Synthesis of chalcogenides and metal complex of 2-phenyl-benzo[1,3,2] dioxophosphinin-4-one

Article abstract of DOI:10.14233/ajchem.2014.15617

The chalcogenides and the metal complexes of 2-phenyl-benzo[1,3,2] dioxophosphinin-4-one are prepared by single step reaction of 2-phenyl-benzo[1,3,2]dioxophosphinin-4-one (1) with DMSO, elemental S, Se and W(CO)₅CH₃CN.

Full text of DOI:10.14233/ajchem.2014.15617

Synthesis of 2-oxo-2-phenyl-2
λ5-benzo[1,3,2] dioxo-
Asian Journal of Chemistry; Vol. 26, No. 7 (2014), 1998-2000
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.15617
Synthesis of Chalcogenides and Metal Complex of 2-Phenyl-benzo[1,3,2]dioxophosphinin-4-one
*
MANJU RANI, DAVENDER KUMAR SHUKLA and ARIF ALI KHAN
University School of Basic & Applied Sciences, Guru Gobind Singh Indraprastha University, Dwarka, Sector16-C, New Delhi-110 078, India
*Corresponding author: Email: khanaarif@hotmail.com
Received: 10 April 2013;
Accepted: 31 January 2014;
Published online: 22 March 2014;
AJC-14946
The chalcogenides and the metal complexes of 2-phenyl-benzo[1,3,2]dioxophosphinin-4-one are prepared by single step reaction of
2-phenyl-benzo[1,3,2]dioxophosphinin-4-one (1) with DMSO, elemental S, Se and W(CO)5CH3CN.
Keywords: Salicylic acid, Phosphorous-chalcogenides, Triethylamine, P-heterocycles.
O
INTRODUCTION
O
Phosphorus heterocycles and their derivatives are of great
interest as bioactive substances with various properties1,2.
Organo-phosphorus compounds also constitute a family of
flame retardants due to their unique combustion inhibition
properties3,4. They have been known to act in both gas phase
and condensed phase5,6. Synthesis of flame retardants with low
flammability and melt dropping limits is in urgent need now-
a-days and is gaining much attention7. In this paper, we report
the synthesis of chalcogenides and metal complexes of 2-
phenyl-benzo[1,3,2]dioxophosphinin-4-one (1). The parent
compound 1 has been synthesized long back8-10 but to best of
our knowledge no chalcogenides and metal complexes of it
has been reported so far.
OH
PhPCl2
Et3N
O
P
OH
O
Ph
(1)
Scheme-I
phosphinin-4-one (2): To a pre-cooled dichloromethane
solution of 2-phenyl-benzo[1,3,2]dioxophosphinin-4-one (2
mmol) at 0 °C, a DMSO (2 mmol) solution in dichloromethane
was added dropwise and stirring was continued for 2 h at
0 °C then at room temperature overnight. The solvent was
removed under reduced pressure and the product was isolated
by recrystallization from diethyl ether at 5 °C as off white
crystalline material, Yield 78 %; m.p. 91-92 °C. Elemental
analysis calculated for C13H9O4P: C, 60.01; H, 3.49. Found:
C, 58.16; H, 3.32. FTIR (cm-1) 1245.9 (P=O); 31P NMR (121.49
MHz, CDCl3) δ 20.422; 1H NMR (300 MHz, CDCl3, Me4Si):
δ 6.840-7.931 (m, 9H, aromatic); 13C NMR (75 MHz, CDCl3):
δ 29.70, 111.64, 117.71, 119.42, 128.63, 128.81,130.62,
130.88, 132.96, 136.61, 162.15, 173.92; GCMS m/z: 260.10,
Mass Fragments: 92(35.07), 120(100.00), 260(37.90).
Synthesis of 2-phenyl-2-thioxo-2λ5-benzo[1,3,2]-
dioxaphosphinin-4-one (3): A solution of 2-phenyl-benzo-
[1,3,2] dioxophosphinin-4-one (1 mmol) and elemental sulphur
(5 mmol) in 25 mL toluene was heated at 108-110 °C for 12 h.
The resulting dark brown solution was filtered hot under nitrogen
and concentrated under reduced pressure. The crude product
thus obtained was recrystallized from diethyl ether at 5 °C as
EXPERIMENTAL
Starting materials and solvents were obtained from Merck
and Spectrochem and were used with further purification. IR
spectra were measured on a Shimadzu IR-460 spectrophoto-
meter. 1H NMR, 13C NMR and 31P NMR spectra were measured
(CDCl3 solution) with a BrukerAV-300 spectrometer (300 MHz
1
for H; and 121.5 MHz for 31P) using CDCl3 as solvent and
internal standard; shifts are given relative to ext. tetramethyl-
silane (1H, 13C) or 85 % H3PO4 (31P). Chemical shifts are
designated using the following abbreviations: s = singlet, d =
doublet, t = triplet, m = multiplet. Mass spectra were recorded
on a Shimadzu GCMS QP2010 plus instrument and fragments
having intensity more than 20 % has been given. Progress of
reaction was monitored by TLC as well as 31P NMR.
Procedure for preparation of compounds (1-5): Synthesis
of 2-phenyl-benzo[1,3,2]dioxophosphinin-4-one (1), prepared
according to literature8 (Scheme-I).

Vol. 26, No. 7 (2014)
Synthesis of Chalcogenides and Metal Complex of 2-Phenyl-benzo[1,3,2]dioxophosphinin-4-one 1999
yellow crystalline material, Yield 29 %; m.p. 118-120 °C.
Elemental analysis calculated for C13H9O3PS: C, 48.32; H, 2.81.
Found: C, 46.26; H, 2.51. FTIR (cm-1) 692.4 (P=S); 31P NMR
(121.49 MHz, CDCl3) δ 70.068; 1H NMR (300 MHz, CDCl3,
Me4Si): δ 7.049-7.835 (m, 9H, aromatic); 13C NMR (75 MHz,
CDCl3): δ116.57, 119.58, 119.64, 124.75, 127.79, 129.01, 129.14,
131.75, 131.92, 137.13; GCMS m/z: 276.00, Mass Fragments:
28.10 (100.00), 120 (30.14), 276.00(7.20).
diethyl ether at 5 °C as off white crystalline solid,Yield 62 %;
m.p. 97-98 °C. Elemental analysis calculated for C18H9O8PW:
C, 38.06; H, 1.60. Found: C, 36.13; H, 1.41. FTIR (cm-1)
1753.2, 1932.5 and 2081.0 (CO); 31P NMR (121.49 MHz,
1
CDCl3) δ 128.015 (1JP-W 180.3 Hz); H NMR (300 MHz,
CDCl3, Me4Si): δ 7.032-7.853 (m, 9H, aromatic); 13C NMR
(75 MHz, CDCl3): δ 116.42, 116.55, 119.56, 124.73, 127.78,
127.95, 128.99, 129.11, 131.70, 137.13, 139.36, 139.88,
155.18, 156.60, 193.76, 193.88, 197.25 197.75.
Synthesis of 2-phenyl-2-selenoxo-2λ5-benzo[1,3,2]
dioxophosphinin-4-one (4) (Scheme-II):A solution of phenyl-
dichlorophosphene (1 mmol) and elemental selenium powder
(5 mmol) in 15 mL toluene was heated at 108-110 °C for 7 h.
The resulting solution was filtered under nitrogen and cool
then it was added drop wise to a solution of salicylic acid in
toluene followed by addition of triethylamine at 0 °C stirred
at room temperature overnight. The crude product thus
obtained was separated by recrystallization from diethyl ether
at 5 °C as orange crystalline solid,Yield 38 %; m.p. 88-90 °C.
Elemental analysis calculated for C13H9O3PSe: C, 56.52; H,
3.28. Found: C, 56.54; H, 3.12. FTIR (cm-1) 596.2 (P=Se); 31P
O
O
O
O
P
W(CO)5CH3CN, THF
20-25 °C, 22 h
Ph
Ph
P
O
O
W(CO)5
(1)
(5)
Scheme-III
RESULTS AND DISCUSSION
1
NMR (121.49 MHz, CDCl3) δ 91.826 (1JP-Se 959.6 Hz); H
Herein, we report synthesis of chalcogenides and metal
complex of 2-phenyl-benzo[1,3,2]dioxophosphinin-4-one (1).
The compound 1 was obtained from cyclo-condensation of
salicylic acid with phenyldichlorophosphene in equimolar
quantities, in presence of triethylamine in dry toluene at room
temperature overnight8. The P-oxide derivative 2 was selec-
tively prepared by reacting compound 1 with DMSO in dry
dichloromethane at 0 ºC. The P-chalcogenides (3) and (4) were
prepared by reacting 2-phenyl-benzo[1,3,2]dioxophosphinin-
4-one (1) with elemental sulphur and selenium powder in dry
toluene at 110 ºC11,12. Tungsten pentacarbonyl complex (5)
was prepared by reacting 1 with W(CO)5CH3CN in THF and
purified by recrystallization with diethyl ether. The compounds
NMR (300 MHz, CDCl3, Me4Si): δ 7.129-8.057 (m, 9H,
aromatic); 13C NMR (75 MHz, CDCl3): δ 113.88, 119.31,
119.98, 125.45, 128.60, 128.91, 129.13, 130.34, 131.59,
132.01, 134.38, 134.62, 137.89; GCMS m/z: 324.00, Mass
Fragments: 64(18.90), 92 (68.23), 120(100), 183.90 (22.93),
323.90 (41.29).
(Note: 2-Phenyl-2-selenoxo-2λ5-benzo[1,3,2]dioxo-
phosphinin-4-one can be prepared by this method but the yield
was low.A solution of 2-phenyl-benzo[1,3,2]dioxophosphinin-
4-one (1 mmol) and selenium powder (5 mmol) in 15 mL
toluene was heated at 110 °C for 7 h. The resulting dark brown
solution was filtered hot under nitrogen and concentrated under
reduced pressure. The crude product was recrystallized from
diethyl ether at 5 °C (yield 60 %).
1
were characterized by IR, H, 13C, 31P and GC-MS spectro-
scopic data.
All the compounds exhibited characteristic absorption
bands for P=O, P=S and P=Se functional groups in the normal
region 1246, 692 and 596 cm-1 showing that they are not invol-
ved in hydrogen bonding. Tungsten pentacarbonyl complex
shows characteristic absorption bands for -CO stretching
vibrations in the region 1753, 1932 and 2081 cm-1.
O
O
O
O
P
DMSO
O
0 °C, 2h
O
P
Ph
1
In the H NMR spectra, the aromatic protons resonated
(2)
as multiplets in the region 6.84-8.06. The 13C NMR chemical
shifts were interpreted based on comparison with carbon
chemical shifts, additivity rules and intensity of the signals
and coupling with phosphorus. Carbon bonded to endocyclic
oxygen gave signals at 130.9-137.9. The carbonyl carbons of
W(CO)5 were appears in the region 193.8-197.7. The remai-
ning carbon shifts were observed in the expected regions.
Phosphorous resonance signals, P=O, P=S and P=Se were
observed at 20.422, 70.068 and 91.826, respectively. Phos-
phorous selenium resonance occurs as triplet with coupling
constant 959.6 Hz due to the phosphorous selenium coupling,
whereas the P-W(CO)5 resonance occurs at 128.01 as triplet
with coupling constant 180.3 Hz due to phosphorous tungsten
coupling. GC-MS of all the compounds exhibited molecular
(M+) and characteristic daughter ion peaks at their respective
expected m/z values.
O
S, Se, Toluene
110 °C, 7-12h
O
Ph
O
(1)
Ph
P
O
X
X= S (3), Se (4)
Scheme-II
Synthesis of 2-phenyl-benzo[1,3,2]dioxophosphinin-4-
one-W(CO)5 complex (5) (Scheme-III):A solution of 2-phenyl-
benzo[1,3,2]dioxophosphinin-4-one (1 mmol) and W(CO)5
CH3CN (1.1 mmol) in 15 mL THF was stirred at 25-30 °C for
22 h. The resulting dark brown solution was filtered under
nitrogen and concentrated under reduced pressure. The crude
product thus obtained was separated by recrystallization from

2000 Rani et al.
Asian J. Chem.
4. S.V. Levchik and E.D. Weil, Polym. Int., 54, 11 (2005).
Conclusion
5. J. Green, in eds.: A. Grand and C.A. Wilkie, Phosphorus-Containing
Flame Retardants, In: Fire retardancy of Polymeric Materials, Marcel
Dekker, Inc; New York (2000).
In conclusion, we have reported a simple route for the
synthesis of chalcogenides and metal complex of 2-phenyl-
benzo[1,3,2]dioxophosphinin-4-one in good to excellent
yields.
6. X.-H. Du, Y.-Z. Wang, X.-T. Chen and X.-D. Tang, Polym. Degrad.
Stab., 88, 52 (2005).
7. S.V. Levchik, G. Camino, M.P. Luda, L. Costa, G. Muller, B. Costes
and Y. Henry, Polym. Adv. Technol., 7, 823 (1996).
ACKNOWLEDGEMENTS
8. S. Kobayashi, T. Kobayashi and T. Saegusa, Chem. Lett., 393 (1979).
9. M. M. Makhamatkhanov, V. V. Vakhidova, F. A. Bakhtiyarova, Kh. E.
Yuldasheva, N. Kh. Maksudov, Deposited Doc., 2152, 6, (1976).
10. V.V. Vakhidova, M.M. Makhamatkhanov, F.A. Bakhtiyarova, Kh.E.
Yuldasheva, N.Kh. Maksudov and A. Akbarov, Uzbek. Khim. Zh., 6,
66 (1977).
The authors (MR,AAK) are thankful to CSIR, New Delhi,
India for financial assistance.
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