Russian Journal of General Chemistry, Vol. 73, No. 6, 2003, pp. 994 995. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 6, 2003,
pp. 1051 1052.
Original Russian Text Copyright
2003 by Vasil’ev, Durmanova, Garifzyanov, Cherkasov.
LETTERS
TO THE EDITOR
Synthesis and Electrode Activity
of 1,12-Bis[di(p-tolyl)phosphinoyl]-
,11-dibutyl-2,11-diaza-5,8-dioxadodecane
2
R. I. Vasil’ev, N. V. Durmanova, A. R. Garifzyanov, and R. A. Cherkasov
Kazan State University, Kazan, Tatarstan, Russia
Received May 29, 2002
Podands with phosphorus-containing terminal groups
exhibit specific host guest complex-forming properties
and can be used as extractants, components of ion-
selective electrodes, membrane carriers, etc. [1 3].
Here we report the synthesis of the firstrepresentatives
of ion-selective electrodes in determination of low con-
centrations of alkali metals. We found that the Ka-
bachnik Fields reaction in a ternary system containing
di(p-tolyl)phosphinous acid (I), Paraform, and 1,10-di-
butyl-1,10-diaza-4,7-dioxadecane provides a conve-
nient synthetic route to 1,12-bis[di(p-tolyl)phosphino-
yl]-2,11-dibutyl-2,11-diaza-5,8-dioxadodecane.
of aza podands with
-aminomethylphosphinoyl
groups and the use of these compound as components
2
(p-MeC H ) PHO + 2CH O + BuNH(CH CH O) CH CH NHBu
6
4 2
2
2
2
2
2
2
I
(
p-MeC H ) P(O)CH N(Bu)(CH CH O) CH CH N(Bu)P(O)(C H Me-p) .
6 4 2 2 2 2 2 2 2 6 4 2
2
H O
2
II
An alternative way to aza podand II is the reaction
of (butylaminomethyl)phosphine oxide III, prepared
from phosphine oxide I, Paraform, and butylamine by
the Kabachnik Fields reaction, with 1,8-dibromo-4,7-
dioxaoctane (IV).
perties of phosphorylated aza podands will be des-
cribed in more detail in further publications.
1
,12-Bis[di(p-tolylphosphinoyl]-2,11-dibutyl-
2
,11-diaza-5,8-dioxadodecane (II). a. A mixture of
2 mmol of di(p-tolyl)phosphinous acid I, 12 mmol
1
of Paraform, and 6 mmol of 1,10-dibutyl-1,10-diaza-
,7-dioxadecane was refluxed with 30 ml of benzene
I + CH O + BuNH
(p-MeC H ) P(O)CH NHBu,
6 4 2 2
2
2
4
K CO
2
3
with a Dean Stark trap for 40 min; therewith, ca. 95%
of water evolved. The mixture was refluxed for an
additional 40 min, the solvent was removed on a
rotary evaporator and then in an oil-pump vacuum
until constant weight. A viscous liquid was obtained,
which was chromatographed on a column of Silica
gel L 100/400, eluent chloroform methanol (10:1), to
obtain 3.3 g (74%) of a light yellow viscous tar-like
2
III + Br(CH CH O) CH CH Br
II.
2
2
2
2
2
2
HBr
The electrode activity of phosphorylated aza podand II
was studied by known procedures [4, 5] on an
example of ion-selective electrodes with a liquid
membrane made on the basis of this compound. It was
found that the electrodes allow a highly selective de-
termination of low concentrations of heavy alkali
liquid,
24.7 ppm (benzene). Found, %: C 73.84;
P
+
+
H 8.76; P 6.96. C H N O P . Calculated, %: C
metal ions (Rb , Cs ). The detection limit is 10 5 M.
Other alkali metals do not interfere with the deter-
mination.
44 62
2
4 2
7
3.74; H 9.21; P 6.66.
b. Dibromide IV, 4.8 mmol, was added dropwise with
stirring at 50 C to a solution of 9.62 mmol of amino-
The results of investigation of the ionophoric pro-
1
070-3632/03/7306-0994$25.00 2003 MAIK Nauka/Interperiodica
Vasil'ev
