Structure of aldose condensation products with 2-hydroxyand 2-sulfanylbenzohydrazides

Article abstract of DOI:10.1134/S1070428010060138

The structure of the condensation products of 2-hydroxy- and 2-sulfanylbenzohydrazides with a series of aldoses (L-arabinose, D-ribose, L-ramnose, D-galactose, D-glucose, D-mannose) was studied by ¹H and ¹³C NMR spectroscopy. The condensation products of monosaccharides with 2-hydroxybenzohydrazide in DMSO-d ₆ solution exist as equilibrium mixtures of linear hydrazone and cyclic pyranose and furanose forms, the cyclic tautomers being represented by two stereoisomers (α- and β-anomers). The aldose condensation products with 2-sulfanylbenzohydrazide in the crystalline state have cyclic 1,3,4-benzothiadiazepine structure, while in DMSO-d ₆ solution they undergo complete or partial isomerization into cyclic pyranose tautomer.

Full text of DOI:10.1134/S1070428010060138

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 6, pp. 860–865. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.V. Alekseev, A.Yu. Ershov, B.V. Chernitsa, V.A. Doroshenko, I.V. Lagoda, S.I. Yakimovich, I.V. Zerova, V.V. Pakal’nis,
V.V. Shamanin, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 6, pp. 865–870.
Structure of Aldose Condensation Products with 2-Hydroxy-
and 2-Sulfanylbenzohydrazides
V. V. Alekseeva, A. Yu. Ershovb, B. V. Chernitsab, V. A. Doroshenkob, I. V. Lagodac,
S. I. Yakimovichd, I. V. Zerovad, V. V. Pakal’nisd, and V. V. Shamaninb
a Military Medical Academy, Ministry of Defense of the Russian Federation, St.-Petersburg, Russia
b Institute of High-Molecular Compounds, Russian Academy of Sciences,
Bol’shoi pr. V.O. 31, St.-Petersburg, 199004 Russia
e-mail: ershov305@mail.ru
c Research Test Center of Medical and Biological Protection, State Research Test Institute of Military Medicine,
Ministry of Defense of the Russian Federation, St.-Petersburg, Russia
d St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
Received October 14, 2009
Abstract—The structure of the condensation products of 2-hydroxy- and 2-sulfanylbenzohydrazides with
a series of aldoses (L-arabinose, D-ribose, L-ramnose, D-galactose, D-glucose, D-mannose) was studied by
1H and 13C NMR spectroscopy. The condensation products of monosaccharides with 2-hydroxybenzohydrazide
in DMSO-d6 solution exist as equilibrium mixtures of linear hydrazone and cyclic pyranose and furanose
forms, the cyclic tautomers being represented by two stereoisomers (α- and β-anomers). The aldose condensa-
tion products with 2-sulfanylbenzohydrazide in the crystalline state have cyclic 1,3,4-benzothiadiazepine struc-
ture, while in DMSO-d6 solution they undergo complete or partial isomerization into cyclic pyranose tautomer.
DOI: 10.1134/S1070428010060138
Condensation products of 2-sulfanylbenzohydra-
zide with monocarbonyl compounds tend to undergo
intramolecular cyclization via nucleophilic addition of
the SH group at the C=N bond with formation of
seven-membered benzo-1,3,4-thiadiazepine ring [1–3].
In some cases this process is reversible, so that equilib-
rium mixture of linear 2-sulfanylbenzoylhydrazone
and cyclic benzothiadiazepine tautomers may exist in
solution.
In continuation of our previous studies [1–3], in the
present work we examined the structure of the conden-
sation products obtained from 2-hydroxy- and 2-sul-
fanylbenzohydrazides IIa and IIb and a series of al-
doses Ia–If. Compounds IIIa–IIIl were synthesized in
good yields (55–90%) by heating equimolar amounts
of the corresponding monosaccharide (L-arabinose,
D-ribose, L-ramnose, D-galactose, D-glucose, D-man-
nose) and hydrazide in boiling methanol for a short
time (see Experimental).
and C and linear hydrazone structure B. In addition,
condensation products IIIg–IIIl derived from aldoses
and 2-sulfanylbenzohydrazide (IIb) could give rise to
seven-membered 1,3,4-benzothiadiazepine form D as
a result of attack by the SH group on the C=N bond. It
should be also taken into account that each cyclic form
A, C, and D may be a mixture of two stereoisomers
[α- and β-anomers for structures A and C and (2R)-
and (2S)-stereoisomers for structure D]. The formation
of analogous seven-membered cyclic 1,3,4-benzoxadi-
azepine tautomers for 2-hydroxybenzoylhydrazones
IIIa–IIIf via attack by the OH group on the C=N bond
should be ruled out. It is known that condensation
products of 2-hydroxybenzohydrazide with aldehydes
and ketones have exclusively linear structure and they
do not tend to undergo the above cyclization [4, 5].
In all experiments, the H and 13C NMR spectra
1
were recorded at definite time intervals starting from
the moment of dissolution until the end of transforma-
tions. In addition, the structure of the compounds
under study in the crystalline state was confirmed by
solid-phase high-resolution 13C NMR spectroscopy
2-Hydroxy- and 2-sylfanylbenzoylhydrazones IIIa–
IIIl are complex tautomeric systems that are capable of
existing as cyclic five- and six-membered tautomers A
860

STRUCTURE OF ALDOSE CONDENSATION PRODUCTS
861
Scheme 1.
H
H
OH
N
N
2
O
OH
1
3
4
S
R
5
HO
D, D'
X = S
HO
O
H
XH
O
XH
H
H
N
N
N
N
R
O
OH
OH
R
O
R
OH
1
5
4
1
5
4
+
H
2
N
2
3
3
HO
NH2
HO
OH
HO
OH
OH
XH
O
OH
α-A, β-A
OH
Ia–If
IIa, IIb
B
IIIa–IIIl
O
XH
H
N
N
R
O
4
3
5
H
1
2
HO
OH
HO
α-C, β-C
X = O (a–f), S (g–l); R = H (L-arabinose) (a, g), (D-ribose) (b, h); R = Me (L-ramnose) (c, i); R = HOCH2 (D-galactose) (d, j),
(D-glucose) (e, k), (D-mannose) (f, l).
the NHCO group and phenolic OH group, respectively,
and the sp3-hybridized C1 atom gives a signal at
δC 90.80 ppm in the 13C NMR spectrum. Taking into
(CPMAS). For example, pyranose form A was ex-
pected to give a signal from the anomeric C1 atom at
δC 85–90 ppm; analogous signal from five-membered
furanose tautomer C is located at δC 95–100 ppm
[6, 7]. The C1 signal of benzothiadiazepine tautomer D
should appear in a stronger field, at δC 70–75 ppm,
which is typical of sp3-hybridized carbon atom in
seven-membered ring, located between sulfur and
nitrogen [1, 2]. Hydrazone structure B should give rise
to a downfield signal at δC 150 ppm (C=N) in the
13C NMR spectrum.
1
account that the H and 13C NMR spectra were
recorded immediately after dissolution, i.e., possible
tautomeric and configurational transformations had no
time to occur, we presumed that the observed spectral
parameters reflect the structure of compound IIIa in
the crystalline state.
1
13
The H and C NMR spectra of IIIa changed with
time, and signals assignable to the second stereoisomer
of six-membered structure A, as well as to linear
tautomer B and furanose structure C, appeared. Struc-
ture B is characterized by a doublet at δ 7.74 ppm in
1
13
The H and C NMR spectra of the condensation
product of 2-hydroxybenzoic acid hydrazide with
L-arabinose (IIIa), recorded in DMSO-d6 immediately
after dissolution, contained one set of signals corre-
sponding to cyclic pyranose structure A. It is charac-
terized by two downfield singlets at δ 10.22 and
1
the H NMR spectrum from the N=CH azomethine
proton and a signal at δC 155.05 ppm (C=N) in the
13C NMR spectrum. The presence of five-membered
furanose tautomer C in a solution of IIIa in DMSO-d6
1
12.20 ppm in the H NMR spectrum from protons in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

ALEKSEEV et al.
862
follows from the presence of signals at δC 84.63 (C4)
Compounds IIIi and IIIk obtained by condensation
of 2-sulfanylbenzohydrazide with ramnose and glucose
behaved differently. After keeping their solution in
13
and 95.55 ppm (C1) in the C NMR spectrum. After
some time, the NMR spectra of compound IIIa no
longer changed, indicating establishment of ring–
chain–ring equilibrium. The equilibrium tautomer
mixture consists of 30% of linear structure B, 45% of
pyranose tautomer A, and 25% of furanose form C.
Analogous pattern was observed for a solution of com-
pound IIIb (condensation product of 2-hydroxybenzo-
hydrazide and D-ribose) in DMSO-d6; the fractions of
structures A–C in the equilibrium tautomer mixture of
IIIb differ insignificantly from those found for com-
pound IIIa.
1
DMSO-d6 for some time, the H and 13C NMR data
indicated formation of cyclic pyranose form A (two
sets of signals were observed due to the presence of
several stereoisomers). Up to 20% of linear hydrazone
tautomer B was detected for ramnose derivative IIIi.
1
13
After equilibration, the H and C NMR spectra con-
tained only signals belonging to pyranose form A. We
succeeded in isolating tautomer A of compound IIIi in
the crystalline state, and its structure was confirmed by
the solid-phase 13C NMR spectrum. In other words,
compounds IIIi and IIIk demonstrated irreversible
transformation of 1,3,4-benzothiadiazepine tautomer D
into tetrahydropyran structure A, which can be ob-
served spectrally.
Unlike arabinose and ribose derivatives IIIa and
IIIb, the condensation products IIIc–IIIf derived from
2-hydroxybenzohydrazide and hexoses do not give rise
to cyclic furanose form C. Compounds IIIc–IIIf in
the crystalline state have cyclic structure A. The cyclic
pyranose structure of crystalline compound IIIe (con-
densation product of 2-hydroxybenzohydrazide with
glucose) was confirmed by its solid-phase 13C NMR
spectrum (see Experimental). In going to solutions in
DMSO-d6, compounds IIIc–IIIf undergo partial trans-
formation into linear hydrazone tautomer B. Insofar as
the fraction of the linear tautomer for all the examined
condensation products of 2-hydroxybenzohydrazide
with aldoses did not exceed 30–40%, the term 2-hy-
droxybenzoylhydrazone should be regarded as arbitrary
as applied to such systems.
1
13
The H and C NMR spectra of the condensation
product of 2-sulfanylbenzohydrazide with mannose
(compound IIIl) stopped to change in 72 h. The
equilibrium mixture consisted of 50% of benzothiadia-
zepine tautomer D, 15% of linear structure B, and 35%
of pyranose form; in addition, each cyclic tautomer
was a mixture of two stereoisomers.
Thus, unlike aldose condensation products with
2-hydroxybenzohydrazide, those derived from 2-sul-
fanylbenzohydrazide undergo cyclization with forma-
tion of seven-membered 1,3,4-benzothiadiazepines.
The observed difference may be interpreted in terms of
considerably higher nucleophilicity of the SH group as
compared to OH. In this respect, compounds IIIg–IIIl
are analogous to the condensation products of aldoses
with thiobenzoic and thioglycolic acid hydrazides,
studied by us previously. As shown in [6, 7], intra-
molecular attack by the sulfur atom at the C=N bond in
the hydrazone fragment of the linear tautomer formed
initially gives rise to equilibrium mixture of cyclic pyr-
anose, dihydro-1,3,4-thiadiazole, and 1,3,4-thiadiazine
tautomers.
A different situation was observed with the conden-
sation products obtained from aldoses and 2-sulfanyl-
1
benzohydrazide. Judging by variation of their H and
13C NMR spectra, compounds IIIg–IIIl in the crystal-
line state have cyclic 1,3,4-benzothiadiazepine struc-
ture D. Solid-phase 13C NMR spectrum was recorded
for glucose condensation product IIIk. 1,3,4-Benzo-
thiadiazepine structure D characteristically displays in
13
the C NMR spectrum a signal in the region δC 75–
80 ppm (C1), which is typical of sp3-hybridized carbon
atom located between sulfur and nitrogen in a seven-
membered ring [1–3]. With the lapse of time, signals
belonging to the second configurational isomer of
benzothiadiazepine form D′ appeared in the 1H and 13C
NMR spectra of solutions of IIIg–IIIl in DMSO-d6,
but it was impossible to assign these signals to partic-
ular (2R)- or (2S)-isomer. The 1H and 13C NMR spectra
of condensation products IIIg, IIIh, and IIIj derived
from arabinose, ribose, and galactose no longer change
in 15–20 days, indicating the absence of linear struc-
ture B and cyclic form A in the equilibrium mixture.
It was interesting to compare tautomeric behavior
of compounds IIIg–IIIl and condensation products of
aldeoses with 3-sulfanylpropionohydrazide, studied
previously [8]. The latter were found to exist in solu-
tion as mixtures of pyranose and seven-membered
1,3,4-thiadiazepine structures, where the ring–ring
tautomeric equilibrium was appreciably displaced
toward the pyranose tautomer. Presumably, the tauto-
meric equilibrium of compounds IIIg–IIIl is displaced
toward 1,3,4-benzothiadiazepine structure due to in-
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STRUCTURE OF ALDOSE CONDENSATION PRODUCTS
863
creased rigidity of the fragment connecting the electro-
philic and nucleophilic centers, which favors formation
of seven-membered ring [9, 10].
(NHCO), 11.99 br.s (OH); β-C (10%): 10.35 br.s
(NHCO), 12.23 br.s (OH). 13C NMR spectrum, δC,
ppm: α-A: 61.80 (C5), 68.08 (C4), 69.63 (C3), 70.99
(C2), 87.35 (C1), 159.35 (Carom–O), 167.21 (C=O);
β-A: 64.30 (C5), 67.40 (C4), 68.93 (C3), 70.10 (C2),
87.70 (C1), 159.77 (Carom–O), 167.21 (C=O); B: 63.30
(C5), 71.99 (C4), 72.00 (C3), 74.42 (C2), 153.74 (C1),
159.60 (Carom–O), 165.25 (C=O); β-C: 63.75 (C5),
70.30 (C3), 72.84 (C2), 83.40 (C4), 95.28 (C1), 116.56–
133.78 (Carom in A–C). Found, %: C 50.76; H 5.60;
N 9.92. C12H16N2O6. Calculated, %: C 50.70; H 5.67;
N 9.85.
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded from
solutions in DMSO-d6 on a Bruker AV-400 spectrom-
eter at 400 and 100 MHz, respectively, using hexa-
methyldisiloxane as internal reference. The solid-phase
13C NMR spectra were obtained on a Bruker AM-500
spectrometer (125 MHz) using a standard procedure
utilizing cross polarization magic angle spinning
(CPMAS) technique (frequency 4.5 kHz; internal ref-
erence hexamethylbenzene). The progress of reactions
and the purity of products were monitored by TLC on
Silufol UV-254 plates using benzene–acetone–acetic
acid (1:1:2 by volume) as eluent. 2-Hydroxy- and
2-sulfanylbenzohydrazides were prepared according to
known methods [11, 12].
L-Ramnose 2-hydroxybenzoylhydrazone (IIIc).
1
Yield 55%, mp 126–127°C. H NMR spectrum, δ,
ppm: α-A (30%): 1.11 d (CH3, J = 6.5 Hz), 10.00 br.s
(NHCO), 12.19 br.s (OH); β-A (50%): 1.34 d (CH3,
J = 6.6 Hz), 10.30 br.s (NHCO), 12.15 br.s (OH);
B (20%): 1.10 d (CH3, J = 6.4 Hz), 7.72 d (HC=N,
J = 4.5 Hz), 11.60 br.s (NHCO), 11.96 br.s (OH).
13C NMR spectrum, δC, ppm: α-A: 18.11 (C6), 68.43
(C5), 69.41 (C3), 70.73 (C2), 72.59 (C4), 88.94 (C1),
159.43 (Carom–O), 168.03 (C=O); β-A: 18.11 (C6),
70.08 (C2), 72.10 (C4), 73.21 (C5), 74.05 (C3), 87.11
(C1), 159.03 (Carom–O), 165.30 (C=O); B: 20.92 (C6),
65.25 (C5), 71.13 (C3), 72.10 (C2), 73.21 (C4), 154.65
(C1), 159.50 (Carom–O), 165.22 (C=O), 116.34–134.26
(Carom in A, B). Found, %: C 52.28; H 5.99; N 9.46.
C13H18N2O6. Calculated, %: C 52.34; H 6.08; N 9.39.
2-Hydroxy- and 2-sulfanylbenzoylhydrazones
IIIa–IIIl (general procedure). A solution of 11 mmol
of 2-hydroxy- or 2-sulfanylbenzohydrazide IIa or IIb
and 10 mmol of the corresponding carbohydrate (Ia–
If) in 25 ml of methanol was heated for 6 h under
reflux. The solvent was removed under reduced pres-
sure, the residue was washed with diethyl ether, and
the resulting crystalline material was filtered off, dried,
and recrystallized from methanol or acetonitrile–meth-
anol (10:1 by volume).
D-Galactose 2-hydroxybenzoylhydrazone (IIId).
1
Yield 75%, mp 189–191°C. H NMR spectrum, δ,
L-Arabinose 2-hydroxybenzoylhydrazone (IIIa).
ppm: α-A (25%): 10.17 br.s (NHCO), 12.15 br.s (OH);
β-A (45%): 10.14 br.s (NHCO), 11.96 br.s (OH);
B (30%): 7.77 d (HC=N, J = 4.5 Hz), 11.60 br.s
(NHCO), 11.96 br.s (OH). 13C NMR spectrum, δC,
ppm: α-A: 63.02 (C6), 69.25 (C3), 70.50 (C2), 70.97
(C4), 72.48 (C5), 88.35 (C1), 159.21 (Carom–O), 166.65
(C=O); β-A: 60.63 (C6), 68.44 (C4), 68.77 (C2), 73.60
(C3), 76.60 (C5), 91.70 (C1), 158.63 (Carom–O), 166.95
(C=O); B: 63.21 (C6), 67.66 (C5), 69.92 (C4), 70.00
(C3), 70.80 (C2), 155.38 (C1), 159.54 (Carom–O), 165.22
(C=O), 114.78–134.22 (Carom in A, B). Found, %:
C 49.74; H 5.85; N 8.87. C13H18N2O7. Calculated, %:
C 49.68; H 5.77; N 8.91.
Yield 65%, mp 191–192°C; published data [11]:
mp 191°C. H NMR spectrum, δ, ppm: α-A (20%):
1
10.22 br.s (NHCO), 12.50 br.s (OH); β-A (25%):
10.22 br.s (NHCO), 12.20 br.s (OH); B (30%): 7.74 d
(HC=N, J = 4.4 Hz), 11.60 br.s (NHCO), 12.11 br.s
(OH); α-C (25%): 10.35 br.s (NHCO), 11.96 br.s (OH).
13C NMR spectrum, δC, ppm: α-A: 63.55 (C5), 67.92
(C4), 69.52 (C3), 70.32 (C2), 85.85 (C1), 159.05 (Carom
–
O), 166.05 (C=O); β-A: 65.30 (C5), 69.01 (C4), 72.35
(C3), 73.65 (C2), 90.80 (C1), 159.31 (Carom–O), 166.65
(C=O); B: 63.88 (C5), 65.52 (C2), 70.29 (C3), 71.13
(C4), 155.05 (C1), 159.50 (Carom–O), 165.31 (C=O);
α-C: 61.83 (C5), 84.63 (C4), 95.55 (C1), 117.44–134.04
(Carom in A–C). Found, %: C 50.63; H 5.84; N 9.78.
C12H16N2O6. Calculated, %: C 50.70; H 5.67; N 9.85.
D-Glucose 2-hydroxybenzoylhydrazone (IIIe).
Yield 70%, mp 196–198°C; published data [11]:
1
D-Ribose 2-hydroxybenzoylhydrazone (IIIb).
mp 198°C. H NMR spectrum, δ, ppm: α-A (30%):
1
Yield 75%, mp 189–190°C. H NMR spectrum, δ,
10.09 br.s (NHCO), 12.00 br.s (OH); β-A (65%):
10.09 br.s (NHCO), 11.87 br.s (OH); B (5%): 7.76 d
(HC=N, J = 4.6 Hz), 11.60 br.s (NHCO), 11.95 br.s
ppm: α-A (20%): 10.02 br.s (NHCO), 12.08 br.s (OH);
β-A (30%): 10.15 br.s (NHCO), 12.00 br.s (OH);
B (40%): 7.78 d (HC=N, J = 4.3 Hz), 11.60 br.s
13
(OH). C NMR spectrum (solid phase), δC, ppm: β-A
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

ALEKSEEV et al.
864
(100%): 59.70 (C6), 68.23 (C4), 69.04 (C2), 74.96 (C5),
79.24 (C3), 90.93 (C1), 112.50, 118.91, 120.57, 128.66,
136.71 (Carom), 160.44 (Carom–O), 172.12 (C=O).
13C NMR spectrum, δC, ppm: α-A: 60.95 (C6), 70.22
(C4), 71.15 (C5), 71.25 (C2), 73.72 (C3), 87.98 (C1),
159.00 (Carom–O), 166.95 (C=O); β-A: 61.42 (C6),
70.50 (C4), 71.55 (C2), 76.85 (C5), 78.18 (C3), 91.05
(C1), 158.55 (Carom–O), 166.95 (C=O); B: 63.50 (C6),
153.80 (C1), 159.47 (Carom–O), 114.37–135.26 (Carom
in A, B). Found, %: C 49.62; H 5.80; N 8.96.
C13H18N2O7. Calculated, %: C 49.68; H 5.77; N 8.91.
(NHCO); β-A (20%): 1.34 d (CH3, J = 6.6 Hz),
10.20 br.s (NHCO); B (20%): 1.10 d (CH3, J =
6.4 Hz), 7.72 d (HC=N, J = 4.5 Hz), 11.76 br.s
(NHCO); D (30%): 1.14 d (CH3, J = 6.5 Hz), 9.52 br.s
(NHCO); D′ (15%): 1.11 d (CH3, J = 6.5 Hz), 9.36 br.s
(NHCO). 13C NMR spectrum, δC, ppm, α-A: 18.04
(C6), 68.21 (C5), 69.36 (C3), 71.09 (C2), 72.55 (C4),
88.11 (C1), 136.75 (Carom–S), 164.06 (C=O); β-A:
18.04 (C6), 70.63 (C2), 73.20 (C4), 73.30 (C5), 74.03
(C3), 87.31 (C1), 136.51 (Carom–S), 166.23 (C=O);
B: 20.82 (C6), 66.16 (C5), 70.04 (C3), 72.19 (C2), 73.25
(C4), 153.99 (C1), 139.70 (Carom–S), 163.20 (C=O);
D: 20.98 (C6), 66.25 (C5), 69.79 (C3), 71.34 (C4), 73.12
(C2), 76.04 (C1), 139.67 (Carom–S), 172.61 (C=O);
D′: 20.98 (C6), 66.40 (C5), 69.79 (C3), 73.01 (C4),
73.75 (C2), 75.80 (C1), 139.51 (Carom–S), 172.70
(C=O), 126.05–133.96 (Carom in A, B, D). Found, %:
C 49.61; H 5.72; N 8.85. C13H18N2O5S. Calculated, %:
C 49.67; H 5.77; N 8.91.
D-Mannose 2-hydroxybenzoylhydrazone (IIIf).
1
Yield 80%, mp 122–125°C. H NMR spectrum, δ,
ppm: α-A (25%): 9.97 br.s (NHCO), 12.09 br.s (OH);
β-A (40%): 10.19 br.s (NHCO), 12.15 br.s (OH);
B (35%): 7.73 d (HC=N, J = 4.5 Hz), 11.60 br.s
(NHCO), 11.96 br.s (OH). 13C NMR spectrum, δC,
ppm: α-A: 61.38 (C6), 67.52 (C4), 70.00 (C3), 70.95
(C2), 73.25 (C5), 88.96 (C1), 159.48 (Carom–O), 167.98
(C=O); β-A: 61.70 (C6), 67.52 (C4), 71.28 (C2), 74.35
(C3), 78.40 (C5), 87.35 (C1), 159.12 (Carom–O), 166.82
(C=O); B: 63.95 (C6), 69.20 (C4), 71.26 (C3), 71.46
(C2), 73.73 (C5), 154.64 (C1), 159.47 (Carom–O), 165.22
(C=O), 115.07–134.72 (Carom in A, B). Found, %:
C 49.77; H 5.70; N 8.85. C13H18N2O7. Calculated, %:
C 49.68; H 5.77; N 8.91.
Compound IIIi was dissolved in a minimal amount
of DMSO, and the solution was kept for 21 days at
25°C. The crystalline solid was filtered off, washed
with diethyl ether, and recrystallized from methanol.
Yield 50%, mp 171–172°C. 13C NMR spectrum (solid
phase), δC, ppm: β-A (100%): 19.66 (CH3), 69.73
(C2), 70.03 (C4), 73.85 (C3), 74.37 (C5), 87.62 (C1),
125.84, 130.27, 132.53, 133.60, 137.61 (Carom),
139.18 (Carom–S), 164.98 (C=O). Found, %: C 49.74;
H 5.86; N 8.86. C13H18N2O5S. Calculated, %: C 49.67;
H 5.77; N 8.91.
L-Arabinose 2-sulfanylbenzoylhydrazone (IIIg).
Yield 60%, mp 177–178°C; published data [12]:
1
mp 175–176°C. H NMR spectrum, δ, ppm: D (75%):
9.22 br.s (NHCO); D′ (25%): 9.24 br.s (NHCO).
13C NMR spectrum, δC, ppm: D: 63.37 (C5), 69.40
(C2), 70.08 (C3), 71.51 (C4), 75.40 (C1), 140.13
(Carom–S), 175.40 (C=O); D′: 63.61 (C5), 69.40 (C2),
70.38 (C3), 71.01 (C4), 74.24 (C1), 140.13 (Carom–S),
172.75 (C=O), 127.90–133.47 (Carom in D, D′). Found,
%: C 48.06; H 5.29; N 9.41. C12H16N2O5S. Calculated,
%: C 47.99; H 5.37; N 9.33.
D-Galactose 2-sulfanylbenzoylhydrazone (IIIj).
1
Yield 90%, mp 165–166°C. H NMR spectrum, δ,
ppm: D (75%): 10.16 br.s (NHCO); D′ (25%):
13
10.03 br.s (NHCO). C NMR spectrum, δC, ppm: D:
63.22 (C6), 68.52 (C5), 69.42 (C4), 69.73 (C3), 69.92
(C2), 75.59 (C1), 140.12 (Carom–S), 173.27 (C=O); D′:
63.22 (C6), 69.39 (C4), 69.43 (C3), 69.68 (C5), 69.79
(C2), 74.43 (C1), 140.12 (Carom–S), 172.78 (C=O),
127.91–133.49 (Carom in D, D′). Found, %: C 47.21;
H 5.55; N 8.54. C13H18N2O6S. Calculated, %: C 47.26;
H 5.49; N 8.48.
D-Ribose 2-sulfanylbenzoylhydrazone (IIIh).
1
Yield 60%, mp 139–140°C. H NMR spectrum, δ,
ppm: D (65%): 10.16 br.s (NHCO); D′ (35%):
10.03 br.s (NHCO). 13C NMR spectrum, δC, ppm: D:
62.90 (C5), 72.52 (C2), 72.54 (C4), 73.02 (C3), 75.30
(C1), 139.79 (Carom–S), 172.89 (C=O); D′: 62.70 (C5),
72.34 (C4), 72.78 (C2), 75.01 (C3), 75.19 (C1), 139.59
(Carom–S), 172.65 (C=O), 127.90–133.84 (Carom in D,
D′). Found, %: C 47.91; H 5.43; N 9.27. C12H16N2O5S.
Calculated, %: C 47.99; H 5.37; N 9.33.
D-Glucose 2-sulfanylbenzoylhydrazone (IIIk).
Yield 75%, mp 175–176°C; published data [12]:
mp 178–179°C. 1H NMR spectrum, δ, ppm: α-A (15%):
10.14 br.s (NHCO); β-A (30%): 10.11 br.s (NHCO);
D (40%): 9.30 br.s (NHCO); D′ (15%): 9.24 br.s
(NHCO). 13C NMR spectrum (solid phase), δC, ppm:
D (100%): 63.12 (C6), 69.28 (C4), 70.03 (C2), 70.60
(C5), 71.4 (C3), 74.57 (C1), 127.19, 129.08, 131.62,
134.56, 135.38 (Carom), 139.97 (Carom–S), 174.66
L-Ramnose 2-sulfanylbenzoylhydrazone (IIIi).
1
Yield 80%, mp 159–161°C. H NMR spectrum, δ,
ppm: α-A (15%): 1.11 d (CH3, J = 6.5 Hz), 10.00 br.s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

STRUCTURE OF ALDOSE CONDENSATION PRODUCTS
865
13
(C=O). C NMR spectrum, δC, ppm: α-A: 60.86 (C6),
70.09 (C4), 71.08 (C5), 71.97 (C2), 73.59 (C3), 88.05
(C1), 136.58 (Carom–S), 165.54 (C=O); β-A: 61.49 (C6),
70.37 (C4), 71.38 (C2), 76.69 (C5), 77.93 (C3), 90.95
(C1), 136.58 (Carom–O), 166.23 (C=O); D: 63.19 (C6),
68.73 (C4), 71.66 (C2), 73.28 (C5), 73.38 (C3), 75.27
(C1), 140.14 (Carom–S), 173.20 (C=O); D′: 63.19 (C6),
68.86 (C4), 71.33 (C2), 72.68 (C5), 73.38 (C3), 74.08
(C1), 139.82 (Carom–S), 172.66 (C=O), 125.90–133.58
(Carom in A, D). Found, %: C 47.31; H 5.53; N 8.40.
C13H18N2O6S. Calculated, %: C 47.26; H 5.49; N 8.48.
REFERENCES
1. Ershov, A.Yu., Lagoda, I.V., Yakimovich, S.I., Pakal’-
nis, V.V., and Shamanin, V.V., Russ. J. Org. Chem.,
2007, vol. 43, p. 1745.
2. Ershov, A.Yu., Lagoda, I.V., Yakimovich, S.I., Pakal’-
nis, V.V., Zerova, I.V., Dobrodumov, A.V., and Sha-
manin, V.V., Russ. J. Org. Chem., 2009, vol. 45, p. 660.
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shov, A.Yu., and Lagoda, I.V., Russ. J. Org. Chem.,
2009, vol. 45, p. 285.
4. Dolgarev, A.V., Lukachina, V.V., and Karpova, O.I.,
D-Mannose 2-sulfanylbenzoylhydrazone (IIIl).
Yield 60%, mp 136–138°C. H NMR spectrum, δ,
Zh. Anal. Khim., 1974, vol. 29, p. 721.
1
5. Flegontov, S.A., Titova, Z.S., Stolyarov, A.P., Buzy-
kin, B.I., and Kitaev, Yu.P., Izv. Akad. Nauk SSSR, Ser.
Khim., 1979, p. 1014.
6. Zelenin, K.N. and Alekseev, V.V., Khim. Geterotsikl.
Soedin., 1992, p. 571.
ppm: α-A (15%): 10.08 br.s (NHCO); β-A (20%):
10.19 br.s (NHCO); B (15%): 7.82 d (HC=N, J =
4.2 Hz), 11.61 br.s (NHCO); D (30%): 10.18 br.s
(NHCO); D′ (20%): 9.98 br.s (NHCO). 13C NMR
spectrum, δC, ppm: α-A: 61.52 (C6), 67.69 (C3), 70.59
(C4), 71.09 (C2), 73.21 (C5), 89.01 (C1), 136.50
(Carom–S), 164.88 (C=O); β-A: 62.06 (C6), 70.70 (C4),
71.40 (C2), 74.30 (C3), 78.30 (C5), 87.69 (C1), 136.71
(Carom–S), 163.34 (C=O); B: 61.62 (C6), 67.51 (C3),
70.90 (C4), 72.19 (C2), 73.58 (C5), 154.15 (C1), 136.89
(Carom–S), 163.34 (C=O); forma D: 63.74 (C6), 69.13
(C3), 69.91 (C4), 71.11 (C2), 71.13 (C5), 75.98 (C1),
139.71 (Carom–S), 172.75 (C=O); D′: 63.61 (C6), 69.32
(C3), 69.90 (C4), 71.23 (C2), 73.39 (C5), 75.73 (C1),
139.58 (Carom–S), 172.80 (C=O), 125.33–133.05 (Carom
in A, B, D). Found, %: C 47.27; H 5.56; N 8.55.
C13H18N2O6S. Calculated, %: C 47.26; H 5.49; N 8.48.
7. Ershov, A.Yu., Lagoda, I.V., Mokeev, M.V., Yakimo-
vich, S.I., Zerova, I.V., Pakal’nis, V.V., and Shama-
nin, V.V., Khim. Geterotsikl. Soedin., 2008, p. 754.
8. Ershov, A.Yu., Lagoda, I.V., Yakimovich, S.I., Zero-
va, I.V., Pakal’nis, V.V., and Shamanin, V.V., Russ. J.
Org. Chem., 2009, vol. 45, p. 1488.
9. Valters, R.E., Fulop, F., and Carbonits, D., Adv. Hetero-
cycl. Chem., 1995, vol. 64, p. 251.
10. Lázár, L. and Fülöp, F., Eur. J. Org. Chem., 2003,
vol. 16, p. 3025.
11. Kahl, R., Chem. Zentrl., 1904, vol. 75, p. 1493.
12. Katz, L., Karger, L.S., Schroeder, W., and Cohen, M.S.,
J. Org. Chem., 1953, vol. 18, p. 1380.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010