Synthesis and biological activities of some Schiff's bases from 4-amino-3-(3-hydroxybutyl)-1H-1, 2, 4-triazole-5-thione

Article abstract of DOI:10.3184/030823409X435928

Sixteen novel Schiff's bases have been synthesised in high yields from 4-amino-3-(3-hydroxybutyl)-1H-1, 2, 4-triazole-5-thione. All the newly synthesised compounds have been characterised by elemental analysis, IR, ¹H NMR, ¹³C NMR an

Full text of DOI:10.3184/030823409X435928

208 RESEARCH PAPER
APRILꢇꢀꢋꢄꢌ±ꢋꢈꢈ
JOURNAL OF CHEMICAL RESEARCH 2009
Synthesis and biological activities of some Schiff's bases from
4-amino-3-(3-hydroxybutyl)-1H-1, 2, 4-triazole-5-thione
Jing Zhanga, Lixue Zhanga*, Xinxiang Leia,b, Changfeng Zhoua, Xiaodan Fua and Haile Zhangc
aCollege of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325027, P.R. China
bChengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, P.R. China
cDepartment of Molecular Biology & Chemistry, Scripps Research Institute, San Diego, CA 92037, USA
Sixteen novel Schiff's bases have been synthesised in high yields from 4-amino-3-(3-hydroxybutyl)-1H-1, 2, 4-triazole-
5-thione. All the newly synthesised compounds have been characterised by elemental analysis, IR, 1H NMR,
13C NMR and MS. Plant growth-regulating activity tests showed that most compounds have remarkable effects on
the growth of wheat and radish at a mass concentration of 50μg mL-1.
Key words: Schiff's bases, 4-amino-3-(3-hydroxybutyl)-1H-1, 2, 4-triazole-5-thione, synthesis, plant growth regulation
1, 2, 4-Triazoles and their heterocyclic derivatives have
been reported to have considerable biological activities such
as analgesic, antitubercular, anthelmintic, antifungal, plant
growth regulating, anticancer and antiviral properties.1-5 Some
Schiff's bases of 1, 2, 4-triazoles possess excellent biological
activities, which have been attracting many researchers'
attention in recent years.6-8 In continuation of our studies on
N-bridged heterocycles,9,10 we report here the synthesis and
biological activities of some Schiff's bases from 4-amino-3-
(3-hydroxybutyl)-1H-1, 2, 4-triazole-5-thione.
Almost all of the substituents at the 3-position in 1, 2, 4-
triazoles synthesised in the past were alkyl or aryl, which
led to their poor water solubility. Our group had synthesised
some 1, 2, 4-triazoles and their derivatives with an aliphatic
side chain containing hydroxyl groups at the 3-position
and improved their water solubility successfully.11-13
With all these considerations in mind, we have synthesised the
title compounds.
benzaldehydes, maintaining pH values during the reaction
DWꢀ ꢂ±ꢃꢀ EHFDXVHꢀ WKHꢀ DFLGLW\ꢀ RIꢀ WKHꢀ UHDFWLRQꢀ PHGLXPꢀ LVꢀ
crucial. In our previous research,14 we tried to add activated
molecular sieves (4Å) and keep the reaction under a nitrogen
DWPRVSKHUHꢁꢀ7KHꢀUHVXOWꢀZDVꢀHQFRXUDJLQJꢀDVꢀDꢀꢂꢄ±ꢅꢄꢆꢀ\LHOGꢀ
of the crude title products was received. The desired products
have been obtained in good yields by means of this method
DQGꢀLGHQWL¿HGꢀRQꢀWKHꢀEDVLVꢀRIꢀHOHPHQWDOꢀDQDO\VLVꢇꢀ,5ꢇꢀ1H NMR,
13C NMR and MS.
The effects of the title compounds 1, 2a–m on sprouting of
wheat and radish seeds have been investigated. After treating
ZLWKꢀ VROXWLRQVꢀ RIꢀ ꢂꢄꢀ ȝJꢀ P/-1ꢀ DQGꢀ ꢈꢄꢀ ȝJꢀ P/-1 of the title
compounds for 7 days (25°C), the germination percentages
have been determined, and from the difference in length
between stems and radicels of seedlings treated with the
title compounds and those treated only with distilled water,
the plant growth regulating activities have been calculated.
The equations of the growth regulating percentage are:
>WKHꢀ DYHUDJHꢀ RIꢀ VDPSOHꢀ OHQJWKꢀ ꢉFPꢊꢀ ±ꢀ WKHꢀ DYHUDJHꢀ RIꢀ WKHꢀ
controls (cm)]/the average of the controls (cm) u100%.
The results are presented in Table 1.
The synthesis route is outlined in Scheme 1. It is
understandable that the products (2a–p) exist in the form
of E FRQ¿JXUDWLRQꢀ EHFDXVHꢀ RIꢀ ORZꢀ HQHUJ\ꢁꢀ :Hꢀ PL[HGꢀ WKHꢀ
1, 2, 4-triazole (1) with more than 10 differently substituted
S
N
NH
O
pyridine / H2O
reflux, 4h
O
+
C
S
N
H2NHN
NHNH2
HO
N
NH2
1
NH
S
N
N
HO
RCHO, ethanol
reflux, 4h
H
2a-p
R
R:
C6H5-
p-FC6H4-
2b:
2f:
2a:
2e:
2i:
2c: p-ClC6H4-
2d: p-BrC6H4-
o-ClC6H4-
o-O2NC6H4-
o-HOC6H4-
p-O2NC6H4-
2g: m-O2NC6H4-
2h:
2l:
2k:
2o:
p-CH3OC6H4- 2 j: o-CH3OC6H4-
p-F3CC6H4-
p-HOC6H4-
m-CH3O,p-HOC6H3-
p-Me2NC6H4- 2p:
2m:
2n: p-CH3C6H4-
Scheme 1
* Correspondent. E-mail: zhanglixuelz@yahoo.com.cn

JOURNAL OF CHEMICAL RESEARCH 2009 209
Table 1 Effect of compounds 1, 2a–m on the plant growth-regulating of wheat and radish
Compounds
Concentrations
Radish
Stalk
Wheat
Stalk
(Pg mL-1)
Germ.
Radicel
Germ.
Radicel
1
50
10
50
10
50
10
50
10
50
10
50
10
50
10
50
10
50
10
50
10
50
10
50
10
50
10
50
10
####
##
#
+ + + + +
**
+ + + + +
**
+ + + + + +
**
+ + + + +
***
+ + +
******
+ + + + +
*****
+ + + + + +
****
+ + + + +
**
+ + + +
**
##
#####
###
#####
###
#####
####
#####
#####
#####
###
******
+
******
***
******
**
******
**
****
**
******
**
******
**
******
***
******
**
******
***
******
**
+
***
*****
***
******
**
******
+
******
**
******
**
******
***
***
*
******
*
******
**
******
****
******
**
******
***
******
*
+ +
***
2a
2b
2c
2d
2e
2f
##
##
###
##
###
##
##
#
+ + + + +
***
+ + + + + +
******
+ + +
+ + + + +
******
+ + + +
**
###
#
#####
#####
####
####
#####
####
#####
####
#####
####
#####
####
####
####
#####
###
###
##
###
##
##
##
###
#
*
2g
2h
2i
+ + +
+ + +
****
*****
+ + + + + +
*
+ + + + +
*
+ + + + +
**
+ + + +
**
+ + + + +
+
+ + + + +
*
+ + + + +
**
+ + + + + +
****
+ + + + +
*
+ + + + + +
*
2j
###
#
2k
2l
##
##
##
#
******
***
****
**
2m
+ + + + + +
***
+ + + + + +
*****
###
####
Germ.,“ # ” represents germination rate. #: <10%; ##: 10–30%; ###: 30–50%; ####: 50–70%; #####: 70–90%; ######: >90%.
“ * ” represents inhibition rate. *: <10%; **: 10–30%; ***: 30–50%; ****: 50–70%; *****: 70–90%; ******: >90%.
“ + ” represents promotion rate. + : <10%; + + : 10–30%; + + + : 30–50%; + + + + : 50–70%; + + + + + : 70–90%; + + + + + + : >90%.
±&+3).13CNMR(DMSO-d6ꢇꢀꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢂꢁꢐꢀꢉ1±&ꢀ ꢀ6ꢊꢇꢀꢈꢂꢋꢁꢐꢀꢉ1±
C = N), 65.5 (CH), 35.2 (CH2), 23.8 (CH2), 21.3 (CH3). MS-ESI (m/z):
189(M+ + 1), 174, 170, 156. Elemental Anal. Calcd for C6H12N4OS:
C, 38.28; H, 6.46; N, 29.76. Found: C, 38.14; H, 6.39; N, 29.68%.
From the data it is evident that most of the title compounds
have remarkable effects on the growth of wheat and radish
DWꢀ Dꢀ PDVVꢀ FRQFHQWUDWLRQꢀ RIꢀ ꢂꢄȝJꢀ P/-1. The germination
percentages of the monocotyledon (wheat) were much better
than the dicotyledon (radish) at two concentration levels. It
was interesting to note that almost all of the compounds
showed stimulative activities towards the growth of the
dicotyledon (radish) at higher concentration, but under the
same conditions it expressed inhibitory activities towards the
growth of the monocotyledon (wheat). The title compounds
show a more pronounced inhibiting effect on the growth of
wheat at higher concentration than the similar compounds our
group synthesised in the past.2,14 It is worthy of further study
to establish a relationship between structure and activity.
Synthesis of 3-(3-hydroxybutyl)-4-(substituted benzylidene) amino-
1H-1, 2, 4-triazole -5-thione (2): general procedure
An appropriate aromatic aldehyde (1.1 mmol, distilled under
reduced pressure before use) was added to a solution of compound
(1) (1.0 mmol, 188 mg) in absolute ethanol (20 mL). The pH value
ZDVꢀ DGMXVWHGꢀ WRꢀ ꢂ±ꢃꢀ ZLWKꢀ GLOXWHGꢀ +&Oꢇꢀ DQGꢀ DSSURSULDWHꢀ DFWLYDWHGꢀ
molecular sieves (4Å) were added. The mixture was stirred and
UHÀX[HGꢀ IRUꢀ ꢍꢀ Kꢀ XQGHUꢀ Dꢀ QLWURJHQꢀ DWPRVSKHUHꢁꢀ 7KHꢀ PL[WXUHꢀ ZDVꢀ
¿OWHUHGꢀWKURXJKꢀFHOLWHꢀDQGꢀZDVKHGꢀZLWKꢀHWKDQROꢁꢀ7KHꢀFUXGHꢀSURGXFWꢀ
REWDLQHGꢀ DIWHUꢀ FRQFHQWUDWLRQꢀ XQGHUꢀ UHGXFHGꢀ SUHVVXUHꢀ ZDVꢀ ¿OWHUHGꢇꢀ
dried and recrystallised from 75% ethanol. The pure products (2a–p)
were afforded.
3-(3-Hydroxybutyl)-4-(benzylidene) amino-1H-1, 2, 4-triazole-5-
thione (2aꢊꢏꢀ<HOORZꢀSRZGHUꢇꢀ\LHOGꢏꢀꢃꢅꢆꢁꢀ0ꢁSꢁꢀꢈꢃꢋ±ꢈꢃꢍꢀƒ&ꢁꢀ,5ꢀꢉFP-1):
3300 (OH, NH), 3139 (ArH), 2926 (CH3ꢊꢇꢀ ꢈꢂꢐꢃꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢂꢈꢃꢀ
ꢉ1±& 6ꢊꢇꢀ ꢈꢍꢐꢌꢀ ꢉDURPDWLFꢀ ULQJꢀ VNHOHWRQꢀ YLEUDWLRQꢊꢇꢀ ꢈꢋꢅꢎꢀ ꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢅꢃꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢐꢁꢐꢅꢀꢉVꢇꢀ
1H, CH=N), 7.91 (m, 2H, ArH), 7.60 (m, 3H, ArH), 4.51 (s, 1H,
2±+ꢊꢇꢀꢎꢁꢃꢌꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢌꢄꢀꢉWꢇ Jꢀ ꢀꢃꢁꢐꢌꢀ+]ꢇꢀꢋ+ꢇꢀ±&+2C=N),
ꢈꢁꢅꢎꢀ ꢉPꢇꢀ ꢋ+ꢇꢀ ±&+2), 1.08 (d, 3H, Jꢀ ꢀ ꢃꢁꢈꢂꢀ +]ꢇꢀ ±&+3). 13C NMR
(DMSO-d6ꢇꢀ ꢅꢂꢀ 0+]ꢇꢀ SSPꢊꢏꢀ ꢈꢃꢎꢁꢂꢀ ꢉ1±& 6ꢊꢇꢀ ꢈꢃꢈꢁꢎꢀ ꢉ3K±&+ 1ꢊꢇꢀ
ꢈꢂꢈꢁꢂꢀꢉ1±& 1ꢊꢇꢀꢈꢎꢋꢁꢃꢇꢀꢈꢎꢋꢁꢋꢇꢀꢈꢋꢐꢁꢋꢇꢀꢈꢋꢌꢁꢃꢇꢀꢃꢍꢁꢐꢀꢉ&+ꢊꢇꢀꢎꢍꢁꢌꢀꢉ&+2),
23.5 (CH2), 21.2 (CH3). MS-ESI (m/z): 277(M+ + 1), 276, 259, 174,
156. Elemental Anal. Calcd for C13H16N4OS: C, 56.50; H, 5.84; N,
20.27. Found: C, 56.31; H, 5.78; N, 20.11%.
ꢀꢁꢂꢀꢁ+\GUR[\EXW\OꢃꢁꢄꢁꢂꢄꢁÀXRUREHQ]\OLGHQHꢃDPLQRꢁꢅ+ꢁꢅꢆꢇꢈꢆꢇꢄꢁWULD]ROHꢁ
5-thione (2b): <HOORZꢀ SRZGHUꢇꢀ \LHOGꢏꢀ ꢅꢈꢆꢁꢀ 0ꢁSꢁꢀ ꢈꢍꢌ±ꢈꢂꢄꢀƒ&ꢁꢀ
IR (cm-1): 3289 (OH, NH), 2963 (ArH), 2925 (CH3ꢊꢇꢀꢈꢂꢐꢂꢀꢉ1±& 1ꢊꢇꢀ
ꢈꢂꢄꢐꢀꢉDURPDWLFꢀULQJꢀVNHOHWRQꢀYLEUDWLRQꢊꢇꢀꢈꢍꢃꢂꢀꢉ1±& 6ꢊꢇꢀꢈꢋꢎꢂꢀꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢅꢃꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢐꢁꢐꢂꢀꢉVꢇꢀ
1H, CH=N), 7.99 (dd, 2H, J1 = 3.62 Hz, J2 = 8.14 Hz, ArH), 7.42
(dd, 2H, J1 = 3.41 Hz, J2ꢀ ꢀꢌꢁꢋꢋꢀ+]ꢇꢀ$U+ꢊꢇꢀꢍꢁꢂꢎꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢃꢃꢀ
ꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢅꢅꢀꢉWꢇꢀꢋ+ꢇꢀJꢀ ꢀꢃꢁꢐꢌꢀ+]ꢇꢀ±&+2C=N), 1.72 (m, 2H,
±&+2), 1.08 (d, 3H, Jꢀ ꢀ ꢃꢁꢈꢂꢀ +]ꢇꢀ ±&+3). 13C NMR (DMSO-d6,
ꢅꢂꢀ 0+]ꢇꢀ SSPꢊꢏꢀ ꢈꢃꢋꢁꢂꢀ ꢉ1±& 6ꢊꢇꢀ ꢈꢃꢈꢁꢎꢀ ꢉ3K±&+ 1ꢊꢇꢀ ꢈꢂꢈꢁꢂꢀ ꢉ1±
C=N), 131.1, 128.9, 116.6, 116.3, 64.9 (CH), 34.7 (CH2), 23.4
(CH2), 21.2 (CH3). MS-ESI (m/z): 295(M+ + 1), 294, 277, 174, 156.
Experimental
Melting points (uncorrected) were taken on an XT-4 melting point
DSSDUDWXVꢁꢀ ,5ꢀ VSHFWUDꢀ ꢉ.%Uꢊꢀ ZHUHꢀ UHFRUGHGꢀ LQꢀ WKHꢀ ꢍꢄꢄꢄ±ꢍꢄꢄꢀ FP-1
range on a Bruker Quinox 55 spectrophotometer. The 1H NMR and
13C NMR spectra were measured at 25°C 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. Elemental analyses of carbon, hydrogen and nitrogen
were determined on a Flash-1112 series elemental analyser. All the
reagents used were AR grade.
Synthesis of 4-amino-3-(3-hydroxybutyl)-1H-1, 2, 4-triazole-5-thione
(1): general procedure
Thiocarbohydrazide was prepared by means of the method from the
literature.2 The thiocarbohydrazide (3.18 g, 30 mmol) was added
to a solution of 4-methyl-J-butyrolactone (1.89 mL, 20 mmol) in
S\ULGLQHꢀꢉꢎꢄꢀP/ꢊꢀDQGꢀZDWHUꢀꢉꢎꢀP/ꢊꢁꢀ7KHꢀPL[WXUHꢀZDVꢀUHÀX[HGꢀIRUꢀ
6 h under stirring. After concentration under reduced pressure, the
yellow crude product formed was recrystallised from alcohol to
give compound (1ꢊꢏꢀ<HOORZꢀFU\VWDOVꢇꢀ\LHOGꢏꢀꢅꢃꢆꢁꢀ0ꢁSꢁꢀꢈꢋꢎ±ꢈꢋꢂꢀƒ&ꢁꢀ
IR (cm-1): 3460 (OH), 2953 (CH3ꢊꢇꢀꢈꢃꢈꢃꢀꢉ1±& 1ꢊꢇꢀꢈꢂꢃꢂꢀꢉ1±& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢍꢄꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢂꢁꢂꢄꢀꢉVꢇꢀ
2H, -NH2ꢊꢇꢀ ꢍꢁꢂꢍꢀ ꢉVꢇꢀ ꢈ+ꢇꢀ 2±+ꢊꢇꢀ ꢎꢁꢃꢃꢀ ꢉPꢇꢀ ꢈ+ꢇꢀ ±2&+ꢊꢇꢀ ꢋꢁꢃꢌꢀ ꢉWꢇꢀ ꢋ+ꢇꢀ
Jꢀ ꢀꢅꢁꢄꢋꢀ+]ꢇꢀ±&+2& 1ꢊꢇꢀꢈꢁꢃꢅꢀꢉPꢇꢀꢋ+ꢇꢀ±&+2), 1.08 (d, 3H, J = 6.15 Hz,

210 JOURNAL OF CHEMICAL RESEARCH 2009
Elemental Anal. Calcd for C13H15FN4OS: C, 53.05; H, 5.14; N, 19.03.
Found: C, 53.28; H, 5.09; N, 18.85%.
Jꢀ ꢀꢅꢁꢄꢎꢀ+]ꢇꢀ±&+2& 1ꢊꢇꢀꢈꢁꢅꢋꢀꢉPꢇꢀꢋ+ꢇꢀ±&+2), 1.08 (d, 3H, J = 6.15 Hz,
±&+3). 13C NMR (DMSO-d6ꢇꢀꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢈꢁꢐꢀꢉ1±& 6ꢊꢇꢀꢈꢃꢄꢁꢃꢀ
ꢉ3K±&+ 1ꢊꢇꢀꢈꢂꢈꢁꢌꢀꢉ1±& 1ꢊꢇꢀꢈꢍꢐꢁꢅꢇꢀꢈꢎꢃꢁꢄꢇꢀꢈꢎꢂꢁꢍꢇꢀꢈꢎꢄꢁꢋꢇꢀꢈꢋꢌꢁꢅꢇꢀꢈꢋꢈꢁꢐꢇꢀ
64.7 (CH), 34.4 (CH2), 23.6 (CH2), 21.3 (CH3). MS-ESI (m/z): 322
(M+ + 1), 304, 275, 174, 156. Elemental Anal. Calcd for C13H15N5O3S:
C, 48.59; H, 4.70; N, 21.79. Found: C, 48.37; H, 4.75; N, 21.61%.
3-(3-Hydroxybutyl)-4-(4-methoxybenzylidene)amino-1H-1, 2, 4-
triazole-5-thione (2iꢊꢏꢀ<HOORZꢀFU\VWDOVꢇꢀ\LHOGꢏꢀꢃꢂꢆꢁꢀ0ꢁSꢁꢀꢈꢎꢃ±ꢈꢎꢌ°C.
IR (cm-1): 3276 (OH, NH), 3085 (ArH), 2942 (CH3ꢊꢇꢀꢈꢂꢐꢃꢀꢉ1±& 1ꢊꢇꢀ
ꢈꢂꢈꢌꢀꢉDURPDWLFꢀULQJꢀVNHOHWRQꢀYLEUDWLRQꢊꢇꢀꢈꢂꢈꢄꢀꢉ1±& 6ꢊꢇꢀꢈꢋꢂꢐꢀꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢃꢐꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢐꢁꢅꢎꢀꢉVꢇꢀ
1H, CH=N), 7.87 (dd, 2H, J1 = 3.68 Hz, J2 = 8.79 Hz, ArH), 7.12
(dd, 2H, J1 = 3.69 Hz, J2ꢀ ꢀꢌꢁꢅꢐꢀ+]ꢇꢀ$U+ꢊꢇꢀꢍꢁꢍꢐꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢌꢃꢀ
ꢉVꢇꢀꢎ+ꢇꢀ±2&+3ꢊꢇꢀꢎꢁꢃꢌꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢅꢂꢀꢉWꢇꢀꢋ+ꢇꢀJꢀ ꢀꢃꢁꢐꢋꢀ+]ꢇꢀ±
CH2& 1ꢊꢇꢀꢈꢁꢅꢋꢀꢉPꢇꢀꢋ+ꢇꢀ±&+2), 1.08 (d, 3H, Jꢀ ꢀꢃꢁꢈꢋꢀ+]ꢇꢀ±&+3).
13C NMR (DMSO-d6ꢇꢀꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢎꢁꢐꢀꢉ1±& 6ꢊꢇꢀꢈꢃꢋꢁꢐꢇꢀꢈꢃꢈꢁꢎꢀ
ꢉ3K±&+ 1ꢊꢇꢀꢈꢂꢈꢁꢎꢀꢉ1±& 1ꢊꢇꢀꢈꢎꢄꢁꢃꢇꢀꢈꢋꢍꢁꢃꢇꢀꢈꢈꢍꢁꢅꢇꢀꢃꢍꢁꢐꢀꢉ&+2), 55.6
(OCH3), 34.7 (CH2), 23.4 (CH), 21.3 (CH3). MS-ESI (m/z): 307 (M+
+ 1), 289, 174, 156, 134. Elemental Anal. Calcd for C14H18N4O2S: C,
54.88; H, 5.92; N, 18.29. Found: C, 54.74; H, 5.85; N, 18.13%.
3-(3-Hydroxybutyl)-4-(2-methoxybenzylidene)amino-1H-1, 2, 4-
triazole-5-thione (2jꢊꢏꢀ<HOORZꢀSRZGHUꢇꢀ\LHOGꢏꢀꢃꢋꢆꢁꢀ0ꢁSꢁꢀꢈꢂꢐ±ꢈꢃꢈ°C.
IR (cm-1): 3325 (OH, NH), 3057 (ArH), 2954 (CH3ꢊꢇꢀꢈꢃꢄꢍꢀꢉ1±& 1ꢊꢇꢀ
ꢈꢂꢈꢐꢀꢉ1±& 6ꢊꢇꢀꢈꢍꢐꢅꢀꢉDURPDWLFꢀULQJꢀVNHOHWRQꢀYLEUDWLRQꢊꢇꢀꢈꢋꢃꢈꢀꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢅꢋꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢈꢄꢁꢎꢈꢀꢉVꢇꢀ
1H, CH=N), 7.90 (m, 1H, ArH), 7.61 (m, 1H, ArH), 7.21 (m, 1H,
$U+ꢊꢇꢀꢅꢁꢈꢈꢀꢉPꢇꢀꢈ+ꢇꢀ$U+ꢊꢇꢀꢍꢁꢂꢈꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢌꢐꢀꢉVꢇꢀꢎ+ꢇꢀ±2&+3),
ꢎꢁꢃꢅꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢅꢅꢀꢉWꢇꢀꢋ+ꢇ Jꢀ ꢀꢅꢁꢄꢈꢀ+]ꢇꢀ±&+2C=N), 1.71 (m,
ꢋ+ꢇꢀ±&+2), 1.08 (d, 3H, Jꢀ ꢀꢃꢁꢈꢌꢀ+]ꢇꢀ±&+3). 13C NMR (DMSO-d6,
ꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢎꢁꢈꢀꢉ1±& 6ꢊꢇꢀꢈꢃꢄꢁꢌꢀꢉ3K±&+ 1ꢊꢇꢀꢈꢂꢃꢁꢈꢇꢀꢈꢂꢈꢁꢅꢀꢉ1±
C=N), 132.4, 131.1, 118.9, 115.9, 112.8, 65.1 (CH), 55.2 (OCH3),
34.5 (CH2), 23.6 (CH2), 21.4 (CH3). MS-ESI (m/z): 307 (M+ + 1),
289, 174, 156. Elemental Anal. Calcd for C14H18N4O2S: C, 54.88; H,
5.92; N, 18.29. Found: C, 54.69; H, 5.87; N, 18.14%.
3-(3-Hydroxybutyl)-4-(4-hydroxybenzylidene)amino-1H-1, 2, 4-
triazole-5-thione (2kꢊꢏꢀ<HOORZꢀFU\VWDOVꢇꢀ\LHOGꢏꢀꢃꢎꢆꢁꢀ0ꢁSꢁꢀꢋꢈꢍ±ꢋꢈꢃ°C.
IR (cm-1): 3144 (OH, NH), 3021 (ArH), 2951 (CH3ꢊꢇꢀꢈꢂꢌꢅꢀꢉ1±& 1ꢊꢇꢀ
ꢈꢂꢄꢐꢀꢉDURPDWLFꢀULQJꢀVNHOHWRQꢀYLEUDWLRQꢊꢇꢀꢈꢍꢐꢅꢀꢉ1±& 6ꢊꢇꢀꢈꢋꢅꢐꢀꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢃꢃꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢈꢄꢁꢎꢃꢀꢉVꢇꢀ
ꢈ+ꢇꢀ$U±2+ꢊꢇꢀꢐꢁꢂꢐꢀꢉVꢇꢀꢈ+ꢇꢀ&+ 1ꢊꢇꢀꢅꢁꢅꢂꢀꢉGGꢇꢀꢋ+ꢇ J1 = 3.69 Hz, J2
= 8.61 Hz, ArH), 6.94 (dd, 2H, J1 = 3.61 Hz, J2 = 8.61 Hz, ArH),
ꢍꢁꢍꢃꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢃꢃꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢅꢍꢀꢉWꢇꢀꢋ+ꢇꢀJ = 7.02 Hz,
±&+2& 1ꢊꢇꢀꢈꢁꢅꢈꢀꢉPꢇꢀꢋ+ꢇꢀ±&+2), 1.07 (d, 3H, Jꢀ ꢀꢃꢁꢈꢋꢀ+]ꢇꢀ±&+3).
13C NMR (DMSO-d6ꢇꢀꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢍꢁꢃꢀꢉ1±& 6ꢊꢇꢀꢈꢃꢈꢁꢅꢇꢀꢈꢃꢈꢁꢋꢀ
ꢉ3K±&+ 1ꢊꢇꢀ ꢈꢂꢈꢁꢋꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢎꢄꢁꢌꢇꢀ ꢈꢋꢎꢁꢄꢇꢀ ꢈꢈꢁꢄꢇꢀ ꢃꢍꢁꢐꢀ ꢉ&+ꢊꢇꢀ ꢎꢍꢁꢅꢀ
(CH2), 23.5 (CH2), 21.2 (CH3). MS-ESI (m/z): 293 (M+ + 1), 275,
209, 174, 156. Elemental Anal. Calcd for C13H16N4O2S: C, 53.41; H,
5.53; N, 19.16. Found: C, 53.30; H, 5.49; N, 19.33%.
3-(3-Hydroxybutyl)-4-(2-hydroxybenzylidene)amino-1H-1, 2, 4-
triazole-5-thione (2lꢊꢏꢀ<HOORZꢀSRZGHUꢇꢀ\LHOGꢏꢀꢃꢈꢆꢁꢀ0ꢁSꢁꢀꢈꢂꢂ±ꢈꢂꢅ°C.
IR (cm-1): 3106 (OH, NH), 3061 (ArH), 2946 (CH3ꢊꢇꢀꢈꢂꢐꢅꢀꢉ1±& 1ꢊꢇꢀ
ꢈꢂꢈꢃꢀꢉDURPDWLFꢀULQJꢀVNHOHWRQꢀYLEUDWLRQꢊꢇꢀꢈꢍꢌꢅꢀꢉ1±& 6ꢊꢇꢀꢈꢋꢌꢂꢀꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢅꢄꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢈꢄꢁꢍꢈꢀꢉVꢇꢀ
ꢈ+ꢇꢀ$U±2+ꢊꢇꢀꢈꢄꢁꢈꢂꢀꢉVꢇꢀꢈ+ꢇꢀ&+ 1ꢊꢇꢀꢅꢁꢌꢅꢀꢉPꢇꢀꢈ+ꢇ ArH), 7.44 (m, 1H,
ArH), 6.97 (m, 2H, $U+ꢊꢇꢀꢍꢁꢋꢄꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢃꢅꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀ
2.76 (t, 2H, Jꢀ ꢀꢃꢁꢐꢐꢀ+]ꢇꢀ±&+2& 1ꢊꢇꢀꢈꢁꢅꢋꢀꢉPꢇꢀꢋ+ꢇꢀ±&+2), 1.08 (d,
3H, Jꢀ ꢀꢃꢁꢈꢂꢀ+]ꢇꢀ±&+3). 13C NMR (DMSO-d6, 75 MHz, ppm): 161.2
ꢉ1±& 6ꢊꢇꢀꢈꢃꢄꢁꢍꢇꢀꢈꢂꢌꢁꢍꢀꢉ3K±&+ 1ꢊꢇꢀꢈꢂꢈꢁꢂꢀꢉ1±& 1ꢊꢇꢀꢈꢎꢍꢁꢋꢇꢀꢈꢋꢅꢁꢎꢇꢀ
119.6, 118.5, 116.7, 64.9 (CH), 34.7 (CH2), 23.4 (CH2), 21.3 (CH3).
MS-ESI (m/z): 293 (M+ + 1), 275, 173, 209, 174, 156. Elemental
Anal. Calcd for C13H16N4O2S: C, 53.41; H, 5.53; N, 19.16. Found: C,
53.34; H, 5.49; N, 19.03%.
ꢀꢁꢂꢀꢁ+\GUR[\EXW\OꢃꢁꢄꢁꢂꢄꢁWULÀXRURPHWK\OEHQ]\OLGHQHꢃDPLQRꢁꢅ+ꢁꢅꢆꢇ
2, 4-triazole-5- thione (2mꢊꢏꢀ<HOORZꢀSRZGHUꢇꢀ\LHOGꢏꢀꢅꢄꢆꢁꢀ0ꢁSꢁꢀꢈꢅꢋ±
173°C. IR (cm-1): 3326 (OH, NH), 3032 (ArH), 2909 (CH3), 1583
ꢉ1±& 1ꢊꢇꢀꢈꢂꢈꢎꢀꢉDURPDWLFꢀULQJꢀVNHOHWRQꢀYLEUDWLRQꢊꢇꢀꢈꢍꢐꢃꢀꢉ1±& 6ꢊꢇꢀ
ꢈꢋꢌꢎꢀ ꢉ& 6ꢊꢇꢀ ꢈꢈꢋꢍꢀ ꢉ±&)3). 1H NMR (DMSO-d6, 300 MHz, ppm):
ꢈꢎꢁꢌꢎꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢈꢄꢁꢋꢅꢀꢉVꢇꢀꢈ+ꢇꢀ&+ 1ꢊꢇꢀꢌꢁꢈꢎꢀꢉGGꢇꢀꢋ+ꢇ J1 = 3.66 Hz,
J2 = 8.16 Hz, ArH), 7.93 (dd, 2H, J1 = 3.67 Hz, J2 = 8.18 Hz,ArH), 4.42
ꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢃꢌꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢌꢈꢀꢉWꢇꢀꢋ+ꢇJꢀ ꢀꢅꢁꢄꢈꢀ+]ꢇꢀ±&+2C=N),
ꢈꢁꢅꢎꢀ ꢉPꢇꢀ ꢋ+ꢇꢀ ±&+2), 1.09 (d, 3H, Jꢀ ꢀ ꢃꢁꢈꢋꢀ +]ꢇꢀ ±&+3). 13C NMR
(DMSO-d6ꢇꢀ ꢅꢂꢀ 0+]ꢇꢀ SSPꢊꢏꢀ ꢈꢃꢈꢁꢍꢀ ꢉ1±& 6ꢊꢇꢀ ꢈꢃꢄꢁꢅꢀ ꢉ3K±&+ 1ꢊꢇꢀ
ꢈꢂꢈꢁꢌꢀꢉ1±& 1ꢊꢇꢀꢈꢎꢃꢁꢋꢇꢀꢈꢎꢋꢁꢈꢇꢀꢈꢎꢈꢁꢅꢇꢀꢈꢋꢐꢁꢈꢇꢀꢈꢋꢃꢁꢈꢉ±&)3), 64.9 (CH),
34.8 (CH2), 23.5 (CH2), 21.2 (CH3). MS-ESI (m/z): 343 (M-1), 173,
172, 170. Elemental Anal. Calcd for C14H15F3N4OS: C, 48.83; H,
4.39; N, 16.27. Found: C, 48.75; H, 4.31; N, 16.09%.
3-(3-Hydroxybutyl)-4-(4-chlorobenzylidene)amino-1H-1,2,4-triazole-
5-thione (2c): :KLWHꢀFU\VWDOVꢇꢀ\LHOGꢏꢀꢃꢌꢆꢁꢀ0ꢁSꢁꢀꢈꢅꢍ±ꢈꢅꢃ°C. IR (cm-1):
3290 (OH, NH), 2958 (ArH), 2926 (CH3ꢊꢇꢀ ꢈꢂꢐꢈꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢂꢄꢃꢀ
ꢉDURPDWLFꢀ ULQJꢀ VNHOHWRQꢀ YLEUDWLRQꢊꢇꢀ ꢈꢍꢃꢃꢀ ꢉ1±& 6ꢊꢇꢀ ꢈꢋꢂꢐꢀ ꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢅꢌꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢈꢄꢁꢄꢍꢀꢉVꢇꢀ
1H, CH=N), 7.93 (dd, 2H, J1 = 3.51 Hz, J2 = 8.62 Hz. ArH), 7.63
(dd, 2H, J1 = 3.53 Hz, J2ꢀ ꢀꢌꢁꢃꢍꢀ+]ꢇꢀ$U+ꢊꢇꢀꢍꢁꢍꢐꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢃꢃꢀ
ꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢅꢌꢀꢉWꢇꢀꢋ+ꢇꢀJꢀ ꢀꢅꢁꢄꢈꢀ+]ꢇꢀ±&+2C=N), 1.72 (m, 2H,
±&+2), 1.08 (d, 3H, Jꢀ ꢀꢃꢁꢈꢂꢀ+]ꢇꢀ±&+3). 13C NMR (DMSO-d6, 75
0+]ꢇꢀ SSPꢊꢏꢀ ꢈꢃꢈꢁꢐꢀ ꢉ1±& 6ꢊꢇꢀ ꢈꢃꢈꢁꢎꢀ ꢉ3K±&+ 1ꢊꢇꢀ ꢈꢂꢈꢁꢃꢀ ꢉ1±& 1ꢊꢇꢀ
137.3, 131.2, 130.2, 129.4, 64.9 (CH), 34.7 (CH2), 23.5 (CH2), 21.2
(CH3). MS-ESI (m/z): 311 (M+ + 1), 293, 282, 174, 156. Elemental
Anal. Calcd for C13H15ClN4OS: C, 50.24; H, 4.86; N, 18.03. Found:
C, 50.17; H, 4.81; N, 17.95%.
3-(3-Hydroxybutyl)-4-(4-bromobenzylidene)amino-1H-1,2,4-triazole-
5-thione (2dꢊꢏꢀ <HOORZꢀ FU\VWDOVꢇꢀ \LHOGꢏꢀ ꢃꢅꢆꢁꢀ 0ꢁSꢁꢀ ꢈꢂꢍ±ꢈꢂꢃ°C.
IR (cm-1): 3288 (OH, NH), 3041 (ArH), 2926 (CH3ꢊꢇꢀꢈꢂꢌꢅꢀꢉ1±& 1ꢊꢇꢀ
ꢈꢂꢈꢈꢀꢉDURPDWLFꢀULQJꢀVNHOHWRQꢀYLEUDWLRQꢊꢇꢀꢈꢍꢌꢃꢀꢉ1±& 6ꢊꢇꢀꢈꢋꢅꢂꢀꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢅꢌꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢈꢄꢁꢄꢍꢀꢉVꢇꢀ
1H, CH=N), 7.85 (dd, 2H, J1 = 3.43 Hz, J2 = 8.49 Hz, ArH), 7.78
(dd, 2H, J1 = 3.48 Hz, J2ꢀ ꢀꢌꢁꢂꢃꢀ+]ꢇꢀ$U+ꢊꢇꢀꢍꢁꢍꢌꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢃꢅꢀ
ꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢅꢐꢀꢉWꢇꢀꢋ+ꢇꢀJꢀ ꢀꢃꢁꢐꢐꢀ+]ꢇꢀ±&+2C=N), 1.71 (m, 2H,
±&+2), 1.08 (d, 3H, Jꢀ ꢀꢃꢁꢈꢂꢀ+]ꢇꢀ±&+3). 13C NMR (DMSO-d6, 75
0+]ꢇꢀ SSPꢊꢏꢀ ꢈꢃꢋꢁꢎꢀ ꢉ1±& 6ꢊꢇꢀ ꢈꢃꢈꢁꢅꢀ ꢉ3K±&+ 1ꢊꢇꢀ ꢈꢂꢋꢁꢄꢀ ꢉ1±& 1ꢊꢇꢀ
132.7, 131.9, 130.8, 126.7, 65.3 (CH), 35.1 (CH2), 23.9 (CH2), 21.6
(CH3). MS-ESI (m/z): 353 (M-1), 172, 170. Elemental Anal. Calcd
for C13H15BrN4OS: C, 43.95; H, 4.25; N, 15.77. Found: C, 49.87; H,
4.18; N, 15.69%.
3-(3-Hydroxybutyl)-4-(2-chlorobenzylidene)amino-1H-1,2,4-triazole-
5-thione (2e): <HOORZꢀSRZGHUꢇꢀ\LHOGꢏꢀꢃꢂꢆꢁꢀ0ꢁSꢁꢀꢈꢂꢎ±ꢈꢂꢂ°C. IR (cm-1):
3306 (OH, NH), 3046 (ArH), 2937 (CH3ꢊꢇꢀ ꢈꢂꢌꢂꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢂꢈꢄꢀ
ꢉDURPDWLFꢀ ULQJꢀ VNHOHWRQꢀ YLEUDWLRQꢊꢇꢀ ꢈꢍꢐꢍꢀ ꢉ1±& 6ꢊꢇꢀ ꢈꢋꢅꢅꢀ ꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢌꢎꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢈꢄꢁꢌꢎꢀꢉVꢇꢀ
1H, CH=N), 8.16 (d, 1H, J = 7.62 Hz, ArH), 7.65 (m, 2H, ArH), 7.54
ꢉPꢇꢀꢈ+ꢇꢀ$U+ꢊꢇꢀꢍꢁꢍꢐꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢃꢐꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢌꢎꢀꢉWꢇꢀꢋ+ꢇ
Jꢀ ꢀꢅꢁꢄꢂꢀ+]ꢇꢀ±&+2& 1ꢊꢇꢀꢈꢁꢅꢍꢀꢉPꢇꢀꢋ+ꢇꢀ±&+2), 1.09 (d, 3H, J = 6.15
+]ꢇꢀ±&+3). 13C NMR (DMSO-d6ꢇꢀꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢈꢁꢋꢀꢉ1±& 6ꢊꢇꢀ
ꢈꢂꢃꢁꢂꢀ ꢉ3K±&+ 1ꢊꢇꢀ ꢈꢂꢋꢁꢄꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢎꢂꢁꢈꢇꢀ ꢈꢎꢎꢁꢐꢇꢀ ꢈꢎꢄꢁꢎꢇꢀ ꢈꢎꢄꢁꢈꢇꢀ
127.9, 127.5, 65.0 (CH), 34.8 (CH2), 23.5 (CH2), 21.2 (CH3). MS-
ESI (m/z): 311 (M+ + 1), 293, 282, 174, 156. Elemental Anal. Calcd
for C13H15ClN4OS: C, 50.24; H, 4.86; N, 18.03. Found: C, 50.11; H,
4.77; N, 17.90%.
3-(3-Hydroxybutyl)-4-(4-nitrobenzylidene)amino-1H-1,2,4-triazole-
5-thione (2fꢊꢏꢀ<HOORZꢀSRZGHUꢇꢀ\LHOGꢏꢀꢅꢈꢆꢁꢀ0ꢁSꢁꢀꢈꢌꢌ±ꢈꢌꢐ°C. IR (cm-1):
3332 (OH, NH), 3139 (ArH), 2946 (CH3ꢊꢇꢀ ꢈꢂꢐꢋꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢂꢈꢐꢀ
ꢉDURPDWLFꢀULQJꢀVNHOHWRQꢀYLEUDWLRQꢊꢇꢀꢈꢂꢈꢋꢀꢉ1±& 6ꢊꢇꢀꢈꢎꢍꢍꢀꢉ122), 1275
(C=S). 1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢌꢃꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀ
10.38 (s, 1H, CH=N), 8.38 (dd, 2H, J1 = 3.62 Hz, J2 = 8.73 Hz, ArH),
8.18 (dd, 2H, J1 = 3.64 Hz, J2ꢀ ꢀꢌꢁꢅꢐꢀ+]ꢇꢀ$U+ꢊꢇꢀꢍꢁꢂꢃꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀ
ꢎꢁꢃꢐꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢌꢎꢀꢉWꢇꢀꢋ+ꢇꢀJꢀ ꢀꢅꢁꢄꢋꢀ+]ꢇꢀ±&+2C=N), 1.74 (m,
ꢋ+ꢇꢀ±&+2), 1.08 (d, 3H, Jꢀ ꢀꢃꢁꢈꢂꢀ+]ꢇꢀ±&+3). 13C NMR (DMSO-d6,
ꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢈꢁꢌꢀꢉ1±& 6ꢊꢇꢀꢈꢂꢐꢁꢐꢀꢉ3K±&+ 1ꢊꢇꢀꢈꢂꢋꢁꢎꢀꢉ1±& 1ꢊꢇꢀ
149.9, 138.7, 130.0, 124.7, 65.4 (CH), 35.2 (CH2), 23.9 (CH2), 21.6
(CH3). MS-ESI (m/z): 320 (M-1), 284, 256, 173. Elemental Anal.
Calcd for C13H15N5O3S: C, 48.59; H, 4.70; N, 21.79. Found: C,
48.47; H, 4.61; N, 21.53%.
3-(3-Hydroxybutyl)-4-(3-nitrobenzylidene)amino-1H-1,2,4-triazole-
5-thione (2gꢊꢏꢀ<HOORZꢀSRZGHUꢇꢀ\LHOGꢏꢀꢃꢐꢆꢁꢀ0ꢁSꢁꢀꢈꢃꢄ±ꢈꢃꢋ°C. IR (cm-1):
3317 (OH, NH), 3113 (ArH), 2954 (CH3ꢊꢇꢀ ꢈꢂꢌꢅꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢂꢈꢋꢀ
ꢉDURPDWLFꢀULQJꢀVNHOHWRQꢀYLEUDWLRQꢊꢇꢀꢈꢂꢋꢐꢀꢉ1±& 6ꢊꢇꢀꢈꢎꢍꢃꢀꢉ122), 1276
(C=S). 1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢌꢍꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀ
10.30 (s, 1H, CH=N), 8.70 (s, 1H, ArH), 8.69 (m, 1H, ArH), 8.34 (m,
ꢈ+ꢇꢀ$U+ꢊꢇꢀꢅꢁꢌꢃꢀꢉWꢇꢀꢈ+ꢇꢀ$U+ꢊꢇꢀꢍꢁꢂꢈꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢅꢄꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀ
2.82 (t, 2H, Jꢀ ꢀꢃꢁꢐꢌꢀ+]ꢇꢀ±&+2& 1ꢊꢇꢀꢈꢁꢅꢍꢀꢉPꢇꢀꢋ+ꢇꢀ±&+2), 1.09 (d,
3H, Jꢀ ꢀꢃꢁꢈꢂꢀ+]ꢇꢀ±&+3). 13C NMR (DMSO-d6, 75 MHz, ppm): 161.4
ꢉ1±& 6ꢊꢇꢀꢈꢃꢄꢁꢎꢀꢉ3K±&+ 1ꢊꢇꢀꢈꢂꢈꢁꢅꢀꢉ1±& 1ꢊꢇꢀꢈꢍꢌꢁꢍꢇꢀꢈꢎꢍꢁꢂꢇꢀꢈꢎꢍꢁꢄꢇꢀ
130.9, 126.7, 122.6, 64.9 (CH), 34.8 (CH2), 23.5 (CH2), 21.2 (CH3).
MS-ESI (m/z): 322 (M+ + 1), 304, 275, 156. Elemental Anal. Calcd
for C13H15N5O3S: C, 48.59; H, 4.70; N, 21.79. Found: C, 48.38; H,
4.77; N, 21.68%.
3-(3-Hydroxybutyl)-4-(2-nitrobenzylidene)amino-1H-1, 2, 4-triazole-
5-thione (2hꢊꢏꢀ <HOORZꢀ SRZGHUꢇꢀ \LHOGꢏꢀ ꢃꢅꢆꢁꢀ 0ꢁSꢁꢀ ꢈꢅꢎ±ꢈꢅꢂ°C.
IR (cm-1): 3328 (OH, NH), 3121 (ArH), 2943 (CH3ꢊꢇꢀ ꢈꢂꢅꢃꢀ ꢉ1±
& 1ꢊꢇꢀ ꢈꢂꢈꢎꢀ ꢉDURPDWLFꢀ ULQJꢀ VNHOHWRQꢀ YLEUDWLRQꢊꢇꢀ ꢈꢍꢐꢐꢀ ꢉ1±& 6ꢊꢇꢀ
1349 (NO2), 1281 (C=S). 1H NMR (DMSO-d6, 300 MHz, ppm):
ꢈꢎꢁꢌꢂꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢈꢄꢁꢌꢌꢀꢉVꢇꢀꢈ+ꢇꢀ&+ 1ꢊꢇꢀꢌꢁꢈꢌꢀꢉPꢇꢀꢋ+ꢇ ArH), 7.89
ꢉPꢇꢀꢋ+ꢇꢀ$U+ꢊꢇꢀꢍꢁꢍꢅꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢃꢌꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢌꢄꢀꢉWꢇꢀꢋ+ꢇ

JOURNAL OF CHEMICAL RESEARCH 2009 211
Biological evaluation
3-(3-Hydroxybutyl)-4-(4-methylbenzylidene)amino-1H-1, 2, 4-
triazole-5-thione (2nꢊꢏꢀ<HOORZꢀFU\VWDOVꢇꢀ\LHOGꢏꢀꢃꢋꢆꢁꢀ0ꢁSꢁꢀꢈꢃꢂ±ꢈꢃꢅꢀƒ&ꢁꢀ
IR (cm-1): 3299 (OH, NH), 2921 (CH3ꢊꢇꢀ ꢈꢂꢐꢅꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢍꢐꢄꢀ
ꢉDURPDWLFꢀ ULQJꢀ VNHOHWRQꢀ YLEUDWLRQꢊꢇꢀ ꢈꢍꢃꢎꢀ ꢉ1±& 6ꢊꢇꢀ ꢈꢋꢃꢋꢀ ꢉ& 6ꢊꢁꢀ
1H NMR (DMSO-d6ꢇꢀꢎꢄꢄꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢎꢁꢅꢎꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢐꢁꢌꢅꢀꢉVꢇꢀ
1H, CH=N), 7.79 (dd, 2H, J1 = 3.67 Hz, J2 = 8.07 Hz, ArH), 7.38
(dd, 2H, J1 = 3.62 Hz, J2ꢀ ꢀꢌꢁꢄꢅꢀ+]ꢇꢀ$U+ꢊꢇꢀꢍꢁꢎꢌꢀꢉVꢇꢀꢈ+ꢇꢀ2±+ꢊꢇꢀꢎꢁꢃꢌꢀ
ꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢅꢅꢀꢉWꢇꢀꢋ+ꢇꢀJꢀ ꢀꢅꢁꢄꢋꢀ+]ꢇꢀ±&+2C=N), 2.40 (s, 3H,
$U±&+3ꢊꢇꢀ ꢈꢁꢅꢈꢀ ꢉPꢇꢀ ꢋ+ꢇꢀ ±&+2), 1.08 (d, 3H, Jꢀ ꢀ ꢃꢁꢈꢂꢀ +]ꢇꢀ ±&+3).
13C NMR (DMSO-d6ꢇꢀꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢎꢁꢅꢀꢉ1±& 6ꢊꢇꢀꢈꢃꢈꢁꢎꢀꢉ3K±
&+ 1ꢊꢇꢀꢈꢂꢈꢁꢂꢀꢉ1±& 1ꢊꢇꢀꢈꢍꢋꢁꢐꢇꢀꢈꢋꢐꢁꢌꢇꢀꢈꢋꢐꢁꢂꢇꢀꢈꢋꢌꢁꢃꢇꢀꢃꢍꢁꢐꢀꢉ&+ꢊꢇꢀꢎꢍꢁꢅꢀ
(CH2), 23.5 (CH2), 21.3 (CH3), 21.2(CH3). MS-ESI (m/z): 291 (M+ +
1), 273, 174, 156. Elemental Anal. Calcd for C14H18N4OS: C, 57.91;
H, 6.25; N, 19.29. Found: C, 57.79; H, 6.17; N, 19.06%.
Similar seeds were picked out and rinsed with sterilised distilled
water four times, then dipped in distilled water for 3 hours at room
temperature. All subsequent manipulations were carried out under a
KRUL]RQWDOꢀODPLQDUꢀÀRZꢁꢀ7ZHQW\ꢀVHHGVꢀRIꢀHDFKꢀVSHFLHVꢀZHUHꢀFKRVHQꢀ
and placed individually in Petri dishes of 9 cm diameter containing
WZRꢀSLHFHVꢀRIꢀ¿OWHUꢀSDSHUꢀDQGꢀꢂꢀP/ꢀVROXWLRQꢀRIꢀWKHꢀWHVWHGꢀFRPSRXQGVꢀ
1, 2a–m or the blank, and all of them were incubated in a growth
chamber at 25°C, with a natural photoperiod and an uninterrupted
supply of sterilised distilled water. Experiments were run in duplicate.
Growth measurements were carried out after 7 days.
7KLVꢀ ZRUNꢀ ZDVꢀ ¿QDQFLDOO\ꢀ VXSSRUWHGꢀ E\ꢀ WKHꢀ 1DWXUDOꢀ 6FLHQFHꢀ
Foundation of Zhejiang Province, China (Project No. M203149).
3-(3-Hydroxybutyl)-4-(4-N, N-dimethylaminobenzylidene)amino-
1H-1, 2, 4-triazole-5- thione (2o): Light yellow powder, yield: 59%.
0ꢁSꢁꢀ ꢈꢌꢋ±ꢈꢌꢍꢀƒ&ꢁꢀ ,5ꢀ ꢉFP-1): 3324 (OH, NH), 3096 (ArH), 2912
(CH3ꢊꢇꢀ ꢈꢂꢐꢍꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢍꢐꢃꢀ ꢉDURPDWLFꢀ ULQJꢀ VNHOHWRQꢀ YLEUDWLRQꢊꢇꢀ
ꢈꢍꢐꢋꢀꢉ1±& 6ꢊꢇꢀꢈꢋꢌꢎꢀꢉ& 6ꢊꢁꢀ1H NMR (DMSO-d6, 300 MHz, ppm):
ꢈꢎꢁꢂꢐꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢐꢁꢎꢐꢀꢉVꢇꢀꢈ+ꢇꢀ&+ 1ꢊꢇꢀꢅꢁꢅꢄꢀꢉGGꢇꢀꢋ+ꢇ J1 = 3.69 Hz,
J2 = 8.79 Hz, ArH), 6.82 (dd, 2H, J1 = 3.66 Hz, J2 = 8.79 Hz, ArH),
ꢎꢁꢃꢃꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢎꢁꢄꢎꢀꢉVꢇꢀꢃ+ꢇꢀ1&+3), 2.72 (t, 2H, J = 6.98 Hz,
±&+2& 1ꢊꢇꢀꢈꢁꢅꢈꢀꢉPꢇꢀꢋ+ꢇꢀ±&+2), 1.09 (d, 3H, Jꢀ ꢀꢃꢁꢈꢂꢀ+]ꢇꢀ±&+3).
13C NMR (DMSO-d6ꢇꢀꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢂꢁꢋꢀꢉ1±& 6ꢊꢇꢀꢈꢃꢈꢁꢎꢀꢉ3K±
&+ 1ꢊꢇꢀꢈꢂꢎꢁꢋꢇꢀꢈꢂꢈꢁꢋꢀꢉ1±& 1ꢊꢇꢀꢈꢎꢄꢁꢍꢇꢀꢈꢈꢌꢁꢌꢇꢀꢈꢈꢈꢁꢃꢇꢀꢃꢂꢁꢄꢀꢉ&+ꢊꢇꢀꢎꢐꢁꢌꢀ
(NCH3), 34.8 (CH2), 23.4 (CH2), 21.3 (CH3). MS-ESI (m/z): 320 (M+
+ 1), 174, 156, 147, 146. Elemental Anal. Calcd for C15H21N5OS: C,
56.40; H, 6.63; N, 21.92. Found: C, 56.28; H, 6.59; N, 21.78%.
3-(3-Hydroxybutyl)-4-(3-methoxy-4-hydroxybenzylidene)amino-
1H-1, 2, 4-triazole- 5-thione (2p): Yellow powder, yield: 63%.
0ꢁSꢁꢀ ꢈꢌꢈ±ꢈꢌꢎꢀƒ&ꢁꢀ ,5ꢀ ꢉFP-1): 3388 (OH, NH), 3104 (ArH), 2944
(CH3ꢊꢇꢀ ꢈꢂꢌꢅꢀ ꢉ1±& 1ꢊꢇꢀ ꢈꢂꢄꢅꢀ ꢉDURPDWLFꢀ ULQJꢀ VNHOHWRQꢀ YLEUDWLRQꢊꢇꢀ
ꢈꢍꢐꢅꢀꢉ1±& 6ꢊꢇꢀꢈꢋꢌꢋꢀꢉ& 6ꢊꢁꢀ1H NMR (DMSO-d6, 300 MHz, ppm):
ꢈꢎꢁꢃꢅꢀꢉVꢇꢀꢈ+ꢇꢀ1±+ꢊꢇꢀꢈꢄꢁꢄꢈꢀꢉ$U±2+ꢊꢇꢀꢐꢁꢂꢐꢀꢉVꢇꢀꢈ+ꢇꢀ&+ 1ꢊꢇꢀꢅꢁꢍꢌꢀꢉVꢇꢀ
1H, $U+ꢊꢇꢀꢅꢁꢎꢎꢀꢉPꢇꢀꢈ+ꢇꢀ$U+ꢊꢇꢀꢃꢁꢐꢎꢀꢉPꢇꢀꢈ+ꢇꢀ$U+ꢊꢇꢀꢍꢁꢂꢂꢀꢉVꢇꢀꢈ+ꢇꢀ±2+ꢊꢇꢀ
ꢎꢁꢌꢂꢀꢉVꢇꢀꢎ+ꢇꢀ±2&+3ꢊꢇꢀꢎꢁꢃꢅꢀꢉPꢇꢀꢈ+ꢇꢀ±2&+ꢊꢇꢀꢋꢁꢅꢃꢀꢉWꢇꢀꢋ+ꢇꢀJ = 6.99 Hz,
±&+2& 1ꢊꢇꢀꢈꢁꢅꢋꢀꢉPꢇꢀꢋ+ꢇꢀ±&+2), 1.08 (d, 3H, Jꢀ ꢀꢃꢁꢈꢌꢀ+]ꢇꢀ±&+3).
13C NMR (DMSO-d6ꢇꢀꢅꢂꢀ0+]ꢇꢀSSPꢊꢏꢀꢈꢃꢍꢁꢃꢀꢉ1±& 6ꢊꢇꢀꢈꢃꢈꢁꢎꢀꢉ3K±
&+ 1ꢊꢇꢀꢈꢂꢈꢁꢍꢇꢀꢈꢂꢈꢁꢈꢀꢉ1±& 1ꢊꢇꢀꢈꢍꢌꢁꢋꢇꢀꢈꢋꢍꢁꢎꢇꢀꢈꢋꢎꢁꢍꢇꢀꢈꢈꢂꢁꢅꢇꢀꢈꢈꢄꢁꢂꢇꢀ
64.9 (CH), 55.7 (OCH3), 34.8 (CH2), 23.5 (CH2), 21.3 (CH3). MS-
ESI (m/z): 323 (M+ + 1), 305, 174, 156, 150. Elemental Anal. Calcd
for C14H18N4O3S: C, 52.16; H, 5.63; N, 17.38. Found: C, 51.99; H,
5.56; N, 17.26%.
Received 22 November 2008; accepted 10 January 2009
Paper 08/0303 doi: 10.3184/030823409X435928
Published online: 21 April 2009
References
1
2
3
B.S. Holla, B. Veerendra, M.K. Shivananda and B. Poojary, Eur. J. Med.
Chem., 2003, 38, 759.
J.Y. Jin, L.X. Zhang, A.J. Zhang, X.X. Lei and J.H. Zhu, Molecules, 2007,
12, 1596.
B.S. Holla, B.S. Rao, K. Shridhara and P.M. Akberali, IL Farmaco, 2000,
55, 338.
4
5
V.K. Chaha, N.S. Ranwa and P.K. Dadheech, J. Phytol. Res., 1998, 11, 201.
M. Sakata, Y. Shirakawa, N. Kamata, Y.S. Hiroshino and O.Y. Jie,
J. Heterocycl. Chem., 2000, 18, 269.
6
7
B.S. Holla, P.M. Akberali and M.K. Shivananda, IL Farmaco., 2001, 56, 919.
X.P. Hui, Y. Zhang, P.F. Xu, Q. Wang, Q. Zhang and Z.Y. Zhang, Chin. J.
Org. Chem (in Chinese)., 2005, 25, 700.
8
9
B.S. Holla, B.S. Rao, B.K. Sarojini, P.M. Akberali and N.S. Kumari, Eur.
J. Med. Chem., 2006, 41, 657.
L.X. Zhang, A.J. Zhang, X.X. Chen, X.X. Lei, X.Y. Nan, D.Y. Chen and
Z.Y. Zhang, Molecules, 2002, 7, 681.
10 X.X. Lei, L.X. Zhang, A.J. Zhang, X.X. Ye and J. Xiong, Magn. Reson.
Chem., 2007, 45, 265.
11 X.X. Ye, Z.F. Chen, A.J. Zhang and L.X. Zhang, J. Chem. Res., 2007, 244.
12 A.J. Zhang, L.X. Zhang and X.X. Lei, Magn. Reson. Chem., 2006, 44, 813.
13 X.X. Ye, J. Zhang, A.J. Zhang and L.X. Zhang, J. Heterocycl. Chem.,
2008, 45, 987.
14 X.X. Ye, Z.F. Chen, A.J. Zhang and L.X. Zhang, Molecules, 2007, 12,
1202.