The Reaction of Phosphorus Decasulfide with some Hydrazides and their Hydrazones: New Route for Construction of Four-membered, Five-membered, and Six-membered Phosphorus Heterocycles

Article abstract of DOI:10.1002/jhet.2902

Reaction of some selected benzoic acid hydrazides 1a–c with phosphorus decasulfide P₄S₁₀ in dry pyridine afforded some novel pyridine solvate of 1,3,4,2-thiadiazaphospholes 2a–c. Similarly, treatment of their corresponding hydrazones 3a–c toward phosphorus decasulfide under the same reaction conditions gave the corresponding thio-analog 4 and 1,3,2-benzoxazaphosphinine and benzodiazaphosphinine pyridine solvates 5a,b, respectively. Treatment of (thio)semicarbazides and their corresponding (thio)semicarbazones with phosphorus decasulfide in dry pyridine yielded the novel 1,2,4,3-triazaphospholidines 6a,b, and 1,3,2-diazaphosphetidines 8a,b, respectively. Moreover, cyclization of (thio)carbohydrazides and their mono-(thio)carbohydrazones with phosphorus decasulfide produced 1,2,4,3-triazaphospholidines 9a,b and 11a,b, respectively. The structures of these products were confirmed from analytical and spectral data.

Full text of DOI:10.1002/jhet.2902

Month 2017
The Reaction of Phosphorus Decasulfide with some Hydrazides and their
Hydrazones: New Route for Construction of Four‐membered, Five‐
membered, and Six‐membered Phosphorus Heterocycles
Somaia M. Abdel‐Kariem* and Tarik E. Ali
Department of Chemistry, Faculty of Education, Ain Shams University, Roxy, Cairo, Egypt
*
E‐mail: somaia.abdelkariem@yahoo.com
Received September 4, 2016
DOI 10.1002/jhet.2902
Published online 00 Month 2017 in Wiley Online Library (wileyonlinelibrary.com).
Reaction of some selected benzoic acid hydrazides 1a–c with phosphorus decasulfide P4S10 in dry
pyridine afforded some novel pyridine solvate of 1,3,4,2‐thiadiazaphospholes 2a–c. Similarly, treatment of
their corresponding hydrazones 3a–c toward phosphorus decasulfide under the same reaction conditions
gave the corresponding thio‐analog 4 and 1,3,2‐benzoxazaphosphinine and benzodiazaphosphinine pyridine
solvates 5a,b, respectively. Treatment of (thio)semicarbazides and their corresponding (thio)semicarbazones
with phosphorus decasulfide in dry pyridine yielded the novel 1,2,4,3‐triazaphospholidines 6a,b, and 1,3,2‐
diazaphosphetidines 8a,b, respectively. Moreover, cyclization of (thio)carbohydrazides and their mono‐
(
thio)carbohydrazones with phosphorus decasulfide produced 1,2,4,3‐triazaphospholidines 9a,b and 11a,b,
respectively. The structures of these products were confirmed from analytical and spectral data.
J. Heterocyclic Chem., 00, 00 (2017).
INTRODUCTION
heterocycles via its reaction with hydrazide compounds.
Herein, we wish to report in detail simple and convenient
route for synthesis of novel phosphorus heterocycles by
cyclization of some selected hydrazides and their
corresponding hydrazones with phosphorus decasulfide in
dry pyridine.
Phosphorus decasulfide P4S10 (also called phosphorus
pentasulfide P S ) is a very important starting material
2
5
for the synthesis of many linear phosphorus and sulfur
compounds but has been used less extensively for the
preparation of cyclic compounds containing the exocyclic
PS2 group [1,2]. Limited heterocyclic compounds
containing the exocyclic PS2 group were prepared by
reactions of phosphorus decasulfide with amide systems
having reactive group at ortho position such as anthra-
nilamide [3], 2‐amino‐3‐carbamoyl‐4,5,6,7‐tetrahydrobenzo[b]
thiophene [4], N,N‐diphenylurea [5], 1,2‐trimethylene‐4‐
amino‐5‐cyanoimidazole [6], 3‐methyl‐4‐carbamoyl‐5‐
aminopyrazole [7], and N‐[cyano(imidazolidin‐2‐ylidene)
methyl]carboxamide [8]. Phosphorus heterocycles are of
potential interest as anti‐inflammatory, herbicides,
insecticides, and fungicides [9–12]. However, to our
knowledge, there is no any attempt to utilize phosphorus
decasulfide as electrophile in synthesis of phosphorus
RESULTS AND DISCUSSION
The reaction of benzoic acid hydrazides 1a–c with
phosphorus decasulfide (P S ) in the presence of
4
10
pyridine for 2 h afforded solvates of 5‐(2‐substituted
phenyl)‐2‐mercapto‐2,3‐dihydro‐1,3,4,2‐thiadiazaphosphole‐
2‐sulfides 2a–c with pyridine in good yields (Scheme 1).
Compounds 2a–c dissolved readily in aqueous NaOH,
acidification surprisingly regenerate 2a–c without
removing pyridine. The reaction mechanism was
suggested to take place with an initial attack of NH2
group to P S , followed by attack from thiol to the C═O
4
10
©
2017 Wiley Periodicals, Inc.

S. M. Abdel-Kariem and T. E. Ali
Vol 000
Scheme 1. Reaction of P
4
S
10 with benzoic acid hydrazides 1a–c.
were coincident with the formula weights and supported
1
3
the identity of the structures. Furthermore, the C‐NMR
spectrum of compound 2b showed characteristic singlets
at δ 160.5 and 162.3 ppm, assigned to the endocyclic
C═N atom of thiadiazaphosphole ring and C‐2 of phenyl
group, respectively. Also, the other aromatic carbon
atoms were recorded in regions 115.9–147.0 ppm.
Similarly, the chemical behavior of benzoic acid
hydrazones 3a–c toward phosphorus decasulfide was also
investigated. Thus, a mixture of each one of the
hydrazones 3a–c with phosphorus decasulfide in dry
0
pyridine
afforded
N ‐[phenylmethylidene]benzoic
thiocarbohydrazide (4) [13,14], 2‐mercapto‐4‐thioxo‐
1,3,2‐benzoxazaphosphinine‐2‐sulfide pyridine solvate
5a, and 2‐mercapto‐4‐thioxo‐1,3,2‐benzodiazaphosphinine‐
2‐sulfide, pyridine solvate 5b, respectively (Scheme 2).
The suggested reaction mechanism for the formation of
these compounds took place in two steps. The first step
was replacing of the oxygen atom of the carbonyl group
by sulfur (sulfuration). The second step was attack of R
group (R═OH, NH ) to P S followed by attack from
group to remove water molecule [3,7] (Scheme 1). The IR
spectra of compounds 2a–c showed the absorption bands
of the NH and P═S groups in the respective regions
2
4 10
NH to the P(S)(SH) moiety to remove hydrogen sulfide
2
ꢀ
1
ꢀ1
3
336–3128 cm and 760–741 cm , respectively. Also,
molecules in case of compounds 5a,b[15,16] (Scheme 2).
The IR spectra of products 4 and 5a,b lacked the
1
their H‐NMR spectra displayed the characteristic broad
singlets of the NH protons at δ 10.48–10.28 ppm and the
absorption bands because of NH , OH, and C═O
2
SH protons at
δ
6.20–6.62 ppm for the
functions present in their precursors 3a–c, respectively,
thiadiazaphosphole rings. Also, the resonance of aromatic
protons agreed with the expected integral intensity ratio,
which confirmed the presence of the pyridine as solvate.
The mass spectra of compounds 2a–c showed their
molecular ion peaks at m/z 325, 341, and 340, which
except compound 4 that displayed NH group at
ꢀ
1
3180 cm . In addition, new absorption bands at 1288,
ꢀ
1
1233, and 1253 cm
appeared in their IR spectra,
1
respectively, attributed to the C═S groups. The H‐NMR
spectra of the products 5a,b lacked OH and NH protons
2
of the parent compounds 3b,c. Also, they showed the
characteristic signals of the pyridine rings at their
1
3
expected chemical shifts. Furthermore, the C‐NMR
spectrum of compound 5a confirmed the presence of the
pyridine ring from resonating its carbon atoms at 121.8
4
Scheme 2. Reaction of P S10 with benzoic acid hydrazones 3a–c.
(C‐β), 129.0 (C‐γ), and 148.7 (C‐α) while the carbon
atom of C═S was revealed at δ 207.0 ppm. Mass spectra
of compounds 4 and 5a,b were measured and confirmed
their molecular weights.
Next, we turned our attention to study the chemical
behavior of phosphorus decasulfide toward (thio)
semicarbazide and (thio)carbohydrazide under the same
previous conditions. Treatment of semicarbazide and
thiosemicarbazide with phosphorus decasulfide in dry
pyridine afforded the novel interesting 1,2,4,3‐
triazaphosphospholidines 6a,b, respectively (Scheme 3).
A plausible mechanism for the reactions proceeded as
previously mentioned mechanism (Scheme 3). The
structures 6a,b were assigned on the basis of
spectroscopic data, which confirmed their similarities in
the spectral data. Compound 6a, for instance, has the
molecular formula of CH N OPS , as indicated by mass
4
3
2
+
1
spectrum at m/z 169 (M ). In the H‐NMR spectrum of
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2017
New Route for Construction of Four-, Five- and Six-membered Phosphorus
Heterocycles
4
Scheme 3. Reaction of P S10 with (thio)semicarbazides and (thio)semicarbazone.
compound 6a, three D O‐exchangeable signals appeared at
compounds in refluxing pyridine gave 4‐amino‐3‐
mercapto‐5‐(oxo/thioxo)‐1,2,4,3‐triazaphospholidine‐3‐
sulfides (9a,b), respectively (Scheme 4). The IR spectrum
of the reaction product revealed, in each case, appearance
of absorption bands because of amino, carbonyl, and
2
δ 5.80 (brs, NHNH), 7.50 (s, SH), and 8.55 (br, NH) ppm
13
[
8]. Also, its C‐NMR spectrum showed one absorption
peak at δ 169 ppm because of carbon atom of the
carbonyl group, which appeared in the infrared spectrum
ꢀ
1
1
at 1678 cm . It is clear that oxygen was not replaced by
sulfur even with the use of a twofold excess of
phosphorus pentasulfide and with an increase in the
reaction time [17].
thiocarbonyl functions. Moreover, the H‐NMR spectrum
of compound 9b revealed four D O‐exchangeable signals
2
at δ 5.23 (br, NH ), 7.12 (s, SH), 8.45 (brs, NH), and
2
13
12.66 (s, NHCS). Also, the C‐NMR spectrum of
compound 9b showed one absorption peak at δ
202.0 ppm because of thiocarbonyl carbon atom. The
formation of products 9a,b was assumed to take place via
an initial attack of NH2 group to P S , which then
We have also cyclized the semicarbazone 7a and
thiosemicarbazone
7b
into
the
novel
1,3,2‐
diazaphosphetidines. Thus, treatment of compounds 7a,b
with one‐half equivalent of phosphorus decasulfide in
refluxing pyridine afforded 2‐mercapto‐4‐(oxo/thioxo)‐1‐
4
10
undergo intramolecular cyclization through attack of NH
and not NH at P(S)(SH) moiety to remove hydrogen
{[phenylmethylidene]amino}‐1,3,2‐diazaphosphetidine‐2‐
2
2
sulfides (8a,b), respectively (Scheme 3). However, if
excess of phosphorus pentasulfide was used in case of
semicarbazone 7a, the only product 8a formed without
any trace of the product 8b [18]. The IR spectra of
compounds 8a,b have absorption bands inherent to
stretching vibrations of the NH groups (3191 and
sulfide molecules under the reaction conditions
(Scheme 4) [19,20].
In order to finally confirm the structure of compounds
9a,b, they were subjected to condense with benzaldehyde
in absolute ethanol to yield the corresponding Schiff
bases 11a,b, respectively, as illustrated in Scheme 4. The
latter compounds could also alternatively be obtained by
ꢀ
1
ꢀ1
3
253 cm ), carbonyl group (1686 cm in compound
ꢀ
1
1
8
a), and P═S groups (752 and 750 cm ). Their H‐
reaction
of
phosphorus
decasulfide
with
NMR spectra are very similar, which displayed two D O‐
monocarbohydrazone 10a and monothiocarbohydrazone
10b, respectively (Scheme 4). The signal of the N‐amino
group, present in the H‐NMR spectrum of compounds
2
exchangeable signals of NH and SH protons for each
one. In addition, the aromatic and azomethine protons
1
13
appeared in the expected chemical shifts. The C‐NMR
spectrum of compound 8a displayed the carbon atoms of
the phenyl group (δ 121.5, 129.3, 132.8, 138.0 ppm),
azomethine (δ 147.4 ppm), and the carbonyl
9a,b, was not detectable for the isolated products 11a,b,
demonstrating the disappearance of this group on
condensation process. In addition, there are singlets at δ
8.69 and 8.00 ppm, characteristic of azomethine protons
for compounds 11a,b, respectively, beside the aromatic
protons of the phenyl groups at regions δ 7.30–7.49 ppm.
(
δ 167.7 ppm). Furthermore, the mass spectral data of the
both compounds recorded their molecular ion peaks at
m/z 257 and 273, respectively.
Prompted by the aforementioned results, we have also
investigated the chemical reactivity of phosphorus
13
Moreover, the C‐NMR spectrum of compound 11a, for
example, revealed four carbon types related to the phenyl
group and two characteristic signals at δ 147.5 and
165.5 ppm because of the azomethine and carbonyl
carbon atoms, respectively.
decasulfide
toward
carbohydrazide
and
thiocarbohydrazide. Thus, reaction of P4S10 with these
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

S. M. Abdel-Kariem and T. E. Ali
Vol 000
4
Scheme 4. Reaction of P S10 with (thio)carbohydrazides and mono‐(thio)carbohydrazones.
CONCLUSIONS
washed several times with water. The obtained products
were crystallized from diluted dimethylformamide to give
the target compounds.
A facile and convenient synthetic method has been
described to attain novel different phosphorus
heterocycles. The methodology depends on reaction of
some benzoic acid hydrazides and their corresponding
hydrazones with phosphorus decasulfide (P S ) in dry
pyridine to give five‐membered and six‐membered
phosphorus heterocycles. Moreover, cyclization of some
carbohydrazides and their corresponding carbohydrazones
with phosphorus pentasulfide under the same conditions
produced novel interesting four‐membered and five‐
membered phosphorus heterocycles.
2‐Mercapto‐5‐phenyl‐2,3‐dihydro‐1,3,4,2‐thiadiazaphosphole‐
2
1
3
‐sulfide, pyridine solvate (2a). Pale brown crystals, mp 99–
ꢀ
1
00°C, yield 87%. IR (KBr), (νmax, cm ): 3195 (br, NH),
1
055 (C─Harom), 1627 (C═N), 1548 (C═C), 760 (P═S). H‐
4
10
NMR (500 MHz, DMSO‐d ): 7.45–7.67 (m, 7H, Ph─H and
6
β‐H), 7.99 (d, 1H, J = 7 Hz, γ‐H), 8.05 (d, 1H, J = 7.6 Hz,
α‐H), 8.10 (d, 1H, J = 6.8 Hz, α‐H), 6.25 (brs, 1H, SH
exchangeable with D O), 10.48 (brs, 1H, NH exchangeable
2
+
with D O). MS (EI, m/z): 325 (M ). Anal. Calcd for
2
C H N PS (325.41): C, 44.29; H, 3.72; N, 12.91; S,
12 12
3
3
2
9.56%. Found: C, 44.02; H, 3.55; N, 12.63; S, 29.27%.
5
‐(2‐Hydroxyphenyl)‐2‐mercapto‐2,3‐dihydro‐1,3,4,2‐
thiadiazaphosphole‐2‐sulfide, pyridine solvate (2b).
Pale
EXPERIMENTAL
yellow crystals, mp 205–207°C, yield 74%. IR (KBr),
ꢀ
1
(
1
νmax, cm ): 3267 (OH), 3128 (NH), 3048 (C─Harom),
The melting point was determined in an open capillary
tube on a digital Stuart SMP‐3 apparatus. Infrared spectra
were measured on FTIR (Nicolet IS10) spectrophotometer
1
640 (C═N), 1589 (C═C), 755 (P═S). H‐NMR
(
500 MHz, DMSO‐d ): 6.20 (brs, 1H, SH exchangeable
6
with D O), 6.94–7.09 (m, 4H, Ar─H), 7.36 (t, 1H,
2
1
using KBr disks. H‐NMR spectra were measured on Jeol
J = 8.4 Hz, β‐H), 7.45 (t, 1H, J = 7.6 Hz, β‐H), 7.84 (d,
1H, J = 6.8 Hz, γ‐H), 8.21 (d, 2H, J = 6.9 Hz, α‐H),
Eca‐500 MHz using DMSO‐d as a solvent and TMS (δ)
6
1
3
as the internal standard. C‐NMR spectra were measured
on Bruker‐600 (150 MHz using CDCl3 as a solvent)
spectrometer and TMS (δ) as the internal standard. Mass
spectra recorded on a Gas Chromatographic GCMSqp
1
0.28 (s, 1H, NH exchangeable with D O), 11.12 (s, 1H,
2
13
OH exchangeable with D O). C‐NMR (150 MHz,
2
CDCl ): 115.9, 116.6, 118.2, 119.5, 126.6, 127.9, 133.7,
3
+
1
47.0, 160.5, 162.3. MS (EI, m/z): 341 (M ). Anal. Calcd
1
000 ex Shimadzu instrument at 70 ev. Elemental
for C H N OPS (341.41): C, 42.22; H, 3.54; N, 12.31;
12
12
2
3
microanalyses were performed using Perkin‐Elmer 2400 II
at the Chemical War department, Ministry of Defense. The
purity of the synthesized compounds was checked by
thin‐layer chromatography.
S, 28.18%. Found: C, 41.95; H, 3.29; N, 12.09; S, 27.89.
5
‐(2‐Aminophenyl)‐2‐mercapto‐2,3‐dihydro‐1,3,4,2‐thiadia
zaphosphole‐2‐sulfide, pyridine solvate (2c).
Yellow
crystals, mp 209–210°C, yield 72%. IR (KBr),
ꢀ
1
(
νmax, cm ): 3437, 3375 (NH ), 3336 (NH), 3064
2
General procedure for reaction of phosphorus
decasulfide with hydrazides and their corresponding
1
(C─Harom), 1620 (C═N), 741 (P═S).
H‐NMR
hydrazones.
Phosphorus decasulfide (2.22 g, 0.005
(
500 MHz, DMSO‐d ): 6.62 (brs, 1H, SH exchangeable
6
mole) was added to a solution of each hydrazide and
hydrazone (0.01 mol) in dry pyridine. The reaction
mixture was heated under reflux for 2–4 h. The contents
were cooled to room temperature and poured into ice‐
cooled water. The separated solids were filtered off and
with D O), 6.67–6.72 (m, 2H, Ar─H), 6.88 (d, 1H,
2
J = 8.4 Hz, Ar─H), 6.98 (br, 2H, NH exchangeable with
2
D O), 7.18 (t, 1H, J = 7.5 Hz, Ar─H), 7.25 (t, 2H,
2
J = 6.9 Hz, β‐H), 7.48 (d, 1H, J = 7.6 Hz, γ‐H), 7.83 (d,
2H, J = 7.6 Hz, α‐H), 10.30 (br, 1H, NH exchangeable
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2017
New Route for Construction of Four-, Five- and Six-membered Phosphorus
Heterocycles
+
1
with D O). MS (EI, m/z): 340 (M ). Anal. Calcd for
(C═S), 703 (P═S). H‐NMR (500 MHz, DMSO‐d6):
2
C H N PS (340.42): C, 42.34; H, 3.85; N, 16.46; S,
7.53 (s, 2H, 2NH exchangeable with D O), 7.75 (s, 1H,
1
2
13
4
3
2
2
8.26%. Found: C, 42.02; H, 3.72; N, 16.21; S, 28.02%.
N ‐[phenylmethylidene]benzoicthiocarbohydrazide (4). Beige
SH exchangeable with D O), 8.54 (brs, 1H, NH
2
0
+
exchangeable with D O). MS (EI, m/z): 185 (M ). Anal.
2
crystals, mp 195–197°C [13,14], yield 81%. IR (KBr),
Calcd for CH N PS (185.23): C, 6.48; H, 2.18; N,
4
3
3
ꢀ
1
(
νmax, cm ): 3180 (NH), 3059 (C─Harom), 1620 (C═N),
22.69; S, 51.93%. Found: C, 6.23; H, 2.07; N, 22.42; S,
51.64%.
1
1
601 (C═C), 1288 (C═S). H‐NMR (500 MHz,
DMSO‐d ): 7.43–7.71 (m, 8H, Ph─H), 7.88–7.89 (m, 2H,
2‐Mercapto‐4‐oxo‐1‐{[phenylmethylidene]amino}‐1,3,2‐dia
6
Ph─H), 8.45 (s, 1H, CH═N), 11.83 (brs, 1H, NH
zaphosphetidine‐2‐sulfide (8a). Beige crystals, mp 195–
+
ꢀ1
1
97 (dec.) °C, yield 59%. IR (KBr), (νmax, cm ): 3191
exchangeable with D O). MS (EI, m/z): 240 (M ). Anal.
2
Calcd for C H N S (240.32): C, 69.97; H, 5.03; N, 11.66;
(NH), 3083 (C─Harom), 1686 (C═O), 752 (P═S).
14 12 2
1
S, 13.34%. Found: C, 69.69; H, 4.86; N, 11.39; S, 13.03%.
H‐NMR (500 MHz, DMSO‐d
6
): 7.36–7.86 (m, 5H,
2
‐Mercapto‐3‐{[phenylmethylidene]amino}‐2,3‐dihydro‐4‐
thioxo‐1,3,2‐benzoxazaphosphinine‐2‐sulfide, pyridine solvate
5a).
Ph─H), 8.15 (brs, 1H, SH exchangeable with D O),
2
8
.69 (s, 1H, CH═N), 10.63 (brs, 1H, NH exchangeable
(
Yellow crystals, mp 226–227°C, yield 68%. IR
13
with D O). C‐NMR (150 MHz, CDCl ): 121.5, 129.3,
132.8, 138.0, 147.4, 167.7. MS (EI, m/z): 257 (M ).
Anal. Calcd for C H N OPS (257.27): C, 37.35; H,
2
3
ꢀ
1
(
KBr), (νmax, cm ): 3058, 3028 (C─Harom), 1630 (C═N),
233 (C═S), 755 (P═S). H‐NMR (500 MHz, DMSO‐d ):
.94–7.07 (m, 4H, Ar─H), 7.30 (d, 1H, J = 7 Hz, β‐H),
.36–7.43 (m, 4H, Ar─H and β‐H), 7.53 (d, 1H, γ‐H),
.71 (d, 2H, J = 6.1 Hz, Ar─H), 7.85 (d, 1H, J = 7.6 Hz,
+
1
1
6
7
7
6
8
8
3
2
3
.13; N, 16.33; S, 24.93%. Found: C, 37.02; H, 3.01; N,
1
6.09; S, 24.67%.
2‐Mercapto‐1‐{[phenylmethylidene]amino}‐4‐thioxo‐1,3,2‐
α‐H), 8.01 (d, 1H, α‐H), 7.78 (brs, 1H, SH exchangeable
diazaphosphetidine‐2‐sulfide (8b).
139–140°C, yield 52%. IR (KBr), (νmax, cm ): 3253
Beige crystals, mp
13
ꢀ1
with D O), 8.44 (s, 1H, CH═N). C‐NMR (150 MHz,
2
CDCl ): 116.1, 118.9, 119.3, 121.8, 124.7, 125.6, 128.7,
(NH), 3030 (C─Harom), 1590 (C═N), 750 (P═S).
3
1
1
28.8, 128.9, 129.0, 138.4, 144.3, 148.7, 151.6, 207.0.
H‐NMR (500 MHz, DMSO‐d ): 7.36–7.40 (m, 3H,
6
+
MS (EI, m/z): 429 (M ). Anal. Calcd for C H N OPS
Ph─H), 7.75–7.77 (m, 2H, Ph─H), 7.95 (s, 1H, SH
19
16
3
3
(429.51): C, 53.13; H, 3.75; N, 9.78; S, 22.40%. Found:
exchangeable with D O), 8.20 (s, 1H, CH═N), 11.40 (s,
2
C, 52.88; H, 3.54; N, 9.59; S, 22.11%.
1H, NH exchangeable with D O). MS (EI, m/z): 273
2
+
2
‐Mercapto‐3‐{[phenylmethylidene]amino}‐4(1H)‐thioxo‐
,3‐dihydro‐1,3,2‐benzodiazaphosphinine‐2‐sulfide, pyridine
solvate (5b). Pale brown crystals, mp 154–158°C, yield
(M ). Anal. Calcd for C H N PS (273.34): C, 35.15;
8
8
3
3
2
H, 2.95; N, 15.37; S, 35.19%. Found: C, 34.82; H, 2.60;
N, 15.06; S, 34.87%.
ꢀ
1
6
7%. IR (KBr), (νmax, cm ): 3378 (NH), 3050
4‐Amino‐3‐mercapto‐5‐oxo‐1,2,4,3‐triazaphospholidine‐
1
(
C─Harom), 1636 (C═N), 1253 (C═S), 749 (P═S). H‐
3‐sulfide (9a).
64%. IR (KBr), (νmax, cm ): 3429, 3201 (br, NH ,
2
White crystals, mp 121–123°C, yield
ꢀ
1
NMR (500 MHz, DMSO‐d ): 6.35 (br, 1H, SH
6
1
exchangeable with D O), 6.54 (t, 1H, J = 6.9 Hz,
NH), 1707 (C═O), 1628 (NH2 def), 790 (P═S). H‐
2
Ar─H), 6.71–6.74 (m, 3H, Ar─H), 7.17 (t, 1H,
J = 7 Hz, Ar─H), 7.40–7.50 (m, 5H, Ar─H, and β‐H),
NMR (500 MHz, DMSO‐d ): 5.53 (br, 2H, NH2
6
exchangeable with D O), 7.34 (s, 1H, SH exchangeable
2
7
.53 (d, 1H, J = 7.5 Hz, γ‐H), 7.66–7.72 (m, 3H, Ar─H
with D O), 8.52 (brs, 1H, NH exchangeable with D O),
2
2
and α‐H), 8.36 (s, 1H, CH═N), 11.58 (s, 1H, NH
11.59 (br, 1H, NH exchangeable with D O). MS (EI,
2
+
+
exchangeable with D O). MS (EI, m/z): 428 (M ). Anal.
2
m/z): 184 (M ). Anal. Calcd for CH N OPS (184.18):
5 4 2
Calcd for C H N PS (428.53): C, 53.25; H, 4.00; N,
C, 6.52; H, 2.74; N, 30.42; S, 34.82%. Found: C, 6.29;
1
9
17
4
3
1
3.07; S, 22.45%. Found: C, 53.03; H, 3.72; N, 12.88;
H, 2.39; N, 30.12; S, 34.59%.
S, 22.08%.
4‐Amino‐3‐mercapto‐5‐thioxo‐1,2,4,3‐triazaphospholidine‐
3‐sulfide (9b). Beige crystals, mp 224–226°C, yield 69%.
3
‐Mercapto‐5‐oxo‐1,2,4,3‐triazaphospholidine‐3‐sulfide
ꢀ
1
(
6a).
Pale brown crystals, mp 262–263°C (Td), yield
IR (KBr), (νmax, cm ): 3267, 3211 (NH , NH), 1646 (NH
2 2
ꢀ
1
1
7
2%. IR (KBr), (νmax, cm ): 3410, 3310, 3206 (NH),
def.), 1157 (C═S), 754 (P═S). H‐NMR (500 MHz,
DMSO‐d ): 5.23 (br, 2H, NH exchangeable with D O),
1
1
678 (C═O), 763 (P═S). H‐NMR (500 MHz,
6
2
2
DMSO‐d ): 5.80 (brs, 2H, 2NH exchangeable with D O),
7.12 (s, 1H, SH exchangeable with D O), 8.45 (brs, 1H,
6
2
2
7
.50 (s, 1H, SH exchangeable with D O), 8.55 (brs, 1H,
2
NH exchangeable with D
2
O), 12.66 (s, 1H, NH
1
3
13
NH exchangeable with D O). C‐NMR (150 MHz,
CDCl ): 169.0. MS (EI, m/z): 169 (M ). Anal. Calcd for
CH N OPS (169.16): C, 7.10; H, 2.38; N, 24.84; S,
3
exchangeable with D O). C‐NMR (150 MHz, CDCl ):
2
2
3
+
+
3
202.0 (C═S). MS (EI, m/z): 198 (M –2H). Anal. Calcd
for CH OPS (200.24): C, 6.00; H, 2.52; N, 27.98; S,
48.04%. Found: C, 5.62; H, 2.31; N, 27.62; S, 47.79%.
4
3
2
N
5
4
3
7.91%. Found: C, 6.82; H, 2.12; N, 24.51; S, 37.64%.
3
‐Mercapto‐5‐thioxo‐1,2,4,3‐triazaphospholidine‐3‐sulfide
3
‐Mercapto‐5‐oxo‐4‐{[phenylmethylidene]amino}‐1,2,4,3‐
(
6b). Pale yellow crystals, mp 245–247 (Td) °C, yield
triazaphospholidine‐3‐sulfide (11a). Yellow crystals, mp
ꢀ
1
ꢀ1
6
6%. IR (KBr), (νmax, cm ): 3413, 3209 (NH), 1182
1
84–185°C, yield 59%. IR (KBr), (νmax, cm ): 3195
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

S. M. Abdel-Kariem and T. E. Ali
Vol 000
(
(
4
NH), 3068 (C─Harom), 1685 (C═O), 1624 (C═N), 753
[6] Nilov, D. B.; Kadushkin, A. V.; Soloveva, N. P.; Sheinker,
Y. N.; Granik, V. G. Chem Heterocycl Compds 2004, 40, 106.
1
P═S). H‐NMR (500 MHz, DMSO‐d ): 7.30–7.49 (m,
6
[7] Nilov, D. B.; Soloveva, N. P.; Nikolaeva, I. S.; Peters, V. V.;
H, Ph─H), 7.75 (d, 1H, Ph─H), 7.85 (s, 1H, SH
Krylova, Y. U. L.; Guskova, T. A.; Granik, V. G. Pharm Chem J 1998,
32, 358.
exchangeable with D O), 8.15 (brs, 1H, NH
exchangeable with D O), 8.69 (s, 1H, CH═N), 11.67
(
(
2
[
8] Kozachenko, A. P.; Shablykin, O. V.; Gakh, A. A.; Rusanov,
E. B.; Brovarets, V. S. Heteroatom Chem 2010, 21, 492.
9] Abdou, W. M.; Kamel, A. A.; Shaddy, A. A. Eur J Med Chem
2010, 45, 5217.
2
1
3
brs, 1H, NH exchangeable with D O).
C‐NMR
2
[
150 MHz, CDCl ): 120.8, 125.5, 132.9, 136.0, 147.5,
3
+
[10] Kroon, F. J.; Kuhnert, P. M.; Henderson, B. L.; Wilkinson,
1
65.5. MS (EI, m/z): 272 (M ). Anal. Calcd for
S. N.; Kinsey‐Henderson, A.; Abbott, B.; Brodie, J. E.; Turner, R. D.
R. Mar Pollut Bull 2012, 65, 167.
C H N OPS (272.28): C, 35.29; H, 3.33; N, 20.58; S,
2
8
9
4
2
3.55%. Found: C, 35.02; H, 3.01; N, 20.27; S, 23.16%.
[11] Dorosti, N.; Delfan, B.; Gholivand, K.; Valmoozi, A. A. E.
3
‐Mercapto‐4‐{[phenylmethylidene]amino}‐5‐thioxo‐1,2,4,3‐
Med Chem Res 2016, 25, 769.
[12] Samota, M. K.; Kumar, A.; Kaur, J.; Mittal, S.; Seth, G.
Phosphorus, Sulfur, Silicon Relat Elem 2006, 181, 1919.
triazaphospholidine‐3‐sulfide (11b).
16–218°C, yield 56%. IR (KBr), (νmax, cm ): 3159
NH), 3024 (C─Harom), 1563 (C═N), 1118 (C═S), 755
P═S). H‐NMR (500 MHz, DMSO‐d ): 7.34–7.40 (m,
H, Ph─H), 7.59–7.61 (m, 2H, Ph─H), 7.85 (s, 1H, SH
exchangeable with D O), 8.00 (s, 1H, CH═N), 8.55 (brs,
Beige crystals, mp
ꢀ
1
2
(
(
3
[
13] Evans, D. M.; Taylor, D. R. J Chem Soc Chem Comunn
1982188.
[14] Evans, D. M.; Hill, L.; Taylor, D. R.Myers, MJ Chem Soc
Perkin Trans 1986, 1, 1499.
15] Golovko, T. V.; Soloveva, N. P.; Granik, V. G. Mendeleev
1
6
[
2
Commun 1995, 5, 191.
1
H, NH exchangeable with D O), 11.84 (brs, 1H, NH
[16] Nilov, D. B.; Kadushkin, A. V.; Soloveva, N. P.; Granik, V. G.
Mendeleev Commun 1995, 5, 67.
2
+
exchangeable with D O), MS (EI, m/z): 288 (M ). Anal.
Calcd for C H N PS (288.35): C, 33.32; H, 3.15; N,
1
3
2
[
17] Bryce, M. R.; Matthews, R. S. J Organomet Chem 1987,
25, 153.
18] Acheson, R. M.; Lines, C. T.; Bryce, M. R.; Dauter, Z.;
Reynolds, C. D.SchmidpeterA J Chem Soc Perkin Trans 1913, 2, 1985.
19] Kaplancikl, Z. A.; Zitouni, G. T.; Ozdemir, A.; Revial, G. Eur J
Med Chem 2008, 43, 155.
20] Chen, M.; Wang, X.‐F.; Wang, S.‐S.; Feng, Y.‐X.; Chen, F.;
Yang, C.‐L. J Fluorine Chem 2012, 135, 323.
8
9
4
3
3
9.43; S, 33.36%. Found: C, 32.98; H, 2.89; N, 19.11; S,
3.09%.
[
[
REFERENCES AND NOTES
[
[1] Andrews, L.; Reynolds, G. G.; Mielke, Z.; McCluskey, M.
Inorg Chem 1990, 29, 5222.
[
[
[
[
2] Ozturk, T.; Ertas, E.; Mert, O. Chem Rev 2010, 110, 3419.
3] Nagarajan, K.; Shenoy, S. J Helv Chim Acta 1985, 68, 900.
4] Nilov, D. B.; Granik, V. G. Mendeleev Commun 2003, 13, 78.
5] Dastychova, L.; Sotolarova, M.; Dastych, D.; Taraba, J.;
SUPPORTING INFORMATION
Additional Supporting Information may be found online
in the supporting information tab for this article.
Necas, M.; Prihoda, J. Polyhedron 2007, 26, 4250.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet