A convenient synthesis and biological activities of novel 6-aryl-3-(1,2,3,4-tetrahydroxybutan-1-yl)-7H-1,2,4-triazolo-[3,4-b][1,3,4] thiadiazines

Article abstract of DOI:10.1002/jhet.5570450407

(Chemical Equation Presented) A series of novel 6-aryl-3-(1,2,3,4- tetrahydroxybutanol-1-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines were easily synthesized in high yields by means of the reactions of 4-amino-5-(1,2,3,4-tetrahydroxybutyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione (1) with substituted ω-bromoacetophenones or ω-chloroacetophenone. Nearly all of the title compounds possess plant growth-promoting activities.

Full text of DOI:10.1002/jhet.5570450407

Jul-Aug 2008
987
A Convenient Synthesis and Biological Activities of Novel
6-Aryl-3-(1,2,3,4-tetrahydroxybutan-1-yl)-7H-1,2,4-triazolo-
[3,4-b][1,3,4]thiadiazines
Xiao-xia Ye 1, 2, 3, Jin Zhang 1, An-jiang Zhang 1, and Li-xue Zhang *1
1College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325027, P.R.China,
E-mail: zhanglixuelz@yahoo.com.cn;
2 Cheng-du Institute of Biology, Chinese Academy of Sciences, Chengdu 610041 P. R. China,
3Department of Chemistry, Wenzhou Medical College, Wenzhou 325035, P. R. China
Received March 29, 2007
H
H H
pyridine
N
NH
HO
O
OH
CH2OH
S
HOH2C
+
S
H2N HN C NH NH2
N
reflux , 4h
OHOHOH
O
NH2
1
1
N
2
N
H
H H
N
N
H
H H
ethanol
13
12 11 10
9
HOH2C
HOH2C
S
H
N
3
S8
reflux, 4h
4N
5N
OHOHOH
OHOHOH
NH2
O
7
6
2a-h
R
Br
R
C CH2
A series of novel 6-aryl-3-(1,2,3,4-tetrahydroxybutanol-1-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines
were easily synthesized in high yields by means of the reactions of 4-amino-5-(1,2,3,4-tetrahydroxybutyl)-
2,4-dihydro-3H-1,2,4-triazole-3-thione (1) with substituted ꢀ-bromoacetophenones or ꢀ-chloroacetophen-
one. Nearly all of the title compounds possess plant growth-promoting activities.
J. Heterocyclic Chem., 45, 987 (2008).
INTRODUCTION
RESULTS AND DISCUSSION
1,2,4-triazolo[3,4-b][1,3,4]thiadiazines are condensed
heterocyclic compounds having wide range of
In spite of R- with electron-withdrawing group or
electron-donating group, the desired products were
obtained in good yields, so the generality of the reaction is
excellent. When 2b-e having electron-withdrawing group
were used, the rate of reactions was much faster than that
in the case of R- with electron-donating group, which can
be observed by the rate of the appearance of precipitation
in the reaction system. The reason is that the electron-
withdrawing group can increase the positive polarity of
the carbonyl carbon, which is favorable for the attack of
amino-group. Nevertheless, we intended to synthesize
6-(4-fluorophenyl)-3-(1,2,3,4-tetrahydroxybutan-1-yl)-
7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine and 6-(2,4-
difluor-ophenyl)-3-(1,2,3,4-tetrahy-droxybutan-1-yl)-7H-
1,2,4-triazolo[3,4-b][1,3,4]thiadiazine when we mixed
compound 1 with 2-bromo-4'-fuoroacetophenone or 2-
chloro-2', 4'-difuoroacetophenone in the same manner as
we did in preparing 2a-h. Unluckily we didn’t succeed
though we had tried several times and at different pH
values. It is still a question to be solved. The solubility of
the newly synthesized compounds, 2a-2h, is much greater
than that of the compounds which we prepared in our
previous research [9-12] (see Table 1). The title
compounds have been investigated for their biological
activities on regulating the growth of wheat and radish
a
applications. A literature survey showed that this kind of
compounds combined the properties of triazoles and
thiadiazines [1,2]; thereby some of them showed wide
spectrum of biological activities, such as antimicrobial,
antibacterial, antifungal, anti-inflammatory, diuretic,
anthelmintic, analgesic and antiparasitic [3]. They can
also be used as plant growth inhibitors [4-8]. Our
researches have been devoted for several years to the
synthesis of a series of novel compounds - 7H-1,2,4-
triazolo[3,4-b][1,3,4]thiadiazines [9-12]. However, we
noticed that, besides our research in this respect, almost
all of the substitutions at 3-, 6- and 7-positions in this kind
of compounds, which are currently available are alkyl or
aryl groups [13-16]. It is disadvantageous to use these
compounds as medicament because of their poor water-
solubility. Considering that the D-ribonic acid residues
play a special role in the body, we have synthesized a
series of new compounds attaching alditolyl residues at
the 3-position of 7H-1,2,4-triazolo[3,4-b][1,3,4]thia-
diazines, which may improve their transportation and
absorption in biological systems.
The structures of all products have been characterized by
1
elemental analysis, IR, H NMR, 13C NMR and MS. The
synthetic route to the compounds is shown in Scheme 1.

988
X.-X. Ye, J. Zhang, A.-J. Zhang, and L.-X. Zhang
Vol 45
Scheme 1
H
H H
pyridine
N
NH
HO
O
OH
CH2OH
S
HOH2C
+
S
H2N HN C NH NH2
N
reflux , 4h
OHOHOH
O
NH2
1
1
2
N
H
H H
N
N
H
H H
12 11 10
N
ethanol
13
9
HOH2C
HOH2C
S
H
N
3
S8
reflux, 4h
4N
5N
OHOHOH
OHOHOH
NH2
O
7
6
2a-h
R
Br
C CH2
R
R: 2a: C6H5-
2c:2,4-2ClC6H3-
2b:p-ClC6H4-
2d:p-BrC6H4-
2f:p-CH3C6H4-
2h:p-C6H5C6H4-
2e: p-O2NC6H4-
2g: p-CH3OC6H4-
the synthetic route to the title compounds
with reference of sterilized distilled water. After treating
with culture solution of 10 μg/mL and 100 μg/mL of the
title compounds 2a-h for 5 days, the growth regulating
percentage has been calculated. The data of biological
activity test are presented in Table 2. The results indicated
that among the tested compounds, almost all the newly
prepared compounds showed moderate to good promoting
effect on the growth of the stalk and the radicel of the
wheat and radish at a mass concentration of 10 μg /mL
and 100 μg /mL. However, it is interesting that 2b showed
a small amount of inhibiting effect on the growth of the
radicel of the radish at 100 μg/mL and 2e showed the
same case, but at 10 μg /mL. Therefore the structure and
activity relationship is worth studying further.
IR Spectra of the Title Compounds. The absence of
NH2, SꢀH and CꢁS absorption bands in the IR spectra
has confirmed that the title compounds 2 were obtained
via cyclocondensation. The stretching vibration peaks of
OH group are at 3200ꢀ3600 cm-1. The CꢀH stretching
vibration peaks of CH2 group are at 2920ꢀ2980 cm-1. The
Table 1
The Water-Solubility of the Title Compounds.
Compounds
2a
2b
2c
2d
2e
2f
2g
2h
Solubility in H2O at
20°C(mg/100mL)
102
240
110
135
35
255
260
66
Table 2
Effect of compounds 2a-h on the plant growth-regulating of wheat and radish.a
Compounds
Concentrations
Radish
Wheat
Stalk
+++
++
++
+++
++
+
+++
++
++
++
++
++
++
Radicel
Stalk
Radicel
(μg/mL )
2a
2b
2c
2d
2e
2f
100
10
100
10
100
10
100
10
100
10
100
10
100
10
100
10
+++
+++++
**
+++
++
++
++
+++
+++
***
++++
+++
+++++
+++
++
++
+++
++
++++
++
++
++
++
++
++
++
++
++
+++
++
++
+++
++
*
+
++
++
++
++
++
++
++
++
++
+++
++
2g
2h
+++
++
+++
+++
++
a: “ + ” represents promotion rate. + : <10%; ++ : 10-30%; +++ : 30-50%; ++++ : 50-70%; +++++ : 70-90%; ++++++: >90%.
“ * ” represents inhibition rate. * : <10%; ** : 10-30%; *** : 30-50%.

Jul-Aug 2008
A Convenient Synthesis and Biological Activities of Novel 6-Aryl-3-(1,2,3,4-
tetrahydroxybutan-1-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines
989
treatment), 5.69 (d, 1H, J=5.8Hz, CH2OH-CHOH-CHOH-
CHOH-), 5.51 (s, 2H, -NH2, disappear upon D2O treatment),
4.90 (d, 1H, OꢀH, J=6.1Hz, disappear upon D2O treatment),
4.83-4.79 (m, 1H, OꢀH, disappear upon D2O treatment), 4.69
(d, 1H, OꢀH, J=4.9Hz, disappear upon D2O treatment), 4.46-
4.44(m, 1H, ꢀOH, disappear upon D2O treatment), 3.94ꢀ3.95
(m, 1H, CH2OH-CHOH-CHOH-), 3.57ꢀ3.61 (m, 2H, CH2OH-),
3.42ꢀ3.48 (m, 1H, CH2OH-CHOH-). 13C NMR (DMSO-d6,
75MHz, ppm): 165.13, 152.05, 72.83, 72.73, 66.11, 62.45. MS-
ESI: m/z (relative intensity, %): 237 [M++1](100), 219 (2.0),
181 (1.5), 159 (3.0). Anal. Calcd for C6H12N4O4S: C, 30.50; H,
5.12; N, 23.72. Found: C, 30.28; H, 5.18; N, 23.46.
characteristic stretching vibrations of the rings of the
products are at 1570ꢀ1600 cm-1 (C=N), 1440ꢀ1520
cm-1(N=CꢀS). The bending vibrations of CꢀSꢀC are in
the region 680ꢀ700 cm-1.
1
1H NMR of the Title Compounds. In the H NMR
spectrum of the intermediate 4-amino-5-(1,2,3,4-tetra-
hydroxybutyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione 1,
there are absorptions at ꢀ 13.55 (s, 1H, NꢀH), 5.51 (s, 2H,
-NH2). In all the title compounds 2, the above two
absorptions have disappeared and the observation of
additional resonances assigned to the SCH2 (ꢀ 4.4ꢀ4.6
ppm), which also confirmed the ring-closure. We note
that, in almost all title compounds (except 2c), there are
broad and single absorption peaks at ꢀ5.1ꢀ6.3 ppm
assigned to the OꢀH. The C10ꢀH absorption peaks in the
title compounds all show clear double peaks.
13C NMR of the Title Compounds. The intermediate
4-amino-5-(1,2,3,4-tetrahydroxybutyl)-2,4-dihydro-3H-
1,2,4-triazole-3-thione exhibited absorption peaks at ꢀ
165.1, 152.1 due to NꢀC=N, NꢀC=S respectively, at ꢁ
72.8, 72.7, 66.1, 62.5 due to the four carbon atoms of the
D-ribonic acid residues. The title compounds showed
absorptions at ꢀ 154ꢀ163, 154ꢀ157, 141ꢀ149 due to
NꢀC=N, NꢀC=S and PhꢀC=N group respectively. The ꢀ
values (114ꢀ143) of the CꢀH of the phenyl group are
different because of the phenyl group with different
substituted groups. The chemical shift values (ꢁ
26.0ꢀ23.0) of SCH2 are decreasing in the order of Ar = 2,
4-dichlorophenyl (25.95), 4-nitrophenyl, phenyl,
4-chlorophenyl, 4-bromophenyl, 4-diphenyl, 4-methyl-
phenyl, 4-methoxylphenyl (22.94).
General Method for the Preparation of 6-ar-yl-3-(1,2, 3,4-
tetrahydroxybutan-1-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thia-
diazines 2a-h. A mixture of 1 (1.0 mmol) and substituted ꢀ-
bromoacetophenones or ꢀ-chloroacetophenone in ethanol (20
mL) was refluxed for 4h under stirring. The solid obtained on
cooling was filtered, washed with cold water, air dried and
recrystallized from C2H5OH to give compounds 2a-h.
6-Phenyl-3-(1, 2, 3, 4-tetrahydroxybutan-1-yl)-7H-1, 2, 4-
triazolo[3, 4-b][1, 3, 4]thiadiazine (2a). This compound was
prepared from 1 and ꢀ-chloroacetophenone and obtained as pale
yellow powder (0.27 g, 80%), mp 139ꢀ141˚Cꢀ (from ethanol).
IR(cm-1): 3293 (OH), 2920 (CH2), 1590 (C=N), 1445 (N=CꢀS) ,
693 (CꢀSꢀC). 1H NMR (DMSO-d6, 300 MHz, ppm):
7.57ꢀ8.07 (m, 5H, Ar-H), 5.87 (br, 4H, OꢀH, disappear upon
D2O treatment), 5.15 (d, 1H, J=6.4Hz, CH2OH-CHOH-CHOH-
CHOH-), 4.41ꢀ4.54 (m, 2H, SCH2), 4.09ꢀ4.13 (m, 1H,
CH2OH-CHOH-CHOH-), 3.57ꢀ3.69 (m, 2H, CH2OH-),
3.45ꢀ3.51 (m, 1H, CH2OH-CHOH-). 13C NMR (DMSO-d6, 75
MHz, ppm): 156.30, 154.51, 141.59, 133.38, 132.37, 129.21,
127.89, 72.83, 72.54, 66.42, 62.74, 23.12. MS-ESI: m/z (relative
intensity, %): 337 [M++1](100), 246 (3.0), 217(2.0). Anal. Calcd
for C14H16N4O4S: C, 49.99; H, 4.79; N, 16.66. Found: C, 49.72;
H, 4.66; N, 16.87.
6-(4-Chlorophenyl)-3-(1,2,3,4-tetrahydroxy-butan-1-yl)-7H-
1,2,4-triazolo[3,4-b][1,3,4]thiadiazine (2b). This compound was
We are grateful for financial support from the Natural
Science Foundation of Zhejiang Province, China (Project
No. M203149).
prepared from
1 and 2-bromo-4'-chloroacetophenone and
obtained as pale yellow powder (0.33 g, 89%), mp 185ꢀ189˚C
(from ethanol). IR(cm-1): 3505 (OH), 2978 (CH2), 1587 (C=N),
1
EXPERIMENTAL
1519 (N=CꢀS) , 698 (CꢀSꢀC). H NMR (DMSO-d6, 300MHz,
ppm): 7.64-8.10 (m, 4H, Ar-H), 6.36 (br, 4H, OꢀH, disappear
upon D2O treatment), 5.16 (d, 1H, J=6.2Hz, CH2OH-CHOH-
CHOH-CHOH-), 4.39-4.55 (m, 2H, SCH2), 4.06-4.10 (m, 1H,
ꢀCH2OH-CHOH-CHOH-), 3.58-3.66 (m, 2H, CH2OH-), 3.48-
3.50 (m, 1H, CH2OH-CHOH-). 13C NMR (DMSO-d6, 75MHz,
ppm): 155.51, 154.51, 141.66, 137.33, 132.15, 129.70, 129.32,
72.84, 72.34, 66.35, 62.72, 23.05. MS-ESI: m/z (relative
intensity, %): 373 [M++2] (35), 371 [M+](100), 323 (0.5). Anal.
Calcd for C14H15ClN4O4S: C, 45.35; H, 4.08; N, 15.11. Found:
C, 45.50; H, 4.15; N, 14.92.
Mps (uncorrected) were taken on an XT-4 melting point
apparatus; IR spectra were determined on a Nicolet 670FT-IR
using the smart OMNI-Sampler in the range 4000ꢀ400 cm-1; 1H
NMR and 13C NMR spectra were measured on a Bruker Avance-
300 NMR spectrometer respectively in DMSO-d6 solution using
TMS as an internal reference; MS spectra were recorded on an
Agilent 1100 LC/MS. The contents of carbon, hydrogen and
nitrogen were determined on a Flash-1112 series elemental
analyzer.
4-Amino-5-(1,2,3,4-tetrahydroxybutyl)-2,4-dihydro-3H-
1,2,4-triazole-3-thione (1). To a solution of D-(+)-ribonic ꢂ-
lactone (1.24 g, 8 mmol) dissolved in pyridine was added
thiocarbohydrazide (0.89 g, 8 mmol), which was prepared by
means of the method from literature [17]. The mixture was
refluxed for 4 h under stirring. After concentration under
reduced pressure, the crude product was recrystallized from
alcohol to afford compound 1 as white powder, 1.69 g (89%),
mp 156-158˚C (from ethanol). IR(cm-1): 3347 (OH), 2940
(CH2), 1603 (C=N), 1507 (N=CꢀS). 1H NMR (DMSO-d6,
300MHz, ppm): 13.55 (s, 1H, NꢀH, disappear upon D2O
6-(2,4-Dichlorophenyl)-3-(1,2,3,4-tetrahydroxybutan-1-yl)-
7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine (2c). This compound
was prepared from 1 and 2,2',4'-trichloro-acetophenone and
obtained as white powder (0.32 g, 80%), mp 180-182˚C (from
ethanol). IR(cm-1): 3240 (OH), 2930 (CH2), 1581 (C=N), 1466
(N=CꢀS), 702 (CꢀSꢀC). 1H NMR (DMSO-d6, 300MHz, ppm):
7.11ꢀ7.87 (m, 3H, Ar-H), 5.72 (br, 1H, OꢀH, disappear upon
D2O treatment), 4.94 (d, 1H, J=8.1Hz, CH2OH-CHOH-CHOH-
CHOH-), 4.68(br, 3H, OꢀH, disappear upon D2O treatment),
4.23(s, 2H, SCH2), 4.02-4.05 (m, 1H, CH2OH-CHOH-CHOH-),
3.58-3.66 (m, 2H, CH2OH-), 3.46-3.49 (m, 1H, CH2OH-CHOH).

990
X.-X. Ye, J. Zhang, A.-J. Zhang, and L.-X. Zhang
Vol 45
13C NMR (DMSO-d6, 75MHz, ppm): 154.61, 154.41, 140.31,
136.33, 133.63, 132.73, 132.51, 129.89, 128.14, 73.20, 72.89,
65.95, 62.63, 25.95. MS-ESI: m/z (relative intensity, %): 407
Anal. Calcd for
C14H14Cl2N4O4S: C, 41.49; H, 3.48; N, 13.83. Found: C, 41.26;
H, 3.32; N, 14.02.
CHOH-CHOH-), 4.38-4.56 (m, 2H, SCH2), 4.07-4.11 (m, 1H,
ꢀCH2OH-CHOH-CHOH-), 3.87(s, 3H, OCH3), 3.57-3.65 (m,
2H, CH2OH-), 3.44-3.49 (m, 1H, CH2OH-CHOH-). 13C NMR
(DMSO-d6, 75MHz, ppm): 162.94, 156.88, 154.29, 142.38,
130.05, 125.08, 114.75, 72.74, 71.96, 66.53, 62.76, 55.82, 22.94.
MS-ESI: m/z (relative intensity, %): 367[M++1](100), 247 (2.0).
Anal. Calcd for C15H18N4O5S: C, 49.17; H, 4.95; N, 15.29.
Found: C, 49.38; H, 5.05; N, 15.56.
[M++2](66), 405 [M+](100), 371 (2.0).
6-(4-Bromophenyl)-3-(1,2,3,4-tetrahydroxy-butan-1-yl)-7H-
1,2,4-triazolo[3,4-b][1,3,4]thiadiazine (2d). This compound
was prepared from
1
and 2,4'-dibromoacetophenone and
6-(4-Diphenyl)-3-(1,2,3,4-tetrahydroxybutan-1-yl)-7H-1,2,
4-triazolo[3,4-b][1,3,4]thiadiazine (2h). This compound was
prepared from 1 and 4-phenylphenacyl bromid and obtained as
pale yellow crystal (0.36 g, 87%), mp 192-194˚Cꢀ (from
ethanol). IR(cm-1): 3323 (OH), 2930 (CH2), 1595 (C=N), 1519
(N=CꢀS), 702 (CꢀSꢀC). 1H NMR (DMSO-d6, 300MHz, ppm):
7.41-8.16 (m, 9H, Ar-H), 5.09 (br, 4H, OꢀH, disappear upon
D2O treatment), 5.14 (d, 1H, J=6.8Hz, CH2OH-CHOH-CHOH-
CHOH-), 4.40-4.55 (m, 2H, SCH2), 4.10-4.15 (m, 1H, CH2OH-
CHOH-CHOH-), 3.61-3.72 (m, 2H, CH2OH-), 3.46-3.52 (m,
1H, CH2OH-CHOH-). 13C NMR (DMSO-d6, 75MHz, ppm):
155.42, 154.46, 143.70, 141.30, 138.89, 132.31, 129.25, 128.49,
128.29, 127.31, 127.05, 72.94, 72.66, 66.28, 62.74, 23.03. MS-
ESI: m/z (relative intensity, %): 413[M++1](100), 293 (2.0),
279(1.0). Anal. calcd. (%) for C20H20N4O4S: C, 58.24; H, 4.89;
N, 13.58. Found: C, 58.02; H, 4.78; N, 13.76.
obtained as pale yellow powder (0.37g, 90%). mp 195-200˚Cꢀ
(from ethanol). IR(cm-1): 3514 (OH), 2979 (CH2), 1584 (C=N),
1
1520 (N=CꢀS), 696 (CꢀSꢀC). H NMR (DMSO-d6, 300MHz,
ppm): 7.81-8.02 (m, 4H, Ar-H), 6.20 (br, 4H, OꢀH, disappear
upon D2O treatment), 5.19 (d, 1H, J=5.7Hz, CH2OH-CHOH-
CHOH-CHOH-), 4.41-4.57 (m, 2H, SCH2), 4.06-4.10 (m, 1H,
CH2OH-CHOH-CHOH-), 3.57-3.66 (m, 2H, CH2OH-), 3.44-
3.50 (m, 1H, CH2OH-CHOH-). 13C NMR (DMSO-d6, 75MHz,
ppm): 156.00, 154.53, 141.91, 132.42, 132.28, 129.88, 126.42,
72.81, 72.20, 66.41, 62.73, 23.05. MS-ESI: m/z (relative
intensity, %): 417 [M++2](100), 415 [M+](100), 414(1.0). Anal.
Calcd for C14H15BrN4O4S: C, 40.49; H, 3.64; N, 13.49. Found:
C, 40.26; H, 3.28; N, 13.77.
6-(4-Nitrophenyl)-3-(1,2,3,4-tetrahydroxy-butan-1-yl)-7H-
1,2,4-triazolo[3,4-b][1,3,4]thiadiazine (2e). This compound
was prepared from 1 and 2-bromo-4'-nitroacetophenone and
obtained as yellow powder (0.35 g, 92%), mp 199-200˚Cꢀ(from
ethanol). IR(cm-1): 3361 (OH), 2960 (CH2), 1578 (C=N), 1522
(N=CꢀS), 686 (CꢀSꢀC). 1H NMR (DMSO-d6, 300MHz, ppm):
8.23-8.43 (m, 4H, Ar-H), 5.77 (br, 4H, OꢀH, disappear upon
D2O treatment), 5.15 (d, 1H, J=6.2Hz, CH2OH-CHOH-CHOH-
CHOH-), 4.47-4.61 (m, 2H, SCH2), 4.07-4.11 (m, 1H, CH2OH-
CHOH-CHOH-), 3.60-3.66 (m, 2H, CH2OH-), 3.45-3.50 (m,
1H, CH2OH-CHOH-). 13C NMR (DMSO-d6, 75MHz, ppm):
154.59, 154.39, 149.30, 141.27, 139.12, 129.13, 124.04, 72.68,
72.31, 66.17, 62.53, 23.12. MS-ESI: m/z (relative intensity, %):
382[M++1](100), 352 (7.0), 352 (6.0), 262 (2.0). Anal. Calcd for
C14H15N5O6S: C, 44.09; H, 3.96; N, 18.36. Found: C, 44.26; H,
4.08; N, 18.02.
Biological Evaluation.
Effect of compounds 2a-h on the vegetative growth of
wheat and radish plant. Seeds were rinsed with sterilized
distilled water four times. All subsequent manipulations were
carried out under a horizontal laminar flow. Twenty seeds of
each species were chosen and individually placed in culture
dishes of 9cm diameter containing two pieces of filter paper and
5 mL solution of the tested compounds 2a-h (10 μg /mL and 100
μg/mL, respectively), and were incubated in a growth chamber
at 25˚C, with a 16h/8h photoperiod. The set of controls with
sterilized distilled water were simultaneously prepared. Plant
lengths were recorded on the 5th day for the treated plants and
for the set controls. Experiments were run in duplicate. The
equations of the growth regulating percentage (the stalk and the
radicel of the wheat and radish) are: {the average of sample
length (cm) – the average of the controls (cm)}/the average of
the controls (cm)*100%.
6-(4-Methylphenyl)-3-(1,2,3,4-tetrahydroxy-butan-1-yl)-
7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine (2f). This compound
was prepared from 1 and 2-bromo-4'-methyl-acetophenone and
obtained as pale yellow crystal (0.27 g, 77%), mp 172-174˚C
(from ethanol). IR(cm-1): 3257 (OH), 2970 (CH2), 1595 (C=N),
1
1519 (N=CꢀS), 694 (CꢀSꢀC). H NMR (DMSO-d6, 300MHz,
REFERENCES
ppm): 7.41-8.00 (m, 4H, Ar-H), 6.16 (br, 4H, OꢀH, disappear
upon D2O treatment), 5.22 (d, 1H, J=5.4Hz, CH2OH-CHOH-
CHOH-CHOH-), 4.41-4.59 (m, 2H, SCH2), 4.07-4.11 (m, 1H,
ꢀCH2OH-CHOH-CHOH-), 3.60-3.67 (m, 2H, CH2OH-), 3.44-
3.50 (m, 1H, CH2OH-CHOH-), 2.41(s, 3H, -CH3). 13C NMR
(DMSO-d6, 75MHz, ppm): 157.36, 154.43, 143.10, 142.44,
130.22, 129.84, 128.02, 72.73, 71.95, 66.53, 62.75, 23.10, 21.23.
MS-ESI: m/z (relative intensity, %): 351[M++1](100), 246 (1.0).
Anal. Calcd for C15H18N4O4S: C, 51.42; H, 5.18; N, 15.99.
Found: C, 51.20; H, 5.06; N, 16.22.
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upon D2O treatment), 5.21 (d, 1H, J=5.4Hz, CH2OH-CHOH-
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