SPECIAL FEATURES OF THE INTERACTION OF PYRIDINE AND QUINOLINE DERIVATIVES
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Interaction of 2,3-dibromopropionic acid with
isonicotinic acid. A mixture of 2.32 g (0.01 mol) of
2,3-dibromopropionic acid and 1.23 g (0.01 mol) of
isonicotinic acid in 10 ml of acetonitrile was boiled
during 40 h. The formed precipitate was filtered off,
washed with acetonitrile, and dried in a vacuum.
Yield 1.9 g of the mixture II, III in the ratio of 1:3
ppm (J, Hz): 3.72 d.d (1H, J1 9.7, J2 4.7), 3.87 d.d
(1H, J1 10.7, J2 9.7), 4.43 d.d (1H, J1 10.7, J2 4.7),
7.66 d.d.d (1H, C6H4, J1 8.2, J2 5.9, J3 1.1), 7.80 d.d.d
(1H, C6H4, J1 8.5, J2 5.4, J3 1.5), 7.98 d.d (1H, C6H4,
J1 8.2, J2 1.5), 8.18 d.d (1H, C6H4, J1 8.5, J2 1.1), 8.12
d (1H, C5H2N, J 8.5), 8.43 d (1H, C5H2N, J 8.5),
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11.00 br.s (2H, COOH). H NMR spectrum of IX
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1
(according to H NMR spectrum). H NMR spectrum
(DMSO-d6–CCl4, 1:3), δ, ppm (J, Hz): 6.00 and 6.45
s (2H, =CH2), 7.66 d.d.d (1H, C6H4, J1 8.2, J2 5.9, J3
1.1), 7.80 d.d.d (1H, C6H4, J1 8.5, J2 5.4, J3 1.5), 7.98
d.d (1H, C6H4, J1 8.2, J2 1.5), 8.18 d.d (1H, C6H4, J1
8.5, J2 1.1), 8.12 d (1H, C5H2N, J 8.5), 8.43 d (1H,
C5H2N, J 8.5), 11.00 br.s (2H, COOH).
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of the salt II corresponded to that shown above. H
NMR spectrum of the salt III (DMSO-d6–CCl4, 1:3),
δ, ppm (J, Hz): 7.20 d (1H, =CHCOOH, J 13.0), 8.50
m (3H, Pyr, =CHN+), 9.62 m (2H, Pyr), 12.00 br.s
(2H, COOH).
Interaction of triphenylphosphine with N-vinyl-
isonicotinic acid hydrochloride (I). A mixture of
1.15 g (0.005 mol) of N-vinylisonicotinic acid
hydrochloride (I) and 2.62 g (0.01 mol) of triphenyl-
phosphine in 7 ml of acetonitrile was boiled for 40 h.
After filtration of the reaction mixture and treatment
with ether, 1.4 g of the mixture of salts was obtained
[1H NMR data: 0.6 g (45%) of IV and 0.8 g (62.5%)
Interaction of 2,3-dibromopropionic acid with
quinaldinic acid. A mixture of 2.32 g (0.01 mol) of
2,3-dibromopropionic acid and 1.73 g (0.01 mol) of
quinaldinic acid in 15 ml of acetonitrile was boiled
during 20 h. The formed precipitate was filtered off,
washed with acetonitrile, and dried in a vacuum.
Yield 0.55 g (21.5%) of quinaldinic acid hydro-
bromide. After treating similarly to the previous
reaction, 2.82 g (69.6%) of salt X was obtained, mp
170°С. Found, %: С 39.64; H 3.02; N 3.76. C13H11O4·
NBr2. Calculated, %: С 39.49; H 2.78; N 3.54.
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of V]. H NMR spectrum and 31P NMR spectrum of
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the salt IV corresponded to the literature data [3]. H
NMR spectrum of V (DMSO-d6–CCl4, 1:3), δ, ppm,
2.63 m (2H, CH2), 3.88 m (2H, CH2), 7.65–8.00 m
(18H, Ph, Pyr). 31P NMR spectrum: δР 31.30 ppm.
Interaction of X with triphenylphosphine. A
mixture of 1 g (0.0025 mol) of salt X and 1.31 g
(0.005 mol) of triphenylphosphine was boiled in
acetonitrile for 20 h. After filtering off 0.42 g (98%)
of the formed quinaldinic acid, the filtrate was poured
into ether, the precipitate was filtered off, washed
with ether, and dried in a vacuum. Yield 0.5 g (50%)
of 3-(triphenylphosphiniumbromido)propionic acid
Interaction of the mixture of salts IV, V with
methyl iodide. Triple amount of methyl iodide
(acetonitrile solution) was added at room temperature
to 0.5 g of the mixture of IV and V. After 1 day of
incubation, the mixture was poured into ether. The
formed crystals were filtered off, washed with ether,
and dried in a vacuum. Yield 0.56 g of mixture of IV,
V, and VI in the ratio of 4:0.5:5 (according to 1H and
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XI, mp 190°С. H NMR spectrum (DMSO-d6–ССl4,
1:3) δ, ppm (J, Hz): 2.62 d.d (2H, CH2COOH, J 11.1,
7.7), 3.68 d.d (2H, CH2P, J 13.5, 7.7), 7.71–7.92 m
(15H, Ph3P), 12.55 br.s (1H, COOH). 31Р NMR
spectrum: δР 30.16 ppm. Found, %: С 80.84; H 4.90;
Br 19.41; Р 7.61. C21H20BrО2P. Calculated, %: C
60.72; H 4.82; Br 19.28; P 7.47. After removal of the
solvents, 0.35 g (50%) of triphenylphosphine oxide,
mp 154°С, was obtained.
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31P NMR spectra). H NMR spectrum of VI (DMSO-
d6–CCl4, 1:3), δ, ppm: 3.10 m (2H, CH2), 3.65 s (3H,
Ме), 4.00 m (2H, CH2), 7.60 m (18H, Ph, Pyr). 31P
NMR spectrum: δР 29.90 ppm.
Interaction of 2,3-dichloropropionic acid with
quinaldinic acid. A mixture of 0.72 g (0.005 mol) of
2,3-dichloropropionic acid and 0.86 g (0.005 mol) of
quinaldinic acid in 10 ml of acetonitrile was boiled
during 20 h. The formed precipitate was filtered off,
washed with acetonitrile, and dried in a vacuum.
Yield 0.3 g (30%) of quinaldinic acid hydrochloride.
From the acetonitrile solution, after ether treatment, a
mixture of salts VIII and IX was obtained, in the
Interaction of 2,3-dihalopropionic acids with
harmine. A mixture of 0.01 mol of 2,3-dichloro-
propionic and 2,3-dibromopropionic acid with
0.01 mol of harmine in 150 ml of ether was boiled
during 30 h. The precipitate was filtered off, washed
with ether, and dried in a vacuum. Yield, respec-
tively, 2.1 g (60%) of salt XIIa, mp 275°С and 2.63 g
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ratio of 3:1 (according to H NMR spectrum). H
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NMR spectrum of VIII (DMSO-d6–CCl4, 1:3), δ,
(59%) of salt XIIb, mp 265°С. H NMR spectrum of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013