Ditolyldithiophosphato derivatives of phosphorus(III) and phosphorus(V)

Article abstract of DOI:10.1007/s00706-007-0836-6

O,O′-Ditolylphosphorodithioates of phosphorus(III), [(o-, m-, or p-CH₃C₆H₄O)₂PS₂] _n PCl_3-n , and phosphorus(V), [(o-, m-, or p-CH ₃C₆H₄O)₂-PS₂] _n POCl_3-n , (n = 1, 2, and 3) were isolated as colorless viscous liquids by the reaction of PCl₃ and POCl₃ with sodium ditolylphosphorodithioate, (o-, m-, or p-CH₃C ₆H₄O)₂PS₂Na, in 1:1, 1:2, and 1:3 molar ratios in toluene. These compounds were characterized by elemental analyses, molecular weight measurements, IR, and NMR (¹H, ³¹P, and ¹³C) spectroscopic studies, which indicated a less common monodentate linkage of dithiophosphate moieties in both phosphorus(III) and phosphorus(V) derivatives leading to a tetrahedral geometry around the phosphorus atom.

Full text of DOI:10.1007/s00706-007-0836-6

Monatsh Chem 139, 747–752 (2008)
DOI 10.1007/s00706-007-0836-6
Printed in The Netherlands
Ditolyldithiophosphato derivatives of phosphorus(III) and phosphorus(V)
Bhawana Gupta, Suresh Magotra, Sushil K. Pandey
Department of Chemistry, University of Jammu, Jammu, India
Received 27 September 2007; Accepted 24 October 2007; Published online 24 April 2008
# Springer-Verlag 2008
Abstract O,O0-Ditolylphosphorodithioates of phos-
manner [5–11]. However, some compounds with less
phorus(III), [(o-, m-, or p-CH3C6H4O)2PS2]nPCl3 ꢀ n
,
common monodentate linkages have also been de-
scribed [12, 13]. It is pertinent to mention that these
dithiophosphato derivatives find extensive appli-
cations in various fields, like agriculture [14, 15],
industries [16, 17], and analytical studies [18, 19].
A literature survey revealed scanty information on
O,O0-ditolyldithiophosphate ligands and their deriv-
atives compared to dialkyl- and alkylenedithiopho-
sphates [20–24]. In fact, no systematic study or
review is available, in particular on the ditolyldithio-
phosphates. We have recently reported a convenient
synthesis route of ditolyldithiophosphate ligands
[25, 26]. These new ligands appeared to be potential
chelating ligands to both metals and metalloids [27,
28]. In addition, some ditolyldithiophosphates have
also found their use as rubber vulcanizers [29], aero-
floats [30], polymerization catalysts [31], and in
agriculture as acaricides or herbicides [32]. The
compound Sb[S2P(O2C6H4CH3)2]3 is reported as a
passivation agent in petroleum refining [33]. In view
of the above interesting facets of dithiophosphate
chemistry and the utility of phosphorus compounds
in biological activities [34, 35], it was considered to
be of interest to extend the investigations on ditolyl-
dithiophosphate derivatives particularly having more
than one phosphorus moieties in the molecule. Thus,
we report herein the synthesis and characterization
of phosphorus(III) and phosphorus(V) derivatives of
ditolyldithiophosphates by reacting sodium ditolyl-
phosphorodithioates with PCl3 and POCl3 in differ-
ent stoichiometries.
and phosphorus(V), [(o-, m-, or p-CH3C6H4O)2-
PS2]nPOCl3ꢀ n, (n ¼ 1, 2, and 3) were isolated as col-
orless viscous liquids by the reaction of PCl3 and
POCl3 with sodium ditolylphosphorodithioate, (o-,
m-, or p-CH3C6H4O)2PS2Na, in 1:1, 1:2, and 1:3 molar
ratios in toluene. These compounds were characterized
by elemental analyses, molecular weight measure-
ments, IR, and NMR (1H, 31P, and 13C) spectroscopic
studies, which indicated a less common monodentate
linkage of dithiophosphate moieties in both phospho-
rus(III) and phosphorus(V) derivatives leading to a
tetrahedral geometry around the phosphorus atom.
Keywords Cresyl; Ditolyl; Phosphorus compounds; Dithio-
phosphates.
Introduction
Dialkylphosphonates [(RO)2PO]ꢀ, dialkylthiophos-
phonates
[(RS)2PO]ꢀ,
dialkyldithiophosphates
[(OR)2PS2]ꢀ, and O,O0-alkylenedithiophosphates
[OGOPS2]ꢀ have attracted wide attention in acade-
mia in particular for providing various bonding
aspects with metals and metalloids [1–4]. A varieties
of complexes have been reported in which the dithio-
phosphate ligands behave, normally, in a bidentate
Correspondence: Sushil K. Pandey, Department of Chemistry,
University of Jammu, Baba Saheb Ambedkar Road, Jammu
180 006 (J & K), India. E-mail: kpsushil@rediffmail.com

748
B. Gupta et al.
Results and discussion
23, 36, 37]. Appearance of a new absorption band of
medium intensity in the range ꢀꢀ¼ 652–552 cmꢀ1,
which is overlapped slightly with the ꢀꢀP–S vibration
of the dithiophosphate moiety, may be attributed to
the formation of new ꢀꢀP–S chemical linkage. The
absorption bands of strong intensity present in the
regions ꢀꢀ¼ 1185–1139 cmꢀ1 and ꢀꢀ¼ 959–913 cmꢀ1
are tentatively assigned for ꢀꢀ(P)–O–C and ꢀꢀP–O–(C)
vibrations. The ꢀꢀP¼S vibrations of the dithiophos-
phate moiety occurred in the region ꢀꢀ¼ 782–655 cmꢀ1.
Aromatic ꢀꢀC–H vibrations were observed in their
characteristic range of ꢀꢀ¼ 2983–2921 cmꢀ1 for all
compounds. The phosphoryl (ꢀꢀP¼O) absorption
bands in the derivatives 4a–4i appeared in the range
of ꢀꢀ¼ 1340–1294 cmꢀ1. Bands at ꢀꢀ¼ 627–505 cmꢀ1
have been assigned to the ꢀꢀP–Cl vibrations in the
compounds 3a–3f and 4a–4f. The disappearance of
the band for ꢀꢀP–Cl absorption in the spectra of the
compounds 3g–3i and 4g–4i is suggestive of re-
placement of all three chlorine atoms attached to
PCl3 and POCl3 by the dithiophosphate ligand.
The 1H NMR spectra of these compounds display
a singlet for the methyl and a multiplet for tolyl ring
protons at ꢁ ¼ 2.3 ppm and ꢁ ¼ 7.0–8.2 ppm. These
chemical shift values did not indicate any shift com-
parable to the parent dithiophosphate ligands.
Reactions of sodium O,O0-(o-, m-, or p-ditolyl)phos-
phorodithioate or (o-, m-, or p-CH3C6H4O)2PS2Na
(1a–1c), with phosphorus trichloride, PCl3 (2a), and
phosphorus oxychloride, POCl3 (2b), in 1:1, 2:1,
and 3:1 molar ratio in refluxing toluene resulted in
the formation of (o-, m-, or p-ditolyl) dithiophosphato
derivatives of phosphorus(III), [(CH3C6H4O)2PS2]n-
PCl3 ꢀ n (3a–3i), and of phosphorus(V), [(CH3C6-
H4O)2PS2]nPOCl3 ꢀ n, (4a–4i), (n ¼ 1, 2 or 3) as
colorless viscous liquids in 85–92% yield (Scheme 1).
The syntheses of the compounds have been
achieved by cleavage of the phosphorus-chlorine
bond present in phosphorus trichloride and phospho-
rus oxychloride. The removal of chloride ion might
take place as a consequence of a nucleophilic dis-
placement with the dithiophosphate moiety as illus-
trated in Scheme 2.
The elemental analyses of these compounds (C,
H, Cl, and S) were found to be consistent with their
molecular formula. These derivatives are non-vola-
tile, soluble in common organic solvents viz. toluene,
benzene, chloroform and methylenechloride, but in-
soluble in n-hexane. Although these compounds ap-
peared to be moisture sensitive, they can be stored
unchanged for a long time under dry conditions. The
monomeric nature of these compounds was con-
firmed by the molecular weight determination of
few compounds.
The 31P NMR chemical shifts clearly indicated
two different types of chemically non-equivalent
phosphorus atom. The trivalent phosphorus atom in
the compounds 3a–3i appeared in the region ꢁ ¼
193.6–197.5 ppm, which show the shielding of phos-
phorus atom to the extent of about ꢁ ¼ 24–28 ppm
IR spectra of these derivatives have been interpret-
ed on comparative basis with literature reports [20–
Scheme 1
Scheme 2

Ditolyldithiophosphato derivatives of phosphorus(III) and phosphorus(V)
749
from its position in free phosphorus trichloride
(31P ¼ 221 ppm). The phosphorus atom of phospho-
ryl (P¼O) group in the compounds 4a–4i appeared
as singlet in the region ꢁ ¼ 6.5–13.7 ppm, which is
deshielded compared to its position at ꢁ ¼ 1.9 ppm in
free phosphorus oxychloride. The chemical shift of
the phosphorus atom of dithiophosphate moiety was
found as doublet in the range ꢁ ¼ 80.1–88.2 ppm.
Perhaps, this is due to the asymmetrical nature of
the phosphorus nuclei in the molecule and also due
to monodentate mode of bonding of dithiophosphate
ligand towards the other phosphorus atom.
Fig. 1 X and Y ¼ Cl for 3a–3c; X ¼ 1a–1c and Y ¼ Cl for
3d–3f; X and Y ¼ 1a–1c for 3g–3i
In the 13C NMR spectra of some representative
compounds (3a, 3f, 3h, 4a, 4e, and 4i), the chemical
shift for the ꢀCH3 carbon attached to the tolyl rings
were found in the region ꢁ ¼ 17.4–17.5 ppm. The
chemical shifts for ortho-, meta-, and para- carbons
were found in the region ꢁ ¼ 121.7–130.4, 124.4–
129.4 and 126.4–131.3 ppm. The shifts for C–O car-
bon of O,O0-(meta- or para-ditolyl)dithiophosphato
derivatives of P(III) (3f and 3h) and P(V) (4e and 4i)
were found in the region 154.3–154.7 ppm. This is
indicative of intramolecular hydrogen bonding be-
tween a proton attached to one of the ortho carbons
of one tolyl ring and the oxygen atom O–(C) of the
other tolyl ring. However, the shift for C–O carbon
of O,O0-(ortho-ditolyl)dithiophosphato derivatives
(3a, 4a) was observed in the normal range ꢁ ¼
150.8–151.1 ppm, showing the absence of intramo-
lecular hydrogen bonding. The presence of hydrogen
bonding in O,O0-(meta- or para-ditolyl)dithiophos-
phato derivatives is also confirmed by chemical shift
for the C–(CH3) carbon (ꢁ ¼115.1–115.8 ppm) com-
pared to the shift in O,O0-(ortho-ditolyl)dithiopho-
sphato derivative, which lies in the normal region
(ꢁ ¼122.0–122.2 ppm). Perhaps, the low field swing
for the chemical shift due to the C–(CH3) carbon of
O,O0-(meta- or para-ditolyl)dithiophosphato deriva-
tives is owing to hydrogen bonding between proton
attached to the (ortho) carbon of one tolyl ring with
the oxygen atom of other tolyl ring.
Fig. 2 X and Y ¼ Cl for 4a–4c; X ¼ 1a–1c and Y ¼ Cl for
4d–4f; X and Y ¼ 1a–1c for 4g–4i
with literature reports [20–23, 36, 37], a probable
geometry around the phosphorus(III) and phosphor-
us(V) in different coordination spheres may tentative-
ly be assigned to these compounds. The 31P spectra of
the compounds (3a–3i) display a doublet, which is
suggestive of a monodentate linkage of the dithio-
phosphate ligand, hence only one sulfur atom of the
dithiophosphate ligand might be attached to the
phosphorus(III) atom leaving another sulfur atom
non-bonded. Therefore, a distorted tetrahedral ge-
ometry is assigned around the phosphorus(III) atom
in the compounds 3a–3i in which the fourth position
is occupied by a lone pair of electrons (Fig. 1).
Considering the similar aspects, the compounds 4a–
4i might have akin geometrical arrangement around
the phosphorus(V) atom of POCl3 except that a lone
pair of electrons on the phosphorus(III) is replaced
by a doubly bonded oxygen atom (Fig. 2).
Experimental
Moisture was carefully excluded throughout the experimental
manipulations by using standard Schlenk’s technique. Toluene
and benzene were freshly dried by refluxing over sodium,
followed by distillation. Sulfur was estimated gravimetrically
as barium sulfate (Messenger’s method) and chlorine was
estimated volumetrically by Volhard’s method. Elemental
analyses were conducted using a Leco CHNS-932 analyzer;
their results were well in accord with the calculated values.
Molecular weights were determined by cryoscopic method in
freezing benzene. IR spectra were recorded in nujol mulls in
the range of ꢀꢀ¼ 4000–200 cmꢀ1 on a Perkin Elmer-557 spec-
Structural features
It was not possible to assign precisely the struc-
ture of these compounds since these compounds
are viscous liquids and can not be crystallized. How-
ever, on the basis of elemental analyses, molecular
weight determination, and spectroscopic studies like
IR and NMR (1H, 13C, and 31P) and in conjunction

750
B. Gupta et al.
trophotometer. The 1H and 13C NMR spectra were recorded in
CDCl3 on a Brucker DRX 300 (120 MHz) using TMS as
external reference. The 31P NMR spectra were recorded in
CDCl3 using H3PO4 (85%) as external reference on a
Brucker DRX 300 (120 MHz).
ꢁ ¼ 2.3 (s, 12H, CH3 of cresol), 7.0–7.9 (m, 16H, C6H4) ppm;
31P NMR (120MHz, CDCl3): ꢁ ¼ 82.3 (d, dithio), 193.6 (s,
PCl) ppm.
Bis(bis(m-tolyloxy)phosphorothioylthio)phosphorus(III)-
chloride (3e, C28H28O4P3S4Cl)
(Bis(o-tolyloxy)phosphorothioylthio)phosphorus(III)chloride
(3a, C14H14O2PS2Cl2)
According to the procedure described for 3a, 1.16g of (m-
CH3C6H4O)2PS2Na (1b) (0.35 mmol) and 0.24g of PCl3 (2a)
(0.17 mmol) were used to give 3e as a colorless viscous liquid.
Yield: 2.41 g (88%); M.W. calcd. for C28H28O4P3S4Cl: 685.13,
found: 662.12; IR (nujol): ꢀꢀ¼ 2983b, 1142s, 948s, 687m,
12H, CH3 of cresol), 7.1–8.0 (m, 16H, C6H4) ppm; 31P NMR
(120 MHz, CDCl3): ꢁ ¼ 82.6 (d, dithio), 193.8 (s, PCl) ppm.
To a toluene suspension (ꢁ35 cm3) of sodium O,O0-(o-dito-
lyl)phosphorodithioate, 1.12g (o-CH3C6H4O)2PS2Na (1a)
(0.33 mmol) was added dropwise a toluene solution
(ꢁ15 cm3) of 0.46 g PCl3 (2a) (0.34 mmol) by using a drop-
ping funnel with constant stirring at room temperature. The
contents were refluxed for ꢁ3 h during which a white precipi-
tate of NaCl was formed. The reaction was allowed to reach
room temperature, then filtered through an alkoxy funnel fitted
with a G-4 sintered disc followed by evaporation of excess
of solvent from the filtrate under reduced pressure. The prod-
uct was finally dried in vacuo for 3 h, which yielded [(o-
CH3C6H4O)2PS2PCl2] (3a) as colorless viscous liquid. Yield:
1.25g (90%); M.W. calcd. for C14H14O2PS2Cl2: 411.23,
found: 398.72; IR (nujol): ꢀꢀ¼ 2981b, 1163s, 926s, 760m,
1
598m, 541w cmꢀ1; H NMR (120 MHz, CDCl3): ꢁ ¼ 2.3 (s,
Bis(bis(p-tolyloxy)phosphorothioylthio)phosphorus(III)-
chloride (3f, C28H28O4P3S4Cl)
According to the procedure described for 3a, 1.89 g of (p-
CH3C6H4O)2PS2Na (1c) (0.56mmol) and 0.39g of PCl3
(2a) (0.28 mmol) were used to give 3f as a colorless viscous
liquid. Yield: 3.46g (89%); M.W. calcd. for C28H28O4P3S4Cl:
685.13, found: 696.42; IR (nujol): ꢀꢀ¼ 2923b, 1159s, 918s,
1
595m, 525w cmꢀ1; H NMR (120 MHz, CDCl3): ꢁ ¼ 2.3 (s,
720m, 651m, 505w cmꢀ1 1H NMR (120 MHz, CDCl3):
;
6H, CH3 of cresol), 7.0–7.9 (m, 8H, C6H4) ppm; 13C NMR
(120 MHz, CDCl3): ꢁ ¼ 17.4 (s, CH3), 150.9–151.1 (m, C–O),
122.0 (d, C–CH3), 123.2–123.7 (m, C-ortho), 124.5–125.7
(m, C-meta), 126.8–131.3 (m, C-para) ppm; 31P NMR
(120 MHz, CDCl3): ꢁ ¼ 80.1 (d, dithio), 195.0 (s, PCl2) ppm.
ꢁ ¼ 2.3 (s, 12H, CH3 of cresol), 7.0–8.0 (m, 16H, C6H4)
ppm; 13C NMR (120MHz, CDCl3): ꢁ ¼ 17.4 (s, CH3), 154.3
(m, C–O), 115.2(d, C–CH3),126.6–130.4(m, C-ortho),127.2–
129.4 (m, C-meta); 126.6–129.6 (m, C-para) ppm;31P NMR
(120 MHz, CDCl3): ꢁ ¼ 83.1 (d, dithio), 196.2 (s, PCl) ppm.
(Bis(m-tolyloxy)phosphorothioylthio)phosphorus(III)-
chloride (3b, C14H14O2PS2Cl2)
Tris(bis(o-tolyloxy)phosphorothioylthio)phosphorus(III)
(3g, C42H42O6P4S6)
According to the procedure described for 3a, 1.06g of (m-
CH3C6H4O)2PS2Na (1b) (0.31 mmol) and 0.43 g of PCl3 (2a)
(0.31 mmol) were used to give 3b as a colorless viscous liquid.
Yield: 1.21 g (92%); M.W. calcd. for C14H14O2PS2Cl2: 411.23,
found: 401.14; IR (nujol): ꢀꢀ¼ 2922b, 1146s, 959s, 782m,
6H, CH3 of cresol), 7.1–8.0 (m, 8H, C6H4) ppm; 31P NMR
(120 MHz, CDCl3): ꢁ ¼ 80.6 (d, dithio), 197.5 (s, PCl2) ppm.
According to the procedure described for 3a, 2.26 g of (o-
CH3C6H4O)2PS2Na (1a) (0.68 mmol) and 0.37g of PCl3
(2a) (0.22 mmol) were used to give 3g as a colorless viscous
liquid. Yield: 5.53 g (85%); IR (nujol): ꢀꢀ¼ 2976b, 1170s,
1
928s, 758m, 597m cmꢀ1; H NMR (120MHz, CDCl3): ꢁ ¼
1
596m, 528w cmꢀ1; H NMR (120 MHz, CDCl3): ꢁ ¼ 2.3 (s,
2.3 (s, 18H, CH3 of cresol), 7.0–7.9 (m, 24H, C6H4) ppm; 31
P
NMR (120 MHz, CDCl3): ꢁ ¼ 84.9 (d, dithio), 195.2 (s, P of
PCl3) ppm.
(Bis(p-tolyloxy)phosphorothioylthio)phosphorus(III)chloride
(3c, C14H14O2PS2Cl2)
Tris(bis(m-tolyloxy)phosphorothioylthio)phosphorus(III)
(3h, C42H42O6P4S6)
According to the procedure described for 3a, 1.28g of
(p-CH3C6H4O)2PS2Na (1c) (0.38 mmol) and 0.52 g of PCl3
(0.38 mmol) (2a) were used to give 3c as a colorless viscous
liquid. Yield: 1.43g (90%); IR (nujol): ꢀꢀ¼ 2981b, 1162s,
922s, 725m, 652m, 511w cmꢀ1; 1H NMR (120 MHz, CDCl3):
ꢁ ¼ 2.3 (s, 6H, CH3 of cresol), 7.0–8.0 (m, 8H, C6H4) ppm;
31P NMR (120 MHz, CDCl3): ꢁ ¼ 81.2 (d, dithio), 197.7 (s,
PCl2) ppm.
According to the procedure described for 3a, 2.75g of (m-
CH3C6H4O)2PS2Na (1b) (0.82 mmol) and 0.37g of PCl3 (2a)
(0.27 mmol) were used to give 3h as a colorless viscous liquid.
Yield: 6.96 g (88%); IR (nujol): ꢀꢀ¼ 2926b, 1154s, 946s,
18H, CH3 of cresol), 7.0–8.1 (m, 24H, C6H4) ppm; 13C NMR
(120MHz, CDCl3): ꢁ ¼ 17.5 (s, CH3), 154.6 (m, C–O), 115.1
(d, C–CH3), 127.2–130.1 (m, C-ortho), 126.3–129.2 (m, C-
meta), 127.9–130.2 (m, C-para) ppm; 31P NMR (120 MHz,
CDCl3): ꢁ ¼ 86.8 (d, dithio), 196.8 (s, P of PCl3) ppm.
1
720m, 600m cmꢀ1; H NMR (120 MHz, CDCl3): ꢁ ¼ 2.3 (s,
Bis(bis(o-tolyloxy)phosphorothioylthio)phosphorus(III)-
chloride (3d, C28H28O4P3S4Cl)
Tris(bis(p-tolyloxy)phosphorothioylthio)phosphorus(III)
(3i, C42H42O6P4S6)
According to the procedure described for 3a, 1.31 g of (o-
CH3C6H4O)2PS2Na (1a) (0.39 mmol) and 0.27g of PCl3
(2a) (0.19 mmol) were used to give 3d as a colorless viscous
liquid. Yield: 2.35g (87%); IR (nujol): ꢀꢀ¼ 2982b, 1162s,
926s, 760m, 601m, 523w cmꢀ1; 1H NMR (120 MHz, CDCl3):
According to the procedure described for 3a, 2.53 g of (p-
CH3C6H4O)2PS2Na (1c) (0.76 mmol) and 0.34 g of PCl3 (2a)
(0.25 mmol) were used to give 3i as a colorless viscous liquid.

Ditolyldithiophosphato derivatives of phosphorus(III) and phosphorus(V)
751
Yield: 6.05 g (83%); M.W. calcd. for C42H42O6P4S6: 959.04,
found: 984.17; IR (nujol): ꢀꢀ¼ 2923b, 1160s, 918s, 726m, 652m
of cresol), 7.0–8.0 (m, 24H, C6H4) ppm; 31P NMR (120MHz,
(2b) (0.18 mmol) were used to give 4e as a colorless viscous
liquid. Yield: 2.21 g (86%); IR (nujol): ꢀꢀ¼ 2960b, 1153s,
1
cmꢀ1
;
1H NMR (120MHz, CDCl3): ꢁ ¼ 2.3 (s, 18H, CH3
922, 658m, 560m, 1300m, 608w cmꢀ1; H NMR (120 MHz,
CDCl3): ꢁ ¼ 2.3 (s, 12H, CH3 of cresol), 7.7–8.0 (m, 16H,
C6H4) ppm; 13C NMR (120MHz, CDCl3): ꢁ ¼ 17.4 (s, CH3),
154.7 (m, C–O), 115.6 (d, C–CH3), 123.2–124.1 (m,
C-ortho), 124.7–125.6 (m, C-meta), 128.2–127.7 (m, C-para)
ppm; 31P NMR (120MHz, CDCl3): ꢁ ¼ 87.6 (d, dithio), 13.4
(s, POCl) ppm.
CDCl3): ꢁ ¼ 85.1 (d, dithio), 195.5 (s, P of PCl3) ppm.
(Bis(o-tolyloxy)phosphorothioylthio)(oxo)phosphorus(V)-
chloride (4a, C14H14O3P2S2Cl2)
According to the procedure described for 3a, 0.95g of (o-
CH3C6H4O)2PS2Na (1a) (0.28mmol) and 0.43 g of POCl3
(2b) (0.28 mmol) were used to give 4a as a colorless viscous
liquid. Yield: 1.12 g (92%); IR (nujol): ꢀꢀ¼ 2967b, 1147s, 936s,
657m, 552m, 1328m, 620w cmꢀ1; 1H NMR(120 MHz, CDCl3):
Bis(bis(p-tolyloxy)phosphorothioylthio)(oxo)phosphorus(V)-
chloride (4f, C28H28O5P3S4Cl)
According to the procedure described for 3a, 1.01 g of (p-
CH3C6H4O)2PS2Na (1c) (0.30 mmol) and 0.23 g of POCl3
(2b) (0.15 mmol) were used to give 4f as a colorless viscous
liquid. Yield: 1.81 g (85%); IR (nujol): ꢀꢀ¼ 2958b, 1154s,
924s, 662m, 562m, 1294m, 612w cmꢀ1; 1H NMR (120 MHz,
CDCl3): ꢁ ¼ 2.3 (s, 12H, CH3 of cresol), 7.8–8.1 (m, 16H,
C6H4) ppm; 31P NMR (120MHz, CDCl3): ꢁ ¼ 88.2 (d, dithio),
13.6 (s, POCl) ppm.
ꢁ ¼ 2.3 (s, 6H, CH3 of cresol), 7.8–8.2 (m, 8H, C6H4) ppm; 13
C
NMR (120MHz, CDCl3): ꢁ ¼ 17.5 (s, CH3), 150.9–151.0 (m,
C–O), 122.2 (d, C–CH3), 121.7–130.0 (m, C-ortho), 124.4–
125.9 (m, C-meta), 126.4–127.1 (m, C-para) ppm; 31P NMR
(120MHz, CDCl3): ꢁ ¼ 82.0 (d, dithio), 6.5 (s, POCl2) ppm.
(Bis(m-tolyloxy)phosphorothioylthio)(oxo)phosphorus(V)-
chloride (4b, C14H14O3P2S2Cl2)
According to the procedure described for 3a, 1.13g of (m-
CH3C6H4O)2PS2Na (1b) (0.34 mmol) and 0.52g of POCl3
(2b) (0.34 mmol) were used to give 4a as a colorless viscous
liquid. Yield: 1.30 g (90%); M.W. calcd. for C14H14O3P2S2Cl2:
427.23, found: 406.14; IR (nujol): ꢀꢀ¼ 2972b, 1139s, 938s,
Tris(bis(o-tolyloxy)phosphorothioylthio)(oxo)phosphorus(V)
(4g, C42H42O7P4S6)
According to the procedure described for 3a, 1.42 g of (o-
CH3C6H4O)2PS2Na (1a) (0.42 mmol) and 0.22 g of POCl3
(2b) (0.14 mmol) were used to give 4g as a colorless viscous
liquid. Yield: 3.63 g (87%); M.W. calcd. for C42H42O7P4S6:
975.04, found: 993.28; IR (nujol): ꢀꢀ¼ 2963b, 1148s, 913s,
655m, 561m, 1332m, 625w cmꢀ1 1H NMR (120MHz,
;
CDCl3): ꢁ ¼ 2.3 (s, 6H, CH3 of cresol), 7.7–8.0 (m, 8H,
C6H4) ppm; 31P NMR (120MHz, CDCl3): ꢁ ¼ 82.7 (d, dithio),
6.7 (s, POCl2) ppm.
665m, 560m, 1318m cmꢀ1 1H NMR (120 MHz, CDCl3):
;
ꢁ ¼ 2.3 (s, 18H, CH3 of cresol), 7.8–8.2 (m, 24H, C6H4)
ppm; 31P NMR (120MHz, CDCl3): ꢁ ¼ 87.3 (d, dithio), 13.5
(s, PO) ppm.
(Bis(p-tolyloxy)phosphorothioylthio)(oxo)phosphorus(V)-
chloride (4c, C14H14O3P2S2Cl2)
According to the procedure described for 3a, 1.07 g of (p-
CH3C6H4O)2PS2Na (1c) (0.32 mmol) and 0.49 g of POCl3
(2b) (0.32 mmol) were used to give 4c as a colorless viscous
liquid. Yield: 1.26g (92%); IR (nujol): ꢀꢀ¼ 2970b, 1143s, 942s,
Tris(bis(m-tolyloxy)phosphorothioylthio)(oxo)phosphorus(V)
(4h, C42H42O7P4S6)
According to the procedure described for 3a, 1.51g of (m-
CH3C6H4O)2PS2Na (1b) (0.45 mmol) and 0.23 g of POCl3
(2b) (0.15 mmol) were used to give 4h as a colorless viscous
liquid. Yield: 3.95 g (89%); M.W. calcd. for C42H42O7P4S6:
975.04, found: 961.03; IR (nujol): ꢀꢀ¼ 2971b, 1152s, 918s,
670m, 559m, 1340m, 627w cmꢀ1 1H NMR (120MHz,
;
CDCl3): ꢁ ¼ 2.3 (s, 6H, CH3 of cresol), 7.8–8.1 (m, 8H,
C6H4) ppm; 31P NMR (120MHz, CDCl3): ꢁ ¼ 82.3 (d, dithio),
6.4 (s, POCl2) ppm.
668m, 565m, 1320m cmꢀ1 1H NMR (120 MHz, CDCl3):
;
ꢁ ¼ 2.3 (s, 18H, CH3 of cresol), 7.7–8.0 (m, 24H, C6H4)
ppm; 31P NMR (120MHz, CDCl3): ꢁ ¼ 87.1 (d, dithio), 13.4
(s, PO) ppm.
Bis(bis(o-tolyloxy)phosphorothioylthio)(oxo)phosphorus(V)-
chloride (4d, C28H28O5P3S4Cl)
According to the procedure described for 3a, 1.86 g of (o-
CH3C6H4O)2PS2Na (1a) (0.56 mmol) and 0.43 g of POCl3
(2b) (0.28 mmol) were used to give 4d as a colorless viscous
liquid. Yield: 3.26g (83%); M.W. calcd. for C28H28O5P3S4Cl:
701.13, found: 719.86; IR (nujol): ꢀꢀ¼ 2956b, 1156s, 918s,
Tris(bis(p-tolyloxy)phosphorothioylthio)(oxo)phosphorus(V)
(4i, C42H42O7P4S6)
According to the procedure described for 3a, 1.97 g of (p-
CH3C6H4O)2PS2Na (1c) (0.59 mmol) and 0.30 g of POCl3
(2b) (0.19 mmol) were used to give 4i as a colorless viscous
liquid. Yield: 5.27 g (91%); IR (nujol): ꢀꢀ¼ 2962b, 1150s,
666m, 555m, 1297m, 617w cmꢀ1 1H NMR (120MHz,
;
CDCl3): ꢁ ¼ 2.3 (s, 12H, CH3 of cresol), 7.8–8.2 (m, 16H,
C6H4) ppm; 31P NMR (120MHz, CDCl3): ꢁ ¼ 83.5 (d, dithio),
13.7 (s, POCl) ppm.
917s, 670m, 562m, 1326m cmꢀ1
;
1H NMR (120 MHz,
CDCl3): ꢁ ¼ 2.3 (s, 18H, CH3 of cresol), 7.8–8.1 (m, 24H,
C6H4) ppm; 13C NMR (120MHz, CDCl3): ꢁ ¼ 17.5 (s, CH3),
154.5 (m, C–O), 115.8 (d, C–CH3), 122.6–123.1 (m, C-or-
tho), 125.8–126.5 (m, C-meta), 127.7–128.4 (m, C-para)
ppm; 31P NMR (120MHz, CDCl3): ꢁ ¼ 87.6 (d, dithio),
13.6 (s, PO) ppm.
Bis(bis(m-tolyloxy)phosphorothioylthio)(oxo)phosphorus(V)-
chloride (4e, C28H28O5P3S4Cl)
According to the procedure described for 3a, 1.22g of (m-
CH3C6H4O)2PS2Na (1b) (0.36 mmol) and 0.28g of POCl3

752
B. Gupta et al.
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Acknowledgement
We are grateful to Central Drug Research Institute, Lucknow
for providing spectral facilities.
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