz, 2H-2), 5.13–5.18 (m, 4H, 2H-
3, 2H-4), 4.80 (d, 2H, J 8.5 Hz, 2H-1), 4.27 (dd, 2H, J 5.0, 5.0 Hz, 2H-
6a), 4.15 (dd, 2H, J 1.5, 1.5 Hz, 2H-6b), 3.84 (m, 2H, 2H-5), 3.81 (s,
6H, 2OCH3), 2.09, 2.04, 2.03, 2.02 (4s, 24H, 8CH3CO); 13C NMR
(300 MHz, CDCl3): d 170.87, 170.52, 169.68, and 169.42 (8C,
8COCH3), 163.46 (2C, 2C-S), 90.48 (2C, 2C-1), 73.87 (2C, 2C-5),
73.33 (2C, 2C-3), 72.87 (2C, 2C-2), 68.67 (2C, 2C-4), 62.37 (2C,
2C-6), 56.80 (2C, 2OCH3), 21.09, 21.01, 20.89, and 20.86 (8C,
8COCH3). Anal. Calcd for C32H44HgN2O20S2 (1041.41): C, 36.91; H,
4.26; N, 2.69; S, 6.16; Hg, 19.26. Found: C, 36.96; H, 4.21; N,
2.63; S, 6.12; Hg, 19.13.
CHCl3); IR (KBr)
m
/cmꢀ1: 3477 (m, OH), 3323 (m, NH), 1745 (s,
C@O), 1520 (m, NH(C@S)), 1228 and 1035 (s, C–O–C); 1H NMR
(CDCl3, 500 MHz): d 7.06 (d, 1H, J 9.0 Hz, NH), 5.58 (t, 1H, J 9.0,
9.0 Hz, H-1), 5.36 (t, 1H, J 9.5, 9.5 Hz, H-2), 5.08 (t, 1H, J 10.0,
9.5 Hz, H-3), 4.99 (t, 1H, J 9.5, 9.5 Hz, H-4), 4.52 (m, 1H, OCH2-
CHOH), 4.27 (dd, 1H, J 8.0, 7.5 Hz, H-6a), 4.14 (d, 1H, J 14.5 Hz,
H-6b), 3.95 (m, 1H, CHOH), 3.86 (m, 1H, H-5), 2.10, 2.09, 2.06,
2.05 (4s, 12H, 4CH3CO), 1.93 (s, 1H, OH), 1.46 (m, 4H, CH2CH2CH3),
0.95 (t, 3H, J 7.0, 6.5 Hz, CH2CH2CH3); 13C NMR (300 MHz, CDCl3): d
192.29 (C@S), 171.37, 170.87, 170.08, and 169.80 (4C, 4COCH3),
83.47 (C-1), 75.30 (C-5), 73.91 (C-3), 72.92 (C-2), 70.75 (C-4),
69.62 (C-10), 68.41 (C-20), 61.82 (C-6), 35.44 (C-30), 20.92 and
20.78 (4C, 4COCH3), 18.79 (C-40), 14.19 (C-50). Anal. Calcd for
C20H31NO11S (493.53): C, 48.67; H, 6.33; N, 2.84; S, 6.50. Found:
C, 48.61; H, 6.39; N, 2.78; S, 6.56.
3.3.2. Bis[O-ethyl N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)
thiocarbamato]mercury (3b)
White powder; yield 90%; dt 96.8 °C; [
a]D +43.63 (c 2.0, CHCl3);
IR (KBr)
m
/cmꢀ1: 1752 (s, C@O), 1626 (m, C@N), 1229 and 1042 (s,
3.2.19. O,O0-Ethyl 1,2-di[N-(2,3,4,6-tetra-O-acetyl-b-
glucopyranosyl)thiocarbamate] (2s)
D
-
C–O–C); 1H NMR (CDCl3, 500 MHz): d 5.29 (t, 2H, J 9.5, 9.5 Hz, 2H-
2), 5.11–5.16 (m, 4H, 2H-3, 2H-4), 4.79 (d, 2H, J 8.5 Hz, 2H-1), 4.26
(dd, 2H, J 6.0, 4.5 Hz, 2H-6a), 4.25 (m, 4H, 2OCH2), 4.14 (d, 2H, J
12.0 Hz, 2H-6b), 3.84 (m, 2H, 2H-5), 2.08, 2.06, 2.02, 2.01 (4s,
24H, 8CH3CO), 1.21 (t, 6H, J 3.5, 5.0 Hz, 2OCH2CH3); 13C NMR
(300 MHz, CDCl3): d 170.96, 170.58, 169.71, and 169.42 (8C,
8COCH3), 162.76 (2C, 2C-S), 90.53 (2C, 2C-1), 73.81 (2C, 2C-5),
73.40 (2C, 2C-3), 72.86 (2C, 2C-2), 68.70 (2C, 2C-4), 66.05 (2C,
2OCH2), 62.37 (2C, 2C-6), 21.08, 20.96, 20.91, and 20.87 (8C,
8COCH3), 14.47 (2C, 2CH3). Anal. Calcd for C34H48HgN2O20S2
(1069.47): C, 38.18; H, 4.52; N, 2.62; S, 6.00; Hg, 18.76. Found: C,
38.22; H, 4.57; N, 2.67; S, 6.05; Hg, 18.69.
White powder; yield 25%; mp 165.1–166.3 °C; [
a
]
D
+10.11 (c
2.0, CHCl3); IR (KBr)
m
/cmꢀ1: 3327 (m, NH), 1745 (s, C@O), 1523
(m, NH(C@S)), 1227 and 1037 (s, C–O–C): 1H NMR (CDCl3,
500 MHz): d 7.08 (br, 2H, 2NH), 5.61 (t, 2H, J 8.5, 8.5 Hz, 2H-1),
5.35 (t, 2H, J 9.0, 9.0 Hz, 2H-2), 5.15 (t, 2H, J 9.5, 9.0 Hz, 2H-3),
4.95 (t, 2H, J 9.0, 9.5 Hz, 2H-4), 4.31 (dd, 2H, J 9.5, 12.5 Hz, 2H-
6a), 4.15 (d, 2H, J 11.0 Hz, 2H-6b), 3.92 (m, 4H, CH2CH2), 3.84 (m,
2H, 2H-5), 2.12–2.06 (m, 24H, 8CH3CO); 13C NMR (300 MHz,
CDCl3): d 185.67 (2C, C@S), 171.89, 170.83, 170.00, and 169.85
(8C, 8COCH3), 83.01 (2C, 2C-1), 73.63 (2C, 2C-5), 72.85 (2C, 2C-3),
71.09 (2C, 2C-2), 68.57 (2C, 2C-4), 61.96 (2C, 2C-6), 60.35 (2C,
2OCH2), 21.09, 20.95, 20.88, and 20.72 (8C, 8COCH3). Anal. Calcd
for C32H44N2O20S2 (840.82): C, 45.71; H, 5.27; N, 3.33; S, 7.63.
Found: C, 45.77; H, 5.22; N, 3.38; S, 7.60.
3.3.3. Bis[O-propyl N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyr-
anosyl)thiocarbamato]mercury (3c)
White powder; yield 86%; dt 92.5 °C; [
IR (KBr)
a]D +45.32 (c 2.0, CHCl3);
m
/cmꢀ1: 1755 (s, C@O), 1616 (m, C@N), 1228 and 1045 (s,
3.2.20. O,O0-Propyl 1,2-di[N-(2,3,4,6-tetra-O-acetyl-b-
glucopyranosyl)thiocarbamate] (2t)
D
-
C–O–C); 1H NMR (CDCl3, 500 MHz): d 5.31 (t, 2H, J 9.5, 9.5 Hz, 2H-
2), 5.11–5.16 (m, 4H, 2H-3, 2H-4), 4.81 (d, 2H, J 8.0 Hz, 2H-1), 4.28
(dd, 2H, J 5.0, 5.0 Hz, 2H-6a), 4.20 (m, 4H, 2OCH2), 4.16 (dd, 2H, J
3.5, 2.0 Hz, 2H-6b), 3.87 (m, 2H, 2H-5), 2.10, 2.05, 2.04, 2.03 (4s,
White powder; yield 40%; mp 117.6–118.4 °C; [
a]D +9.23 (c 2.0,
CHCl3); IR (KBr)
m
/cmꢀ1: 3327 (m, NH), 1745 (s, C@O), 1523 (m,

Y. Zhou et al. / Carbohydrate Research 344 (2009) 1289–1296
1295
24H, 8CH3CO), 1.62 (m, 4H, 2CH2CH3), 0.95 (t, 6H, J 7.5, 7.5 Hz,
2CH2CH3); 13C NMR (300 MHz, CDCl3): d 170.84, 170.48, 169.66,
and 169.28 (8C, 8COCH3), 163.15 (2C, 2C-S), 90.53 (2C, 2C-1),
73.76 (2C, 2C-5), 73.32 (2C, 2C-3), 72.80 (2C, 2C-2), 71.56 (2C,
2OCH2), 68.66 (2C, 2C-4), 62.32 (2C, 2C-6), 22.07 (2C, 2CH2),
21.02, 20.84, and 20.81 (8C, 8COCH3), 10.80 (2C, 2CH3). Anal. Calcd
for C36H52HgN2O20S2 (1097.52): C, 39.40; H, 4.78; N, 2.55; S, 5.84;
Hg, 18.28. Found: C, 39.46; H, 4.73; N, 2.59; S, 5.81; Hg, 18.20.
C–O–C); 1H NMR (CDCl3, 500 MHz): d 5.30 (t, 2H, J 9.5, 9.5 Hz, 2H-
2), 5.12–5.18 (m, 4H, 2H-3, 2H-4), 4.80 (d, 2H, J 8.0 Hz, 2H-1), 4.28
(dd, 2H, J 5.0, 4.5 Hz, 2H-6a), 4.24 (t, 4H, J 12.0, 11.5 Hz, 2OCH2),
4.15 (d, 2H, J 6.5 Hz, 2H-6b), 3.85 (m, 2H, 2H-5), 2.10, 2.07, 2.05,
2.03 (4s, 24H, 8CH3CO), 1.60 (m, 4H, 2CH2(CH2)3CH3), 1.30 (m,
12H, 2CH2(CH2)3CH3), 0.89 (t, 6H, J 7.0, 6.5 Hz, 2CH2(CH2)3CH3);
13C NMR (300 MHz, CDCl3): d 171.00, 170.62, 169.71, and 169.39
(8C, 8COCH3), 162.59 (2C, 2C-S), 90.57 (2C, 2C-1), 73.86 (2C, 2C-
5), 73.48 (2C, 2C-3), 72.86 (2C, 2C-2), 70.42 (2C, 2OCH2), 68.70
(2C, 2C-4), 62.36 (2C, 2C-6), 31.65, 28.74, 26.10, and 22.78 (8C,
8CH2), 21.08, 21.00, 20.93, and 20.88 (8C, 8COCH3), 14.29 (2C,
2CH3). Anal. Calcd for C42H64HgN2O20S2 (1181.69): C, 42.69; H,
5.46; N, 2.37; S, 5.43; Hg, 16.97. Found: C, 42.63; H, 5.41; N,
2.43; S, 5.46; Hg, 16.88.
3.3.4. Bis[O-2-propyl N-(2,3,4,6-tetra-O-acetyl-b-
D
-glucopy-
ranosyl)thiocarbamato]mercury (3d)
White powder; yield 82%; dt 103.4 °C; [
a
]
D
+40.92 (c 2.0,
CHCl3); IR (KBr)
m
/cmꢀ1: 1755 (s, C@O), 1620 (m, C@N), 1228 and
1044 (s, C–O–C); 1H NMR (CDCl3, 500 MHz): d 5.32 (t, 2H, J 9.5,
9.5 Hz, 2H-2), 5.25 (m, 2H, 2OCH), 5.12–5.17 (m, 4H, 2H-3, 2H-
4), 4.82 (d, 2H, J 6.5 Hz, 2H-1), 4.32 (dd, 2H, J 5.5, 5.5 Hz, 2H-6a),
4.18 (d, 2H, J 9.5 Hz, 2H-6b), 3.87 (m, 2H, 2H-5), 2.10, 2.08, 2.05,
2.03 (4s, 24H, 8CH3CO), 1.24 (m, 12H, 2CH(CH3)2); 13C NMR
(300 MHz, CDCl3): d 171.01, 170.61, 169.71, and 169.36 (8C,
8COCH3), 162.00 (2C, 2C-S), 90.62 (2C, 2C-1), 73.82 (2C, 2C-5),
73.75 (2C, 2C-3), 73.53 (2C, 2C-2), 72.82 (2C, 2OCH), 68.78 (2C,
2C-4), 62.39 (2C, 2C-6), 22.38 and 21.68 (2C, 2CH3), 21.07, 20.91,
and 20.87 (8C, 8COCH3). Anal. Calcd for C36H52HgN2O20S2
(1097.52): C, 39.40; H, 4.78; N, 2.55; S, 5.84; Hg, 18.28. Found: C,
39.44; H, 4.82; N, 2.50; S, 5.89; Hg, 18.19.
3.3.8. Bis[O-cyclohexyl N-(2,3,4,6-tetra-O-acetyl-b-D-glucopy-
ranosyl)thiocarbamato]mercury (3h)
White powder; yield 87%; dt 78.5 °C; [
a]D +36.36 (c 2.0, CHCl3);
IR (KBr)
m
/cmꢀ1: 1753 (s, C@O), 1617 (m, C@N), 1224 and 1041 (s,
C–O–C); 1H NMR (CDCl3, 500 MHz): d 5.30 (t, 2H, J 9.5, 9.5 Hz, 2H-
2), 5.13–5.16 (m, 4H, 2H-3, 2H-4), 5.08 (m, 2H, 2OCH), 4.81 (d, 2H, J
8.5 Hz, 2H-1), 4.30 (dd, 2H, J 5.0, 5.5 Hz, 2H-6a), 4.17 (d, 2H, J
9.5 Hz, 2H-6b), 3.87 (m, 2H, 2H-5), 2.10, 2.05, 2.03, 2.02 (4s, 24H,
8CH3CO), 1.31–1.70 (m, 20H, 2(CH2)5); 13C NMR (300 MHz, CDCl3):
d 171.02, 170.62, 169.72, and 169.31 (8C, 8COCH3), 161.89 (2C, 2C-
S), 90.67 (2C, 2C-1), 77.87 (2C, 2OCH), 73.79 (2C, 2C-5), 73.49 (2C,
2C-3), 72.78 (2C, 2C-2), 68.73 (2C, 2C-4), 62.36 (2C, 2C-6), 31.67,
30.82, 25.57, 23.60, and 23.39 (10C, 10CH2), 21.06, 20.91, 20.86
and 20.84 (8C, 8COCH3). Anal. Calcd for C42H60HgN2O20S2
(1177.65): C, 42.84; H, 5.14; N, 2.38; S, 5.44; Hg, 17.03. Found: C,
42.80; H, 5.19; N, 2.33; S, 5.48; Hg, 16.94.
3.3.5. Bis[O-butyl N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)
thiocarbamato]mercury (3e)
White powder; yield 84%; dt 86.3 °C; [
a]D +37.47 (c 2.0, CHCl3);
IR (KBr)
m
/cmꢀ1: 1752 (s, C@O), 1611 (m, C@N), 1227 and 1043 (s,
C–O–C); 1H NMR (CDCl3, 500 MHz): d 5.31 (t, 2H, J 9.5, 9.5 Hz, 2H-
2), 5.12–5.18 (m, 4H, 2H-3, 2H-4), 4.81 (d, 2H, J 8.5 Hz, 2H-1), 4.28
(dd, 2H, J 4.5, 5.0 Hz, 2H-6a), 4.24 (m, 4H, 2OCH2), 4.16 (d, 2H, J
6.5 Hz, 2H-6b), 3.85 (m, 2H, 2H-5), 2.08, 2.05, 2.04, 2.03 (4s, 24H,
8CH3CO), 1.58 (m, 4H, 2CH2CH2CH3), 1.35 (m, 4H, 2CH2CH2CH3),
0.92 (t, 6H, J 7.5, 7.0 Hz, 2CH2CH2CH3); 13C NMR (300 MHz, CDCl3):
d 170.96, 170.59, 169.70, and 169.39 (8C, 8COCH3), 162.72 (2C, 2C-
S), 90.56 (2C, 2C-1), 73.86 (2C, 2C-5), 73.50 (2C, 2C-3), 72.90 (2C,
2C-2), 70.05 (2C, 2OCH2), 68.76 (2C, 2C-4), 62.40 (2C, 2C-6),
30.80 (2C, 2CH2), 21.05, 20.96, 20.90, and 20.86 (8C, 8COCH3),
19.62 (2C, 2CH2), 14.18 (2C, 2CH3). Anal. Calcd for
C38H56HgN2O20S2 (1125.57): C, 40.55; H, 5.01; N, 2.49; S, 5.70;
Hg, 17.82. Found: C, 40.61; H, 5.05; N, 2.44; S, 5.74; Hg, 17.75.
3.3.9. Bis[O-octyl N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)
thiocarbamato]mercury (3i)
White powder; yield 84%; dt 64.9 °C; [
a]D +31.67 (c 2.0, CHCl3);
IR (KBr)
m
/cmꢀ1: 1745 (s, C@O), 1641 (m, C@N), 1228 and 1038 (s,
C–O–C); 1H NMR (CDCl3, 500 MHz): d 5.31 (t, 2H, J 9.5, 9.5 Hz, 2H-
2), 5.15–5.20 (m, 4H, 2H-3, 2H-4), 4.80 (d, 2H, J 8.5 Hz, 2H-1), 4.30
(dd, 2H, J 4.5, 4.5 Hz, 2H-6a), 4.25 (m, 4H, 2OCH2), 4.18 (d, 2H, J
8.5 Hz, 2H-6b), 3.87 (m, 2H, 2H-5), 2.09, 2.00, 1.99, 1.97 (4s, 24H,
8CH3CO), 1.60 (m, 8H, 2(CH2)2(CH2)5CH3), 1.17 (m, 20H,
2(CH2)2(CH2)5CH3), 0.90 (t, 6H, J 7.0, 6.0 Hz, 2(CH2)2(CH2)5CH3);
13C NMR (300 MHz, CDCl3): d 171.00, 170.61, 169.70, and 169.38
(8C, 8COCH3), 162.62 (2C, 2C-S), 90.60 (2C, 2C-1), 73.86 (2C, 2C-
5), 73.49 (2C, 2C-3), 72.87 (2C, 2C-2), 70.37 (2C, 2OCH2), 68.70
(2C, 2C-4), 62.35 (2C, 2C-6), 29.44, 28.77, and 26.40 (12C,
12CH2), 21.08, 21.01, 20.93, and 20.88 (8C, 8COCH3), 14.36 (2C,
2CH3). Anal. Calcd for C46H72HgN2O20S2 (1237.79): C, 44.64; H,
5.86; N, 2.26; S, 5.18; Hg, 16.21. Found: C, 44.68; H, 5.81; N,
2.21; S, 5.14; Hg, 16.13.
3.3.6. Bis[O-amyl N-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)
thiocarbamato]mercury (3f)
White powder; yield 85%; dt 89.8 °C; [
a]D +34.02 (c 2.0, CHCl3);
IR (KBr)
m
/cmꢀ1: 1754 (s, C@O), 1614 (m, C@N), 1223 and 1042 (s,
C–O–C); 1H NMR (CDCl3, 500 MHz): d 5.31 (t, 2H, J 9.5, 9.5 Hz, 2H-
2), 5.12–5.18 (m, 4H, 2H-3, 2H-4), 4.81 (d, 2H, J 8.5 Hz, 2H-1), 4.28
(dd, 2H, J 5.0, 5.0 Hz, 2H-6a), 4.22 (m, 4H, 2OCH2), 4.15 (d, 2H, J
8.0 Hz, 2H-6b), 3.83 (m, 2H, 2H-5), 2.10, 2.05, 2.04, 2.03 (4s, 24H,
8CH3CO), 1.60 (m, 4H, 2CH2(CH2)2CH3), 1.32 (m, 8H,
2CH2(CH2)2CH3), 0.90 (t, 6H, J 6.0, 6.5 Hz, 2CH2(CH2)2CH3); 13C
NMR (300 MHz, CDCl3): d 170.91, 170.55, 169.64, and 169.33 (8C,
8COCH3), 162.59 (2C, 2C-S), 90.54 (2C, 2C-1), 73.92 (2C, 2C-5),
73.58 (2C, 2C-3), 72.96 (2C, 2C-2), 70.37 (2C, 2OCH2), 68.86 (2C,
2C-4), 62.44 (2C, 2C-6), 28.61, 28.50 and 22.56 (6C, 6CH2), 21.00,
20.93, 20.86, and 20.81 (8C, 8COCH3), 14.18 (2C, 2CH3). Anal. Calcd
for C40H60HgN2O20S2 (1153.63): C, 41.65; H, 5.24; N, 2.43; S, 5.56;
Hg, 17.39. Found: C, 41.62; H, 5.20; N, 2.48; S, 5.59; Hg, 17.31.
Acknowledgments
This work was supported by the Natural Science Foundation of
Jiangsu Province, China (No. BK2005094) and the Science & Tech-
nology Development Foundation of Nanjing Agricultural Univer-
sity, China (No. 0506F0005).
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