Synthesis of aromatic azomethines by condensation of substituted benzaldehydes with 4-Aminophenylene-N-imide of maleopimaric acid

Article abstract of DOI:10.1134/S1070363210070170

Preparative method of synthesis of aromatic azomethines by condensation of substituted benzaldehydes of vanillin series with 4-aminophenylene-N-imide of maleopimaric acid was developed. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070363210070170

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 7, pp. 1320–1323. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © Е.А. Dikusar, М.P. Bei, А.P. Yuvchenko, V.I. Potkin, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 7, pp. 1154–
1
157.
Synthesis of Aromatic Azomethines
by Condensation of Substituted Benzaldehydes
with 4-Aminophenylene-N-imide of Maleopimaric Acid
a,b
b
b
a
Е. А. Dikusar , М. P. Bei , А. P. Yuvchenko , and V. I. Potkin
a
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
ul. Surganova 13, Minsk, 198013 Belarus
e-mail: dikusar@ifoch.bas-net.by
b
Institute of Chemistry of New Materials, National Academy of Sciences of Belarus, Minsk, Belarus
Received October 8, 2009
Abstract—Preparative method of synthesis of aromatic azomethines by condensation of substituted
benzaldehydes of vanillin series with 4-aminophenylene-N-imide of maleopimaric acid was developed.
DOI: 10.1134/S1070363210070170
Levopimaric acid I is a constituent of turpentine
of stochiometric ratio of compounds V and VI, 1:1) in
the mixture of anhydrous methanol and dimethyl-
formamide (1:1) for 3–4 h. Yields of azomethines
VIIа–VIIx, VIIIа–VIIIn were 78–88%.
obtained from a gum of coniferous trees, in particular,
from pine (Pinus Silvestris L.) [1]. Maleopimaric acid
III is a diene adduct, which forms by Diels-Alder
reaction from levopimaric acid I and maleic anhydride
II [2–10]. Maleopimaric acid III is convenient and
accessible synthon for preparation of compounds
possessing wide spectrum of biological, anti-
inflammatory, nematocidal, and fungicidal activity [6-
Azomethines IIIa–IIIx and IVa–IVn are crystal-
line substances, soluble in DMF, DMSO and insoluble
in methanol, diethyl ether, chloroform, and hydro-
1
carbons. Their structure was proved by IR and Н
NMR spectroscopy, elemental analysis data (see the
1
0], and also for monomer synthesis [11, 12]. The high
1
table). According to the Н NMR data, the purity of the
biological activity of maleopimaric acid derivatives is
caused by stereochemical features of their 13α-
configuration, which resembles by the structure the
stereochemistry of A, B, and C rings of steroid
hormones [4, 13].
obtained compounds is 92±1%.
The IR spectra of azomethines IIIa–IIIx and IVa–
IVn contain the following characteristic absorption
–
1
bands (ν, cm ): OHacid 2200–3600; СHAr 3080–3005,
8
1
1
70–650; СНaliphatic 2995–2830; C=O 1780–1620; C=N
630–1625; С=СAr 1600±5, 1515±2, 1388±2; CO
290–1002. In the IR spectrum of compound IIIs the
In this work a new preparative approach to 4-
aminophenylene-N-imide of maleopimaric acid V was
developed on the basis of reaction of maleopimaric
acid III with 4-phenylenediamine IV in toluene under
reflux. The obtained compound V contains reactive
amino group and may be used as a suitable synthon for
synthesis of aromatic azomethines. 4-Amino-
phenylene-N-imide of maleopimaric acid V we
succeeded to introduce into condensation with
substituted benzaldehydes of vanillin series VI to
obtain functionally substituted aromatic azomethines
containing maleopimaric acid fragment VIIа–VIIx,
VIIIа–VIIIn. The reaction was carried out by
refluxing the mixture of starting materials (with the use
presence of NO -group was confirmed by
characteristic absorption bands in the region of 1534
and 1351 cm . The IR spectra of carborane-containing
2
–1
azomethines IIIw, IIIx, IVm, and IVn contain the
following absorption bands: СНcarb. 3–0170 (IIIw, IVm),
3
034 (IIIx, IVn); BH 2680–2657 cm .
1
In the Н NMR spectra of azomethines IIIa–IIIx
and IVa–IVn the signals of protons of maleopimaric
acid fragment appear in the following ranges (δ, ppm):
0.64-0.56 s (3H, MeC ), 0.96–0.94 d (6H, Me
1
2
18
C ),
2
1
1.05–1.18 s (3H, MeC ), 5.35–5.55 br. s (1H, C=CH),
1
320

SYNTHESIS OF AROMATIC AZOMETHINES
1321
Me
O
O
O
Me
Me
Me
O
O
O
Me
Me
II
Me
CO H
Me
CO H
2
2
I
III
Me
Me
Me
O
N
O
CHO
NH2
1
,4-H NC H NH
2
6
4
2
+
R
IV
R1
Me
CO H
2
V
VI
2
0
1
9
Me
Me 18
1
O
6
2
2
1
7
5
7
R1
4
1
Me
N
O
N
C
8
1
3
3
2
2
H
1
2
14
R
9
1
1
1
2
0
Me
CO H
1
6
15
VIIа−VIIx, VIIIа−VIIIn
1
1
1
VII, R = R = H (a); R = H, R = MeO (b); R = MeO, R = HO (c), MeO (d), MeC(O)O (e), EtС(O)О (f), PrС(O)О (g),
Me
C=C(Me)С(O)О (n), С
-O NC С(О)О (s), MeOС(О)О (t), EtOС(О)О (u), 1-AdС(О)О (v), o-HCB10
2
CHС(O)О (h), BuС(O)О (i), Me
2
CHCH
2
С(О)О (j), Me(CH
2
)
6
С(O)О (k), Me(CH
2
)
8
С(O)О (l), Me(CH
2
)
H
H
16С(O)О (m),
С(О)О (r),
10С(O)О (x);
CHС(O)О (f), BuС(O)О (g),
С(О)О (i), MeOС(О)O (j), EtOС(О)O (k), 1-AdС(О)О (l), o-HCB10 10С(O)О (m),
H
3
2
6
Н
5
СН(Ме)СН
2
С(O)О (o), С
6
Н
5
С(O)О (p), 2,4-Cl
2
C
H
6
H
3
С(O)О (q), 4-BrC
6
4
2
6
1
H
4
10С(O)О (w), m-HCB10
1
VIII, R = EtO, R = HO (a), MeO (b), MeC(O)O (c), EtС(O)О (d), PrС(O)О (e), Me
Me CHCH С(О)О (h), 4-MeC
10С(O)О (n).
2
2
2
6
H
4
H
m-HCB10
H
1
9
.70–10.10 br.s (1Н, COOH). In the Н NMR spectra
corresponding structural fragments of ester groups
[15].
of azomethines IIIb–IIIx, IVb, VIa the signals of
МеО-group protons appear as singlets at 3.85–
EXPERIMENTAL
1
3
.91 ppm. The Н NMR spectra of compounds IVа–
IVn and VIb contain signals of EtO-group protons as a
triplet at 0.90–1.30 ppm (Ме) and a quartet at 3.80–
The IR spectra were taken on an IR Fourier-
spectrophotometer Protege-460 (Nicolet) using a film
or pellets with KBr. The Н NMR spectra were
1
4
.20 ppm (СН ). The signals of aromatic protons in
2
compounds IIIa–IIIx, IVa–IVn, V, VIа, VIb are
located in the range of 6.60–7.95 ppm. Azomethine
protons HC=N appear as a singlet at 8.45–8.50 ppm,
characteristic of Е-configuration of azomethines [14].
registered on a Tesla BS-587A spectrometer (100 MHz)
from 5% solution in DMSO-d , chemical shifts were
6
determined relative to internal ТМS. Elemental
analysis was made on C, H, N, O, S-analyzer Vario
EL-III Elementar, error 0.1%.
1
In the IR and Н NMR spectra of azomethines
IIIa–IIIx and IVa–IVn there are absorption bands and
Esters of vanillin and vanillin aldehyde VI were
proton signals, which confirm the presence of the
obtained by procedures [16–21].
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010

1
322
DIKUSAR et al.
Yields, melting points, and elemental analysis data of azomerines VIIa–VIIx, VIIIa–VIIIn
Found, %
Yield,
Calculated, %
H
Comp. no
mp, °С
Formula
%
C
H
N
C
N
VIIа
VIIb
VIIc
VIId
VIIe
VIIf
VIIg
VIIh
VIIi
87
88
78
84
88
86
81
85
86
88
85
87
82
88
85
88
86
82
85
83
83
80
83
87
79
80
82
83
88
84
85
81
79
80
82
82
80
82
270–271
232–233
240–241
255–256
238–239
221–222
214–215
192–193
238–239
157–158
85–86
77.12
75.19
73.24
73.54
72.40
72.65
72.89
72.94
73.15
72.98
73.85
74.53
75.90
73.22
75.18
74.37
68.02
67.34
70.13
70.82
71.00
75.15
62.23
62.34
73.52
73.84
72.57
72.94
73.10
72.80
73.43
73.58
75.03
70.87
71.36
75.20
62.64
7.43
7.32
7.29
7.38
7.06
7.37
7.36
7.26
7.45
7.51
7.92
8.19
8.84
7.16
7.11
6.69
5.90
5.93
6.27
6.90
7.06
7.52
6.98
7.06
7.31
7.57
7.32
7.58
7.61
7.50
7.65
7.42
7.13
7.10
7.18
7.51
7.03
7.17
4.52
4.29
4.20
3.99
3.87
3.83
3.66
4.85
3.56
3.90
3.43
3.18
2.65
3.74
3.42
3.50
3.14
3.11
5.05
3.65
3.78
3.56
3.15
3.35
4.02
3.92
3.83
3.80
3.48
3.72
3.61
3.29
3.25
3.84
3.51
3.38
3.14
3.22
C
C
C
C
C
C
C
C
C
37
38
38
39
40
41
42
42
43
H
H
H
H
H
H
H
H
H
42
44
44
46
46
48
50
50
52
N
N
N
N
N
N
N
N
N
2
2
2
2
2
2
2
2
2
O
O
O
O
O
O
O
O
O
4
5
6
6
7
7
7
7
7
76.79
74.97
73.05
73.33
72.02
72.33
72.60
72.60
72.86
72.86
73.57
74.01
75.47
72.81
74.78
74.15
67.75
66.91
69.84
70.36
70.67
74.78
61.94
61.94
73.33
73.59
72.33
72.60
72.86
72.86
73.10
73.10
74.58
70.67
70.96
74.97
62.35
62.35
7.31
7.29
7.10
7.26
6.95
7.11
7.25
7.25
7.39
7.39
7.78
8.02
8.82
6.98
7.06
6.64
5.81
5.86
6.12
6.79
6.94
7.43
6.85
6.85
7.26
7.41
7.11
7.25
7.39
7.39
7.53
7.53
6.92
6.94
7.09
7.55
6.98
6.98
4.84
4.60
4.48
4.39
4.20
4.11
4.03
4.03
3.95
3.95
3.73
3.60
314
VIIj
VIIk
VIIl
C
43
H
52
58
62
78
48
54
48
N
N
N
N
N
N
N
2
2
2
2
2
2
2
O
O
O
O
O
O
O
7
7
7
7
7
7
7
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
46
48
56
42
48
45
45
45
45
40
41
49
41
41
39
40
41
42
43
43
44
44
47
41
42
50
42
42
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
74–75
VIIm
VIIn
VIIo
VIIp
42–43
201–202
92–93
4.04
3.63
3.84
3.51
3.47
5.43
4.10
4.02
3.56
3.52
3.52
4.39
4.29
4.11
4.03
3.95
3.95
3.88
3.88
3.70
4.02
3.94
3.50
3.46
3.46
127–128
104–105
184–185
181, decomp.
243–244
238–239
161–162
>310
a
VIIq
46Cl
2
N
2
O
7
b
VIIr
47BrN
2
O
7
VIIs
VIIt
VIIu
VIIv
47
46
48
58
54
54
46
48
48
50
52
52
54
54
52
48
50
60
56
56
N
N
N
N
3
2
2
2
O
O
O
O
9
8
8
7
c
VIIw
B
10
10
N
2
O
7
7
d
VIIx
302–303
245–246
257–258
264–265
206–207
117–118
108–109
105–106
92–93
B
N
2
O
VIIIa
VIIIb
VIIIc
VIIId
VIIIe
VIIIf
VIIIg
VIIIh
VIIIi
VIIIj
VIIIk
VIIIl
N
N
N
N
N
N
N
N
N
N
N
N
2
2
2
2
2
2
2
2
2
2
2
2
O
O
O
O
O
O
O
O
O
O
O
O
6
6
7
7
7
7
7
7
7
8
8
7
124–125
207–208
211–212
124–25
e
VIIIm
291–292
296–297
B
10
N
2
O
7
7
f
VIIIn
62.45
B
10
N
2
O
a
b
c
Found Сl, %: 8.51. Calculated Cl, %: 8.89. Found Br, %: 9.55. Calculated Br, %: 9.89. Found B, %: 13.19. Calculated B, %: 13.60.
d
e
f
Found B, %: 13.28. Calculated B, %: 13.60. Found B, %: 12.76. Calculated B, %: 13.36. Found B, %: 12.97. Calculated B, %: 13.36.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010

SYNTHESIS OF AROMATIC AZOMETHINES
1323
4
-Aminophenylene-N-imide of maleopimaric acid
“Dendrochemistry and Organic Synthesis”), Syktyvkar:
Nauch. Tsentr Resp. Komi, 1996, p. 45.
7. Pakhushinda Panda and Himadri Panda, Pesticides,
(
V). A solution of 10 g (0.025 mol) of maleopimaric
acid and 2.70 g (0.025 mol) of p-phenylenediamine
was refluxed in toluene for 6 h. Reaction progress was
monitored by TLC method using Silufol UV–254
plates, eluent hexane-acetone (2:1.6). Imide precipitate
was filtered off, washed with toluene (10×2) and
boiling water (50×2), dried in air. The boiling point of
the obtained imidoacid V (309–310ºС) corresponds to
literary data [22].
1
988, vol. 22, no. 1, p. 38.
. Ayer, W.A. and McDonald, C.E., Canad. J. Chem.,
965, vol. 43, no. 5, p. 1429.
. UK Patent no. 1400481, 1975, Ross. Zh. Khim., 1976,
O 130P.
8
9
1
8
1
0. Schuller, W.H. and Lawrence, R.V., J. Chem. and
Engineer. Data, 1967, vol. 12, no. 2, p. 267.
1. Penczek, P., Rocz. Chem., 1970, vol. 44, no. 9, p. 1815.
2. Lewis, J.B., Lloyd, W.D., and Hedrick, G.W., J. Org.
Chem., 1960, vol. 25, no. 7, p. 1206.
3. Fizer, L. and Fizer, M., Steroidy (Steroids), Moscow:
1
1
Functionally substituted aromatic azomethines
VIIa–VIIx, VIIIa–VIIIn). A mixture of 1 mmol of
-aminophenylene-N-imide of maleopimaric acid V
and 1 mmol of substituted benzaldehydes of vanillin
series VI, 10 ml of anhydrous methanol and 10 ml of
anhydrous DMF was refluxed for 3–4 h. The reaction
mixture was diluted with 50–60 ml of water. The
precipitated product was filtered off on a glass porous
filter, washed with water and cold methanol, dried in
air for 5–6 h at 40–50°С.
(
4
1
1
Mir, 1964, p. 19.
4. Dayer, D.R., Prilozheniya absorbtsionnoi spektroskopii
organicheskikh soedinenii (Applications of Absorption
Spectroscopy of Organic Compounds), Moscow:
Khimiya, 1970, p. 92.
5. Dikusar, E.A., Kozlov, N.G., Tlegenov, R.T., and
Uteniyazov, K.U., Azometiny na osnove vanilina i
vanillalya (Azomethine on The Basis of Vanillin and
Vanillin Aldehyde), Nukus: “Karakalpakstan,” 2007.
1
1
REFERNCES
6. Dikusar, E.A., Vyglazov, O.G., Moyseychuk, K.L.,
Zhukovskaya, N.A., and Kozlov, N.G., Zh. Prikl. Khim.,
2005, vol. 78, no. 1, p. 122.
1
. Zandermann, V., Prirodnye smoly, skipidary, talovoye
maslo (khimiya tekhnologia) [Natural Resins,
i
Turpentines, Talovoe Oil (Chemistry and Technology)],
Moscow: Lesnaya Promyshlennost’, 1964, p. 149.
. Nikitin, V.M., Khimiya terpenov i smolyanykh kislot
1
1
1
2
7. Dikusar, E.A. and Kozlov, N.G., Khim. Prirod. Soedin.,
2
005, № 1, p. 74.
2
8. Dikusar, E.A. and Kozlov, N.G., Zh. Org. Khim., 2005,
vol. 41, no. 7, p. 1015.
9. Dikusar, E.A., Zh. Prilk. Khim., 2006, vol. 79, no. 6,
(Chemistry of Terpenes and Resinic Acids), Moscow:
Goslesbumizdat, 1952, p. 326.
3
. Gonis, G., Slezak, F.B., and Lawson, N.E., Ind. and
Engl. Chem. Prod. Res. and Develop., 1973, vol. 12,
no. 4, p. 326.
p. 1043.
0. Dikusar, E.A., Kozlov, N.G., Potkin, V.I., Zvereva, T.D.,
Yuvchenko, A.P., Bey, M.P., and Kovganko, N.V.,
Khim. Prirod. Soedin., 2006, no. 5, p. 434.
1. Dikusar, E.A., Potkin, V.I., Kozlov, N.G., Yuvchen-
ko, A.P., Bey, M.P., and Kovganko, N.V., Zh. Org.
Khim., 2008, vol. 44, no. 9, p. 1321.
4
5
6
. Ayer, W.A., McDonald, C.E., and Stothers, J.B., Canad.
J. Chem., 1963, vol. 41, no. 5, p. 1113.
2
. Scebacher, W., Hufner, A., Haslinger, E., and Weis, R.,
Monatsh. Chem., 1998, vol. 129, nos. 6–7, p. 697.
. Tolstikov, G.A., Tolstikov, O.V., Khlebnikov, T.B.,
Zakharov, I.V., and Zamaraev, K.I., Book of Abstracts,
22. Bujnova, E.F., Solntsev, A.N., and Volozhin, A.I., Vesti
Nats. Akad. Nauk Belarusi, Ser. Khim., 1996, no. 4,
p. 118.
2
oe Soveshchanie “Lesokhimiya i оrg. sintez” (II Conf.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010