Organic derivatives of alkylene dithiophosphates part III: Synthesis and properties of 2-(p-nitrophenyl) and 2-(p-nitrobenzoyl) derivatives of alkylene dithiophosphates

Article abstract of DOI:10.1080/10426500210659

Reactions of p-bromonitrobenzene and p-nitrobenzoyl chloride with ammonium salt of alkylene dithiophosphates (OGOPS₂N⁺H₄: G = -CMe₂CMe₂-, -CH₂CMe₂CH₂-, -CMe₂

Full text of DOI:10.1080/10426500210659

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Organic Derivatives of Alkylene Dithiophosphates Part
III: Synthesis and Properties of 2-( p -nitrophenyl)
and 2-( p -nitrobenzoyl) Derivatives of Alkylene
Dithiophosphates
Chandra S. Sharma a , Mukesh K. Sharma a & Padam N. Nagar a
a Department of Chemistry , University of Rajasthan , Jaipur, India
Published online: 27 Oct 2010.
To cite this article: Chandra S. Sharma , Mukesh K. Sharma & Padam N. Nagar (2002) Organic Derivatives of Alkylene
Dithiophosphates Part III: Synthesis and Properties of 2-( p -nitrophenyl) and 2-( p -nitrobenzoyl) Derivatives of Alkylene
Dithiophosphates, Phosphorus, Sulfur, and Silicon and the Related Elements, 177:4, 981-987, DOI: 10.1080/10426500210659
To link to this article: http://dx.doi.org/10.1080/10426500210659
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:981–987
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
ORGANIC DERIVATIVES OF ALKYLENE
DITHIOPHOSPHATES PART III: SYNTHESIS
AND PROPERTIES OF 2-(p-NITROPHENYL)
AND 2-(p-NITROBENZOYL) DERIVATIVES OF
ALKYLENE DITHIOPHOSPHATES
Chandra S. Sharma, Mukesh K. Sharma, and Padam N. Nagar
Department of Chemistry, University of Rajasthan, Jaipur, India
(Received June 2, 2001; accepted October 17, 2001)
Reactions of p-bromonitrobenzene and p-nitrobenzoyl chloride with
ammonium salt of alkylene dithiophosphates (OGOPS +H : G =
2 N
4
CMe2CMe2
,
CH2CMe2CH2
,
CMe2CH2CHMe ,
CH2CH2
CHMe ) in 1:1 molar ratio in refluxing benzene solution yields:
non-volatile yellow colored solids and red colored viscous liquids
respectively of the type OGOP(S)SR (R = C6H4NO2, (O)CC6H4NO2)
which are monomeric in nature. The newly synthesized complexes
have been characterized by physico-chemical and spectroscopic tech-
niques (M.W., IR, NMR [1H and 31P]). On the basis of above studies,
the formation of P S C and P S C(O) chemical bonds has been
established.
Keywords: IR; NMR spectra; O,O0-alkylene dithiophosphates;
p-bromonitrobenzene, p-O,O0-alkylene dithiophosphato-(S)-nitro-
benzene; p-nitrobenzoyl chloride
INTRODUCTION
In continuation to our earlier investigations on metal, organometal and
organic derivatives of phosphonate and phosphate esters1 11 it was con-
sidered of interest to the synthesize and characterize the complexes of
the type OGOP(S)SC6H4NO2 and OGOP(S)SC(O)C6H4NO2.
RESULTS AND DISCUSSION
Reactions of p-bromonitrobenzene and p-nitrobenzoyl chloride with
ammonium salt of alkylene dithiophosphates in 1:1 molar ratio have
Address correspondence to P. N. Nagar, Department of Chemistry, University of
Rajasthan, Jaipur 302 004, India.
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C. S. Sharma et al.
been carried out in refluxing benzene for 10 h and 6 h which yield
yellow colored solids (A) and red colored viscous liquids (B) respectively.
C6H6
A. OGOPS2NH4 + BrC6H4NO2
→ OGOPS2C6H4NO2+NH4Br ↓
10 hrs.
C6H6
B. OGOPS2NH4 + CI(O)C6H4NO2 → OGOPS2C(O)C6H4NO2
6 hrs.
+ NH4CI ↓
(where G = CMe2CMe2
,
CH2CMe2CH2
,
CMe2CH2CHMe ,
CH2CH2CHMe )
Desired products have been isolated by stripping off the solvent from
the filtrate under reduced pressure. These derivatives are nonvolatile,
monomeric, soluble in common organic solvents and get decomposed
on heating at 140 C. It has been observed that the reactivity of the
alkylene dithiophosphate group toward substituted aromatic halide ion
is increased by taking deactivating nitro group at para position in aro-
matic ring. It seems that the nucleophillic displacement of the bromide
ion by alkylene dithiophosphato group is faster by taking deactivating
groups at para position. In our earlier publication it was reported that
the synthesis of 2-acetanilide (benzanilide) alkylene dithiophosphates
requires longer refluxing 28 h.10
IR SPECTRA
IR spectra of these derivatives shows the following characteristic
changes:
1
1. A stretching vibration at 3080–3060 cm in all the complexes may
be ascribed to aromatic C H stretching vibrations.
2. Nitro group in these derivatives shows absorption band at 1150–
1
1530 cm which shows slight shift toward lower wave numbers
(15 cm 1) in comparison to p-bromonitrobenzene. It may be due to
lesser nucleophillicity of dithio moiety in comparision to the bromide
ion present in the p-bromonitrobenzene.
1
3. The absorption band in the region 1145–1130 cm
and 885–
1
870 cm may be assign to (P) O C and P O (C) stretching vi-
brations respectively.
4. A strong absorption band due to dioxaphospholane and dioxaphos-
1
phorinane ring vibrations is present in the region 955–910 cm
.
5. A sharp band assigned to P S absorptions in the region 780–
1
765 cm indicates shifting toward higher frequency with respect

Organic Derivatives of Alkylene Dithiophosphates Part III
983
to its position in the free ligand. This shifting is due to presence of
deactivating nitro group in the aromatic ring.
1
6. New bands have been observed in the region 680–625 cm which
may be due to the C S bond. Appearance of this bond supports the
formation of P(S)S
C6H4NO2 linkage in these derivatives.
C
||
O
7. The absorption bands of medium intensities in the region 565–
1
540 cm have been attributed to P S asymmetric and symmetric
vibrations.
NMR SPECTRA
1H NMR spectral data of these derivatives are tabulated in Table I
and show characteristic resonance signal due to glycoxy and aromatic
protons. A multiplet for OCH2 and O CH protons has been observed
due to long range coupling with phosphorus atom. A multiplet has been
observed in the region 7.7–7.9 ppm, which was assigned to aromatic
protons while aromatic protons of p-bromonitrobenzene appeared as
distorted doublet.
31P NMR spectra of these derivatives show single resonance signal
in the region 70.28–94.09 ppm which indicates purity of these com-
plexes. A comparison of the chemical shift values indicates that phos-
phorous atom is more deshielded ( 77.99–70.28 ppm) in the complexes
OGOP(S)SC(O)C6H4NO2, thus shifting the NMR signal to upfield. It
may be due to deactivating effects of both carbonyl and nitro groups. In
the complexes OGOP(S)SC6H4NO2 the 31P signal have been shifted
upfield (Table I).
EXPERIMENTAL
Stringent precautions were taken to exclude moisture during the ex-
perimental manipulations. Solvents were dried by standard methods.
p-bromonitrobenzene and p-nitrobenzoyl chloride, alkylene dithiophos-
phates were prepared by the methods reported in literature.12 Sul-
fur was estimated gravimetrically as barrium sulphate (messenger’s
method).12 Molecular weiglets were determined by the “Knauer vapour
pressure osmometer” using chloroform solutions at 45 C. Infrared spec-
tra recorded in nujol mull (4000–200 cm 1) on Perkin-Elmer spec-
trophotometer. Carbon and hydrogen analyses were performed on a
Perkin-Elmer CHNS/O analyser. 1H NMR spectra were recorded in
CDCl3 solution on a 90MHz JEOL FX 90Q spectrometer using TMS as

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C. S. Sharma et al.
an internal reference. 31P NMR spectra were recorded in CHCl3 using
H3PO4 as an external reference. The other complexes were synthesized
by similar route. The experimental details of a representative complex
is being described below. Analytical results are summarized in Table II.
Preparation of OCMe2CMe2OP(S)SC6H4NO2
p-bromonitrobenzene (0.96 gm) was dissolved in 30 ml benzene. To this,
a solution of ammonium tetramethylene dithiophosphate (1.09 gm) was
added slowly and refluxed for 10 h. The precipitated ammonium bro-
mide was filtered off. The solvent was removed from the filtrate under
reduced pressure to obtain the desired product, yellow sticky solid. The
compound on analyses show: C, 42.98; H, 4.58; N, 18.83% calculated for
OCMe2CMe2OP(S)SC6H4NO2. The above procedure was adopted for all
the other reactions. Relevant data are given in Table II.
Preparation of OCMe2CMe2OP(S)SC(O)C6H4NO
2
Ammonium tetramethylene dithiophosphate (1.12 g) was refluxed
with p-nitrobenzoyl chloride (0.90 g) in benzene for 6 h. Ammonium
chloride was removed by filtration. A red colored product was sepa-
rated out by removing the solvent from the filtrate. The compound
on analysis show C, 43.21%; H, 4.43%; S, 17.73; calculated for the
OCMe2CMe2OP(S)SC(O)C6H4 NO2. The above procedure was adopted
for all other reactions. Relevant data are given in Table II.
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Organic Derivatives of Alkylene Dithiophosphates Part III
987
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