SPECIAL FEATURES OF ALKALINE HYDROLYSIS
1091
1
phine oxide (IIIb). Н NMR spectrum, δ, ppm: 4.83– J 7.3 Hz), 1.29–1.37 m (3Н, СН СН СН ), 3.92 q (2Н,
2
2
3
4
6
7
.90 m (1Н, –CH=CH ), 4.96–5.05 m (1Н, –CH=CH ),
СН СН СН , J 7.3 Hz), 6.1 d.d (1Н, СН=СНО, J 12.6,
2 2 3
2
2
+
.28 d.d.d.d (1Н, –CH=CH , J 16.9, 10.9, 10.1, 1.8 Hz),
11.3 Hz), 6.8–7.02 m (2Н, Р CH=CH ), 7.2 d (1H,
2
+
31
.07 d.d [1Н, –С(Ph)=CH, J 18.9, 10.9 Hz], 7.06–8.0
CH=CHO, J 13.3 Hz), 7.5–7.8 m (15Н, Ph P ).
Р
3
3
1
m [15Н, Р(О)Ph , СНPh]. Р NMR spectrum: δP
NMR spectrum: δ 24.18 ppm. Found, %: Cl 8.23.
2
P
3
0.93 ppm.
С
0
(
25
Н
26ClОР. Calculated, %: Cl 8.69. Regenerated
.41 g (41%) of the starting phosphonium salt. 0.19 g
48.3%) of triphenylphosphine was obtained from the
b. 0.34 g (3.0 mmol) of potassium tert-butoxide
was added to a vigorously stirred suspension of 0.66 g
1.5 mmol) of salt III in 15 mL of THF under dry
ethereal extracts; mp 74–76°С, no depression of
melting point when mixed with a reference sample.
(
nitrogen stream at –5 to –10°С, and the mixture was
incubated at that temperature during 3 h and filtered.
The filtrate was extracted twice with anhydrous THF.
The solvent was removed in vacuum from the
combined THF extracts; the residue was washed with
anhydrous diethyl ether and dried in vacuum. Yield
Alkaline hydrolysis of (4-ethoxybuta-1,3-dien-1-
yl)triphenylphosphonium
chloride
(V).
The
experiment was performed as described for phospho-
nium salts I–IV. 0.54 g (69.4%) of triphenylphosphine
oxide (mp 155–156°С) and 0.12 g (14.4%) of diphenyl
0
.6 g (IIIa : IIIb ≈1 : 2).
(
4-ethoxybuta-1,3-dienyl)phosphine oxide (Vа) were
obtained from 1.12 g (2.8 mmol) of salt V and 4.6 g
Alkaline hydrolysis of [4-(2-hydroxyethylsulfanyl)-
buta-1,3-dien-1-yl]triphenylphosphonium chloride
IV) was performed as described for compound I. 0.48 g
82.2%) of triphenylphosphine oxide was obtained
with mp 155–156°С, showing no depression of
melting point when mixed with a reference sample.
1
(
28 mmol) of 25% aqueous NaOH. Н NMR spectrum,
δ, ppm: 1.3 t (3Н, СН СН , J 7.3 Hz), 3.89 q (2Н,
2
3
(
(
СН СН , J 7.3 Hz), 5.72 d.d (1Н, СН=СНО, J 13.1,
2
3
+
1
6
0.8 Hz), 6.08 d.d (1Н, Р CH=CH, J 24.0, 16.1 Hz),
.92 d (1H, CH=CHO, J 13.1 Hz), 7.01–7.17 m (1Н,
Р CH=CH), 7.4–7.63 m (10Н, Ph P). Р NMR
+
31
2
(4-Ethoxybuta-1,3-dien-1-yl)triphenylphosphonium
spectrum: δ 26.01 ppm. Found, %: С 72.87; Н 6.05; Р
P
chloride (V). 1.06 g (23 mmol) of ethanol and 0.16 g
1.5 mmol) of triethylamine were added to 1 g
1.5 mmol) of buta-1,3-dien-1,4-diylbis(triphenylphos-
phonium)chloride in 20 mL of chloroform; the reaction
mixture was stirred at 35–40°С during 10 h and
washed with water; the organic layer was dried with
1
1
0.12. С Н О Р. Calculated, %: С 72.48; Н 6.38; Р
0.40.
18 19 2
(
(
Alkaline hydrolysis of (4-propoxybuta-1,3-dien-
1
-yl)triphenylphosphonium chloride (VI) was per-
formed similarly. 0.78 g (71.9%) of triphenylphos-
phine oxide (mp 155–156°С, no depression of melting
point when mixed with a reference sample) and 0.14 g
СаСl ; the solvent was removed in vacuum; the residue
2
was washed with anhydrous ether, dried in vacuum,
and purified by re-precipitation. Yield 0.26 g (43.9%).
(
11.5%) of diphenyl(4-propoxybuta-1,3-dienyl)phos-
1
phine oxide (VIа) were obtained from 1.6 g (3.9 mmol)
Н NMR spectrum, δ, ppm: 1.32 t (3Н, СН СН , J
2
3
of salt VI and 6.3 g (39 mmol) of 25% aqueous NaOH.
7
.2 Hz), 4.02 q (2Н, СН СН , J 7.2 Hz), 6.09 d.d (1Н,
2 3
1
Н NMR spectrum, δ, ppm: 0.99 t (3Н, СН СН СН ,
СН=СНО, J 12.7, 11.2 Hz), 6.83–7.05 m (2Н,
2
2
3
+
J 7.2 Hz), 1.62–1.75 m (2Н, СН СН СН ), 3.8 t
Р CH=CH), 7.21 d (1H, CH=CHO, J 13.3 Hz), 7.52–
2
2
3
+
31
(
2Н,СН СН СН , J 7.2 Hz), 5.73 d.d (1Н, СН=СНО,
7
.82 m (15Н, Ph P ). Р NMR spectrum: δ 24.1 ppm.
2 2 3
3
P
J 13.0, 10.9 Hz), 6.06 d.d (1Н, РCH=CH, J 23.9, 15.9
Hz), 6.91 d (1H, CH=CHO, J 13.0 Hz), 7.02–7.18 m
Found, %: Cl 9.34. С Н ClОР. Calculated, %: Cl
2
4
24
8
.99. Regenerated 0.44 g (44%) of the starting phos-
phonium salt. 0.17 g (43.3%) of triphenylphosphine
oxide was obtained from the ethereal extracts; mp 74–
6°С, no depression of melting point when mixed with
a reference sample.
31
(
1Н, РCH=CH), 7.38–7.62 m (10Н, Ph P). Р NMR
2
spectrum: δ , 26.24 ppm. Found, %: С 72.74; Н 6.35;
P
Р 10.12. С Н О Р. Calculated, %: С 73.08; Н 6.73; Р
7
19 21
2
9
.94.
(4-Propoxybuta-1,3-dien-1-yl)triphenylphosphonium
Alkaline hydrolysis of [4-(diethylamino)buta-
chloride (VI) was obtained similarly from 1 g (1.5 mmol)
of buta-1,3-dien-1,4-diylbis(triphenylphosphonium)
1,3-dien-1-yl]triphenylphosphonium chloride (VII)
was performed similarly. 0.5 g (74.9%) of triphenyl-
phosphine oxide (mp 155–156°С) and 0.1 g (12.8%) of
diphenyl(4-diethylaminobuta-1,3-dienyl)phosphine
oxide (VIIа) were obtained from 1 g (2.4 mmol) of
chloride, 1.4 g (23 mmol) of propanol, and 0.16 g
1
(
1.5 mmol) of triethylamine. Yield 0.28 g (45.7%). Н
NMR spectrum, δ, ppm: 1.12 t (3Н, СН СН СН ,
2
2
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015