ELECTROCHEMICAL OXIDATION OF TERTIARY PHOSPHINES
1481
3
1
Fraction 3: compound IIIb – 59, Vb – 9, VIb – 15,
hexane. The P NMR spectrum of the hexane extract
is depicted in Fig. 2d. The residue after extraction was
chromatographed on a glass column 30 cm in height
and 15 mm in diameter, adsorbent silica gel Acros
Organics (0.035–0.070μ, pore diameter 6 nm), eluent
dichloromethane, developing in iodine vapor.
VIIb – 17%.
1
The H NMR spectrum of compound VIIb (first
chromatographic fraction), δ, ppm (CDCl ): 0.91 t
3
3
(
J HH 6.0 Hz, CH CH CH P), 1.60 m (CH CH CH P),
3 2 2 3 2 2
4
5
2
2
.18 m (CH CH CH P), 1.18 and 1.23 (s, H and H ),
3 2 2
3
2
2
1
.11 (s, H ), 3.06 (s, H ), 5.18 d ( J 17.8 Hz, H ).
PH
The chromatographic fractions composition is
1
3
1
The H NMR spectra of the third chromatographic
based on the data of P NMR spectroscopy:
fraction, δ, ppm (CDCl ): the strongest peaks (com-
pound IIIb): 0.92 t ( J 6.0 Hz, CH CH CH P), 1.60
3
3
Fraction 1: compound Vc – 11, VIc – 14, VIIc – 75%.
HH
3
2
2
m (CH CH CH P), 2.18 m (CH CH CH P).
Fraction 2: compound IIIc – 30, Vc – 17, VIc – 21,
VIIc – 22, VIIIc – 10%.
3
2
2
3
2
2
Preparative electrochemical oxidation of
tripropylphosphine in the presence of camphene on
a glassy carbon electrode. In a mixture of acetonitrile
Fraction 3: compound IIIc – 63, Vc – 13, VIc – 13,
VIIc – 8, VIIIc – 3%.
(
5
70 ml) and tetrahydrofuran (10 ml) was dissolved
.0 g (0.04 mol) of sodium perchlorate, 1.4 g (0.0103
1
The H NMR spectrum of compound VIIc (first
chromatographic fraction) δ, ppm (CDCl ): 0.92 t
3
mol) of camphene, and 1.2 g (0,0075 mol) of
tripropylphosphine. The electrolysis was carried out at
3
(
JHH 6.0 Hz, CH CH CH CH P), 1.44 m (CH CH ·
3 2 2 2 3 2
–
2
CH CH P), 1.48 m (CH CH CH CH P), 2.27 m
2
2
3
2
2
2
the anode current density 0.04–2 μA cm , the elec-
trode potential varied from 0.7 to 1.2 V. Through the
electrolyte was passed 180 Q of electric current. After
the end of electrolysis the solution was evaporated in a
vacuum. The residue was treated with methylene
chloride (100 ml) for separation of the electrosynthesis
products from the sodium perchlorate. The methylene
chloride extract was evaporated. The reaction mixture
4
5
(
CH CH CH CH P), 1.05 and 1.07 s (H and H ), 2.02
3
3
2
2
2
2
2
1
s (H ), 3.01 s (H ), 5.20 t ( J 17.8 Hz, H ).
PH
The second fraction (Table 3) was chromato-
graphed further with ethanol as eluent. Compositon of
31
the obtained is based on the data of P NMR spectra:
Fraction 1: compound Vc – 28, VIc – 25, VIIc – 42,
VIIIc – 5%.
3
1
composition (by the data of P NMR spectroscopy) is
shown in the table.
Fraction 2: compound IIIc – 35, Vc – 14, VIc – 18,
VIIc – 24, VIIIc – 9%.
Preparative electrochemical oxidation of tributyl-
phosphine in the presence of camphene on a
platinum electrode. In a mixture of acetonitrile
Fraction 3: compound IIIc – 48, Vc – 5, VIc – 5,
VIIc – 14, VIIIc – 28%.
(
5
(
40 ml) and tetrahydrofuran (10 ml) was dissolved
.434 g (0,044 mol) of sodium perchlorate, 5.012 g
0.0369 mol) of camphene, and 6.983 g (0.034 mol) of
1
The H NMR spectum of the third chromatographic
fraction, δ, ppm (CDCl ): 0.92 m (CH CH CH CH P),
3
3
2
2
2
1
.44 m (CH CH CH CH P), 1.48 m (CH CH CH ·
3
2
2
2
3
2
2
tributylphosphine a (by adding by portions). The
electrolysis was carried out at the anode current
3
CH P), 2.25 m (CH CH CH CH P), 3.90 (d.t, J
6.0 Hz, J PH 2.0 Hz, POCH ).
2
3
2
2
2
HH
3
–
2
2
density 0.1–2 μA cm , the electrode potential varied
from 0.7 to 0.9 V. Through the electrolyte was passed
Preparative electrochemical oxidation of
tributylphosphine in the presence of camphene on a
glassy carbon electrode. In a mixture of acetonitrile
(65 ml) and tetrahydrofuran (15 ml) was dissolved
7.57 g (0.06 mol) of sodium perchlorate, 4.97 g
(0.036 mol) of camphene, and 11.88 g (0.059 mol) of
tributylphosphine a (by adding portionwise). The
electrolysis was carried out at the anode current
density 0.1–1 μA cm , the electrode potential varied
from 0.7 to 1.2 V. Through the electrolyte was passed
2268 Q of electric current. After the end of electrolysis
the solution was evaporated in a vacuum. The residue
was treated with methylene chloride (100 ml) for
2
105 Q of electric current. After the end of electrolysis
the solution was evaporated in a vacuum. The residue
was treated with methylene chloride (100 ml) for
separation of the electrosynthesis products from the
sodium perchlorate. The methylene chloride extract
was evaporated. The reaction mixture composition (by
31
the data of P NMR spectroscopy) is shown in the
table. The reaction mixture was treated with a solution
of triethylamine (3.78 g, 0.036 mol) in diethyl ether
–
2
(
10 ml) and stirred for half an hour. Ethereal layer was
removed: it contained only parent tributylphosphine
δP –32 ppm). To the reaction mixture was added
(
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 7 2009