O-Tolyl/benzyl dithiocarbonates of phosphorus(III) and (V): Syntheses and characterization

Article abstract of DOI:10.1007/s00706-011-0704-2

O-Tolyl/benzyl dithiocarbonates, ROCS₂Na (R = o-, m-, or p-CH₃C₆H₄-, and -CH₂C ₆H₅), were synthesized and characterized. These new ligands reacted with PCl3/POCl3 in refluxing to

Full text of DOI:10.1007/s00706-011-0704-2

Monatsh Chem (2012) 143:1087–1095
DOI 10.1007/s00706-011-0704-2
ORIGINAL PAPER
O-Tolyl/benzyl dithiocarbonates of phosphorus(III) and (V):
syntheses and characterization
•
•
•
Bhawana Gupta Nidhi Kalgotra Savit Andotra
Sushil K. Pandey
Received: 22 June 2011 / Accepted: 13 December 2011 / Published online: 10 January 2012
Ó Springer-Verlag 2012
Abstract O-Tolyl/benzyl dithiocarbonates, ROCS2Na
(R = o-, m-, or p-CH3C6H4–, and –CH2C6H5), were syn-
thesized and characterized. These new ligands reacted with
PCl3/POCl3 in refluxing toluene which resulted in the
formation of phosphorus(III) and phosphorus(V) tolyl/
[10]. The synthetic and structural chemistry of xanthates
witnessed increased attention through the pioneering work
of Winter, Hoskins, and others [11–14]. Subsequently,
extensive structural analyses were performed by Haiduc
and Tiekink, which showed that these ligands can coordi-
nate to metal atoms in a monodentate, isobidentate, or
anisobidentate fashion. Metal xanthates are extensively
used as pharmaceuticals [15], fungicides [16], pesticides
[17], corrosion inhibitors [18], agricultural reagents [19],
and quite recently in therapy for HIV infections [20]. The
last two decades have witnessed a tremendous develop-
ment of new radical reactions designed for organic
synthesis [21, 22]. Xanthates are not only convenient pre-
cursors for transforming an alcohol into the corresponding
alkane [23], but also are extremely efficient and versatile
sources of radicals, e.g., in carbon–carbon bond forming
reactions [24].
benzyl dithiocarbonates corresponding to [(ROCS2)nPCl3-n
]
and [(ROCS2)nPOCl3-n] (R = o-, m-, or p-CH3C6H4–, and
–CH2C6H5; n = 1, 2, 3). These pale yellow liquid
compounds were characterized by IR, mass, and NMR (1H,
13C, and 31P) spectral studies, which suggest the dithio-
carbonate ligands bind in a monodentate mode leading to
P–S–C linkages in these derivatives.
Keywords Dithiocarbonate Á Phosphorus compounds Á
Total synthesis Á Spectroscopy
Introduction
Phosphorus is a vital component of biological cytoplasm
and is also an essential element for plant growth. Phos-
phorus derivatives are used in numerous applications, e.g.,
water treatment [25], agrochemical products [26, 27], fire
protection [28], oil field drilling [29, 30], fine chemicals
[31, 32], and plastic additives [33, 34]. Although there are
some restrictions on the use of certain organophosphorus
compounds in developed countries, these compounds are
still widely employed in several developing countries
owing to their effectiveness in plague control [35]. Certain
organophosphorus compounds containing substituted
p-toluidine moieties were prepared for evaluation as cancer
chemotherapeutic agents [36].
O-Alkyldithiocarbonates (ROCS2-) [1, 2] are an important
class of 1,1-dithiolate ligands along with dithiocarbamates
(R2N–CS2-) [3, 4], dithiocarboxylates (RCS2-), dithio-
phosphates ((RO)2PS2-) [5–8], and other related phosphor-
-
1,1-dithiolate ligands. Metallic derivatives of ROCS2
ligands have been known since 1815, when these were first
prepared by Zeise, who also termed them xanthates, a name
derived from the Greek xanthos (yellow), owing to the
yellow color of lead xanthates [9]. Their applications to the
vulcanization of rubber, as fungicides, and as flotation
agents in metallurgy have been described in the literature
Surprisingly, in spite of years of chemistry of the exten-
sive and long-term use of alkyl xanthates as ligands [37–44],
structural and spectroscopic characterization has been rather
limited with regard to the aryl xanthates [45, 46]. Fackler
et al. [45], however, reported the synthesis of thallium aryl
B. Gupta Á N. Kalgotra Á S. Andotra Á S. K. Pandey (&)
Department of Chemistry, University of Jammu, Baba Saheb
Ambedkar Road, Jammu 180006, Jammu and Kashmir, India
e-mail: kpsushil@rediffmail.com
123

1088
B. Gupta et al.
PCl3 (2a)
xanthates which in turn were used for the metathetical
synthesis of other metal derivatives. We report herein the
synthesis and characterization of O-tolyl/benzyl dithiocar-
bonates of phosphorus(III) and (V) by the reaction of sodium
O-tolyl/benzyl dithiocarbonates with PCl3 and POCl3.
[(ROCS2)nPCl3-n
]
3a-3l
Toluene
Reflux
n ROCS2Na
1a-1d
[(ROCS2)nP(O)Cl3-n
]
P(O)Cl3 (2b)
4a-4l
R = o-, m-, or p-CH3C6H4- (3a-3c, 3e-3g, 3i-3k, 4a-4c, 4e-4g, and 4i-4k);
and C6H5CH2- (3d, 3h, 3l, 4d, 4h, and 4l)
Results and discussion
Scheme 2
Alkyl xanthates are usually synthesized by mixing KOH/
NaOH with alcohols (excess) to produce ROK/RONa fol-
lowed by insertion of CS2 [9]. We, however, synthesized
tolyl/benzyl xanthates by using sodium metal and toluene
as solvent instead of KOH/NaOH and the parent alcohol as
solvent. Reaction of sodium metal with ortho-, meta-, and
para-cresols (o-, m-, and p-CH3C6H4OH) and benzyl
alcohol (C6H5CH2OH) in 1:1 stoichiometric ratio in re-
fluxing toluene resulted in the formation of sodium
methylphenolates (o-, m-, and p-CH3C6H4ONa) and
sodium phenylmethanolate (C6H5CH2ONa) as creamish
viscous pasty masses. Addition of an equimolar amount of
CS2 to these at 0–5 °C forms the corresponding sodium salt
of (o-, m-, and p-cresyl/benzyl) dithiocarbonates as a pale
yellow solid (Scheme 1).
phosphorus trichloride and needed longer reaction times
(10–12 h at reflux) to ensure their completion. It is
assumed that this might be due to the high electronegativity
of oxygen and steric bulk of POCl3, which thereby makes
the nucleophilic displacement of chloride ions from the
phosphorus oxychloride moiety difficult compared with
that from phosphorus trichloride.
IR spectra
The characteristic stretching bands in the IR spectra
(4,000–400 cm-1) were assigned by comparison with lit-
erature data [37–49]. The IR spectra show the characteristic
sharp band for m (C–O–C) and broad band for m (C=C)
(tolyl and benzyl ring stretching) in the range 1,043–1,015
and 1,607–1,581 cm-1, respectively. The strong frequency
bands for m (C=S) and (C–S) appeared in the range
1,194–1,160 and 945–920 cm-1; the separation between
these bands is quite large (240–150 cm-1) as is usually
observed in the case of monodentate linkages [50]. Also the
strong band due to C=S stretching vibrations present in
the spectra of sodium salts of tolyl/benzyl dithicarbonates
1a–1d in the region 1,145–1,140 cm-1 is shifted towards
higher frequency in the spectra of compounds 3a–3l and
4a–4l and is present in the range 1,194–1,160 cm-1. This
shifting indicates, most probably, a monodentate chelation
of the dithiocarbonate moiety with phosphorus. The IR
spectra of compounds 3a–3l and 4a–4l show the appear-
ance of a new band of medium intensity for m (P–S) in the
region 564–520 cm-1, indicating the formation of a bond
between the phosphorus atom and dithiocarbonate moiety.
The phosphoryl m (P=O) absorption band in the derivatives
4a–4l appeared in the region 1,290–1,262 cm-1, i.e.,
shifted toward lower wavenumber in comparison with its
position in phosphorus oxychloride (1,365 cm-1). This
shifting may be due to replacement of the more electro-
negative chlorine atom by the dithiocarbonate moiety. The
absorption bands at 442–425 (3a–3h) and 625–612 cm-1
(4a–4h) are assigned to m (P–Cl) and (P(O)–Cl) vibrations,
respectively, which show a negative shift compared with m
These sodium salts appear to be hygroscopic in nature,
soluble in methanol, ethanol, acetone, and tetrahydrofuran,
insoluble in most hydrocarbon solvents, and sparingly
soluble in chloroform and dichloromethane. These com-
pounds are non-volatile even under reduced pressure and
tend to decompose on heating. Reactions of phosphorus
trichloride, PCl3 (2a), and phosphorus oxychloride, POCl3
(2b), with the sodium salt of (o-, m-, and p-cresyl/benzyl)
dithiocarbonates, (o-, m-, and p-CH3C6H4OCS2)Na/
(C6H5CH2OCS2)Na (1a–1d), in 1:1, 1:2, and 1:3 molar
ratios were carried out in refluxing toluene which resulted
in compounds [(ROCS2)nPCl3-n] 3a–3l and [(ROCS2)n-
POCl3-n] 4a–4l (R = o-, m-, and p-CH3C6H4– and
–CH2C6H5; n = 1, 2, 3) as pale yellow viscous liquids in
80–90% yield (Scheme 2).
The compounds were isolated by evaporation under
reduced pressure. These derivatives are non-volatile,
monomeric, and soluble in common organic solvents. All
these compounds are obtained in sufficient purity as
revealed by spectral studies.
It is observed that the reactions of phosphorus oxy-
chloride are less facile than the corresponding reactions of
CS2
Toluene
Reflux
ROCS2Na
1a 1d
RONa
ROH + Na
0-5 °C
-
1a 1c
R = o-, m-, or p-CH3C6H4- (
-
), and C6H5CH2- (1d)
(P–Cl) and (P(O)–Cl) vibrations of PCl3 (585–550 cm-1
and POCl3 (645–630 cm-1). However, the disappearance
)
Scheme 1
123

O-Tolyl/benzyl dithiocarbonates of phosphorus(III) and (V)
1089
of these absorption bands in the IR spectra of compounds
3i–3l and 4i–4l indicates the complete removal of the
chloride ion, which led to the formation of the P–S–C
chemical linkage in these derivatives.
reflects the fact that the environment around the CS2 car-
bon is the one most affected by the formation of the P–S
covalent bond, thereby supporting the authenticity of these
compounds.
31P NMR
Mass spectra
In the 31P NMR spectra of compounds 3a–3d, the signal for
the phosphorus atom was found at d = 192.6–193.6 ppm,
i.e., 23–30 ppm upfield from its position in free phosphorus
trichloride (221 ppm). The phosphorus signal of com-
pounds 3e–3l was observed at 166.3–184.5 ppm, i.e.,
14–26 ppm upfield compared with the corresponding sig-
nals for derivatives 3a–3d. The further lowering in the
chemical shifts may be attributed to the replacement of the
more electronegative chloride moieties by the dithio moi-
eties. The phosphorus signal for compounds 4a–4l was
observed at 6.5–19.5 ppm, i.e., downfield compared with
its position in free POCl3 (-1.9 ppm). The shielding in
these compounds compared with compounds 3a–3l may be
correlated to the presence of the more electronegative
oxygen atom. The appearance of only one phosphorus
signal may be considered as an authentication of the purity
of the compounds.
The mass spectra of the dithiocarbonate ligands showed a
molecular ion peak [M?] at m/z = 206.1, suggesting the
compounds were monomeric in nature. Some other peaks
corresponding to [CS2] 76.0, [HCS2OH] 94.0, and
[C8H7OS2]2 366.0 were also observed. The mass spectra of
a few representative phosphorus(III) and (V) compounds
3a, 3f, 3k, 3l, 4b, 4e, 4g and 4l had their molecular ion peak
[M?] at 285.5, 432.9, 580.8, 580.8, 301.1, 448.9, 448.9 and
596.8, respectively, which supported the assigned mono-
meric structure. Common peaks at 366.0, 108.0, and 76.0
were observed in the spectra of all the representative
compounds due to the fragments [C8H7OS2]2, [C7H8OH],
and [CS2]. In addition to these molecular ion peaks, some
other strong peaks were also observed, which were formed
after the consecutive elimination of different groups.
Moreover, compounds 3a and 4b that contain multiple
chlorine atoms also show isotopic peaks of chlorine. The
overlap of these isotope patterns was observed in the mass
spectra. So, an isotopic envelope of three different peaks
with distinctive ratios one to another spanning 2 mass units
is observed around the molecular ion peak in the mass
spectra of compounds 3a and 4b. The most intense isotopic
peak in the mass spectra of compounds 3a and 4b at 285.0
and 301.0 was set at 100% and the percentage of other
isotopic peaks was compared relative to it.
1H NMR
1
In the H NMR spectra, the signals for the –CH3 (tolyl
ring) and –CH2 (benzyl ring) protons were observed at
d = 2.2–2.4 and 4.5–4.6 ppm as singlets. The protons of
the C6H4 (tolyl ring) and C6H5 (benzyl ring) gave signals in
the range 6.6–7.1 and 7.1–7.2 ppm as multiplets. Com-
pounds 3a–3l and 4a–4l did not show any appreciable
deviation compared to the sodium salts of the dithiocar-
bonate ligands 1a–1d.
Structural features
On the basis of our IR, mass, and NMR (1H, 13C, and 31P)
spectral studies and in conjunction with the literature
reports [37–49], a probable geometry may be assigned to
these compounds. It is evident from the 13C NMR spectra
of all compounds that the peak in the region
d = 165.0–201.7 ppm is characteristic of the CS2 group
which further supports the authenticity of these com-
pounds. Therefore, in conjunction with the literature
reports [37–49], the following type of general structure
may be deduced for the sodium salt of (o-, m-, and p-cresyl/
benzyl) dithiocarbonate ligands akin to that of ditolyldi-
thiophosphate [51]. The 31P chemical shift values favor the
formation of these compounds with a monodentate linkage
between the dithiocarbonate ligand and the phosphorus
atom. Thus, a probable geometry around the phospho-
rus(III) (3a–3l) and phosphorus(V) (4a–4l) in different
coordination spheres may tentatively be assigned to these
compounds as shown in Fig. 1.
13C NMR
The 13C NMR spectra of these ligands and their derivatives
showed signals for all carbon nuclei in their characteristic
regions. The signals for methyl (–CH3) and methylene
(–CH2) carbon occurred in the range d = 19.6–21.4 and
70.8–71.4 ppm, respectively. The carbon nuclei of phenyl
groups (–C6H5 and –C6H4) displayed their resonance in the
region 112.0–135.3 ppm. The carbon attached to the
methyl and methylene group in the respective compounds
appeared at 122.9–135.2 and 136.8–137.4 ppm, respec-
tively. The signal in the region 147.3–152.9 ppm was due
to the carbon attached to the oxygen in the tolyl deriva-
tives. The signal for the dithiocarbonate carbon (–(O)CS2)
appeared at 163.6–175.8 ppm in compounds 3a–3l and
4a–4l, whereas these signals were observed at 195.1–
200.7 ppm in the parent ligands 1a–1d. Presumably, this
123

1090
B. Gupta et al.
Fig. 1 Proposed structures of
the prepared dithiocarbonates
S
S
O
C
Na
CH2
O
C
Na
H3C
S
S
1a-1c
1d
Z
S
S
P
X
O
C
H3C
Y
X and Y = Cl for 3a-3c and 4a-4c; X = (o-, m-, p-CH3C6H4OCS2-) and Y = Cl for 3e-3g and 4e-4g;
X and Y = (o-, m-, p-CH3C6H4OCS2-) for 3i-3k and 4i-4k; Z = lone pair of electrons for 3a-3c, 3e-3g, and
3i-3k and doubly bonded oxygen for 4a-4c, 4e-4g, and 4i-4k
Z
S
P
X
CH2
O
C
S
Y
X and Y = Cl for 3d and 4d; X = (C6H5CH2OCS2-) and Y = Cl for 3h and 4h;
X and Y = (C6H5CH2OCS2-) for 3l and 4l; Z = lone pair of electrons for 3d, 3h, and 3l
and doubly bonded oxygen for 4d, 4h, and 4l
Sodium O-(2-methylphenyl)carbonodithioate
(1a, C8H7NaOS2)
Experimental
To a toluene solution (ca. 40 cm3) of 2.00 g freshly
Toluene (Thomas Baker, b.p. 110 °C) and n-hexane
(Thomas Baker, b.p. 68–69 °C) were freshly dried over
sodium wire. Cresols (o-, m-, and p-) and benzyl alcohol
(Thomas Baker, b.p. 191, 203, 202, and 205 °C) were also
purified by distillation prior to use. The mass spectra were
recorded on a Bruker esquire3000_00037 spectrophotom-
eter. IR spectra were recorded either as KBr pellets or
Nujol mulls in the range of 4,000–400 cm-1 on a Shima-
dzu 8201 PC and Perkin Elmer 557 spectrophotometer. The
1H, 13C, and 31P NMR spectra were recorded in CDCl3 on a
Bruker Avance II 400 spectrometer using TMS as internal
distilled o-cresol (18.50 mmol) was added 0.43 g sodium
metal (18.50 mmol). The contents were refluxed for 3 h
until white precipitates started appearing and the refluxing
was continued until sodium metal was completely dis-
solved. The contents were cooled using an ice bath at
0–5 °C. Subsequently, CS2 was added to the reaction
mixture dropwise over a period of 30 min with constant
stirring. The contents were further stirred for 3 h during
which the color changed from white to yellow. Compound
1a was isolated by filtration using a funnel fitted with a G-4
sintered disc. The salt so obtained was washed with
n-hexane and finally dried under reduced pressure that
resulted in the formation of o-CH3C6H4OCS2Na (1a) as
pale yellow solid. Yield: 65%; m.p.: 197 °C (dec); IR
1
reference for H and 13C or H3PO4 (85%) as external ref-
erence for 31P. The elemental analyses (C, H, Cl, and S) of
these compounds were found to be consistent with their
molecular formula. Sulfur was analyzed gravimetrically as
BaSO4 by Messenger’s method and chlorine was estimated
volumetrically by Volhard’s method. Elemental analyses of
C and H were carried out on a CHNS-932 Leco elemental
analyzer. Moisture was carefully excluded throughout the
experimental manipulations by using standard Schlenk
techniques.
(KBr): m = 3,022, 1,590, 1,142, 1,042, 1,004 cm
;
1H
-1
ꢀ
NMR (CDCl3): d = 2.3 (s, 3H, CH3), 6.6 (d, 1H, ortho),
6.7 (m, 2H, meta), 6.9 (t, 1H, para) ppm; 13C NMR
(CDCl3): d = 22.9 (CH3), 114.3 (C-ortho), 120.0 (C-para),
123.3 (C–CH3), 126.1–128.8 (C-meta), 167.0 (C–O),
195.1 (OCS2) ppm; EI-MS: m/z (%) = 366.2 (90)
123

O-Tolyl/benzyl dithiocarbonates of phosphorus(III) and (V)
1091
[(o-CH3C6H4OCS2)2]-, 336.2 (22) [(C6H5CS2)2]-, 206.1
(100) [o-CH3C6H4OCS2Na]?, 183.0 (44) [o-CH3C6H4OCS2]-,
168.0 (44) [o-C6H5OCS2]-, 130.0 (22) [o-CH3C6H4ONa]-,
108.0 (22) [o-CH3C6H4OH]?, 91.0 (11) [o-CH3C6H4]?, 76.0
(9) [CS2]?.
86%; IR (Nujol): ꢀm = 3,320, 1,583, 1,163, 1,017, 926, 556,
1
442 cm-1; H NMR (CDCl3): d = 2.2 (s, 3H, CH3), 6.7
(m, 2H, meta), 6.8 (d, 1H, ortho), 7.0 (t, 1H, para) ppm;
13C NMR (CDCl3): d = 19.7 (CH3), 114.3 (C-ortho),
119.1 (C-para), 122.9 (C–CH3), 130.0–130.2 (C-meta),
152.5 (C–O), 165.2 (OCS2) ppm; 31P NMR (CDCl3):
Sodium O-(3-methylphenyl)carbonodithioate
(1b, C8H7NaOS2)
d = 192.6 ppm;
EI-MS:
m/z
(%) = 366.5
(95)
[(o-CH3C6H4OCS2)2]?, 285.5, 287.5, 289.5 (100, 50, 4)
[o-CH3C6H4OCS2PCl2]-, 249.7 (9) [o-CH3C6H4OCS2P
Cl]-, 214.2 (13) [o-CH3C6H4OCS2P]-, 195.0, 197.0,
199.0 (47, 24, 2) [CS2OHPCl2]-, 108 (26) [o-CH3C6
H4OH]-, 96.0 (7) [PS2H]?, 76.0 (7) [CS2]-.
Compound 1b was synthesized according to the procedure
described for 1a; 2.00 g of m-CH3C6H4OH (18.50 mmol)
and 0.43 g of Na (18.50 mmol) were used to give 1b as a
yellow solid. Yield: 67%; m.p.: 196 °C (dec); IR (KBr):
-1
;
1H NMR
ꢀ
m = 3,023, 1,596, 1,140, 1,040, 1,002 cm
(CDCl3): d = 2.3 (s, 3H, CH3), 6.6 (m, 2H, ortho), 6.8 (d,
1H, para), 7.0 (t, 1H, meta) ppm; 13C NMR (CDCl3):
d = 22.7 (CH3), 112.7–116.4 (C-ortho), 127.0 (C-para),
129.7 (C-meta), 135.0 (C–CH3), 167.0 (C–O), 197.5
(OCS2) ppm.
(3-Methylphenyl)oxycarbonothioylthiophosphorus(III)
dichloride (3b, C8H7Cl2OPS2)
The synthesis of 3b was carried out as described for 3a;
1.00 g of 1b (4.85 mmol) and 0.67 g of PCl3 (4.85 mmol)
were used to give 3b as a pale yellow viscous liquid. Yield:
ꢀ
84%; IR (Nujol): m = 3,362, 1,584, 1,162, 1,018, 927, 535,
Sodium O-(4-methylphenyl)carbonodithioate
(1c, C8H7NaOS2)
1
430 cm-1; H NMR (CDCl3): d = 2.2 (s, 3H, CH3), 6.8
(m, 2H, ortho), 6.9 (d, 1H, para), 7.0 (t, 1H, meta) ppm;
13C NMR (CDCl3): d = 20.3 (CH3), 112.0–115.1
(C-ortho), 120.0 (C-para), 131.8 (C-meta), 134.3 (C–CH3),
150.3 (C–O), 166.9 (OCS2) ppm; 31P NMR (CDCl3):
d = 192.3 ppm.
Compound 1c was synthesized according to the procedure
described for 1a; 2.00 g of p-CH3C6H4OH (18.50 mmol)
and 0.43 g of Na (18.50 mmol) were used to give 1c as a
yellow solid. Yield: 65%; m.p.: 196 °C (dec); IR (KBr):
-1
m = 3,022, 1,593, 1,142, 1,040, 1,007 cm
;
1H NMR
ꢀ
(CDCl3): d = 2.3 (s, 3H, CH3), 6.8 (d, 2H, ortho), 6.9 (d,
2H, meta) ppm; 13C NMR (CDCl3): d = 22.0 (CH3), 117.0
(C-ortho), 128.7 (C–CH3), 129.6 (C-meta), 166.0 (C–O),
195.6 (OCS2) ppm.
(4-Methylphenyl)oxycarbonothioylthiophosphorus(III)
dichloride (3c, C8H7Cl2OPS2)
The synthesis of 3c was carried out as described for 3a;
1.00 g of 1c (4.85 mmol) and 0.67 g of PCl3 (4.85 mmol)
were used to give 3c as a pale yellow viscous liquid. Yield:
Sodium O-benzylcarbonodithioate (1d, C8H7NaOS2)
Compound 1d was synthesized according to the procedure
described for 1a; 2.00 g of C6H5CH2OH (18.50 mmol) and
0.43 g of Na (18.50 mmol) were used to give 1d as a
yellow solid. Yield: 75%; m.p.: 186 °C (dec); IR (KBr):
ꢀ
87%; IR (Nujol): m = 3,401, 1,602, 1,165, 1,017, 920, 532,
428 cm-1; 1H NMR (CDCl3): d = 2.2 (s, 3H, CH3), 6.7 (d,
2H, ortho), 7.0 (d, 2H, meta) ppm; 13C NMR (CDCl3):
d = 20.4 (CH3), 115.4 (C-ortho), 130.1 (C–CH3), 130.5
(C-meta), 152.9 (C–O), 167.4 (OCS2) ppm; 31P NMR
(CDCl3): d = 193.0 ppm.
-1
;
1H NMR
ꢀ
m = 2,991, 1,610, 1,145, 1,045, 1,008 cm
(CDCl3): d = 4.5 (s, 2H, CH2), 7.1–7.2 (m, 5H, C6H5)
ppm; 13C NMR (CDCl3): d = 75.2 (CH2), 121.0–123.1
(C-ortho), 125.0–126.2 (C-meta), 126.4 (C-para), 140.2
(C–CH2), 200.7 (OCS2) ppm.
Benzyloxycarbonothioylthiophosphorus(III) dichloride
(3d, C8H7Cl2OPS2)
The synthesis of 3d was carried out as described for 3a;
1.00 g of 1d (4.85 mmol) and 0.67 g of PCl3 (4.85 mmol)
were used to give 3d as a pale yellow viscous liquid. Yield:
(2-Methylphenyl)oxycarbonothioylthiophosphorus(III)
dichloride (3a, C8H7Cl2OPS2)
ꢀ
90%; IR (Nujol): m = 3,384, 1,583, 1,162, 1,043, 926, 523,
To a suspension of 1.00 g 1a (4.85 mmol) in toluene (ca.
35 cm3) was added a toluene solution (ca. 15 cm3) of
0.67 g phosphorus trichloride (4.85 mmol). The reaction
mixture was vigorously stirred for about 3 h. Subsequently,
the contents were refluxed for 6 h during which a white
precipitate of NaCl was formed. The reaction mixture was
allowed to reach room temperature then filtered through a
funnel fitted with a G-4 sintered disc. The excess solvent
was then removed under reduced pressure followed by
drying in vacuo for 3 h, which yielded o-CH3C6H4
OCS2PCl2 (3a) as pale yellow viscous liquid. Yield:
1
430 cm-1; H NMR (CDCl3): d = 4.5 (s, 2H, CH2), 7.1–
7.2 (m, 5H, C6H5) ppm; 13C NMR (CDCl3): d = 71.2
(CH2), 126.1–126.2 (C-ortho), 127.5–127.6 (C-meta),
128.0 (C-para), 137.4 (C–CH2), 166.9 (OCS2) ppm; 31P
NMR (CDCl3): d = 193.6 ppm.
Bis[(2-methylphenyl)oxycarbonothioylthio]phosphorus(III)
chloride (3e, C16H14ClO2PS4)
Compound 3e was prepared by a similar procedure as
described for 3a; 1.00 g of 1a (4.85 mmol) and 0.33 g of
PCl3 (2.42 mmol) were used to give 3e as a pale yellow
123

1092
B. Gupta et al.
viscous liquid. Yield: 85%; IR (Nujol): ꢀm = 3,359, 1,581,
viscous liquid. Yield: 89%; IR (Nujol): ꢀm = 3,386, 1,601,
1
1,165, 1,017, 923, 536, 429 cm-1
;
1H NMR (CDCl3):
1,190, 1,040, 945, 530 cm-1; H NMR (CDCl3): d = 2.2
d = 2.2 (s, 6H, CH3), 6.6 (d, 2H, ortho), 6.7 (m, 4H, meta),
7.1 (t, 2H, para) ppm; 13C NMR (CDCl3): d = 19.8 (CH3),
114.0 (C-ortho), 119.4 (C-para), 123.0 (C–CH3), 129.1–
129.5 (C-meta), 152.3 (C–O), 169.2 (OCS2) ppm; 31P
NMR (CDCl3): d = 184.5 ppm.
(s, 9H, CH3), 6.6 (d, 3H, ortho), 6.9 (m, 6H, meta), 7.1 (t,
3H, para) ppm; 13C NMR (CDCl3): d = 19.7 (CH3), 114.3
(C-ortho), 119.1 (C-para), 122.9 (C–CH3), 129.1–129.5
(C-meta), 152.5 (C–O), 170.0 (OCS2) ppm; 31P NMR
(CDCl3): d = 169.6 ppm.
Bis[(3-methylphenyl)oxycarbonothioylthio]phosphorus(III)
chloride (3f, C16H14ClO2PS4)
Tris[(3-methylphenyl)oxycarbonothioylthio]phospho-
rus(III) (3j, C24H21O3PS6)
Compound 3f was prepared by a similar procedure as
described for 3a; 1.00 g of 1b (4.85 mmol) and 0.33 g of
PCl3 (2.42 mmol) were used to give 3f as a pale yellow
Compound 3j was prepared by a similar procedure as
described for 3a; 1.00 g of 1b (4.85 mmol) and 0.22 g of
PCl3 (1.60 mmol) were used to give 3j as a pale yellow
ꢀ
ꢀ
viscous liquid. Yield: 87%; IR (Nujol): m = 3,420, 1,583,
viscous liquid. Yield: 87%; IR (Nujol): m = 3,406, 1,607,
1
1,163, 1,023, 930, 550, 440 cm-1 1H NMR (CDCl3):
;
1,194, 1,017, 945, 538 cm-1; H NMR (CDCl3): d = 2.2
d = 2.2 (s, 6H, CH3), 6.8 (m, 4H, ortho), 6.9 (d, 2H, para),
7.0 (t, 2H, meta) ppm; 13C NMR (CDCl3): d = 20.8 (CH3),
111.9–114.7 (C-ortho), 121.2 (C-para), 132.0 (C-meta),
134.2 (C–CH3), 150.9 (C–O), 164.4 (OCS2) ppm; 31P
NMR (CDCl3): d = 180.3 ppm; EI-MS: m/z (%) = 432.9
(51) [(m-CH3C6H4OCS2)2PCl]?, 366.5 (100) [(m-CH3C6
H4OCS2)2]?, 282.7 (64) [m-CH3C6H4OCS2PClSH]-,
259.4 (80) [P(CS2)3]?, 252.7 (11) [ClP(OHCS2)2]?, 170.2
(13) [C6H5OCS2H]?, 108.0 (18) [m-CH3C6H4OH]?, 76
(10) [CS2]?.
(s, 9H, CH3), 6.8 (m, 6H, ortho), 6.9 (d, 3H, para), 7.0 (t,
3H, meta) ppm; 13C NMR (CDCl3): d = 20.3 (CH3),
112.1–114.8 (C-ortho), 121.0 (C-para), 131.8 (C-meta),
134.3 (C–CH2), 150.3 (C–O), 171.5 (OCS2) ppm; 31P
NMR (CDCl3): d = 169.6 ppm.
Tris[(4-methylphenyl)oxycarbonothioylthio]phospho-
rus(III) (3k, C24H21O3PS6)
Compound 3k was prepared by a similar procedure as
described for 3a; 1.00 g of 1c (4.85 mmol) and 0.22 g of
PCl3 (1.60 mmol) were used to give 3k as a pale yellow
ꢀ
Bis[(4-methylphenyl)oxycarbonothioylthio]phosphorus(III)
chloride (3g, C16H14ClO2PS4)
viscous liquid. Yield: 89%; IR (Nujol): m = 3,385, 1,586,
1
1,180, 1,018, 940, 535 cm-1; H NMR (CDCl3): d = 2.2
Compound 3g was prepared by a similar procedure as
described for 3a; 1.00 g of 1c (4.85 mmol) and 0.33 g of
PCl3 (2.42 mmol) were used to give 3g as a pale yellow
(s, 9H, CH3), 6.7 (d, 6H, ortho), 7.1 (d, 6H, meta) ppm; 13
C
NMR (CDCl3): d = 20.4 (CH3), 115.4 (C-ortho), 129.3
(C-meta), 130.1 (C–CH3), 152.1 (C–O), 172.8 (OCS2)
ppm; 31P NMR (CDCl3): d = 167.2 ppm; EI-MS: m/z
(%) = 580.8 (56) [p-(CH3C6H4OCS2)3P]?, 490.6 (12) [p-
(CH3C6H4OCS2)2PCS2OH]?, 474.6 (15) [p-(CH3C6H4
OCS2)2PCS2H]?, 400.5 (16) [p-CH3C6H4OCS2P(CS2
OH)2]?, 397.5 (21) [p-(CH3C6H4OCS2)2P]?, 366.5 (10)
[p-(CH3C6H4OCS2)2]-, 310.4 (100) [(CS2OH)3P]-, 259.4
(26) [P(CS2)3]-, 217.2 (5) [(CS2OH)2P]-, 108.1 (34)
[p-CH3C6H4OH]?, 96.1 (10) [PS2H]?, 76.1 (8) [CS2]?.
ꢀ
viscous liquid. Yield: 87%; IR (Nujol): m = 3,417, 1,602,
1,160, 1,018, 928, 537, 428 cm-1
;
1H NMR (CDCl3):
d = 2.4 (s, 6H, CH3), 6.9 (d, 4H, ortho), 7.1 (d, 4H, meta)
ppm; 13C NMR (CDCl3): d = 19.6 (CH3), 115.5 (C-ortho),
129.2 (C–CH3), 129.3 (C-meta), 152.1 (C–O), 168.5
(OCS2) ppm; 31P NMR (CDCl3): d = 184.5 ppm.
Bis(benzyloxycarbonothioylthio)phosphorus(III) chloride
(3h, C16H14ClO2PS4)
Compound 3h was prepared by a similar procedure as
described for 3a; 1.00 g of 1d (4.85 mmol) and 0.33 g of
PCl3 (2.42 mmol) were used to give 3h as a pale yellow
Tris(benzyloxycarbonothioylthio)phosphorus(III)
(3l, C24H21O3PS6)
Compound 3l was prepared by a similar procedure as
described for 3a; 1.00 g of 1d (4.85 mmol) and 0.22 g of
PCl3 (1.60 mmol) were used to give 3l as a pale yellow
ꢀ
viscous liquid. Yield: 89%; IR (Nujol): m = 3,382, 1,584,
1,165, 1,015, 920, 526, 425 cm-1 1H NMR (CDCl3):
;
d = 4.6 (s, 4H, CH2), 7.1–7.2 (m, 10H, C6H5) ppm; 13C
NMR (CDCl3): d = 71.0 (CH2), 126.0–126.2 (C-ortho),
127.6–127.8 (C-meta), 128.2 (C-para), 137.3 (C–CH2),
169.0 (OCS2) ppm; 31P NMR (CDCl3): d = 181.4 ppm.
ꢀ
viscous liquid. Yield: 90%; IR (Nujol): m = 3,462, 1,581,
1
1,185, 1,015, 942, 525 cm-1; H NMR (CDCl3): d = 4.5
(s, 6H, CH2), 7.1–7.2 (m, 15H, C6H5) ppm; 13C NMR
(CDCl3): d = 71.2 (CH2), 126.1–126.2 (C-ortho), 127.6–
127.8 (C-meta), 128.0 (C-para), 137.4 (C–CH2), 175.8
(OCS2) ppm; 31P NMR (CDCl3): d = 167.2 ppm; EI-MS:
m/z (%) = 580.8 (100) [(C6H5CH2OCS2)3P]?, 490.6 (9)
[(C6H5CH2OCS2)2PCS2OH]?, 400.5 (7) [C6H5CH2OCS2
P(CS2OH)2]?, 397.5 (7) [(C6H5CH2OCS2)2P]-, 366.5 (71)
Tris[(2-methylphenyl)oxycarbonothioylthio]phospho-
rus(III) (3i, C24H21O3PS6)
Compound 3i was prepared by a similar procedure as
described for 3a; 1.00 g of 1a (4.85 mmol) and 0.22 g of
PCl3 (1.60 mmol) were used to give 3i as a pale yellow
123

O-Tolyl/benzyl dithiocarbonates of phosphorus(III) and (V)
1093
[(C6H5CH2OCS2)2]?, 310.4 (51) [P(CS2OH)3]-, 259.4
(24) [P(CS2)3]-, 214.2 (27) [C6H5CH2OCS2P]?, 108.1
(20) [C6H5CH2OH]?, 76.0 (10) [CS2]?.
1,265, 1,170, 1,017, 935, 620, 530 cm-1
;
1H NMR
(CDCl3): d = 4.6 (s, 2H, CH2), 7.1–7.2 (m, 5H, C6H5)
ppm; 13C NMR (CDCl3): d = 70.8 (CH2), 126.0–126.1
(C-ortho), 127.5–127.6 (C-meta), 128.1 (C-para), 137.4
(C–CH2), 165.4(OCS2)ppm;31PNMR(CDCl3): d = 7.5 ppm.
[(2-Methylphenyl)oxycarbonothioylthio]oxophosphorus(V)
dichloride (4a, C8H7Cl2O2PS2)
The synthesis of 4a was carried out as described for 3a
except the refluxing period, which was about 10 h; 1.00 g
of 1a (4.85 mmol) and 0.74 g of POCl3 (4.85 mmol) were
used to give 4a as a pale yellow viscous liquid. Yield: 80%;
Bis[(2-methylphenyl)oxycarbonothioylthio]oxophospho-
rus(V) chloride (4e, C16H14ClO3PS4)
Compound 4e was synthesized according to the procedure
described for 4a except the refluxing period, which was
about 11 h; 1.00 g of 1a (4.85 mmol) and 0.37 g of POCl3
(2.42 mmol) were used to give 4e as a pale yellow viscous
ꢀ
IR (Nujol): m = 3,448, 1,584, 1,266, 1,165, 1,043, 927,
1
617, 525 cm-1; H NMR (CDCl3): d = 2.2 (s, 3H, CH3),
ꢀ
6.8 (d, 1H, ortho), 6.9 (m, 2H, meta), 7.0 (t, 1H, para) ppm;
13C NMR (CDCl3): d = 19.8 (CH3), 114.2 (C-ortho),
118.7 (C-para), 129.2 (C–CH3), 129.8–130.3 (C-meta),
148.0 (C–O), 163.6 (OCS2) ppm; 31P NMR (CDCl3):
d = 6.5 ppm.
liquid. Yield: 81%; IR (Nujol): m = 3,386, 1,584, 1,270,
1,164, 1,018, 926, 621, 524 cm-1 1H NMR (CDCl3):
;
d = 2.2 (s, 6H, CH3), 6.9 (d, 2H, ortho), 7.0 (m, 4H, meta),
7.1 (t, 2H, para) ppm; 13C NMR (CDCl3): d = 20.8 (CH3),
115.2 (C-ortho), 119.4 (C-para), 129.0 (C–CH3), 129.8–
130.3 (C-meta), 148.3 (C–O), 169.0 (OCS2) ppm; 31P
NMR (CDCl3): d = 15.2 ppm; EI-MS: m/z (%) = 448.9
(100) [(o-CH3C6H4OCS2)2POCl]?, 413.5 (7) [(o-CH3C6H4
OCS2)2PO]?, 358.9 (34) [(o-CH3C6H4OCS2)POCl(C-
S2OH)]?, 323.4 (21) [(o-CH3C6H4OCS2)PO(CS2OH)]?,
268.7 (57) [(CS2OH)2POCl]?, 234.7 (51) [(CS2)2POCl]-,
199.2 (34) [(CS2)2PO]?, 108.1 (76) [o-CH3C6H4OH]?,
96.1 (14) [PS2H]?, 76.1 (8) [CS2]?.
[(3-Methylphenyl)oxycarbonothioylthio]oxophosphorus(V)
dichloride (4b, C8H7Cl2O2PS2)
Compound 4b was synthesized according to the procedure
described for 4a; 1.00 g of 1b (4.85 mmol) and 0.74 g of
POCl3 (4.85 mmol) were used to give 4b as a pale yellow
ꢀ
viscous liquid. Yield: 80%; IR (Nujol): m = 3,383, 1,585,
1,267, 1,160, 1,040, 932, 612, 520 cm-1 1H NMR
;
(CDCl3): d = 2.2 (s, 3H, CH3), 6.8 (m, 2H, ortho), 6.9
(d, 1H, para), 7.0 (t, 1H, meta) ppm; 13C NMR (CDCl3):
d = 20.3 (CH3), 112.1–115.2 (C-ortho), 120.0 (C-para),
130.3 (C-meta), 135.2 (C–CH3), 147.3 (C–O), 169.0
(OCS2) ppm; 31P NMR (CDCl3): d = 6.5 ppm; EI-MS:
m/z (%) = 366.5 (67) [(m-CH3C6H4OCS2)2]?, 301.1,
303.1, 305.1 (100, 50, 4) [m-CH3C6H4OCS2POCl2]-,
230.2 (15) [m-CH3C6H4OCS2PO]?, 216.2 (8) [C6H5OC-
S2PO]?, 211.0, 213.0, 215.0 (16, 8, 1) [POCl2CS2OH]-,
158.6 (13) [CS2POCl]?, 124.1 (10) [POCS2H]-, 108.1 (15)
[m-CH3C6H4OH]?, 96.1 (7) [PS2H]?, 76.1 (14) [CS2]?.
Bis[(3-methylphenyl)oxycarbonothioylthio]oxophospho-
rus(V) chloride (4f, C16H14ClO3PS4)
Compound 4f was synthesized according to the procedure
described for 4e; 1.00 g of 1b (4.85 mmol) and 0.37 g of
POCl3 (2.42 mmol) were used to give 4f as a pale yellow
ꢀ
viscous liquid. Yield: 80%; IR (Nujol): m = 3,385, 1,584,
1,276, 1,165, 1,043, 930, 617, 525 cm-1
;
1H NMR
(CDCl3): d = 2.2 (s, 6H, CH3), 6.8 (m, 4H, ortho), 6.9
(t, 2H, meta), 7.0 (d, 2H, para) ppm; 13C NMR (CDCl3):
d = 20.8 (CH3), 112.1–115.2 (C-ortho), 119.9 (C-para),
130.3 (C-meta), 135.2 (C–CH3), 148.4 (C–O), 164.9
(OCS2) ppm; 31P NMR (CDCl3): d = 15.0 ppm.
[(4-Methylphenyl)oxycarbonothioylthio]oxophosphorus(V)
dichloride (4c, C8H7Cl2O2PS2)
Compound 4c was synthesized according to the procedure
described for 4a; 1.00 g of 1c (4.85 mmol) and 0.74 g of
POCl3 (4.85 mmol) were used to give 4c as a pale yellow
Bis[(4-methylphenyl)oxycarbonothioylthio]oxophospho-
rus(V) chloride (4g, C16H14ClO3PS4)
Compound 4 g was synthesized according to the procedure
described for 4e; 1.00 g of 1c (4.85 mmol) and 0.37 g of
POCl3 (2.42 mmol) were used to give 4g as a pale yellow
ꢀ
viscous liquid. Yield: 82%; IR (Nujol): m = 3,356, 1,584,
1,262, 1,175, 1,015, 940, 625, 529 cm-1 1H NMR
;
ꢀ
(CDCl3): d = 2.2 (s, 3H, CH3), 6.8 (d, 2H, ortho), 7.1 (d,
2H, meta) ppm; 13C NMR (CDCl3): d = 21.2 (CH3), 120.2
(C-ortho), 130.5 (C–CH3), 135.3 (C-meta), 148.6 (C–O),
163.6 (OCS2) ppm; 31P NMR (CDCl3): d = 6.5 ppm.
viscous liquid. Yield: 83%; IR (Nujol): m = 3,418, 1,585,
1,280, 1,172, 1,032, 943, 615, 560 cm-1 1H NMR
;
(CDCl3): d = 2.2 (s, 6H, CH3), 6.9 (d, 4H, ortho), 7.0 (d,
4H, meta) ppm; 13C NMR (CDCl3): d = 21.4 (CH3), 120.2
(C-ortho), 131.2 (C–CH3), 134.8 (C-meta), 148.6 (C–O),
172.3 (OCS2) ppm; 31P NMR (CDCl3): d = 15.2 ppm; EI-
MS: m/z (%) = 448.9 (100) [(p-CH3C6H4OCS2)2POCl]?,
366.1 (20) [(p-CH3C6H4OCS2)2]?, 268.7 (36) [(CS2OH)2
POCl]-, 234.9 (11) [(CS2)2POCl]?, 199.9 (11) [(CS2)2
PO]?, 108.1 (22) [p-CH3C6H4OH]?, 76.1 (28) [CS2]?.
(Benzyloxycarbonothioylthio)oxophosphorus(V)
dichloride (4d, C8H7Cl2O2PS2)
Compound 4d was synthesized according to the procedure
described for 4a; 1.00 g of 1d (4.85 mmol) and 0.74 g of
POCl3 (4.85 mmol) were used to give 4d as a pale yellow
ꢀ
viscous liquid. Yield: 85%; IR (Nujol): m = 3,412, 1,586,
123

1094
B. Gupta et al.
Bis(benzyloxycarbonothioylthio)oxophosphorus(V) chlo-
ride (4h, C16H14ClO3PS4)
POCl3 (1.62 mmol) were used to give 4l as a pale yellow
ꢀ
viscous liquid. Yield: 86%; IR (Nujol): m = 3,362, 1,585,
1
Compound 4h was synthesized according to the procedure
described for 4e; 1.00 g of 1d (4.85 mmol) and 0.37 g of
POCl3 (2.42 mmol) were used to give 4h as a pale yellow
1,277, 1,185, 1,024, 942, 540 cm-1; H NMR (CDCl3):
d = 4.6(s, 6H, CH2), 7.1–7.2(m, 15H, C6H5) ppm; 13C NMR
(CDCl3): d = 71.4 (CH2), 125.7–125.9 (C-ortho),
126.7–126.8 (C-meta), 128.0 (C-para), 136.8 (C–CH2),
171.5 (OCS2) ppm; 31P NMR (CDCl3): d = 19.5 ppm;
EI-MS: m/z (%) = 596.8 (72) [(C6H5CH2OCS2)3PO]?,
446.6 (8) [(C6H5CH2OCS2)2POSH]?, 417.5 (19)
[(C6H5CH2OCS2)2POH]-, 275.8 (100) [(CS2)3PO]-, 263.0
(12) [C6H5CH2OCS2POSH]-, 230.2 (20) [C6H5CH2OC-
S2PO]?, 199.8 (25) [(CS2)2PO]?, 146.2 (15) [(SH)3PO]?,
108.1 (38) [C6H5CH2OH]?, 76.1 (19) [CS2]?.
ꢀ
viscous liquid. Yield: 85%; IR (Nujol): m = 3,402, 1,585,
1,285, 1,180, 1,024, 944, 612, 564 cm-1; 1H NMR (CDCl3):
d = 4.5 (s, 4H, CH2), 7.2 (m, 10H, C6H5) ppm; 13C NMR
(CDCl3): d = 71.2 (CH2), 125.7–125.8 (C-ortho), 126.9–
127.1 (C-meta), 127.9 (C-para), 137.0 (C–CH2), 167.8
(OCS2) ppm; 31P NMR (CDCl3): d = 14.9 ppm.
Tris[(2-methylphenyl)oxycarbonothioylthio]oxophospho-
rus(V) (4i, C24H21O4PS6)
Compound 4i was synthesized according to the procedure
described for 4a except the refluxing period, which was
about 12 h; 1.00 g of 1a (4.85 mmol) and 0.25 g of POCl3
(1.62 mmol) were used to give 4i as a pale yellow viscous
Acknowledgments SKP gratefully acknowledges the financial
assistance from the University Grants Commission, New Delhi. We
are grateful to Sophisticated and Analytical Instrumentation Facility
(SAIF), Chandigarh and Indian Institute of Integrative Medicine
(IIIM), Jammu, for providing spectral facilities.
ꢀ
liquid. Yield: 82%; IR (Nujol): m = 3,432, 1,603, 1,290,
1
1,185, 1,018, 942, 537 cm-1; H NMR (CDCl3): d = 2.2
(s, 9H, CH3), 6.8 (d, 3H, ortho), 6.9 (m, 6H, meta), 7.0 (t,
3H, para) ppm; 13C NMR (CDCl3): d = 19.7 (CH3), 114.1
(C-ortho), 118.7 (C-para), 128.2-129.2 (C-meta), 129.0
(C–CH3), 147.3 (C–O), 168.6 (OCS2) ppm; 31P NMR
(CDCl3): d = 19.4 ppm.
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53:74
Tris[(3-methylphenyl)oxycarbonothioylthio]oxophospho-
rus(V) (4j, C24H21O4PS6)
Compound 4j was synthesized according to the procedure
described for 4i; 1.00 g of 1b (4.85 mmol) and 0.25 g of
POCl3 (1.62 mmol) were used to give 4j as a pale yellow
ꢀ
viscous liquid. Yield: 80%; IR (Nujol): m = 3,429, 1,602,
1
1,282, 1,183, 1,025, 943, 538 cm-1; H NMR (CDCl3):
d = 2.2 (s, 9H, CH3), 6.6 (m, 6H, ortho), 7.0 (d, 3H, para),
7.1 (t, 3H, meta) ppm; 13C NMR (CDCl3): d = 20.3 (CH3),
112.2–114.7 (C-ortho), 120.0 (C-para), 131.2 (C-meta),
134.2 (C–CH3), 148.3 (C–O), 169.2 (OCS2) ppm; 31P
NMR (CDCl3): d = 19.5 ppm.
Tris[(4-methylphenyl)oxycarbonothioylthio]oxophospho-
rus(V) (4k, C24H21O4PS6)
Compound 4k was synthesized according to the procedure
described for 4i; 1.00 g of 1c (4.85 mmol) and 0.25 g of
POCl3 (1.62 mmol) were used to give 4k as a pale yellow
18. Palecek U, Marhoul A, Nemeova J, Sourek V (1966) Chem
Prumysl 16:558
ꢀ
viscous liquid. Yield: 81%; IR (Nujol): m = 3,379, 1,603,
1
1,285, 1,180, 1,018, 944, 555 cm-1; H NMR (CDCl3):
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