NOVEL METHOD FOR THE SYNTHESIS OF DISELENOPHOSPHINATES
227
temperature for 2–3 min. The 31P NMR spectrum of
the reaction mixture showed two signals: a singlet at
was added to a solution of 0.321 g (1.00 mmol) of
bis(2ꢀphenylethyl)phosphine selenide 1a in 5 mL of
ether. A colorless crystalline precipitate formed (20–
26.50 ppm and a doublet at 69.70 ppm (1JPH
=
25°C, 10 min). The supernatant solution (containing
199.5 Hz) due to salt 2a and secondary phosphine 3a
respectively. The solvent was removed, and the residue
was washed with anhydrous ether ( mL) and dried
,
secondary phosphine 3a according to 31P NMR) was
decanted, the precipitate was washed with ether
2 × 5
(1
× 5 mL) and dried in vacuum to give 0.216 g (86%
in vacuum to give 0.191 g (87% yield) of potassium
yield) of diisopropylammonium bis(2ꢀphenylꢀ
bis(2ꢀphenylethyl)diselenophosphinate 2a as colorless
°C. IR (KBr, ν
, cm–1): 564, 521
ethyl)diselenophosphinate
4 as colorless crystals, mp
crystals, mp 208–210
190–192
°
C. IR (KBr,
ν
, cm–1): 2755, 2706 (
ν
NH),
1
(
νas PSe2), 496, 484 (νs PSe2). H NMR (D2O, δ],
1
567 (νas PSe2), 476 (νs PSe2). H NMR (CDCl3,
, Hz): 1.55 (d, 6H, 3
ppm, J JHH = 6.5 Hz, Me), 2.51–
δ
],
ppm): 2.13–2.19 (m, 4H, CH2P), 2.61–2.68 (m, 4H,
CH2Ph), 6.80–6.88 (m, 10H, Ph). 13C NMR (D2O,
2.58 (m, 4H, CH2P), 3.06–3.13 (m, 4H, CH2Ph),
3.43–3.50 (m, 2H, CH), 7.16–7.27 (m, 10H, Ph),
1
δ
], ppm): 30.92 (CH2Ph), 42.99 (d, JCP = 35.4 Hz,
CH2P), 126.27 (pꢀC), 128.45 (oꢀC), 128.71 (mꢀC),
8.63 (s, 2H, NH). 13C NMR (CDCl3,
(Me), 30.42 (CH2Ph), 43.71 (d, JCP = 37.1 Hz,
δ
], ppm): 20.13
3
141.32 (d, JCP = 15.9 Hz, ipsoꢀC). 31P NMR (D2O,
1
1
δ
], ppm): 26.45 (+ doublet of satellites, JSeP
=
CH2P), 48.31 (CH), 125.59 (
128.18 (
ꢀC), 141.52 (d, 3JCP = 17.3 Hz, ipsoꢀC). 31P
NMR (CDCl3, ], ppm): 21.02 (+ doublet of satelꢀ
lites, 1 SeP = 569.1 Hz). 77Se NMR (CDCl3,
], ppm):
–63.09 (d, 1
SeP = 569.1 Hz).
pꢀC), 128.11 (oꢀC),
557.4 Hz). 77Se NMR (D2O,
δ], ppm): –63.09 (d,
m
1JSeP = 557.4 Hz).
δ
For C16H18KPSe2 anal. calcd. (%): C, 43.84;
H, 4.14; P, 7.07; Se, 36.03.
J
δ
J
Found (%): C, 43.90; H, 4.17; P, 7.19; Se, 36.10.
For C22H34NPSe2 anal. calcd. (%): C, 52.70;
H, 6.83; P, 6.18; Se, 31.50.
Potassium bis[2ꢀ(2ꢀmethylꢀ1ꢀpyridylꢀ5)ethyl]diseꢀ
lenophosphinate (2b). A solution of 0.033 g (0.50 mmol)
of KOH · 0.5Н2О in 2 mL of EtOH was added to a
solution of 0.351 g (1.00 mmol) of bis[2ꢀ(2ꢀmethylꢀ1ꢀ
pyridylꢀ5)ethyl]phosphine selenide 1b in 5 mL of
Found (%): C, 52.76; H, 6.87; P, 6.60; Se, 32.05.
ACKNOWLEDGMENTS
EtOH. The mixture was stirred at 20–25°C for 2–3 min.
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project no. 08–03–00251).
The 31P NMR spectrum of the reaction mixture
showed the presence of secondary phosphine 3b (d,
1
–72.50 ppm, JPH = 200 Hz) and salt 2b (s,
25.74 ppm). The solvent was removed, the residue was
washed with anhydrous ether (2 × 5 mL) and dried in
vacuum to give 0.190 g (81% yield) of potassium bis[2ꢀ
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DOKLADY CHEMISTRY Vol. 428
Part 1
2009