Reaction of 2,4-diaryl-1,3-dithia-2,4-diphosphetane-2,4-disulfides with resorcinol

Full text of DOI:10.1134/S1070363212020296

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 2, pp. 342–343. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © I.S. Nizamov, L.A. Al’metkina, G.R. Sabirzyanova, E.N. Nikitin, A.R. Burilov, M.A. Pudovik, 2012, published in Zhurnal Obshchei
Khimii, 2012, Vol. 82, No. 2, pp. 347–348.
LETTERS
TO THE EDITOR
Reaction of 2,4-Diaryl-1,3-dithia-2,4-diphosphetane-2,4-disulfides
with Resorcinol
I. S. Nizamova,b, L. A. Al’metkinab, G. R. Sabirzyanovab, E. N. Nikitinb,
A. R. Burilova, and M. A. Pudovika
a State Budgetary-Funded Institution of Science,
A.E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Center of Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: isnizamov@mail.ru
b Kazan (Volga Region) Federal University, Kazan, Tatarstan, Russia
Received June 9, 2011
DOI: 10.1134/S1070363212020296
Bisdithiophosphonic acids containing two α,ω-
dithiophosphoryl groups [1, 2] are of interest as the
podand-like compounds in substitution, intercalation,
addition, and complexation reactions to create on their
basis antioxidants for polymers, antioxidant additives
for lubricating oils, corrosion inhibitors, extractants of
metal ions, etc. [3–9]. The reactions of 2,4-dialkyl- or
diaryl-1,3-dithia-2,4-diphosphetane-2,4-disulfides with
glycols are used to obtain bisdithiophosphonic acids
[1–8]. At the same time the reaction of catechol with
2,4-diferrocenyl-1,3-dithia-2,4-diphosphetane-2,4-di-
sulfide results in 1,3,2-dioxaphospholane derivative
[10], which is a secondary product formed during the
desulfurization of the intermediate phenylene
bisdithiophosphonic acid. In contrast, resorcinol II was
found to react with 2,4-diaryl-1,3-dithia-2,4-diphos-
phetane-2,4-disulfides Ia and Ib in benzene at 20°C
for 10 days (Ia) or at 60°C for 2 h (Ib) to give O,O'-
(benzene-1,3-diyl) bis(aryldithiophosphonic) acids
(IIIa, IIIb) as solids. The 31P NMR spectra of acids
IIIa and IIIb contain one characteristic signal [11] at
88.1 and 87.9 ppm, respectively.
S
S
S
P
HO
OH
S
O
O
Ar
Ar
Ar
P
P
Ar
P
S
+
HS
S
SH
II
IIIа, IIIb
Iа, Ib
O
HO
(b).
Ar =
(a),
O,O'-(Benzene-1,3-diyl) bis(3,5-di-tert-butyl-4-hyd-
roxyphenyldithiophosphonate) (IIIa). To a suspend-
sion of 0.6 g of phosphetane Ia in 15 ml of anhydrous
benzene under an argon atmosphere at 20°С was added
by portions 0.11 g of resorcinol II. The mixture was
stirred at 20°С for 8 h, then filtered and evaporated at
40°С within 1 h at 0.5 Hg mm and for 1 h at 0.02 Hg
mm. Yield 0.6 g (85%), mp 80–81°С. IR spectrum, ν,
2913 s, 2872 m [νas,s(СН3)], 2538 w.br (S–H), 2437
w.br (S–H), 1594 m, 1478 s (C—···С, Ar), 1429 v.s
[δas(СН3)], 1364 m [δs(СН3)], 1111 s, 1119 v.s [(P)O–C],
1
973 s (О–С), 660 m (P=S), 595 m (P–S). Н NMR
spectrum, δ, ppm (J, Hz): 1.47 s and 1.50 s [36Н,
(СН3)3С], 2.59 m (2Н, PSH), 5.03 m (2Н, HO), 6.42 t
4
3
(1Н, 2-C6HO2P, JHP 2.2), 6.69 t (1Н, 5-C6HO2P, JHH
3
8.3), 7.07 d and 7.13 d (2Н, 4,6-C6HO2P, JHH 8.3),
7.83 d and 7.92 d (4Н, 2,6-C6H2P, JРH 15.9). Mass
cm–1: 3618 m (Н–О), 3085 w (—···С–Н, Ar), 2959 s,
3
342

REACTION OF 2,4-DIARYL-1,3-DITHIA-2,4-DIPHOSPHETANE-2,4-DISULFIDES
spectrum (EI), m/z (Irel, %): 711 (5) [М]+. Found, %: С
343
REFERENCES
57.32; Н 6.44; Р 8.63; S 16.43. C34H48O4P2S4.
Calculated, %: С 57.44; Н 6.81; Р 8.71; S 16.04. М
711.0.
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O,O'-(Benzene-1,3-diyl) bis(4-phenoxyphenyldi-
thiophosphonate) (IIIb) was prepared similarly from
1.0 g of phosphetane Ib and 0.21 g of resorcinol II.
Yield 0.8 g (67%), mp 46–48°С. IR spectrum, ν, cm–1:
3064 w, 3030 w (—···С–Н, Ar), 2352 w.br (S–H), 1584
v.s, 1488 v.s (С—···С, Ar), 1122 s [(P)O–C], 930 v.s.br
1
(О–С), 695 s (P=S), 520 m (P–S). Н NMR spectrum,
δ, ppm (J, Hz): 2.19 m (2Н, PSH), 6.94 two d (4Н,
3,5-C6H2О, 3JНH 7.4), 7.02 two d (4Н, 3,5-C6H2Р, 3JНH
7.9), 7.18 two d (2Н, 4-C6HО, 3JНH 7.4), 7.34 d.d (4Н,
3
3
2,6-C6H2О, JНH 7.4), 7.83 d. d (4Н, 2,6-C6H2Р, JНH
3
7.9, JРH 13.4). Mass spectrum (MALDI TOF), m/z:
638 [M]+. Found, %: С 56.20; Н 3.91; Р 9.40; S 20.46.
C30H24O4P2S4. Calculated, %: С 56.41; Н 3.79; Р 9.70;
S 20.08. М 638.7.
The IR spectra were recorded on a Bruker Vector
22 IR Fourier-spectrometer (KBr pellets or mulls in
mineral oil). The 1Н NMR spectra were registered on a
Bruker Avance-600 (600 MHz) spectrometer in
CDCl3; the 31Р NMR spectra, on a Bruker CXP-100
(36.5 MHz) spectrometer in benzene relative to
external 85% Н3РО4. The mass spectra (EI) were
measured on a DFS Thermo Electron Corporation
(70 eV). The MALDI TOF mass spectra were obtained
on an Ultrafex Bruker (UV, 337 nm, matrix 1,8,9-
trihydroxyanthracene).
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ACKNOWLEDGMENTS
11. Crutchfield, M.M., Dungan, C.H., Letcher, J.H., Mark, V.,
and Van Wazer, J.R., Topics in Phosphorus Chemistry.
P31 Nuclear Magnetic Resonance, New York: Wiley
and Sons, 1967, vol. 5.
This study was financially supported by the Russian
Foundation for Basic Research (grant no 11-03-00264-а).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 2 2012