ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 7, pp. 1466–1468. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © I.S. Nizamov, G.T. Gabdullina, L.A. Al’metkina, I.D. Nizamov, R.A. Cherkasov, 2008, published in Zhurnal Obshchei Khimii, 2008,
Vol. 78, No. 7, pp. 1228–1230.
LETTERS
TO THE EDITOR
O,O'-Ethylenedioxydiethylene bis[S-(triphenylplumbyl)
(3,5-di-tert-butyl-4-hydroxyphenyl)phosphonodithioate]
I. S. Nizamova,b,c, G. T. Gabdullinac, L. A. Al’metkinaa,
I. D. Nizamova, and R. A. Cherkasova
aKazan State University, ul. Kremlevskaya 8, Kazan, Tatarstan, 428008 Russia
e-mail: Ilyas Nizamov@ksu.ru; nizamov@iopc.knc.ru
bArbuzov Institute of Organic and Physical Chemistry, Kazan Research Centrer,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
cТatar State Humanitarian and Pedagogical University, Kazan, Tatarstan, Russia
Received November 27, 2007
DOI: 10.1134/S1070363208070347
Sulfur-containing derivatives of four-coordinate
phosphorus thio acids with a PS2E structural fragment
(E is a main subgroup element) are of great practical
interest as additives to lubricant oils, regulators of
rubber vulcanization, extractants, complex-forming
agents, pesticides, etc. They are of interest for solving
basic problems of organoelement chemistry, such as
mutual influence of atoms in a heteroatomic group on
an example of PS2E system, electronic and steric
structure, and stereochemistry. Earlier we synthesized
highly biologically active oligomeric and monomeric
S-trialkylplumbyl phosphorodithioates by the proto-
deplumbation of tetraalkylplumbanes with phosphoro-
dithioic acids [1, 2].
[4, 5]. These compounds, in our opinion, are by-
products formed by the reaction of acetonitrile with bis
(arylphosphonodithioic acid) as a primary product,
since, as shown earlier, bis(methylphosphonodithioic
acids) react with acetonitrile to give cyclic trithiopyro-
phosphonates and thioacetamide [6]. We found that the
most convenient inert solvent for the reaction of 2,4-
bis(3,5-di-tert-butyl-4-hydroxyphenyl)-1,3,2λ5,4λ5-di-
thiadiphosphetane 2,4-disulfide (I) with triethylene
glycol (II) is absolute benzene, that allowed us to
obtain acid III at 50º within 1.5 h. Acid III was
converted into the corresponding diammonium salt IV
whose reaction with triphenylplumbane (V) gave ester
VI as crystals.
In the present work we describe the synthesis of
diplumbyl derivatives of bis(arylphosphonodithioic
acids). Among them, bis(phosphonodithioic acids)
with two terminal phosphorodithioyl groups are
interesting ligands [3–6]. The first examples of stable
bis(phosphonothioic acids) with methyl groups at the
phosphorus atom have been synthesized by one of us
by the reaction of 2,4-dimethyl-1,3,2λ5,4λ5-dithiadi-
phosphetane 2,4-disulfide with glycols at a 1:1 ratio in
an Et2O suspension at ~20° C [3]. At the same time,
the corresponding bis(arylphosphonodithioic acids)
could not be obtained pure by the reaction of
1,3,2λ5,4λ5-dithiaphosphetane 2,4-disulfides with aryl
substituents at the phosphorus atom with glycols in
acetonitrile at 70–80°C [4, 5]. From the reaction mix-
tures, dioxaphosphorinane sulfides, cyclic trithiopyro-
phosphonates, and thioacetamide have been isolated
O,O'-Ethylenedioxydiethylene
bis[S-hydrogen
(3,5-di-tert-butyl-4-hydroxyphenyl)phosphonodi-
thioate] (III). A mixture of 5.0 g of dithiadiphos-
phetane disulfide I and 1.2 g of glycol II in 15 ml of
absolute benzene was heated for 1.5 h at 50°С with
stirring and then cooled and filtered. The filtrate was
evaporated for 1 h under a vacuum of 0.5 mm Hg at
40°С and 1 h under a vacuum of 0.06 mm Hg at 40°С
to obtain 4.8 g (77%) of acid III. IR spectrum (film),
ν, cm–1: 3619 s [ν(O–H)]; 2958 s, 2873 s [νas,s(СН3),
νas,s(CH2)]; 2478 m.br [ν(S–H)]; 1582 m, 1480 m
[ν(C=C), Ar]; 1429 vs [δas(CH3)], 1036 vs.br
[ν(P)O–C]; 957 s.br [ν(OC–C)]; 656 vs [ν(P=S)]; 504
1
m [ν(P–S)]. Н NMR spectrum, δ , ppm: 1.48 s [36H,
(CH3)3C]; 2.37 m and 2.64 m (2H, S–H); 3.72 s (4H,
3
COCH2CH2OC); 3.84 t (4H, POCH2CH2O, JHH 4.7);
3
3
4.39 d.t (4H, POCH2CH2О, JHH 4.7, JPH 10.0); 5.69
1466