Synthesis of new surfactants mono and bipolar derived from 1,2,4-triazole-5-thione

Article abstract of DOI:10.1081/SCC-200036625

3-Phenyl-1,2,4-triazole-5-thione (PTS) and 3-methyl-1,2,4-triazole-5-thione (MTS) are prepared in two steps. The first is a condensation of the thiosemicarbazide with the benzoyl chloride and the acetyl chloride for the PTS and MTS respectively in pyridinic medium. This step leads to the formation of 1-benzoylthiosemicarbazide and 1-acetylthiosemicarbazide. The 1-acetylthiosemicarbazide is also prepared with a new method consisted of a simple solvolysis the thiosemicarbazide in acetic acid for 4 hr. The second is the intramolecular cyclization in methanol with the presence of the sodium methalate leads to the formation of the PTS and the MTS in good yields. The alkylation of MTS and PTS under the conditions of solid-liquid phase transfer catalysis (PTC) allowed us to synthesize some new mono and bipolar surfactants compounds derived from 1,2,4-triazole-5-thione in good yields.

Full text of DOI:10.1081/SCC-200036625

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Synthesis of New Surfactants
Mono and Bipolar Derived
from 1,2,4‐Triazole‐5‐thione
Driss Chebabe a , Ahmed Dermaj a , Zine El
Abidine Ait Chikh a , Najat Hajjaji a , Isabelle
Rico‐Lattes b & Armand Lattes b
a Laboratoire de Synthèse Organique et Réactivité,
Département de Chimie, Faculté des Sciences, BP
133, 14000, Kénitra, Maroc
b Laboratoire des IMRCP, UA 470 CNRS, Université
Paul Sabatier, Toulouse, France
Version of record first published: 12 Jan 2011
To cite this article: Driss Chebabe, Ahmed Dermaj, Zine El Abidine Ait Chikh, Najat
Hajjaji, Isabelle Rico‐Lattes & Armand Lattes (2004): Synthesis of New Surfactants
Mono and Bipolar Derived from 1,2,4‐Triazole‐5‐thione, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry,
34:22, 4189-4198
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 22, pp. 4189–4198, 2004
Synthesis of New Surfactants Mono
and Bipolar Derived from
1,2,4-Triazole-5-thione
1
Driss Chebabe,1, Ahmed Dermaj,
*
Zine El Abidine Ait Chikh,1 Najat Hajjaji,1
Isabelle Rico-Lattes,2 and Armand Lattes2
1
` ´ ´
Laboratoire de Synthese Organique et Reactivite,
´ ´ ´
Departement de Chimie, Faculte des Sciences, Kenitra, Maroc
2
´
Laboratoire des IMRCP, UA 470 CNRS, Universite
Paul Sabatier, Toulouse, France
ABSTRACT
3-Phenyl-1,2,4-triazole-5-thione (PTS) and 3-methyl-1,2,4-triazole-
5-thione (MTS) are prepared in two steps. The first is a condensation of
the thiosemicarbazide with the benzoyl chloride and the acetyl chloride
for the PTS and MTS respectively in pyridinic medium. This step leads
to the formation of 1-benzoylthiosemicarbazide and 1-acetylthiosemi-
carbazide. The 1-acetylthiosemicarbazide is also prepared with a new
method consisted of a simple solvolysis the thiosemicarbazide in acetic
*
` ´ ´
Correspondence: Driss Chebabe, Laboratoire de Synthese Organique et Reactivite,
´ ´ ´
Departement de Chimie, Faculte des Sciences, BP 133, 14000 Kenitra, Maroc;
E-mail: d_chebabe@hotmail.com.
4189
DOI: 10.1081/SCC-200036625
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

4190
Chebabe et al.
acid for 4 hr. The second is the intramolecular cyclization in methanol
with the presence of the sodium methalate leads to the formation of the
PTS and the MTS in good yields. The alkylation of MTS and PTS under
the conditions of solid–liquid phase transfer catalysis (PTC) allowed us
to synthesize some new mono and bipolar surfactants compounds
derived from 1,2,4-triazole-5-thione in good yields.
Key Words: 1,2,4-Triazole-5-thione; Intramolecular cyclization;
Alkylation; PTC; Surfactant.
INTRODUCTION
Heterocyclic compounds present various applications especially in
pharmacology[1–3] and metal surface treatments.[4] Many studies have
shown that triazole derivatives have useful corrosion inhibition effects.[5–8]
In our laboratory we have shown that 3-methyl-1,2,4-triazole-5-thione (1)
and 3-phenyl-1,2,4-triazole-5-thione (2) were found to have a marked inhibit-
ing effect of brass corrosion in the neutral medium.[9,10]
Because 1,2,4-triazole-5-thione surfactants monopolar, bipolar and
bicatenar are interesting from synthetic and applied points of view; we devel-
oped a method to prepare new triazole derivatives of general formula
(Scheme 1).
RESULTS AND DISCUSSION
This study describes the synthesis of monopolar, bipolar, and bicatenar
surfactants of 1,2,4-triazole-5-thione derivatives.
1,2,4-Triazole-5-thione is not commercially available so we prepared it
by using Jones’s method described elswhere,[11] as shown in Scheme 2.
The yields were about 60%. The special conditions for this reaction are
presented in the experimental section.
In our laboratory, we developed a new method of synthesis of the 1-acet-
ylthiosemicarbazide by heating thiosemicarbazide and acetic acid during 4 hr
(Scheme 3).
The intramolecular cyclization in ethanol and in the presence of sodium
leads to the formation of the MTS in 80%.
Our method appears very interesting compared to the one described in the
literature.[11] In fact it is a soft and short method.
The products 1 and 2 have been purified and characterized by infrared
1
(IR), H NMR, and 13C NMR spectra.

Synthesis of New Surfactants
4191
Scheme 1. Synthetic compounds.
To investigate chemical behavior of compounds 1 and 2, they were
reacted with some alkyl bromide using PTC method, which gave isolated
monopolar surfactants (1a, 1b, 1c, and 1d) and (2a, 2b, 2c, and 2d) respect-
ively. The examination of the 1H NMR and 13C NMR spectra of the
products showed formation of the monopolar surfactants derived from
1,2,4-triazole-5- thione.
The compounds 1a–c have been found as corrosion inhibitor of carbon
steel in acidic medium.[12] We have shown that compound 1c was the best
inhibitor and its efficiency increases with increasing immersion time.
Furthermore, it was interesting to examine the behavior of compounds 1
and 2 with some 1,n-dibromoalkane, which leads to give the bis alkylation
form 1e and 1f in good yield. These compounds obtained were identified by
1H NMR, IR, mass spectra, and microanalysis data.
It is remarkable that the NH group in 3-methylalkylthio-1,2,4,-triazole
can be alkylated. To obtain a bicatenar surfactant compound, we have
reacted 1d with n-dodecylbromide in DMF using PTC solid-liquid

4192
Chebabe et al.
Scheme 2. Synthetic method to obtain the compounds 1 and 2.
method for 24 hr leads to a mixture of two isomerization products 1g
(50%) and 1h (50%) in accord with usual 1,3-hydrogen transfer in the
1,2,4-triazole derivatives. Paper chromatography was tried with various sol-
vents, and the best results were obtained with n-hexane–ethylacetate
mixtures (80 : 20), the Rf values are R1g ¼ 0,77 and R1h ¼ 0,56. The struc-
1
tures of the products have been characterized by H NMR, 13C NMR, and
mass spectra. All the synthesized surfactants compounds are summarized in
Scheme 4.
The correct structures assignment of 1g and 1h were made especially by
1
analysis of 13C NMR spectra. On the basis of the H NMR data, one cannot
distinguish between these isomers. on the other hand the analysis of their
13C NMR spectra shows that the one of the compound 1g presents two
signals to 11.91 ppm and to 14.19 ppm correspondent to the methyl groups,
whereas one of the compound 1h presents only one signal to 14.1 ppm corres-
pondent to the three methyl groups. It can be interpreted by steric effect caused
by the presence of the alkyl chain close to the methyl group in position 3 of the
cycle. To confirm these two structures, the mass spectra under electronic impact
reveals the presence of a peak at m/z ¼ 224 in the spectra assigned to the
compound 1g which corresponds to the CH3–C ¼ Nþ–N–(CH2)11–CH3
Scheme 3. Synthetic method to obtain 1-acetylthiosemicarbazide.

Synthesis of New Surfactants
4193
Scheme 4. Synthetic method to obtain the compounds 1a–d, 2a–d, and 1e–h
.
fragment. The non-existence of this fragment in the structure 1h confirms the
results gotten on the basis of the 13C NMR spectra.
EXPERIMENTAL
1. Melting point: Melting points (MP) were obtained on a Kofler
Prolabo apparatus.
2. Nuclear magnetic resonance (NMR): 1H NMR spectra were recorded
on a Varian EM 360 at 60 MHz with TMS as internal standard.
13C NMR data were recorded at 75.469 MHz by using a Bruker AC
200 WB spectrophotometer. In the description of spectra, letters m,
s, and t mean, respectively, multiplet, singulet and triplet.
3. IR Spectra: Perkin–Elmer 577 spectrometer was used to record
IR spectra.
4. Mass spectra were recorded on a Nermag R10-10 instrument:
Chemical Ionization (DCI/NH3).
5. All columns chromatography were carried out by using merck of
silica gel 60 (0.063–0.200 mm)

4194
Chebabe et al.
GENERAL METHOD TO OBTAIN
1,2,4-TRIAZOLE-5-THIONE (1, 2)
1-Alkyl (ou 1-aryl) Thiosemicarbazide
a) Our method (R ¼ CH3)
Twenty milliliters of acetic acid, which contained 4.55 g (50 mmol) of
colorless thiosemicarbazide was refluxed on a steam bath for 4 hr. The acetic
acid was removed by evaporation. The 1-acetylhiosemicarbazide was obtained
1
and recrystallized from water (yield, 70%), H NMR (200 MHz, DMSO d6)
d: 9.72(s,H); 9.16(s,H); 7.84(s,H); 7.71(s,H); 1.8(S,3H). 13C NMR(50 MHz,
DMSO d6): 181.70, 168.82, 20.77.
b) R ¼ CH3 or C6H5
1-Acetylhiosemicarbazide (or 1-benzoylthiosemicarbazide) was prepared
by the addition of 2.355 g (30 mmol) of acetyl chloride (or benzoylchloride)
to a stirred suspension of 2.7 g (30 mmol) of thiosemicarbazide and 30 mL of
dry pyridine. The temperature was maintained between –5 and 08C through-
out the addition. After standing at room temperature for 24 hr most of the
pyridine was removed by evaporation under reduced pressure.
3-Methyl-1,2,4-triazole-5-thione
To effect cyclization to 3-methyl-1,2,4-triazole-5-thione, the 1-acetylthio-
semicarbazide was dissolved in 40 mL of ethanol and 3.24 g (60 mmol) of
sodium was added. The mixture was heated for 24 hr on the steam bath, and
then the solvent was removed by evaporation under reduced pressure. This
residue was dissolved in 6 mL of water and 6 mL of concentrated hydrochloric
acid. A precipitated solid was washed with water and dried air, the sample was
recrystalized from water, the yield was 80%, mp . 2648C. IR (KBr, cm21):
1607(nC¼N), 1108(nc¼S), 3450(nNH). 1H NMR (60 MHz, DMSO d6) d:
13.80 (s, 2H), 2.37 (s, 3H). 13C NMR (75 MHz, DMSO d6) d: 156.70,
148.75, 12.72.
3-Phenyl-1,2,4-triazole-5-thione (2)
1-Benzoylthiosemicarbazide was dissolved in 18 mL of methanol, and
3,24 g (60 mol) of sodium methylate was added. The mixture was heated for

Synthesis of New Surfactants
4195
24 hr in the steam bath, and then the solvent was removed by evaporation
under reduced pressure. This residue was dissolved in 6 mL of water and
6 mL of concentrated hydrochloric acid. A precipitated solid was recrystalized
from water, the yield was 53%, mp . 2648C. IR (KBr, cm21): 1628 (nC¼N),
1
1070(nc¼S), 3066 (nN-H). H NMR (60 MHz, DMSO d6) d: 14.50 (s, 2H),
8.67–7.50 (m, 5H). 13C NMR (75 MHz, DMSO d6) d: 181.92, 165.77,
132.36, 131.69, 128.10, and 127.76.
GENERAL METHOD FOR OBTAINING
MONOCATENAR SURFACTANTS
S-Alkylthio-1,2,4-triazole (1a, 1b, 1c, 1d)
A mixture of 3-methyl-1,2,4-triazole-5-thione (0.575 g, 5 mmol), alkyl
bromide (5 mmol), potassium carbonate (K2CO3) (0.759 g, 5.5 mmol), tetra-
butylammonium bromide (BABA) (0.161 g, 0.5 mmol) in 25 mL of DMF
was stirred at room temperature for 24 hr. The resulted solution was filtered
through a filter paper, and then the solvent was removed by evaporation
under reduced pressure and the obtained product was recrystallized from
ethanol.
S-Alkylthio-1,2,4-triazole (2a, 2b, 2c, and 2d)
By the same procedure used above, 3-phenyl-1,2,4-triazole-5-thione was
condensed by different alkyl bromide to obtain the corresponding mono-
catenar surfactants 2a, 2b, 2c, and 2d. The products were purified by using
a column chromatography on silica gel eluting with n-hexane–ethyl acetate
(80 : 20).
The 1H NMR, IR spectra, and physical characteristics of isolated products
1a–d and 2a–d are summarized in Tables 1 and 2.
GENERAL METHOD FOR OBTAINING BIPOLAR
SURFACTANTS 1e, 1f
1,n-bis[5-(1,2,4-triazolyl)thio]alkane 1e and 1f were prepared from a sol-
ution of 1,15 g, (10 mmol) of 3-methyl-1,2,4-triazole-5thione, 30 mL of DMF,
5 mmol of 1,n-dibromoalkane (n ¼ 10,12), 2,76 g, (20 mmol)of K2CO3 and
0,322 g, (1 mmol) of BTBA. The mixture was stirred at room temperature
for 24 hr. The resulted solution is filtered through a filter paper, and then the

4196
Chebabe et al.
Table 1. Data of 1H NMR and IR of S-alkylthio-1,2,4-triazole (1a–d and 2a–d).
1H NMR (CDCl3)
IR (KBr)
yNH
Products d(CH3)
d(C6H5)
d(CH2a (S)) d((CH2)n-CH3) yC¼S
1a
1b
1c
1d
2a
2b
2c
2d
2.70
(s)
—
—
—
—
3.20 (t)
3.30 (t)
3.27 (t)
3.30 (t)
3.30 (t)
3.30 (t)
3.26 (t)
3.30 (t)
[0.66–2.10]
(m)
—
—
—
—
—
—
—
—
3438
3428
3448
3458
3458
3438
3465
3448
2.67
(s)
[0.67–2.10]
(m)
2.67
(s)
[0.67–2.07]
(m)
2.67
(s)
[0.67–2.07]
(m)
—
[7.43–8.63]
(m)
[0.63–2.06]
(m)
—
—
—
[7.50–8.66]
(m)
[0.60–2.08]
(m)
[7.53–8.56]
(m)
[0.66–2.00]
(m)
[7.57–8.57]
(m)
[0.70–2.08]
(m)
Table 2. Physical characteristics of isolated products (1a–d and 2a–d).
Analysis
MP
(8C)
Yield
(%)
(M þ 1)þ
(m/z)
Products
%C
%H
%N
%S
1a
98
85
51
52
59
72
65
60
75
89
256
270
284
298
318
332
346
360
Calc.: 61.06
9.78 16.43 12.52
Tr.:
Calc.: 62.34 10.02 15.58 11.87
Tr.: 62.34 10.68 15.76 12.04
Calc.: 63.55 10.31 14.82 11.31
Tr.: 62.32 10.77 14.81 11.42
Calc.: 64.54 10.42 14.12 10.76
Tr.: 62.33 10.76 13.96 10.65
Calc.: 68.02
Tr.: 68.10
Calc.: 68.76
Tr.: 68.72
Calc.: 69.51
Tr.: 69.43
Calc.: 70.09
Tr.: 70.25
61.08 10.29 16.85 12.97
1b
1c
1d
2a
2b
2c
2d
102
92
73
8.50 13.22 10.08
8.95 13.65 10.25
88
8.75 12.67
9.20 13.06
9.04 12.16
9.56 12.49
9.18 11.68
9.76 12.15
9.65
9.94
9.28
9.46
8.90
9.05
75
80

Synthesis of New Surfactants
4197
1
Table 3. Data H NMR and IR spectra of 1,n-bis[5-(1,2,4-triazolyl) thio] alkane 1e
and 1f.
1HNMR (DMSO d6 þ TFA)
IR (KBr)
Products
d(CH3)
d(CH2 a(S))
d((CH2)n)
yC¼S
yNH
1e
1f
2.92 (s)
2.52 (s)
3.48 (t)
3.16 (t)
[1.00–2.20] (m)
[0.95–2.00] (m)
—
—
3416
3421
Table 4. Physical characteristics of the bipolar surfactants 1e and 1f.
Analysis
MP
(8C)
Yield
(%)
(M þ 1)þ
(m/z)
Products
%C
%H
%N
%S
1e
164
163
72
72
369
397
Calc.:
Tr.:
52.17
51.73
54.54
53.90
7.61 22.83 17.39
8.01 22.08 16.86
8.08 21.21 16.16
8.33 20.89 15.87
1f
Calc.:
Tr.:
solvent was removed by evaporation under reduced pressure. A sample was
1
recrystallized from ethanol. The products have been characterized by H
NMR, IR, mass, and microanalysis data. The characteristics of the products
are presented in Tables 3 and 4.
SYNTHESIS OF BICATENAR SURFACTANTS 1g, 1h
A mixture of 5-dodecylthio-3-methyl-1,2,4-triazole 1,415 g, (5 mol),
K2CO3 (1,38 g, 10 mmol), tetrabutylammoniumbromide (0,161 g, 0,5 mmol)
and (1,245 g, 5 mmol) of dodecylbromide in 30 mL of DMF was stirred at
room temperature for 24 hr. The solvent was evaporated. The residue was
separated by column chromatography (silica gel -n-hexane/ethyl acetate
(80 : 20)) to give the 1g (50%, liquid) and 1h (50%, mp , 508C).
1
1g: H NMR (60 MHz, CDCl3) d: 4.20 (t,2H), 3,37 (t,2H), 2,47 (s,3H),
[0,66–2,07] (m, nH). 13C NMR (75 MHz, CDCl3) d: 158.89, 152.56, 48.45,
[32.19–22.71], 14.18 (2CH3), 11.90 (1CH3). Mass: (M þ 2)þ ¼ 454,3;
†
[CH3–C ¼ N–N–(CH2)11–CH3]þ ¼ 224.
†
1
1h: H NMR (60 MHz, CDCl3) d: 4.20 (t,2H), 3,20 (t,2H), 2,50 (s,3H),
[0,6–2,17] (m, nH). 13C NMR (75 MHz, CDCl3) d: 160.30, 151.47, 48.32,
[33.61–22.68], 14.07 (3CH3). Mass: Mþ ¼ 452.5.
†

4198
Chebabe et al.
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