New method for synthesis of aromatic diimide dicarboxylic acid diallyl esters

Article abstract of DOI:10.1134/S107042721103013X

New method is suggested for synthesis aromatic diimide dicarboxylic acid diallyl esters from the corresponding acids under the action of allyl halides in aprotic polar solvents in the presence of anhydrous K₂CO ₃.

Full text of DOI:10.1134/S107042721103013X

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 3, pp. 412–415. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © B.A. Tagiev, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 3, pp. 420–423.
ORGANIC SYNTHESIS AND INDUSTRIAL
ORGANIC CHEMISTRY
New Method for Synthesis of Aromatic Diimide Dicarboxylic
Acid Diallyl Esters
B. A. Tagieva,b
a Chemical Department, Faculty of Science and Letters, Kafkas University, Kars, Turkey
b Institute of Polymeric Materials, National Academy of Sciences of Azerbaijan, Sumgait, Azerbaijan
Received June 3, 2010
Abstract—New method is suggested for synthesis aromatic diimide dicarboxylic acid diallyl esters from the
corresponding acids under the action of allyl halides in aprotic polar solvents in the presence of anhydrous
K2CO3.
DOI: 10.1134/S107042721103013X
It is known that allyl resins produced from allyl
monomers are construction materials possessing
exclusive electrical and mechanical properties at room
temperature. However, their application had been
restricted by their poor heat resistance, because shape
and size preservation at elevated temperatures is highly
important for quite a number of electrical products [1].
To improve the heat resistance of allyl resins, amide
groups were introduced into the backbone [2], which
improved the heat resistance of target products, but
final articles were nonmachinable.
synthesis of diallyl esters of fully aromatic diimide
dicarboxylic acids, which have been synthesized
previously only from chloranhydrides of the cor-
responding acids and allyl alcohol [3, 4]. The diallyl
esters were synthesized by the reaction of aromatic
diimidodicarboxylic acids with allyl halides in the
presence of anhydrous K2CO3 (Scheme 1).
The starting aromatic bis(imidocarboxylic) acids
(Ia–Ic) were synthesized by the methods described in
[4, 10–12] in 75–90% yield. Aromatic diimide dicer-
boxylic acid bisallyl esters (IIIa–IIIc) were obtained
using the above scheme by heating of bis(imido-
carboxylic) acids (Ia–Ic) with an excess amount of an
allyl halide in such aprotic solvents as N,N-dimethyl-
acetamide (DMAc) and N,N-dimethylformamide
(DMF) in the presence of K2CO3 as an acid acceptor.
Later, allyl monomers with aryl imide groups of
varied structure were synthesized in [3] and easily
machinable heat-resistant allyl polymeric materials
were produced from these monomers. Similarly, new
aryl imide-containing diallyl monomers and heat-
resistant machinable polymeric materials based on
these monomers were obtained [4].
The composition and structure of bisallyl esters
(IIIa–IIIc) synthesized by the new method were
1
characterized by IR and H NMR spectra and elemen-
It is known that the carboxy group of aromatic
imidocarboxylic acids has a higher reactivity in
nucleophilic substitution reactions [5–7]. Therefore,
potassium salts of these acids [8], or acid themselves in
the presence of catalysts [9], can enter into a reaction
with an excess amount of epichlorohydrin to form
glycidyl ethers in high yield (80–90%). Aryl imide-
containing bisallyl esters have been synthesized from
N-allyl-4-phthalimidocarboxylic acid and various
aliphatic and arylaliphatic dihalide compounds [2]. A
new method is suggested on the basis of these data for
tal analysis data.
The IR spectra of compounds IIIa–IIIc contain
absorption bands at 725, 1725, and 1785 cm–1, charac-
teristic of aromatic imide rings. The absorption bands
at 1640 and 3200–3700 cm–1 can be assigned to,
respectively, the C=C allyl double bond and C–H
bonds. The absorption peak at 1720 cm–1, charac-
teristic of the C=O ester group appears combined with
the imide absorption. The characteristic absorption
bands observed in the IR spectra of compounds IIIa–
412

NEW METHOD FOR SYNTHESIS OF AROMATIC DIIMIDE
413
Scheme 1.
CO
CO
OC
N
Ar
N
+ 2XCH2
CH
II
CH2
OC
HO2C
CO2H
N
Ia−Ic
CO
OC
OC
N
Ar
CO
CO2CH2CH
(Merck),
CH2
CHCH2O2C
CH2
CH2
IIIa−ΙΙIc
(b),
(a),
(c); X = Cl, Br.
Ar =
CH3
IIIc are in good agreement with the data previously
diaminodiphenylmethane
1,4-diamino-
obtained for similar compounds [4].
benzene (Merck), 2,4-diaminotoluene (Merck), tri-
mellitic anhydride (Merck), N,N-dimethylacetamide
(Merck), N,N-dimethylformamide (Merck), and K2CO3
(Merck).
1
The H NMR spectra of bisallyl esters IIIa–IIIc
contain signals with chemical shifts of 7.00–8.50 ppm,
characteristic of aromatic protons. In addition, the
chemical shifts of 6.00–6.16, 5.25–5.50, and 4.82–
4.96 ppm can be attributed to, respectively, =C–H,
=CH2, and –CH2– protons of the allyl group. The
chemical shifts of 3.26–3.38 and 2.00–2.25 ppm are
characteristic of protons of the –CH2– group in
compound IIIa and protons of –CH3 in compound
IIIc. These characteristic chemical shifts occur in the
1H NMR spectrum of bisallyl ester IIIc (see the
figure). The chemical shifts observed for the syn-
thesized bisallyl esters (IIIa–IIIc) are also in good
agreement with published data [4].
N,N'-Bis(4-carboxyphthalimido)-4,4'-diphenyl-
methane (Ia) was produced by condensation of tri-
mellitic anhydride (TMA) (20 mmol) with 4,4'-di-
aminodiphenylmethane (10 mmol) in DMF (50 ml) by
the previously described method [4, 10–12]. Yield
90%, mp 370°C (from DMAc) (according to published
data [12], mp 372°C).
N,N'-Bis(4-carboxyphthalimido)-1,4-benzene (Ib)
was produced by condensation of TMA (20 mmol)
with 1,4-diaminobenzene (10 mmol) in DMF (45 ml)
[4, 10–12]. Yield 87%; mp 435–438°C (from DMAc)
(according to published data [113], 428–430°C).
EXPERIMENTAL
N,N'-Bis(4-carboxyphthalimido)-2,4-toluene (Ic)
was produced by condensation of TMA (20 mmol)
All the starting substances were used without
additional purification: allyl bromide (Fluka), 4,4'-
δ, ppm
1H NMR spectrum of N,N'-bis(4-allyloxycarbonylphthalimido)-2,4-toluene (IIIc) in DMSO-d6. (δ) Chemical shift.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 3 2011

414
TAGIEV
with 2,4-diaminotoluene (10 mmol) in DMF (45 ml)
[4, 10–12]. Yield 75%, mp 368–370°C (from DMAc)
(according to published data [12], 371°C).
Yield 2.10 g (84%); mp 282–284°C. Found, %: C
71.24, 71.30; H 4.26, 4.30; N 4.39, 4.42. C37H26N2O8.
Calculated, %: C 70.92, H 4.18, N 4.47.
N,N'-Bis(4-allyloxycarbonylphthalimido)-4,4'-di-
phenylmethane (IIIa). A reaction vessel with a mag-
netic rabble, thermometer, reflux, and Dean–Stark
apparatus was charged with a solution of 2.18 g of
compound Ia (4 mmol) in 40 ml of DMAc and with
1.10 g of anhydrous K2CO3 (4 mmol). The mixture
was agitated for 15 min at room temperature, 8 ml of
toluene was added, and the resulting mixture was
heated on a water bath at 125–130°C until water
ceased to be released. After water was removed, 2 ml
of allyl bromide (sixfold excess) and about 50 mg of
KI was added. The agitation of the reaction mixture
was continued for 4 h at a temperature of 130°C. After
the reaction was complete, the mixture was cooled to
50–60°C and poured into 300 g of icy water acidified
with hydrochloric acid. The resulting yellowish white
precipitate was filtered off, washed on the filter with
water and then with acetone, and dried in air and then
in a vacuum. Yield of dry raw product 2.20 g (88%);
mp 278–280°C. On being recrystallized from DMAc,
product IIIa had the form of fine light yellow grains.
IR spectrum, cm–1 (KBr): 1785, 1725, and 725
(imide group); 1640 (C=C of the allyl group); 3600–
3200 (C–H); and 1720 (C=O of the ester group is
overlapped by the absorption of the imide group).
1H NMR spectrum (400 MHz, DMSO-d6), δ, ppm:
8.42–8.48 d (Hb + Hb', 2H), 8.30–8.36 s (Hc + Hc', 2H),
8.08–8.12 d (Ha + Ha', 2H), 7.42–7.48 (two overlapped
doublets, Hd + Hd', 4H), 7.38–7.42 (two overlapped
doublets, He + He', 4H), 6.2–6.16 m (Hh + Hh', 2H),
5.30–5.46 d.d (Hi + Hi', 4H), 4.86–4.94 d (Hg + Hg',
4H), 4.08 s (Hf + Hf ', 2H).
N,N'-Bis(4-allyloxycarbonylphthalimido)-1,4-
benzene (IIIb) was produced by the reaction of
compound (Ib) (5 mmol) with allyl bromide (5 ml)
(sixfold excess) in DMAc (80 ml) in the presence of
anhydrous K2CO3 (5 mmol) by the method for
synthesis of compound IIIa, described above. Yield of
yellowish white unpurified dry product 73%; mp 294–
296°C (with decomposition). On being recrystallized
from DMF, product IIIb had the form of grayish white
Scheme 2.
O
C
O
C
O
C
O
C
c
a
c'
a'
e'
d
d'
e
O
O
g
CH2
N
fCH2
N
g'
CH2
b'
b
C
O
C
O
h'CH
hCH
iCH2
i'CH2
IIIa
O
C
O
C
O
O
d
d'
CH2
c
c'
O
O
C
CH2
C
eCH
e'CH
N
N
b'
b
C
C
a'
a
fCH2
f C' H2
O
O
C
O
O
IIIb
O
C
O
C
d
d'
c
a
c'
a'
CH2
O
O
CH2
C
eCH
e'CH
N
N
b'
b
C
O
C
O
fCH2
f C' H2
CH3
IIIc
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 3 2011

NEW METHOD FOR SYNTHESIS OF AROMATIC DIIMIDE
415
fine grains. Yield 68%; mp 308–310°C (with decom-
position). Found, %: C 67.34, 67.32; H 3.83, 3.85; N 5.14,
5.18. C30N20N2O8. Calculated, %: C 67.16; H 3.76; N 5.22.
IR spectrum cm–1 (KBr): 1785, 1725, and 725
(imide group); 1640 (C=C of the allyl group); 3600–
3200 (C–H); 1720 (C=O of the ester group is
overlapped by the absorption of the imide group).
(2) Three allyl esters: N,N'-bis(4-allyloxycarbonyl-
phthalimido)-4,4'-diphenylmethane, N,N'-bis(4-allyloxy-
carbonylphthalimido)-1,4-benzene, and N,N'-bis(4-
allyloxycarbonylphthalimido)-2,4-toluene were syn-
thesized by the new method and characterized.
ACKNOWLEDGMENTS
1H NMR spectrum, δ, ppm: 8.42–8.50 d (Hb + Hb',
2H), 8.32–8.38 s (Hc + Hc', 2H), 8.10–8.14 d (Ha + Na',
2H), 7.60–7.66 s (protons of the C6H4 group, 4H), 6.05–
6.15 m (He + He', 2H), 5.30–5.50 d (Hf + Hf ', 4H), 4.90 d
(Hd + Hd', 4H).
The author is grateful to Javid Zaza and Barysh
Anyl (Ataturk University, Erzurum, Turkey) for
measurements of 1H NMR spectra of the bisallyl esters
synthesized.
REFERENCES
N,N'-Bis(4-allyloxycarbonylphthalimido)-2,4-
toluene (IIIc) was produced by the reaction of
compound Ic (2 mmol) with allyl bromide (2 ml)
(sixfold excess) in DMAc (20 ml) in the presence of
anhydrous K2CO3 by the method for synthesis of
compound IIIa, described above. On being recrystal-
lized from DMAc, product IIIc had the form of fine
yellowish gray ball-shaped crystals. Yield 75%; mp
287–288°C. Found, %: C 67.86, 67.90; H 4.16, 4.12; N
4.98, 4.96. C31H22N2O8. Calculated, %: C 67.63, H 4.03,
N 5.09.
IR spectrum, cm-1 (KBr): 1785, 1725, and 725
(imide group); 1640 (C=C of the allyl group); 3600–
3200 (C–H); 1720 (C=O of the ester group is
overlapped by the absorption of the imide group);
2930–2910 and 1385–1375 (CH3–Ar).
1H NMR spectrum, δ, ppm: 8.40–8.48 d (Hb + Nb',
2H), 8.30 s (Hc + Hc', 2H), 8.05–8.10 d (Ha + Ha', 2H),
7.50–7.60 s (1H), 7.40–7.48 d (1H) and 7.10–7.18 d
(1H) are aromatic protons of the (CH3)C6H3 group (a
total of 3H), 6.0–6.14 m (He + He', 2H), 5.30–5.50 d.d (Hf
+ Hf ', 4H), 4.84–4.90 d (Hd + Hd', 4H), 2.00–2.60 s
(protons of the CH3 group, 3H).
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CONCLUSIONS
vol. 82, pp. 1556–1569.
(1) A new method for synthesis of aromatic diimide
dicarboxylic acid diallyl esters was developed.
13. De Abajo, J., Babe, S.G., and Fontan, J., Angew.
Macromol. Chem., 1971, vol. 19, pp. 121–134.
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