Synthesis of some thionocarbamates from O-isopropyl xanthate and amines using Pd/Ti-HMS-10 as catalyst in water

Article abstract of DOI:10.1007/s13738-016-0903-1

Abstract: Ti-HMS materials with different Si/Ti ratio (5, 10, 20 and 30) were prepared and used as the support for a palladium-containing (1?wt%) catalyst. The materials, analyzed by XRD and SEM techniques, were tested in the synthesis of some thionocarba

Full text of DOI:10.1007/s13738-016-0903-1

J IRAN CHEM SOC
DOI 10.1007/s13738-016-0903-1
ORIGINAL PAPER
Synthesis of some thionocarbamates from O‑isopropyl xanthate
and amines using Pd/Ti‑HMS‑10 as catalyst in water
Reza Ranjbar‑Karimi1 · Masumeh Asadi1 · Alireza Talebizadeh1 · Samira Saeednia1,2
Sayed Mohammad Sayedbagheri2
·
Received: 8 March 2016 / Accepted: 3 June 2016
© Iranian Chemical Society 2016
Abstract Ti-HMS materials with different Si/Ti ratio (5,
10, 20 and 30) were prepared and used as the support for a
palladium-containing (1 wt%) catalyst. The materials, ana-
lyzed by XRD and SEM techniques, were tested in the syn-
thesis of some thionocarbamates from reaction of sodium
O-isopropyl carbonodithioate with the corresponding
amines. The best yield was obtained with 3 mmol% of the
catalyst (Pd/Ti-HMS-10) in water as solvent after 10–15-h
heating at 75 °C. The structures of the products were iden-
Introduction
Dialkyl thionocarbamates or thionourethanes are derivatives
of carbamothioic O-acid [1]. Their structural characteristics,
direct bonding of the carbonyl and thiocarbonyl group and
nitrogen, contribute to their broad range of biological activi-
ties, such as insecticidal [2, 3], germicidal and pesticidal
[4–6], herbicidal [7–9], bactericidal [10, 11] and fungicidal
[10, 12]. In addition, thionocarbamates are oily liquids that
function well in alkaline flotation circuits (pH 7–12) and in
particular with porphyritic copper, Cu/Mo, Cu/Au. They are
effective with highly oxidized or slimy ores. Also O-alkylth-
ionocarbamates were used as polymerization accelerators
1
tified by spectroscopy techniques such as H-NMR, 13C-
NMR, IR and elemental analysis.
Graphical Abstract
Keywords Thionocarbamate · Xanthate · Catalyst ·
Mesoporous silica
and selective floto reagents [13]. There are several meth-
ods for the preparation of alkyl thionocarbamates, such as
aminolysis of alkaline salts of xanthogenacetic acid with
or without a catalyst. As an example, an alkyl thionocar-
bamate was synthesized from diethyl dixanthogenate, xan-
thate and amines in the presence of manganese (II) acetate
and Ni-zeolite catalysts [14]. Thionocarbamates can also
be prepared by the reaction of xanthogenates and amines in
the presence of nickel and palladium salt catalysts [15]. The
oxidation of an amine salt of xanthogenic acid, by hydro-
gen peroxide and sodium hypochlorite, led to a high yield
of isopropyl thionocarbamate [13]. Recently, N-(3- and
4-substituted phenyl)-O-isobutyl thionocarbamates were
* Reza Ranjbar-Karimi
r.ranjbarkarimi@vru.ac.ir
1
Department of Chemistry, Faculty of Science, Vali-e-Asr
University, Rafsanjan 77176, Islamic Republic of Iran
2
Department of Chemistry, Shahid Beheshti University, G. C.,
PO Box 19396 4716, Tehran, Iran
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J IRAN CHEM SOC
synthesized from O-isobutyl xanthate and 3- and 4-substi-
tuted anilines in the presence of a nanoplatinum modified
multiwalled carbon nanotube, and Pt/NH2Ph-MWCNT and
Pt/PDA-MWCNT catalysts [16] and also a novel dithiocar-
bamate compound, S-benzoyl-N,N-diethyldithiocarbamate
(BEDTC), have been synthesized via one-pot reaction of
diethylamine, carbon disulfide, sodium hydroxide and ben-
zoyl chloride using abundant carbon disulfide as a solvent
[17].
Hexagonal mesoporous silica (HMS), prepared by neu-
tral template pathway [18], has been reported as a suitable
support for a range of catalysts. HMS supports, modified
by the introduction of Al, Ti, Zr, etc., were reported to
have higher activities in comparison with the MCM-41
supports [19]. The differences observed in the catalytic
activity can be due to their textural properties. Halachev
et al. [20] reported higher catalytic activity of a NiW/(P)
Ti-HMS catalyst in hydrogenation of naphthalene in com-
parison with a conventional alumina-supported catalyst.
Chiranjeevi et al. [21, 22] studied the hydrodesulfurization
and hydrogenation activity in thiophene and cyclohexene
conversion over W, NiW, CoW, Mo, NiMo, CoMo-based
catalysts supported on HMS and Al-HMS. The CoMo/Al-
HMS catalyst manifested superior activity in hydrodesul-
furization of thiophene, while the NiMo/Al-HMS catalyst
was more active in the hydrogenation of cyclohexene. The
catalytic behavior for the hydrodesulfurization reaction of
dibenzothiophenes of sulfided Mo and W phases deposited
on HMS, Al-HMS, ZrAl-HMS and Ti-HMS substrates was
reported by Pawelec et al. [23], who observed that tung-
sten catalysts prepared from HPW precursor display higher
activity than molybdenum catalysts prepared from HPMo
precursors. Mesoporous materials supporting gold cata-
lysts, including Au/Ti-HMS (DP) and Au/Ti-HMS, have
already been prepared by different methods successfully
and used in direct synthesis of H2O2 [24]. In the present
work, we would like to report the synthesis, characteriza-
tion and the catalytic activity of Pd/Ti/HMS catalysts in the
synthesis of some thionocarbamates. The supports, cata-
lysts and products were characterized by XRD, SCM, IR,
1H- 13C-NMR and elemental analysis.
Fig. 1 XRD patterns of: a HMS, b Ti-HMS-30, c Ti-HMS-20, d Ti-
HMS-10, e Ti-HMS-5
Results and discussion
Preparation and characterization of catalyst
Ti-HMS materials with different Si/Ti ratios were obtained
and characterized after calcination by XRD and SEM
techniques for establishing structure and texture. The
XRD traces of Ti-HMS are shown in Fig. 1. For the HMS
Fig. 2 XRD patterns of: a Pd/HMS, b Pd/Ti-HMS-30, c Pd/Ti-
HMS-20, d Pd/Ti-HMS-10, e Pd/Ti-HMS-5
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Fig. 3 SEM image of Pd/Ti-HMS-10
Scheme 1 Synthesis of O-iso-
propyl ethylcarbamothioate 3a
Table 1 Optimization of the concentration of Pd/Ti-HMS-10 for syn-
thesis of O-isopropyl ethylcarbamothioate 3a
Table 2 Formation of 3a with different catalysts
Entry
Catalyst
X (mmol%)
Time (h)
Yield (%)
Entry
Pd/Ti-HMS-10 (mmol%)
Time (h)
Yield (%)
1
–
–
5
5
5
5
5
5
5
5
5
3
4
4
6
16
13
14
8
5
5
1
2
3
4
5
6
–
1
2
3
4
5
12
12
12
10
10
10
5
68
75
93
93
93
2
Ni-Salen
3
NiSO4.6H2O
Ti-HMS-20
65
15
12
61
21
34
78
77
93
87
90
4
5
aHg/Ti-HMS-10
aNi/Ti-HMS-10
aCu/Ti-HMS-10
aZn/Ti-HMS-10
aPd/Ti-HMS-5
bPd/Ti-HMS-5
bPd/Ti-HMS-10
bPd/Ti-HMS-20
bPd/Ti-HMS-30
6
8
7
8
8
8
Reaction conditions: sodium O-isopropyl carbonodithioate
(1.0 mmol), ethylamine (2.0 mmol), H2O (5 mL), 75 °C
9
10
10
10
14
16
10
11
12
13
and Ti-HMS supports in different mole ratios, the XRD
recorded in the 2θ interval from 0.5° to 9° showed a reflec-
tion at 2θ = 1.5°–3° which represents a characteristic of
mesoporous HMS materials and is also indexed on a hex-
agonal lattice. The presence of this peak was first reported
by Tanev and Pinnavaia [18] for the HMS material and by
Gotier and Tuel [25] for the Ti-HMS material. It can be
noted that the intensities of XRD peaks decrease and their
peaks become broader with the Ti content increasing in the
samples. It suggests that the mesoporous structures of HMS
become less uniform upon the introduction of Ti into the
framework and the hexagonal lattice is destroyed partly. The
pore diameters of these samples increase firstly and then
decrease with the increasing of Ti content, which agrees
with the previous results of the literature [25]. The increase
Reaction conditions: sodium O-isopropyl carbonodithioate
(1.0 mmol), ethylamine (2.0 mmol), H2O (5 mL), 75 °C
a 5 wt%, b1 wt%
in pore diameters is due to the existence of titanium in the
isolated Ti4+ form, while the decrease indicates the forma-
tion of TiO2 [26]. The deposition of the Pd (1 wt%) results
less changes in the XRD patterns. Like support, Pd/Ti/HMS
shows the XRD patterns in low angle with less decreased
in intensity (Fig. 2). We can conclude that the incorporation
of Ti into the HMS framework results in the formation of
highly dispersed Pd phase. Scanning electron microscopy
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J IRAN CHEM SOC
Table 3 Formation of 3a, in the presence of catalytic amount of Pd/
Ti-HMS-10 in different solvents
The model reaction is carried out in different solvents by
using 3 mmol% of Pd/Ti-HMS-10 as a catalyst (Table 3).
Among various solvents tested, water yielded the best
results.
Entry
Solvent
Time (h)
Yield (%)
1
2
3
4
H2O
10
10
10
10
93
75
60
80
The results of the reaction of sodium O-isopropyl car-
bonodithioate 1a with various amine and diamine 2a–i
are summarized in Table 4. The reactions of the primary
amines 2a–d with sodium O-isopropyl carbonodithioate 1a
were carried out in water (5 mL) at 75 °C in the presence of
3 mmol% of Pd/Ti-HMS-10. The reactions were complete
in 10 h affording the corresponding O-isopropyl alkylcar-
bamothioate 3a–d in 85–93 % yields (Table 4, entries 1–4).
The reaction of primary diamines 2e–g with O-isopropyl
carbonodithioate 1a gave corresponding bis-thionocarba-
mate 3a–g in good yields. Reaction of secondary amines
such as morpholine 2h and piperazine 2i with sodium
O-isopropyl carbonodithioate 1a in the presence of Pd/Ti-
HMS-10 gave O-isopropyl morpholine-4-carbothioate 3h
and O,O-diisopropyl piperazine-1,4-bis(carbothioate) 3i,
respectively. The structure of all compounds was confirmed
with IR, 1H-NMR and 13C-NMR spectra.
Pd/Ti-HMS-10 catalyst was also found to be reusable,
although gradual decline of activity was observed. Better
results were obtained when, after the first run, the catalyst
was separated by centrifugation, and the remained cata-
lyst was washed with acetone and dried at 100 °C over-
night, and reused. Apparently, the treatment with acetone
removed tars more efficiently from the catalyst surface. In
Table 5, the comparison of efficiency of catalyst after five
times is reported.
MeOH
EtOH
DMSO
pictures of Pd/Ti/HMS material are shown in Fig. 3, which
also shows the morphology of this material. It reveals that
Ti–HMS is made up of submicrometer-sized free standing
or aggregated particles, which causes the decrease in the
surface area of Pd/Ti/HMS support compared to pure HMS
material. These samples show particles of irregular mor-
phology which are fairly uniform in size.
Synthesis of thionocarbamates
In an initial reaction, we attempted to synthesize the O-iso-
propyl ethylcarbamothioate 3a starting with sodium O-iso-
propyl carbonodithioate 1a and ethylamine 2a by using
3 mmol% of Pd/Ti-HMS-10 in water in which the reaction
was monitored by TLC (Scheme 1). The isolated product
was identified as O-isopropyl ethylcarbamothioate 3a in
good yield (Table 1, entry 2). In the absence of catalyst, the
O-isopropyl ethylcarbamothioate 3a was obtained in only
5 % yield in 12 h (Table 1, entry 1). Increasing the loading
of Pd/Ti-HMS-10 to 3 mmol% gave the O-isopropyl ethyl-
carbamothioate 3a in 93 % yield in 10 h (Table 1, entry 4).
Thus, an increase in the concentration of catalyst not only
promotes the reaction but also resulted in an increased
yield (Table 1, entries 3 and 4).
Conclusion
The Pd/Ti-HMS-10 catalyst was studied along with
other solid catalysts using the reaction of ethylamine 2a and
sodium O-isopropyl carbonodithioat 1a in 5 mL of water
as a model system for the synthesis of the corresponding
O-isopropyl ethylcarbamothioate derivative 3a. The results
are summarized in Table 2. The results show that the reac-
tions catalyzed by Ni-salen proceed in longer reaction time
and afforded very low product yield. The reactions cata-
lyzed by NiSO4 as a catalyst source yielded moderate prod-
uct of isopropyl ethylcarbamothioate derivative 3a after
13 h (Table 2, entry 3). Also the use of Ti-HMS-20 as a
catalyst source gave low yield of product in 14 h.
Next, we investigated the catalytic activity of Ti-HMS
that was loaded with some metal in different ratio. Addition
of Pd to Ti-HMS support provided a considerable increase
in the yields of the products and reduction in the reaction
times (Table 2, entries 9–13). Among the Pd-supported cat-
alysts tested, Pd/Ti-HMS-10 gave the best result (Table 2,
entry 11).
In conclusion, the presented work describes the opti-
mal synthesis of some substituted thionocarbamates from
sodium O-isopropyl carbonodithioate and various amines
by using 3 mmol% of Pd/Ti-HMS-10 in water. This method
has several unique merits, and the process provided an effi-
cient and convenient protocol for the preparation of thiono-
carbamates derivatives.
Experiment
All materials and solvents were purchased from Sigma-
Aldrich and Merck and were used without any additional
purification. FT-IR spectra of all the final products were
recorded on a Bruker instrument by using the KBr self-sup-
1
ported pellet technique. H NMR spectra were recorded at
300 MHz. 13C NMR spectra were recorded 75 MHz. NMR
spectra were obtained in solution of DMSO-d6 and CDCl3
using tetramethylsilane (TMS) as internal standard. The
1 3

J IRAN CHEM SOC
Table 4 Reaction of amines
with sodium O-isopropyl
carbonodithioate 1a
Entry
1
Amine
Product
Yield (%)
93
2
90
85
3
4
5
6
7
88
85
85
80
8
9
65
60
Table 5 Recycling of Pd/Ti-HMS-10 for the reaction of sodium
O-isopropyl carbonodithioate 1a with ethylamine 2a in water
Preparation of Ti‑HMS
Ti-HMS with different Si/Ti ratios (5, 10, 20 and 30) was
synthesized according to a published procedure by Gotier
and Tuel [25]. For example, the procedure for synthesis of
Ti-HMS-20 is as bellow:
Firstly, a solution of tetraethylorthosilicate (20 mmol)
and titanium isopropoxide (1 mmol) in ethanol (130 mmol)
and isopropanol (20 mmol) was prepared. Then a sec-
ond, solution of dodecylamine (5.4 mmol), distilled water
(13 mL) and hydrochloric acid (37 %) (0.4 mmol) was
prepared. The solution was vigorously stirred, and then
the first solution was slowly added to second solution for
Run no.
Time (h)
Yield (%)
1
2
3
4
5
10
10
13
14
14
93
92
90
90
85
elemental analysis for C, H and N was performed using
apparatus model CE-450 analyzer. TLC analysis was per-
formed on silica gel TLC plates (Merck).
1 3

J IRAN CHEM SOC
about 30 min. After the addition of the last portion of the
first solution, the stirring was maintained for about 15 min,
and the resulting gel was kept at ambient temperature for
18 h. The obtained white solid was recovered by filtration,
washed with distilled water and dried at room temperature,
followed by drying at 100 °C for 5 h. The organic mole-
cules were removed by calcining in air increasing slowly
the temperature up to 650 °C for about 1 h and then keep-
ing the sample at this temperature for 5 h.
O‑Isopropyl methylcarbamothioate (3b)
Sodium O-isopropyl carbonodithioate (1 mmol) and meth-
ylamine (2 mmol) after stirring and heating at 75 °C for
10 h gave O-isopropyl methylcarbamothioate (3b); 90 %;
Oily (Found: C, 45.0; H, 8.1; N, 10.0. C5H11NOS requires:
C, 45.1; H, 8.3; N, 10.5 %). IR (KBr): ν 3263, 2872, 2973,
1515, 1370, 1000, 1300, 1200, 700, 1100 cm−1. H NMR
1
(300 MHz, CDCl3): Major tautomer (58 %): δ = 1.31 (d,
3JHH = 6.0 Hz, CH3-isoprophyl), 3.02 (d, JHH = 5.0 Hz,
3
Preparation of Pd/Ti‑HMS‑10 catalyst (as a typical
procedure)
CH3-methyl), 5.50 (m, CH), 6.33 (bs, NH) ppm. Minor tau-
tomer (42 %): δ = 1.24 (d, 3JHH = 6.0 Hz, CH3-isoprophyl),
3
2.79 (d, JHH = 5.0 Hz, CH3-methyl), 5.50 (m, CH), 7.08
To a solution of Ti-HMS-10 (1.98 g) in 4 mL of water was
added the solution of PdCl2 (0.06 mmol) in 1 mL of water.
The mixture was stirred and heated at 70 °C until the mix-
ture forms a pasty sample and then heated for 12 h at 100 °C.
After evaporation of the solvent and drying, the samples
were calcined at 600 °C for 4 h. Other M/Ti-HMS(x) cata-
lysts were prepared according to typical procedure.
(bs, OH) ppm.13C NMR (75 MHz, CDCl3): Major tautomer
(58 %): δ = 21.83, 31.54, 75.71, 189.58 ppm. Minor tau-
tomer (42 %): δ = 21.78, 29.39, 73.77, 190.65 ppm.
O‑Isopropyl benzylcarbamothioate (3c)
Sodium O-isopropyl carbonodithioate (1 mmol) and ben-
zylamine (1 mmol) after stirring and heating at 75 °C for
12 h gave O-isopropyl benzylcarbamothioate (3c); 85 %;
Oily (Found: C, 42.7; H, 7.0; N, 6.4. C11H15NOS requires:
C, 63.1; H, 7.2; N, 6.7 %). IR (KBr): ν 3248, 2870–3100,
1667, 2000, 1515, 1454, 1338, 1385, 1000–1300, 1193,
General procedure for reaction of amines with sodium
O‑isopropyl carbonodithioate
To a mixture of sodium O-isopropyl carbonodithioate and
water (5 mL), Pd/Ti-HMS-10 (3 mmol%) was added. Then,
amine was added and the reaction mixture was stirred and
heated at 75 °C for appropriate amount of time. The pro-
gress of the reaction was monitored by TLC. After comple-
tion, the reaction mixture was filtered to remove catalyst
and the mixture was diluted with water (10 mL) and the
organic layer was separated and washed with water. The
organic layer was dried over anhydrous MgSO4 and con-
centrated to afford the pure product.
1
700, 1100, 697,736 cm−1. H NMR (300 MHz, DMSO-
3
d6): Major tautomer (65 %): δ = 1.25 (d, JHH = 6.2 Hz,
CH3-isoprophyl), 4.51 (s, CH2), 5.37 (m, CH), 7.20–7.32
(m aromatic-H), 9.82 (bs, OH or NH) ppm. Minor tautomer
(35 %): δ = 1.23 (d, 3JHH = 6.2 Hz, CH3-isoprophyl), 4.20
(s, CH2), 5.40 (m, CH), 7.23–7.36 (aromatic-H), 9.82 (bs,
OH or NH) ppm. 13C-NMR (75 MHz, DMSO-d6): Major
tautomer (65 %): δ = 21.32, 47.75, 74.38, 127.20, 127.41,
129.41, 135.63, 189.37 ppm. Minor tautomer (35 %):
δ = 20.20 44.56, 71.38, 127.90, 128.08, 128.98, 134.33
(aromatic-C), 188.44.
O‑Isopropyl ethylcarbamothioate (3a)
Sodium O-isopropyl carbonodithioate (1 mmol) and eth-
ylamine (2 mmol) after stirring and heating at 75 °C for
10 h gave O-isopropyl ethylcarbamothioate (3a); 93 %;
Oily (Found: C, 48.7; H, 9.0; N, 9.3. C6H13NOS requires:
C, 48.9; H, 8.9; N, 9.5 %). IR (KBr): ν 3254, 2864, 2979,
O‑Isopropyl 4‑methylbenzylcarbamothioate (3d)
Sodium O-isopropyl carbonodithioate (1 mmol) and
4-methylbenzylamine (1 mmol) after stirring and heating
at 75 °C for 12 h gave O-isopropyl 4-methylbenzylcarba-
mothioate (3d); 88 %; Oily (Found: C, 64.1; H, 7.4; N, 6.2.
C12H17NOS requires: C, 64.5; H, 7.7; N, 6.3 %). IR (KBr):
ν 3355, 2870–3100, 1667–2000, 1515, 1446, 1335–1385,
1
1515, 1340, 1396, 1000, 1300, 1200, 700, 1100 cm−1. H
NMR (300 MHz, CDCl3): Major tautomer (51 %): δ = 1.15
(t, 3JHH = 7.0 Hz, CH3-ethyl), 1.26 (d, 3JHH = 6.0 Hz, CH3-
3
isopropyl), 3.51 (q, JHH = 6.5 Hz, CH2-ethyl), 5.48 (m,
1000–1300, 1192, 800–850, 700–1100 cm−1 1H NMR
.
CH), 6.32 (bs, NH) ppm. Minor tautomer (49 %): δ = 1.09
(300 MHz, DMSO-d6): Major tautomer (72.5 %): δ = 1.26
(t, 3JHH = 7.0 Hz, CH3-ethyl), 1.23 (d, 3JHH = 6.0 Hz, CH3-
(d, JHH = 6.2 Hz, CH3-isoprophyl), 2.27 (s, CH3), 4.60
3
3
isoprophyl), 3.23 (q, JHH = 6.5 Hz, CH2-ethyl), 5.48 (m,
(s, CH2), 5.44 (m, CH), 7.09–7.41 (m, aromatic-H), 9.43
CH), 7.26 (bs, OH) ppm. 13C NMR (75 MHz, CDCl3):
Major tautomer (51 %): δ = 14.20, 21.75, 39.76, 75.39,
189.39 ppm. Minor tautomer (49 %): δ = 13.80, 21.75,
37.82, 73.34, 188.70 ppm.
(bs, OH or NH) ppm. Minor tautomer (27.5 %): δ = 1.20
3
(d, JHH = 6.2 Hz, CH3-isoprophyl), 2.27 (s, CH3), 4.23
(s, CH2), 5.44 (m, CH), 7.09–7.41 (aromatic-H), 9.43 (bs,
NH or OH) ppm.13C NMR (75 MHz, DMSO-d6): Major
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J IRAN CHEM SOC
tatomer (72.5 %): δ = 21.92, 22.61, 47.83, 74.07, 127.38,
127.73,128.21, 128.33, 135.58, 135.80, 189.89 ppm. Minor
tatomer (27.5 %): δ = 21.13, 22.61, 45.80, 72.97, 127.84,
127.91, 129.22, 129.60, 136.47, 136.50, 187.77 ppm.
gave O-isopropyl morpholine-4-carbothioate (3h); 65 %;
Oily (Found: C, 50.4; H, 7.8; N, 7.2. C8H15NO2S requires:
C, 50.8; H, 8.0; N, 7.4 %). IR (KBr): ν 2850, 2970, 1480,
1372, 1384, 1287, 1236, 1000, 1300, 1117, 896, 700,
1
1100 cm−1. H NMR (300 MHz, DMSO-d6): δ = 1.28 (d,
O,O‑Diisopropyl propane‑1,3‑diyldicarbamothioate (3e)
3JHH = 6.2 Hz, CH3-isoprophyl), 3.57 (t, 3JHH = 4.2 Hz, 2
3
CH2), 3.94 (t, JHH = 4.2 Hz, 2 CH2), 5.47 (m, CH) ppm.
Sodium O-isopropyl carbonodithioate (2 mmol) and
1,3-propanediamine (1 mmol) after stirring and heating at
75 °C for 12 h gave O,O-diisopropyl propane-1,3-diyldicar-
bamothioate (3e); 85 %; Yellow solid; mp: 207–208 °C
(Found: C, 45.3; H, 7.7; N, 9.7. C11H22N2O2S2 requires: C,
47.5; H, 8.0; N, 10.1 %). IR (KBr): ν 3169, 2870, 2960,
13C NMR (75 MHz, DMSO-d6): δ = 21.98, 46.58, 49.50,
74.81, 186.51 ppm.
O,O‑Diisopropyl piperazine‑1,4‑bis(carbothioate) (3i)
Sodium O-isopropyl carbonodithioate (2 mmol) and piper-
azine (1 mmol) after stirring and heating at 75 °C for 15 h
gave O,O -diisopropyl piperazine-1,4-bis(carbothioate)
(3i); 60 %; Yellow solid; mp: 110–114 °C (Found: C, 49.3;
H, 7.7; N, 9.3. C12H22N2O2S2 requires: C, 49.6; H, 7.6; N,
9.6 %). IR (KBr): ν 2860, 2975, 1492, 1370, 1380, 1227,
1000, 1300, 700, 1100 cm−1. 1H NMR (300 MHz, DMSO-
d6): δ = 1.28 (d, 3JHH = 6.0 Hz, CH3-isoprophyl), 3.52 (s, 4
CH2), 5.41 (m, CH) ppm. 13C NMR (75 MHz, DMSO-d6):
δ = 21.98, 47.38, 73.92, 187.10 ppm.
1
1556, 1207, 1192, 1000, 1300, 700, 1100 cm−1. H NMR
3
(300 MHz, DMSO-d6): δ = 1.25 (d, JHH = 6.1 Hz, CH3-
3
isoprophyl), 1.41 (pent, JHH = 6.7 Hz, 2 CH2), 3.43 (t,
3JHH = 6.7 Hz, CH2-NH), 5.40 (m, CH), 6.01 (bs, NH)
ppm. 13C NMR (75 MHz, CDCl3): δ = 21.13, 32.25, 38.71,
73.61, 188.30.
O,O‑Diisopropyl butane‑1,4‑diyldicarbamothioate (3f)
Sodium O-isopropyl carbonodithioate (2 mmol) and
1,4-butanediamine (1 mmol) after stirring and heating at
75 °C for 13 h gave O,O-diisopropyl butane-1,4-diyldicar-
bamothioate (3f); 85 %; Oily (Found: C, 49.2; H, 8.0; N,
9.9. C12H24N2O2S2 requires: C, 49.3; H, 8.3; N, 9.6 %). IR
(KBr): ν 3235, 2800–2970, 1544, 1370–1380, 1000–1300,
1199, 1100, 700–1100 cm−1. 1H NMR (300 MHz, DMSO-
Acknowledgments The authors wish to thank Vali-e-Asr University
of Rafsanjan for partially funding this work.
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3
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3
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