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KHACHIKYAN et al.
[3-Hydroxylimino-3-(4-methylphenyl)-1-phenyl-
28.85; P 5.62. C27H23Br2OP. Calculated, %: C 58.48;
H 4.15; Br 28.88; P 5.59.
propyl]diphenylphosphine oxide (3a). Yield 0.1 g
1
(83%), mp 111–112°C. H NMR spectrum, δ, ppm:
[(3-Aryl-1,4-quinoxalin-2-yl)methyl]triphenylphos-
phonium bromides (6a–6c). A mixture of 0.001 mol
of salt 1 and 0.11 g (0.001 mol) of o-phenylenediamine
in 5–7 mL of acetonitrile was refluxed for 10–13 h.
The acetonitrile filtrate was treated with diethyl ether.
The precipitate was filtered off, washed with ether, and
dried in a vacuum. For purification the reaction
product was treated with chloroform. The insoluble
precipitate was filtered off, washed with chloroform,
and dried in a vacuum.
2.29 s (3H, CH3), 2.99 d.d.d (1H, CH2, J = 13.5, 7.0,
4.0 Hz), 3.50 d.d.d (1H, CH2, J = 13.5, 12.0, 7.8 Hz),
4.16 d.d.d (1H, CH, J = 11.7, 7.0, 4.0 Hz), 6.91–7.02
m (6HAr), 7.16–7.30 m (6HAr), 7.43–7.58 m (5HAr),
7.95–8.02 m (2HAr), 10.95 s (1H, OH). 31P NMR spec-
trum: δР 31.91 ppm.
[3-(4-Bromophenyl)-3-hydroxylimino-1-phenyl-
propyl]diphenylphosphine oxide (3b). Yield 0.1 g
1
(70.6%), mp 120–121°C. H NMR spectrum, δ, ppm:
3.04 d.d.d (1H, CH2, J = 13.6, 6.6, 4.2 Hz), 3.45 d.d.d
(1H, CH2, J = 13.6, 11.4, 8.4 Hz), 4.19 d.d.d (1H, CH,
J = 11.5, 6.6, 4.2 Hz), 6.95–7.08 m (5HAr), 7.17–7.30
m (7HAr), 7.45–7.58 m (5HAr), 7.95–8.03 m (2HAr),
11.23 s (1H, OH). 31P NMR spectrum: δP 31.83 ppm.
{[3-(4-Methylphenyl)-1,4-quinoxalin-2-yl]methyl}-
triphenylphosphonium bromide (6a). Yield 0.16 g
1
(27.7%), mp 244–245°C. H NMR spectrum, δ, ppm:
2.50 s (3H, CH3), 6.17 d (2H, CH2, J = 14.0 Hz), 7.38–
7.48 m (3HAr), 7.60–7.80 m (11HАr), 7.91–8.06 m
(9HAr). 13С NMR spectrum, δС, ppm: 20.8 (CH3), 32.4
d (CH2, J = 57.7 Hz), 120.1 d (Ci, PPh3, J = 88.9 Hz),
126.4 (CH), 128.7 (CH), 128.8 (CH), 129.1 d (Co,
PPh3, J = 12.9 Hz), 129.6 (CH), 129.6 (CH), 129.8
(CH), 133.6 d (Cm, PPh3, J = 10.3 Hz), 133.6 d (Cp,
PPh3, J = 2.7 Hz), 133.9, 138.0, 138.7, 140.5, 145.3 d
(J = 7.3 Hz), 153.4 d (J = 7.4 Hz). 31P NMR spectrum:
δР 30.14 ppm. Found, %: N 4.80; Br 14.03. C34H30BrN2P.
Calculated, %: N 4.85; Br 13.86.
Reaction of (E)-[(2-aroyl)ethenyl]triphenylphos-
phonium bromides 1 with hydrazine hydrochloride.
To a saturated solution of 0.001 mol of salt 1 in
acetonitrile (or methanol) was added 0.63 g (0.006 mol)
of hydrazine hydrochloride in a minimum amount of
water. The reaction mixture was refluxed for 30 h and
then poured into 200 mL of water. The reaction
products were extracted with chloroform and
reprecipitated with diethyl ether. For purification the
material obtained was treated with methanol. The
precipitate which had not dissolved in methanol was
filtered off, washed with methanol, and dried in a
vacuum. Compounds 5a (0.019 g, 11%) and 5b (0.017 g,
7%) were obtained. After removing methanol from the
filtrate, the residue was boiled in acetone. The
insoluble precipitate was filtered off, washed with
acetone, and dried in a vacuum.
{[3-(4-Bromophenyl-1,4-quinoxalin-2-yl)methyl}-
triphenylphosphonium bromide (6b). Yield 0.26 g
1
(41%), mp 253–254°C. H NMR spectrum, δ, ppm:
6.25 d (2H, CH2, J = 14.1 Hz), 7.45 br.d (1HAr, J =
8.2 Hz), 7.58–7.78 m (13HАr), 7.92–8.05 m (7HАr),
8.11–8.17 m (2HAr). 31P NMR spectrum: δР 30.15 ppm.
Found, %: N 4.28; Br 24.96. C33H27Br2N2P. Cal-
culated, %: N 4.36; Br 24.92.
[2-(4-Methylbenzoyl)ethyl]triphenylphosphonium
bromide (4a). Yield 0.17 g (34.8%), mp 227–228°C.
1H NMR spectrum, δ, ppm: 2.41 s (3Н, СН3), 3.42–
3.53 m (2Н, СН2), 3.90–4.01 m (2Н, СН2), 7.20–7.26
m (2НАr), 7.69–7.78 m (6HАr), 7.81–7.95 m (11HАr).
31P NMR spectrum: δР 26.82 ppm. Found, %: C 68.67;
H 5.30; Br 16.39; P 6.37. C28H26BrOP. Calculated, %:
C 68.71; H 5.32; Br 16.36; P 6.34.
Triphenyl{[3-(4-chlorophenyl-1,4-quinoxalin-2-
yl]methyl}phosphonium bromide (6c). Yield 0.22 g
1
(36.8%), mp 235–236°C. H NMR spectrum, δ, ppm:
5.93 d (2H, CH2, J = 14.0 Hz), 7.50 br.d (1HAr, J =
8.2 Hz), 7.63–7.84 m (12HАr), 7.86–7.95 m (7HАr),
31
8.00–8.05 m (2HAr), 8.08 br.d (1HAr, J = 8.2 Hz). P
NMR spectrum: δР 30.12 ppm. Found, %: N 4.64; Br
13.34. C33H27BrClN2P. Calculated, %: N 4.68; Br 13.29.
[2-(4-Bromobenzoyl)ethyl]triphenylphosphonium
bromide (4b). Yield 0.18 g (32.5%), mp 248–249°C.
1H NMR spectrum, δ, ppm: 3.41–3.51 m (2Н, СН2),
3.81–3.92 m (2Н, СН2), 7.62–7.67 m (2НАr), 7.71–
7.79 m (6HАr), 7.82–7.92 m (11HAr). 31P NMR spec-
trum: δP 30.73 ppm. Found, %: C 58.51; H 4.12; Br
Filtrates (solutions in chloroform) were diluted with
diethyl ether. The precipitate formed was filtered off,
washed with ether and dried in a vacuum. Next, the
material obtained was treated with anhydrous acetone.
The insoluble precipitate was filtered off, washed with
acetone, and dried in a vacuum. Compounds 4a–4c
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 7 2017