Efficient synthesis of maleopimaric acid N-arylimides

Article abstract of DOI:10.1134/S1070363215050047

An efficient approach toward synthesis of maleopimaric acid N-arylimides starting from rosin maleic anhydride adduct without isolation of maleopimaric acid has been elaborated. Terpenoid diimide diacids and their esters have been synthesized based on the

Full text of DOI:10.1134/S1070363215050047

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 5, pp. 1034–1039. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © M.P. Bei, A.P. Yuvchenko, N.V. Puchkova, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 5, pp. 735–740.
Efficient Synthesis of Maleopimaric Acid N-Arylimides
M. P. Bei, A. P. Yuvchenko, and N. V. Puchkova
Institute of Chemistry of New Materials, National Academy of Sciences of Belarus,
ul. Skoriny 36, Minsk, 220141 Belarus
e-mail: mixa@ichnm.basnet.by
Received January 15, 2015
Abstract—An efficient approach toward synthesis of maleopimaric acid N-arylimides starting from rosin
maleic anhydride adduct without isolation of maleopimaric acid has been elaborated. Terpenoid diimide diacids
and their esters have been synthesized based on the obtained N-arylimides. Thermal stability of the products
has been estimated by derivatography.
Keywords: rosin, aromatic amine, maleopimaric acid, imide, ester
DOI: 10.1134/S1070363215050047
One of the promising applications of renewable
wood-chemical raw materials is synthesis of certain
valuable chemicals. The best accessible individual
terpenoid compound isolated from adduct of rosin
(product of pine turpentine treatment) with maleic
anhydride is maleopimaric acid I, a convenient
synthon for preparation of compounds possessing a
wide range of useful properties and application.
Aliphatic amides, imides, and amide-imides have been
the described among nitrogen-containing derivatives of
maleopimaric acid [1–4]; the compounds have shown a
set of valuable properties such as hepatoprotective [2],
nematicidal [3], fungicidal, and bactericidal [4]
activities. Only a few representatives of acid I
aromatic imides have been known; for example, 4-
aminophenyl imide [5] converted into thermally stable
poly(amido)imides [6], N-(2-methyl-α-naphthyl)imide
displaying antineoplastic activity [7], and 4-carboxy-
phenyl imide prepared from levopimaric acid and p-
carboxyphenylmaleic acid imide [8]. At the same time,
aromatic imides as well as aliphatic imides may
possess diverse biological activity. Since maleopimaric
acid is an accessible chiral acid, it may be used for
separation of optical isomers of amines [9] provided
that the labile anhydride group is converted into the
fragment inert towards amines. Maleopimaric acid N-
arylimides serve as suitable substrates.
refluxing of a mixture of individual acid I with the
corresponding amine (taken in 10 mol % excess or in
equimolar amount) in toluene or pyridine. Reaction of
3- and 4-aminophenylimides with substituted benzal-
dehydes of vanillin series afforded biologically active
azomethines [11, 12].
This work aimed to elaborate an efficient method of
synthesis of maleopimaric acid N-arylimides IIIa–IIIl
from accessible adduct of rosin with maleic anhydride
and aromatic amines IIa–IIl without isolation of
individual acid I (refluxing in toluene during 40 h).
The rosin–maleic anhydride adduct with content of
maleopimaric acid I of about 57% was prepared via
treatment of rosin with maleic anhydride [13, 14].
Under the elaborated conditions, maleopimaric acid
I as a component of the adduct reacted with aromatic
amines IIa–IIl via the anhydride group to form
exclusively N-arylimides IIIa–IIIl as insoluble preci-
pitates that could be easily separated off the unreacted
tar acids, well soluble in toluene. Such preparation of
N-arylimides avoided the stage of maleopimaric acid
isolation, allowing to significantly reduce the process
duration and amount of the consumed organic
solvents; the target imides could be isolated in 51–71%
(with respect to rosin–maleic anhydride adduct) or 60–
99% (with respect to maleopimaric acid contained in
the rosin–maleic anhydride adduct) yield (Scheme 1).
Maleopimaric acid 4-phenyl-(4-methyl-, 4-hyd-
roxy-, 4-bromo-, 4-amino-, 3-amino-, and 3-carboxy-
phenyl)imides have been prepared earlier [10] via
The synthesized imides were colorless (IIIa–IIIc,
IIIf–IIIk) or slightly colored (IIId, IIIe, IIIl) solids
1034

1035
EFFICIENT SYNTHESIS OF MALEOPIMARIC ACID N-ARYLIMIDES
Scheme 1.
O
O
O
O
ArNH2
12
IIа_IIl
16
15
11
9
13
14
20
N
Ar
1
C6H5CH3,
Δ
2
3
O
7
COOH
COOH
IIIа−IIIl
18
I
Ar = С6H5 (а), p-С6H4CH3 (b), o-С6H4CH3 (c), p-С6H4NH2 (d), m-С6H4NH2 (e), p-С6H4OH (f), p-С6H4OCH3 (g), p-С6H4F
(h), p-С6H4Cl (i), m-С6H4Cl (j), p-С6H4Br (k), p-С6H4I (l).
Scheme 2.
O
O
IIId, IIIe, 260_270oC, 2 h, Δ
p,m-NH2C6H4NH2, 8 h, Δ
R
N
N
I
O
O
HOOC
COOH
IV, V
R = 1,4-C6H4 (IV), 1,3-C6H4 (V).
practically insoluble in majority of organic solvents
(benzene, toluene, THF, diethyl ether, acetone, and
DMF) and partially (up to 2–5%) soluble in DMSO;
solubility of p-iodophenylimide IIIl in DMSO was of 25%.
It was found that the reaction of maleopimaric acid
with p-aminoimide IIId (molar ratio of 1.5 : 1) in 1,2-
dichlorobenzene under reflux during 3–8 h yielded
diimide diacid IV in 44–47% yield; that acid has been
earlier obtained from levopimaric acid and N,N'-(1,4-
phenylene)dimaleimide [8]. The reaction of p-amino-
imide IIId with maleopimaric acid in melt (molar ratio
of 1 : 5) at 260–270°C during 2 h afforded the target
product IV with yield of 37% [10] (Scheme 2).
Structures of imides IIIa–IIIl were confirmed by
elemental analysis, IR and 1H NMR spectroscopy, and
mass spectrometry data. According to 1H NMR
spectroscopy, purity of the prepared compounds was of
98±1%.
The reaction of maleopimaric acid with m-
aminoimide IIIe under the similar conditions resulted
in a hardly separable mixture of diimide diacid V and
unreacted starting compounds (1H NMR).
IR spectra of compounds IIIa–IIIl contained no
absorption bands of C=O of anhydride group (1780
and 1840 cm–1), and the bands of C=O stretching at
1690 and 1760 cm–1 appeared, characteristic of imide
ring of maleopimaric acid [15]. Absorption bands at
1500 (C=Carom) and 1390 cm–1 (C–N) were observed in
Diimide diacids IV and V could be prepared in
higher yield via reaction of maleopimaric acid with p-
and m-phenylenediamines (molar ratio of 3 : 1) in 1,2-
dichlorobenzene under reflux; the yield of diimide
diacid IV achieved 68%, pure diacid V was isolated by
preparative TLC in 48% yield. The higher yields of the
target acids IV and V as compared to the reaction of
maleopimaric acid with p- and m-aminoimides IIId
and IIIe could be explained by possibility of the
formation of oligomeric products from the starting
aminoimides IIId and IIIe at 180–260°C [5, 6].
1
the spectra as well. In the H NMR spectra of the
compounds, the signals characteristic of maleopimaric
acid were retained [16], and the signals corresponding
to the protons of N-aryl fragment (6.80–8.05 ppm)
appeared. The mass spectra contained a peak of mole-
cular ion [M + 1]+.
Reaction of aminoimides IIId and IIIe with
maleopimaric acid in solution and in melt was studied.
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BEI et al.
Scheme 3.
O
O
N
N
(СH3O)2SO2 (CH2=CHCH2Br)
IV
K2CO3
O
O
ROOC
COOR
VIа, VIb
R = CH3 (а), СH2CH=CH2 (b).
Treatment of diacid IV with dimethyl sulfate or
allyl bromide in DMF in the presence of K2CO3
afforded dimethyl ester VIa and diallyl ester VIb in 92
and 78% yield, respectively (Scheme 3).
EXPERIMENTAL
IR spectra were recorded with a Bruker Tensor 27
IR Fourier spectrometer (KBr pellets). H and 13C
1
NMR spectra were registered with an AVANCE 500
instrument operating at 500 (1Н) or 125 (13С) MHz
(solutions in DMSO-d6 in the cases of IIIa–IIIl, IV,
V; or in CDCl3 in the cases of VIa–VIb). Mass spectra
were obtained with an Accela mass spectrometer
equipped with an LCQ Fleet mass detector at
atmospheric pressure chemical ionization (APCI)
mode. Elemental analysis was performed with a
VARIO Micro Cube CHNS-analyzer.
The prepared compounds V, VIa, and VIb were
colorless crystalline substances soluble in DMF,
DMSO, acetone, toluene, and chloroform; diacid IV
was soluble in DMF and DMSO and poorly soluble in
common organic solvents.
Composition and structure of compounds IV–VI
were confirmed by elemental analysis, mass spectro-
metry, IR, 1H, and 13C NMR spectroscopy data. Accord-
ing to 1H NMR, purity of the prepared compounds was
of 98±1%. IR spectra of compounds IV–VI contained
the characteristic absorption bands coinciding with the
proposed compounds structure, cm–1: 1770–1780 and
1710–1714 [(C=O)N], 1510−1514 (С=Сarom), and
Thermal stability of the N-arylimides was studied
with a NETZSCH STA 409 PC/PG derivatograph in
argon at heating rate of 5 deg min–1. In the case of
diacid IV, a MOM Q-1500D derivatograph was used,
other conditions being the same.
1
The starting rosin–maleic anhydride adduct was
prepared by treatment of pine turpentine colophony
(1000 g) with maleic anhydride (200 g) under argon at
180–200°C during 8 h. Content of maleopimaric acid
1390–1370 (C–N). H NMR spectra of the products
contained the signals characteristic of acid I [16] and
of N-aryl substituents at 6.81–7.53 ppm.
1
was of 56.7% according to H NMR; softening tem-
Thermal stability of imides IIIa, IIId, IIIf, IIIh–
IIIj, and IIIl was determined by derivatography method
[17]. The compounds were found to be thermally
stable, and their decomposition occurred at 315–320°C
(30–35°C above the decomposition point of the
starting acid I). Thermal stability of p-iodophenyl-
imide IIIl was the same as that of maleopimaric acid
(decomposition point 290°C). Diimide diacid IV
melted at 396–398°C with decomposition.
perature was of 112–114°C, acid number reached
260 mg of KOH per g.
Maleopimaric acid N-arylimides (IIIa–IIIl) (general
procedure). A mixture of 10 g of rosin–maleic anhyd-
ride adduct, 0.0175 mol of the aromatic amine, and
25 mL of toluene was heated under reflux with a con-
denser and Dean–Stark trap during 40 h and then in-
cubated at 18–20°C during 48 h. The imide precipitate
was filtered off, washed with toluene (3 × 5 mL), and
dried in air.
All the prepared compounds are of interest as
potential high-temperature modifiers of industrial
polymeric and elastomeric compositions. Aminoimides
IIId and IIIe, diimide diacids IV and V, and esters
VIa–VIb can be used in synthesis of new polyester-
imide polymers and co-polymers.
Maleopimaric acid N-phenylimide (IIIa). Yield
5.09 g (75.6% with respect to maleopimaric acid), mp
305–307°С. Found, %: С 75.43; Н 8.19; N 2.71.
C30H37NO4. Calculated, %: C 75.76; H 7.84; N 2.94.
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EFFICIENT SYNTHESIS OF MALEOPIMARIC ACID N-ARYLIMIDES
Maleopimaric acid N-(p-methylphenyl)imide
(IIIb). Yield 6.27 g (90.3%), mp 302–304°С. Found,
%: С 76.21; Н 7.79; N 2.68. C31H39NO4. Calculated,
%: C 76.04; H 8.03; N 2.86.
2.15 sextet [1H, (CH3)2CH, J 7 Hz], 2.40 m (1Н,
С7Нeq), 2.66 d (1Н, С15Н, J 8 Hz), 2.94 br.s (1Н,
C12H), 2.98 d.d (1Н, С16Н, J 8, 3 Hz), 5.28 br.s (2H,
NH2), 5.48 s (1Н, С14Н), 6.11 d (1H, Нarom, J 8 Hz),
6.20 s (1H, Нarom), 6.52 d (1H, Нarom, J 8 Hz), 7.03 m
(1H, Нarom). Mass spectrum, m/z: 491 [М + 1]+. Found,
%: С 73.63; Н 7.10; N 5.88. C30H38N2O4. Calculated,
%: C 73.44; H 7.81; N 5.93.
Maleopimaric acid N-(p-hydroxyphenyl)imide
(IIIf). Yield 6.01 g (86.2%), mp 308–310°С. Found,
%: С 73.09; Н 7.44; N 2.93. C30H37NO5. Calculated,
%: C 73.29; H 7.59; N 2.85.
Maleopimaric acid N-(p-methoxyphenyl)imide
(IIIg). Yield 7.12 g (99.3%), mp 286–288°С. IR
spectrum, ν, cm–1: 2587 (О–Н), 1769, 1701 [(C=O)N],
Maleopimaric acid N-(p-bromophenyl)imide (IIIk).
Yield 6.74 g (85.7%), mp 275–277°С. Found, %: С
64.64; Н 7.69; N 2.60. C30H36BrNO4. Calculated, %: C
64.98; H 6.54; N 2.53.
1
1512 (C=Carom), 1399 (C–N). Н NMR spectrum, δ,
ppm: 0.56 s (3H, С20H3), 0.91 d, 0.92 d [6H,
(CH3)2CH, J 7 Hz], 0.96 m (1Н), 1.05 s (3Н, С18Н3),
1.16 m (2Н), 1.30–1.74 m (10Н), 2.15 sextet [1H,
(CH3)2CH, J 7 Hz], 2.42 m (1Н, С7Нeq), 2.68 d (1Н,
С15Н, J 8 Hz), 2.95 br.s (1Н, C12H), 3.00 d.d (1Н,
С16Н, J 8, 2.5 Hz), 3.76 s (3H, СН3О), 5.50 s (1Н,
С14Н), 6.97 m (4H, Нarom). Mass spectrum, m/z: 506
[М + 1]+. Found, %: С 73.90; Н 7.45; N 2.90.
C31H39NO5. Calculated, %: C 73.63; H 7.77; N 2.77.
The spectral parameters of imides IIIa, IIIb, IIIf,
and IIIk coincided with those described in [10].
Maleopimaric acid N-(o-methylphenyl)imide (IIIc).
Yield 5.28 g (76.0%), mp 279–281°С. IR spectrum, ν,
cm–1: 2570 (О–Н), 1771, 1707 [(C=O)N], 1496
1
(C=Carom), 1384 (C–N). Н NMR spectrum, δ, ppm (a
mixture of two antropoisomers in a ratio of 1 : 0.74,
the spectrum of the major one is given): 0.56 s (3H,
С20H3), 0.90 m (1Н), 0.94 d, 0.97 d [6H, (CH3)2CH,
J 7 Hz], 1.05 s (3Н, С18Н3), 1.17 m (2Н), 1.35–1.75 m
(10Н), 1.93 s (3H, СН3С6Н4), 2.17 sextet [1H,
(CH3)2CH, J 7 Hz], 2.33 m (1Н, С7Нeq), 2.70 d (1Н,
С15Н, J 8 Hz), 3.00 br.s (1Н, C12H), 3.08 d.d (1Н,
С16Н, J 8, 2.5 Hz), 5.51 s (1Н, С14Н), 7.05 d (1H,
Maleopimaric acid N-(p-fluorophenyl)imide (IIIh).
Yield 5.52 g (78.8%), mp 306–308°С. IR spectrum, ν,
cm–1: 2579 (О–Н), 1772, 1705 [(C=O)N], 1510 (C=Carom),
1
1394 (C–N). Н NMR spectrum, δ, ppm: 0.56 s (3H,
С20H3), 0.90 m (1Н), 0.91 d, 0.92 d [6H, (CH3)2CH,
J 6 Hz], 1.05 s (3Н, С18Н3), 1.16 m (2Н), 1.34–1.74 m
(10Н), 2.16 sextet [1H, (CH3)2CH, J 6 Hz], 2.42 m
(1Н, С7Нeq), 2.71 d (1Н, С15Н, J 8 Hz), 3.00 br.s (1Н,
C12H), 3.03 d.d (1Н, С16Н, J 8, 3 Hz), 5.51 s (1Н,
С14Н), 7.10 m (2H, Нarom), 7.30 m (2H, Нarom). Mass
spectrum, m/z: 494 [М + 1]+. Found, %: С 73.09; Н
7.70; N 2.99. C30H36FNO4. Calculated, %: C 73.00; H
7.35; N 2.84.
Н
arom, J 7.5 Hz), 7.24–7.33 m (3Н, Нarom). Mass spectrum,
m/z: 491 [М + 1]+. Found, %: С 75.72; Н 7.89; N 2.90.
C31H39NO4. Calculated, %: C 76.04; H 8.03; N 2.86.
Maleopimaric acid N-(p-aminophenyl)imide (IIId).
Yield 6.92 g (99.4%), mp 288–290°С. IR spectrum, ν,
cm–1: 2620 (О–Н), 1768, 1695 [(C=O)N], 1496
1
(C=Carom), 1390 (C–N). Н NMR spectrum, δ, ppm:
0.56 s (3H, С20H3), 0.91 d, 0.92 d [6H, (CH3)2CH,
J 6 Hz], 0.96 m (1Н), 1.04 s (3Н, С18Н3), 1.15 m (2Н),
1.36–1.57 m (7Н), 1.61–1.71 m (3Н), 2.14 sextet [1H,
(CH3)2CH, J 6 Hz], 2.40 m (1Н, С7Нeq), 2.62 d (1Н,
С15Н, J 8 Hz), 2.93 br.s (1Н, C12H), 2.95 d.d (1Н,
Maleopimaric acid N-(p-chlorophenyl)imide (IIIi).
Yield 5.74 g (79.4%), mp 296–298°С. IR spectrum, ν,
cm–1: 2577 (О–Н), 1773, 1706 [(C=O)N], 1493
1
(C=Carom), 1390 (C–N). Н NMR spectrum, δ, ppm:
0.56 s (3H, С20H3), 0.90 m (1Н), 0.91 d, 0.92 d [6H,
(CH3)2CH, J 6 Hz], 1.05 s (3Н, С18Н3), 1.16 m (2Н),
1.32–1.74 m (10Н), 2.15 sextet [1H, (CH3)2CH,
J 6 Hz], 2.41 m (1Н, С7Нeq), 2.71 d (1Н, С15Н, J Hz),
2.96 br.s (1Н, C12H), 3.03 d.d (1Н, С16Н, J 8, 2.5 Hz),
5.51 s (1Н, С14Н), 7.09 d (2H, Нarom, J 9 Hz), 7.53 d
(2H, Нarom, J 9 Hz). Mass spectrum, m/z: 511 [М + 1]+.
Found, %: С 70.89; Н 7.32; N 2.94. C30H36СlNO4.
Calculated, %: C 70.64; H 7.11; N 2.75.
С16Н, J 8, 3 Hz), 5.47 s (1Н, С14Н), 6.53 d (2H, Нarom
,
J 9 Hz), 6.62 d (2H, Нarom, J 9 Hz). Mass spectrum,
m/z: 491 [М + 1]+. Found, %: С 72.44; Н 7.60; N 5.38.
C30H38N2O4. Calculated, %: C 73.44; H 7.81; N 5.93.
Maleopimaric acid N-(m-aminophenyl)imide (IIIe).
Yield 6.12 g (87.9%), mp 349–351°С. IR spectrum, ν,
cm–1: 2620 (О–Н), 1767, 1694 [(C=O)N], 1517 (C=Carom),
1
1388 (C–N). Н NMR spectrum, δ, ppm: 0.56 s (3H,
С20H3), 0.90 m (1Н), 0.93 d [6H, (CH3)2CH, J 7 Hz],
1.05 s (3Н, С18Н3), 1.15 m (2Н), 1.35–1.72 m (10Н),
Maleopimaric acid N-(m-chlorophenyl)imide (IIIj).
Yield 5.89 g (81.5%), mp 273–275°С. IR spectrum, ν,
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BEI et al.
cm–1: 2580 (О–Н), 1774, 1708 [(C=O)N], 1478
product was obtained. The target diimide diacid V was
isolated by preparative TLC on Fluka Silica plates
(10 × 10 cm, eluent hexane–acetone, 1.1 : 1). 0.031 g
(48%) of diacid V with mp 336–338°C was obtained
from 0.1 g of the reaction product. IR spectrum, ν, cm–1:
2550 (О–Н), 1770, 1710 [(C=O)N], 1510 (C=Carom),
1
(C=Carom), 1382 (C–N). Н NMR spectrum, δ, ppm:
0.56 s (3H, С20H3), 0.88 m (1Н), 0.91 d, 0.92 d [6H,
(CH3)2CH, J 6 Hz], 1.05 s (3Н, С18Н3), 1.16 m (2Н),
1.34–1.76 m (10Н), 2.16 sextet [1H, (CH3)2CH,
J 6 Hz], 2.42 m (1Н, С7Нeq), 2.71 d (1Н, С15Н, J 7 Hz),
2.96 br.s (1Н, C12H), 3.04 d.d (1Н, С16Н, J 8, 2.5 Hz),
5.52 s (1Н, С14Н), 7.05 m (1H, Нarom), 7.15 m (1H,
1
1380 (C–N). Н NMR spectrum, δ, ppm: 0.56 s (6H,
С20H3), 0.90 d, 0.93 d [12H, 2(CH3)2CH, J 7 Hz], 1.05
s (6Н, 2С18Н3), 1.18 m (4Н), 1.36–1.72 m (20Н), 2.38
sextet [2H, 2(CH3)2CH, J 7 Hz], 2.39 m (2Н, 2С7Нeq),
2.71 d (2Н, 2С15Н, J 8 Hz), 2.95 br.s (2Н, 2C12H),
3.03 d.d (2Н, 2С16Н, J 8, 3 Hz), 5.47 s (2Н, 2С14Н),
6.81 t (2H, Нarom, J 2 Hz), 7.11 d.d (4Н, Нarom, J 8, 2
Hz), 7.53 t (2Н, Нarom, J 8 Hz). Mass spectrum, m/z:
874 [М + 1]+.
Н
arom), 7.49 m (2Н, Нarom). Mass spectrum, m/z: 511
[М + 1]+. Found, %: С 70.38; Н 7.29; N 2.89.
C30H36СlNO4. Calculated, %: C 70.64; H 7.11; N 2.75.
Maleopimaric acid N-(p-iodophenyl)imide (IIIl).
Yield 5.08 g (59.6%), mp 241–243°С. IR spectrum, ν,
cm–1: 2575 (О–Н), 1773, 1704 [(C=O)N], 1488
1
(C=Carom), 1390 (C–N). Н NMR spectrum, δ, ppm:
0.55 s (3H, С20H3), 0.89 d and 0.91 d [6H, (CH3)2CH,
J 6 Hz], 0.91 m (1Н), 1.04 s (3Н, С18Н3), 1.15 m (2Н),
1.35–1.72 m (10Н), 2.14 sextet [1H, (CH3)2CH,
J 6 Hz], 2.41 m (1Н, С7Нeq), 2.70 d (1Н, С15Н, J 8 Hz),
2.95 br.s (1Н, C12H), 3.02 d.d (1Н, С16Н, J 8, 3 Hz),
5.50 s (1Н, С14Н), 6.87 d (2H, Нarom, J 8 Hz), 7.81 m
(2H, Нarom, J 8 Hz). Mass spectrum, m/z: 602 [М + 1]+.
Found, %: С 59.64; Н 6.11; N 3.04. C30H36INO4.
Calculated, %: C 59.90; H 6.03; N 2.33.
Diacid dimethyl ester (VIa). A mixture of 0.20 g
(0.23 mmol) of diacid IV, 0.086 mL (0.92 mmol) of
dimethylsulfate, and 0.12 g (0.92 mmol) of potassium
carbonate in 2 mL of DMF was stirred during 14 h at
18–20°C. After the reaction was complete, the mixture
was added into 70 mL of water upon vigorous stirring
over 30 min and stirred during 1 h. The precipitate was
filtered off, washed with water (2 × 5 mL), and dried
in air. Yield 92% (0.19 g), mp 268–270°С. IR spec-
trum, ν, cm–1: 1780, 1715 [(C=O)N], 1510 (C=Carom),
1
Diimide-diacid (IV). a. A solution of 0.7 g (0.0014 mol)
of maleopimaric acid N-(4-aminophenyl)imide IIId
and 0.85 g (0.0021 mol) of maleopimaric acid in 3 mL
of 1,2-dichlorobenzene was refluxed during 3–8 h and
then incubated at 18–20°C during 48 h. The precipitate
was filtered off, washed with toluene (3 × 0.5 mL), and
dried in air during 48 h. Yield 44% (3 h), 47% (8 h).
1375 (C–N). Н NMR spectrum, δ, ppm: 0.63 s (6H,
2С20H3), 0.97 m (2Н), 0.97 d and 0.99 d [12H,
2(CH3)2CH, J 7 Hz], 1.17 s (6Н, 2С18Н3), 1.20–1.31 m
(4Н), 1.44–1.81 m (20Н), 2.25 sextet [2H, 2(CH3)2CH,
J 7 Hz], 2.55 m (2Н, 2С7Нeq), 2.60 d (2Н, 2С15Н,
J 8 Hz), 2.96 m (2Н, 2С16Н), 3.16 br.s (2Н, 2C12H),
3.69 s (6Н, 2ОСН3), 5.50 s (2Н, 2С14Н), 7.22 s (4H,
Нarom). Mass spectrum, m/z: 902 [М + 1]+. Found, %: С
74.79; Н 8.27; N 3.26. С54H68N2O8. Calculated, %: C
74.64; H 8.05; N 3.11.
b. A solution of 3 g (0.0075 mol) of maleopimaric
acid and 0.27 g (0.0025 mol) of p-phenylenediamine in
6 mL of 1,2-dichlorobenzene was refluxed during 8 h
and then incubated during 48 h at 18–20°C. The pre-
cipitate was filtered off, washed with toluene (3 × 2 mL),
and dried in air during 48 h. Yield 68% (1.49 g), mp
398–399°С (decomp.). IR spectrum, ν, cm–1: 2550
(О–Н), 1770, 1710 [(C=O)N], 1510 (C=Carom), 1380
(C–N). Mass spectrum, m/z: 874 [М + 1]+. Found, %:
С 74.41; Н 8.07; N 2.97. С54H68N2O8. Calculated, %:
C 74.28; H 7.85; N 3.21. The spectral characteristics
coincided with the reference data [8].
Diacid diallyl ester (VIb) was prepared similarly
from 0.20 g (0.23 mmol) of diacid IV, 0.058 mL
(0.69 mmol) of allyl bromide, and 0.095 g (0.69 mmol)
of potassium carbonate. Yield 78% (0.17 g), mp 165–
167°С. IR spectrum, ν, cm–1: 1774, 1714 [(C=O)N],
1
1514 (C=Carom), 1367 (C–N). Н NMR spectrum, δ,
ppm: 0.63 s (6H, С20H3), 0.96 m (2Н), 0.97 d and 0.99
d [12H, 2(CH3)2CH, J 7 Hz], 1.19 s (6Н, 2С18Н3),
1.24–1.31 m (4Н), 1.43–1.83 m (20Н), 2.50 sextet
[2H, 2(CH3)2CH], 2.56 m (2Н, 2С7Нeq), 2.60 d (2Н,
2С15Н, J 8 Hz), 2.96 m (2Н, 2С16Н), 3.16 br.s (2Н,
2C12H), 4.59 m (4Н, 2ОСН2), 5.23 d (2Н, =СН2, 2Н-
trans, J 10 Hz), 5.33 d (2Н, =СН2, 2Н-cis, J 17 Hz),
5.50 s (2Н, 2С14Н), 5.93 m (2Н, 2СН=СН2), 7.22 s
(4H, Нarom). Mass spectrum, m/z: 954 [М + 1]+. Found,
Diimide-diacid (V). A solution of 3 g (0.0075 mol)
of maleopimaric acid and 0.27 g (0.0025 mol) of m-
phenylenediamine in 6 mL of 1,2-dichlorobenzene was
refluxed during 8 h. The solvent was removed under
reduced pressure (10 mmHg), and 3.24 g of the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015

1039
EFFICIENT SYNTHESIS OF MALEOPIMARIC ACID N-ARYLIMIDES
Org. Khim., 1992, vol. 28, no. 1, p. 211.
%: С 75.81; Н 8.23; N 2.76. C60H76N2O8. Calculated,
9. Fanggui, Y., Hengshan, W., Baojun, H., and Shulin, Z.,
Electrophoresis, 2010, vol. 31, no. 9, p. 1488. DOI:
10.1002/elps. 200900716.
%: C 75.60; H 8.04; N 2.94.
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