Synthesis of β-aroylvinyl derivatives of triphenylphosphine and pyridine based on β-aroylacrylic acids

Article abstract of DOI:10.1134/S1070363214030177

Bromination of β-aroylacrylic acids afforded β-aroyl-α, β-dibromopropionic acids. The latter reacted with pyridine to form 1-(β-aroylvinyl)pyridinium bromides. Reaction of the salts obtained with triphenylphosphine resulted in β-aroylvinyltriphenylphospho

Full text of DOI:10.1134/S1070363214030177

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 3, pp. 511–514. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © R.Dzh. Khachikian, Z.G. Ovakimyan, G.A. Panosyan, M.G. Indzikyan, 2014, published in Zhurnal Obshchei Khimii, 2014, Vol. 84,
No. 3, pp. 453–456.
Synthesis of β-Aroylvinyl Derivatives of Triphenylphosphine
and Pyridine Based on β-Aroylacrylic Acids
R. Dzh. Khachikian, Z. G. Ovakimyan, G. A. Panosyan, and M. G. Indzikyan
Institute of Organic Chemistry, Science and Technology Center of Organic and Pharmaceutical Chemistry,
National Academy of Sciences of Armenia, pr. Azatutyan 26, Yerevan, 0014 Armenia
e-mail: khachikyanraya@gmail.com
Received June 17, 2013
Abstract―Bromination of β-aroylacrylic acids afforded β-aroyl-α,β-dibromopropionic acids. The latter reacted
with pyridine to form 1-(β-aroylvinyl)pyridinium bromides. Reaction of the salts obtained with triphenyl-
phosphine resulted in β-aroylvinyltriphenylphosphonium bromides.
DOI: 10.1134/S1070363214030177
β-Aroylacrylic acids and their derivatives are of
interest due their reactivity and synthetic opportunities.
The reactions of these compounds with various nucleo-
philes [1, 2] including amines [3, 4] have been widely
studied. Recently we have performed reactions of β-
aroylacrylic acids with phosphorus nucleophiles [5–7].
aroylvinyltriphenylphosphonium and 1-(β-aroylvinyl)-
pyridinium bromides starting with β-aroylacrylic acids
and compared the reactivity of the phosphorus and
nitrogen atoms in the molecule.
The bromination of β-aroylacrylic acids afforded β-
aroyl-α,β-dibromopropionic acids Ia–Id (Scheme 1,
Tables 1, 2).
In continuation of these studies we obtained β-
Scheme 1.
Br2
CH
Ar
C
O
CH
CH
COOH
Ar
C
O
CH
COOH
Br Br
Iа−Id
Ar = C6H5 (а), 4-CH3C6H4 (b), 4-ClC6H4 (c), 4-BrC6H4 (d).
The latter reacted with pyridine in a ratio of 1 : 2 in
boiling acetonitrile to give 1-(β-aroylvinyl)pyridinium
bromides IIa–IId in good yields (Scheme 2, Tables 3, 4).
The reaction is likely to occur through dehydro-
bromination and salt formation followed by addition of
pyridine and decarboxylation of iminium salt due to
the effect of the electron-acceptor pyridinium moiety.
Reactions of the obtained 1-(β-aroylvinyl)pyridi-
nium bromides with an equimolar amount of triphenyl-
Table 1. Yields, melting points, and elemental analysis data of compounds Iа–Id
Found, %
Calculated, %
H
Comp.
Yield, %
mp, °C
Formula
no.
C
H
Br
C
Br
40.64
61.27
62.59
86.23
148–149
158–159
142–143
152–153
36.02
37.54
32.24
28.66
2.58
2.09
3.05
1.74
47.56
46.07
–
C10H8Br2O3
C11H10Br2O3
C10H7Br2O3Cl
C10H7Br3O3
35.71
37.71
32.39
28.92
2.38
2.86
2.98
1.69
47.62
45.71
–
Ia
Ib
Ic
Id
57.76
57.83
511

512
KHACHIKIAN et al.
Scheme 2.
COO− HN+
CH CH
C
Ar
C
O
COOH +
CH
N
Ar
C
O
−HBr,
N
Br
Br
Br
+
N
N
C−
−
HN+
CH CH N+
CH COO−
Ar
C
O
Ar
C
O
N
−CO2,
Br
Br
N+
Br−
Ar
CH CH
C
O
IIа−IId
Ar = C6H5 (а), 4-CH3C6H4 (b), 4-ClC6H4 (c), 4-BrC6H4 (d).
An effective method of the synthesis of β-aroyl-
vinyltriphenylphosphonium and -pyridinium bromides
IIa–IId and IIIb–IIId that we developed is a
convenient alternative method for obtaining their
analogs described in the literature.
phosphine resulted in β-aroylvinyltriphenylphospho-
nium bromides IIIb–IIId in high yields (Tables 5, 6).
The formation of these compounds proceeds apparently
through the nucleophilic addition of triphenylphos-
phine to the vinyl group followed by β-cleavage and
elimination of pyridine. Nevertheless, a possibility of
nucleophilic substitution cannot be excluded.
Recently the research in the field of the synthesis of
relatively simple compounds having structural similarity
Table 2. 1H NMR (DMSO-d6 + CCl4, 1 : 3) data for compounds Iа–Id
Comp.
δ, ppm
no.
4.72 d (1H, CH, J 10.1 Hz); 5.67 d (1H, CH, J 10.1 Hz), 7.50–7.56 m (2H, m-C6H5), 7.62–7.68 m (1H, p-C6H5), 8.02–8.07 m
(2H, m-, о-C6H5), br.s (COOH)
Ia
Ib
Ic
2.45 s (3H, CH3), 4.69 d (1H, CH, J 10.1 Hz), 5.59 d (1H, CH, J 10.1 Hz), 7.29–7.34 m (2H, C6H4) and 7.90–7.94 m (2H,
C6H4), br.s (COOH)
4.71 d (1H, CH, J 10.1 Hz), 5.70 d (1H, CH, J 10.1 Hz), 7.50–7.54 m (2H, C6H4), 8.04–8.08 m (2H, C6H4), 13.31 br.s (1H,
Idа COOH)
4.70 d (1H, CH, J 10.1 Hz), 5.71 d (1H, CH, J 10.1 Hz), 7.66–7.71 m (2H, C6H4), 7.96–8.01 m (2H, C6H4), 9.72 br.s (1H,
COOH)
a 13C NMR spectrum, δC, ppm: 47.3 (CH), 47.6 (CH), 128.5 (Ci), 130.4 and 131.6 (CHo,m), 132.0 (Cp), 168.6 (COOH), 191.1 (CO).
Table 3. Yields, melting points, and elemental analysis data of compounds IIа–IId
Found, %
Calculated, %
Comp.
no.
Yield, %
mp, °C
Formula
C
H
Br
N
C
H
Br
N
31.77
41.59
79.32
97.98
160–161
227–228
231–232
235–236
58.01
58.96
50.98
45.66
4.02
4.64
3.42
3.02
27.63
26.42
–
4.89
4.67
4.37
3.81
C14H12BrNO
C15H14BrNO
C14H11BrClNO
C14H11Br2NO
57.93
59.21
51.77
45.53
4.14
4.60
3.39
2.98
27.59
26.32
–
4.83
4.60
4.31
3.79
Ia
Ib
Ic
Id
43.54
43.36
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 3 2014

SYNTHESIS OF β-AROYLVINYL DERIVATIVES OF TRIPHENYLPHOSPHINE
513
Scheme 3.
Br−
−
CH N+
CH CH N+
Br−
+ (C6H5)3P
Ar
C
O
CH
Ar
C
O
P+(C6H5)3
P+(C6H5)3
Br−
CH
CH
Ar
C
O
−
N
IIIb−IIId
Ar = 4-CH3C6H4 (b), 4-ClC6H4 (c), 4-BrC6H4 (d).
to natural antibiotics is extensively developed. It is
presumed that the antibacterial activity of penicilloic
acid and clavicin is due to the presence in their
structure of the fragment –CH=CH–C=O [8, 9]. We
believe that obtained compounds IIa–IId and IIIb–
IIId containing various functional groups are potential
physiologically active compounds.
EXPERIMENTAL
1H, 13C and 31P NMR spectra were recorded on a
Varian Mercury-300 spectrometer operating at 300 MHz
relative to internal TMS.
Bromination of β-aroylacrylic acids. A solution
of 0.05 mol of bromine in 10 mL of chloroform was
Table 4. 1H NMR (DMSO-d6 + CCl4, 1 : 3) data for compounds IIа–IId
Comp.
δ, ppm
no.
7.55–7.62 m (2H, Hm, C6H5), 7.65–7.71 m (1H, Hп, C6H5), 8.32–8.40 m (4H, Ho, C6H5 and Hβ, Py), 8.58 d (1H, =CH, J 13.8 Hz),
IIa
8.79 d (1H, =CH, J 13.8 Hz), 8.83–8.90 m (1H, Hγ, Py), 9.96–10.00 m (2H, Hα, Py)
2.44 s (3H, CH3), 7.44–7.48 m (2H) and 8.11–8.16 m (2H, C6H4), 8.30–8.37 m (2H, Hβ, Py), 8.41 d (1H) and 8.45 d (1H, J 13.9,
IIb
CH=CH), 8.77–8.84 m (1H, Hγ, Py), 9.58–9.62 m (2H, Hα, Py)
7.60–7.65 m (2H) and 8.58–8.60 m (2H, C6H4), 8.30–8.36 m (2H, Hβ, Py), 8.45 d (1H, =CH, J 13.8 Hz), 8.61 d (1H, =CH, J
IIc
13.8 Hz), 8.80–8.90 m (1H, Hγ, Py), 9.58–9.62 m (2H, Hα, Py)
7.84–7.89 m (2H) and 8.13–8.18 m (2H, C6H4), 8.31–8.37 m (2H, Hβ, Py), 8.41 d (1H, =CH, J 13.8 Hz), 8.49 d (1H, =CH, J
IId
13.8 Hz), 8.78–8.85 m (1H, Hγ, Py), 9.58–9.63 m (2H, Hα, Py)
Table 5. Yields, melting points, and elemental analysis data of compounds IIIb–IIId
Found, %
H
Calculated, %
Comp.
no.
Yield, %
mp, °C
Formula
C
Br
P
C
H
Br
P
87.56
49.78
95.73
79–80
82–83
149–150
68.94
64.01
58.81
5.02
4.12
3.37
16.02
–
28.97
6.50 C28H24BrOP
5.98 C27H21BrOPCl
5.56 C27H21Br2OP
69.00
63.84
58.70
4.93
4.14
3.80
16.43
–
29.00
6.36
6.10
5.62
IIIb
IIIc
IIId
Table 6. 1H (DMSO-d6 + CCl4, 1 : 3) and 31P NMR data for compounds IIIb–IIId
Comp. no.
δH, ppm
δP, ppm
IIIbа
2.46 s (3H, CH3), 7.32–7.36 m (2H, C6H4), 7.77–7.99 m (18H, Ar), 8.25 d.d (1H, =CH,
J1 21.2, J2 16.7 Hz)
25.24
7.02–7.78 m (2H) and 7.83–7.87 m (2H, C6H4), 7.80–8.00 m (16H, Ar), 8.22 d.d (1H,
=CH, J1 20.8, J2 16.7 Hz)
7.69–7.73 m (2H) and 7.97–8.02 m (2H, C6H4), 7.78–7.97 m (16H, Ar), 8.25 d.d
(1H,=CH, J1 20.9, J2 16.7 Hz)
25.15
25.15
IIIc
IIId
a
13C NMR spectrum, δC, ppm (assignment was made by DEPT experiment): 116.86 d (JCP 90.9, Ci, PPh3), 121.81 d (JCP 82.8, PCH=CH),
130.06 d (J 13.2), 132.77 d (J 2.3), 134.0 d (J 10.9), 135.08 (JCP 3.0), 148.27 d (JCP 3.3, PCH=CH), 185.56 d (JCP 19.2, CO).
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KHACHIKIAN et al.
added to a solution of 0.05 mol of β-aroylacrylic acid
in 25–30 mL of chloroform within 3 h under vigorous
stirring at room temperature. The crystals formed were
filtered off, washed with chloroform, and dried in a
vacuum. Characteristics of the obtained compounds
Ia–Id are given in Tables 1 and 2.
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