Synthesis of polychlorinated unsaturated cyclic dicarboxylic acid imides

Article abstract of DOI:10.1134/S1070428008100072

A procedure has been developed for the synthesis of 3,4,5,6- tetrachlorocyclohexa-3,5-diene-1,2- and 7,8,9,10-tetrachlorobicyclo[4.4.0]deca- 7,9-diene-3,4-dicarboximides from the corresponding 3,4,5,6,7,7- hexachlorobicyclo[2.2.1]hept-5-ene-2,3- and 1,8,9,10,11,11-hexachlorotricyclo[6. 2.1.02,7]undec-9-ene-4,5-dicarboxylic anhydrides and pyridine in dimethylformamide. Steric structure of the products has been studied.

Full text of DOI:10.1134/S1070428008100072

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 10, pp. 1438–1443. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © M.S. Salakhov, V.S. Umaeva, A.I. Alikhanova, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 10,
pp. 1462–1467.
Synthesis of Polychlorinated Unsaturated Cyclic
Dicarboxylic Acid Imides
M. S. Salakhov, V. S. Umaeva, and A. I. Alikhanova
Institute of Polymeric Materials, National Academy of Sciences of Azerbaidjan,
ul. S. Vurguna 124, Sumgaiyt, 5004 Azerbaidjan
Received July 17, 2007
Abstract—A procedure has been developed for the synthesis of 3,4,5,6-tetrachlorocyclohexa-3,5-diene-1,2-
and 7,8,9,10-tetrachlorobicyclo[4.4.0]deca-7,9-diene-3,4-dicarboximides from the corresponding 3,4,5,6,7,7-
hexachlorobicyclo[2.2.1]hept-5-ene-2,3- and 1,8,9,10,11,11-hexachlorotricyclo[6.2.1.02,7]undec-9-ene-4,5-di-
carboxylic anhydrides and pyridine in dimethylformamide. Steric structure of the products has been studied.
DOI: 10.1134/S1070428008100072
Chlorine-containing unsaturated cyclic carboxylic
acid anhydrides IIIa and IIIb are promising monomers
for the preparation of cage-like hinged polyimides that
are characterized by enhanced fire and heat resistance
[1, 2] and are available via Diels–Alder polycondensa-
tion of compounds IIIa and IIIb with various bis-
maleimides [3]. The synthesis of unsaturated cyclic an-
hydrides IIIa and IIIb was reported previously [4–7].
They were prepared by hydrolysis of the correspond-
ing Diels–Alder adducts, 3,4,5,6-tetrachloro-7,7-di-
methoxybicyclo[2.2.1]hept-5-ene-2,3- [4] and
1,8,9,10-tetrachloro-11,11-dimethoxytricyclo-
[6.2.1.02,7]undec-9-ene-4,5-dicarboxylic anhydrides Ia
and Ib with fixed steric structure, followed by thermol-
ysis of intermediately isolated keto anhydrides IIa and
IIb (Scheme 1).
According to the X-ray diffraction data, anhydride
Ia has endo configuration. Among four possible stereo-
isomers, endo,endo, endo,exo, exo,endo, and exo,exo,
compound Ib was found to exist as a single endo,exo
isomer with a boat conformation of the cyclohexane
ring [6, 7].
In continuation of our studies in this field, the
present article describes a new procedure for the syn-
thesis of anhydrides IIIa and IIIb and the corre-
sponding dicarboximides VIb, VIc, VIIb, and VIIc
from Diels–Alder adducts, 1,4,5,6,7,7-hexachlorobicy-
clo[2.2.1]hept-5-ene-2,3- and 1,8,9,10,11,11-hexa-
Scheme 1.
Cl
Cl
Cl
O
O
O
Cl
MeO
Cl
Cl
Cl
Cl
Concd. H2SO4
Concd. H2SO4
O
O
O
O
MeO
Cl
n
n
n
O
O
O
Cl
Cl
Cl
Ia, Ib
IIa, IIb
IIIa, IIIb
n = 0 (a), 1 (b).
OMe
Cl
OMe
MeO
Cl
MeO
Cl
Cl
O
O
Cl Cl
Cl Cl
O
O
O
O
Ia
Ib
1438

SYNTHESIS OF POLYCHLORINATED UNSATURATED CYCLIC ...
1439
Scheme 2.
Cl
Cl
Cl
Cl
Cl
Cl
DMF, pyridine
O
X
O
X
Cl Cl
Cl
Cl
O
O
IVa–IVc
IIIa, VIb, VIc
Cl
Cl
Cl
Cl
Cl
Cl
DMF, pyridine
O
O
Cl Cl
Cl
Cl
X
X
O
O
Va–Vc
IIIb, VIIb, VIIc
IIIa, IIIb, IVa, Va, X = O; IVb, IVc, Vb, Vc, VIb, VIc, VIIb, VIIc, X = NR; IV–VII, R = H2NCH2CH2 (b),
4-(4-H2N-3-MeOC6H3CH2)-2-MeOC6H4 (c).
chlorotricyclo[6.2.1.02,7]undec-9-ene-4,5-dicarboxylic
anhydrides and dicarboximides IVa–IVc and Va–Vc,
by treatment with pyridine in dimethylformamide
(Scheme 2). The presence of a primary amino group in
molecules of initial imides IVb, IVc, Vb, and Vc did
not affect their reaction with pyridine.
of stretching vibrations of C=C bonds, high- and
medium-intensity carbonyl absorption bands in the
region 1710–1780 cm–1, and absorption bands at 680–
800 cm–1 due to vibrations of C–Cl bonds.
Compounds IIIa, IIIb, VIb, VIc, VIIb, and VIIc
displayed in the UV spectra absorption maxima at
λ 246 nm (IIIa, VIb, VIc) and 285–287 nm (IIIb,
VIIb, VIIc), which are typical of cisoid homoannular
diene systems [8].
The structure of compounds IIIa, IIIb, VIb, VIc,
VIIb, and VIIc was confirmed by the IR spectra which
contained absorption bands at 1600–1601 cm–1 typical
Scheme 3.
Cl
O
O
Cl
Cl
Δ
IIIa, VIb, VIc
+
X
X
O
O
X
O
O
Cl
VIIIa–VIIIc
Xa–Xc
Cl
Cl
O
X
O
O
Cl
Cl
Δ
VIIIa–VIIIc, Δ
IIIa, VIb, VIc
+
IIIb, VIIb, VIIc
X
X
O
O
O
IXa–IXc
XIa–XIf
Cl
O
O
O
Cl
Δ
IIIb, VIIb, VIIc
+
X
X
X
Cl
O
O
O
Cl
IXa–IXc
XIIa–XIIc
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

SALAKHOV et al.
1440
Scheme 4.
O
Cl
Cl
X
O
Cl
Cl
O
O
Cl
Cl
X
O
X
X
O
Cl Cl
O
O
IIIa, VIb, VIc
Xa–Xc
X = O (a), H2NCH2CH2N (b), 4-(4-H2N-3-MeOC6H3CH2)-2-MeOC6H4N (c).
Scheme 5.
O
Cl
X
O
Cl
Cl
Cl
O
Cl
X
O
O
O
Cl
X
Cl
Cl
O
X
O
IIIb, VIIb, VIIc
XIa–XIc
The presence of a conjugated double bond system
in IIIa, IIIb, VIb, VIc, VIIb, and VIIc was confirmed
by their Diels–Alder reactions with maleic and tetra-
hydrophthalic anhydrides and imides VIIIa–VIIIc and
IXa–IXc. We showed previously [9] that anhydrides
IIIa and IIIb readily react with maleic anhydride
(VIIIa) to give the corresponding dianhydrides Xa–
XIIa. Our present study has shown that anhydrides
IIIa and IIIb and imides VIb, VIc, VIIb, and VIIc
also readily react not only with maleic acid derivatives
VIIIa–VIIIc but also with tetrahydrophthalic anhy-
dride and imides IXa–IXc. The Diels–Alder reactions
of IIIa, VIb, and VIc with tetrahydrophthalic anhy-
dride (IXa) and imides IXb and IXc and of com-
pounds IIIb, VIIb, and VIIc with maleic anhydride
(VIIIa) and imides VIIIb and VIIIc gave adducts
XIa–XIf having the same molecular constitution but
different melting points (Scheme 3).
Taking into account endo orientation of the addends
and the possibility for maleic acid derivatives to
approach the diene system in IIIa, VIb, VIc at both
syn and anti side, the bicyclic fragment in the adduct
should have exo,exo configuration (Xa–Xc; Scheme 4).
As shown previously with the aid of Stewart–Briegleb
models [10, 11], the tricyclic fragment in XIa–XIf
should have exo,exo,endo (XIa–XIc; Scheme 5) or
endo,exo,exo structure (XId–XIf).
as equilibrium mixtures of two conformations syn- and
anti-boat (Scheme 6).
Scheme 6.
O
X
O
X
O
O
syn
anti
In the reactions with anhydrides IIIa and IIIb or
imides VIb, VIc, VIIb, and VIIc, both conformers of
dienophiles IXa–IXc are equally accessible for the
formation of endo-oriented complex; therefore, attack
on diene IIIa, VIb, or VIc by anhydride or imide IXa–
IXc should involve mainly the syn conformer to give
endo,exo,exo-adduct XId–XIf (Scheme 7), whereas
analogous Diels–Alder adducts XIa–XIc obtained
from dienes IIIb, VIIb, and VIIc should have
exo,exo,endo configuration. Compounds XIIa–XIIc
should be formed as endo,exo,exo,endo isomers
(Scheme 8).
EXPERIMENTAL
The UV spectra were recorded on a Specord-UV
spectrophotometer from solutions in methanol with
a concentration of 3.0×10–4 M. The NMR spectra were
measured on a Tesla BS-487C spectrometer at 80 MHz
According to the NMR data [6, 8], tetrahydro-
phthalic anhydride (IXa) and imides IXb and IXc exist
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

SYNTHESIS OF POLYCHLORINATED UNSATURATED CYCLIC ...
1441
Scheme 7.
O
X
Cl
O
O
Cl
Cl
X
Cl
Cl
O
X
O
X
O
Cl Cl
Cl
O
O
IIIa, VIb, VIc
XId–XIf
Scheme 8.
O
X
Cl
Cl
Cl
Cl
O
Cl
O
Cl
O
O
X
Cl
X
Cl
O
O
X
O
IIIb, VIIb, VIIc
XIIa–XIIc
Compound VIb. Yield 78%, mp 90–91°C (from
chloroform–hexane), Rf 0.87. Found, %: C 35.91;
H 2.01; Cl 42.77; N 8.01. M 329.0. C10H8Cl4N2O2.
Calculated, %: C 36.36; H 2.42; Cl 43.03; N 8.48.
M 330.0.
using carbon tetrachloride as solvent and hexamethyl-
disiloxane as internal reference. The purity of the prod-
ucts was checked by thin-layer chromatography on
Silufol plates using benzene–dichloroethane–acetic
acid (4:1.5:1, by volume) as eluent; spots were de-
tected under UV light [12].
Compound VIc. Yield 80%, mp. 165–167°C (from
chloroform–hexane), Rf 0.90. Found, %: C 51.99;
H 3.10; Cl 26.31; N 5.04. M 526.0. C23H18Cl4N2O4.
Calculated, %: C 52.27; H 3.41; Cl 26.89; N 5.30.
M 528.0.
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hept-5-ene-
2,3-dicarboxylic anhydride (IVa) [13], 1,8,9,10,11,11-
hexachlorotricyclo[6.2.1.02,7]undec-9-ene-4,5-dicar-
boxylic anhydride (Va) [14], anhydrides VIa and VIIa
[15, 16], N-substituted maleimides VIIIb and VIIIc
[13], and tetrahydrophthalimides IXb and IXc [15]
were synthesized by known methods.
endo,exo-7,8,9,10-Tetrachlorobicyclo[4.4.0]deca-
7,9-diene-3,4-dicarboxylic anhydride (IIIb) and
imides VIIb and VIIc were synthesized in a similar
way from 0.1 mol of anhydride Va and imides Vb and
Vc, respectively, using 5 ml of pyridine.
Compound IIIb. Yield 90%, mp 160–162°C (from
benzene), Rf 0.90. Found, %: C 32.91; H 0.51;
Cl 48.88. M 341.0. C8H2Cl4O3. Calculated, %: C 33.33;
H 0.69; Cl 49.30. M 342.0.
endo-3,4,5,6-Tetrachlorocyclohexa-3,5-diene-1,2-
dicarboxylic anhydride (IIIa) and imides VIb and
VIc (general procedure). Pyridine, 3 ml, was added
dropwise to a solution of 0.1 mol anhydride IVa or
imide IVb or IVc in 20 ml of DMF at room tempera-
ture. The mixture spontaneously warmed up to 35°C. It
was allowed to cool down to 20°C and poured into ice
water under stirring. The precipitate was filtered off
and washed with water until neutral washings.
Compound VIIb. Yield 98%, mp 120–122°C (from
methanol), Rf 0.91. Found, %: C 43.28; H 3.14;
Cl 36.41; N 7.04. M 382.5. C14H14Cl4N2O2. Calculated,
%: C 43.75; H 3.64; Cl 36.98; N 7.29. M 384.0.
Compound IIIa. Yield 86%, mp 138–139°C (from
methanol), Rf 0.85. Found, %: C 32.91; H 0.51;
Cl 48.88. M 287.5. C8H2Cl4O3. Calculated, %: C 33.33;
H 0.69; Cl 49.30. M 288.0.
Compound VIIc. Yield 92%, mp 226–228°C (from
acetone), Rf 0.92. Found, %: C 55.10; H 3.91;
Cl 23.98; N 4.30. M 580.0. C27H24Cl4N2O4. Calculated,
%: C 55.67; H 4.12; Cl 24.40; N 4.81. M 582.0.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

SALAKHOV et al.
1442
exo,exo-1,4,7,8-Tetrachlorobicyclo[2.2.2]oct-7-
anhydride (IXa) or imide IXb or IXc, respectively, in
20 ml of benzene was heated for 2 h under reflux.
After cooling, the precipitate was filtered off and dried
at room temperature.
ene-2,3:5,6-tetracarboxylic dianhydride (Xa) and
diimides Xb and Xc (general procedure). A mixture
of 0.01 mol of anhydride IIIa or imide VIb or VIc and
0.01 mol of maleic anhydride VIIIa or maleimide
VIIIb or VIIIc, respectively, was dissolved in 20 ml of
acetone. The mixture spontaneously warmed up to
38°C and was left to stand for 12 h. The precipitate
was filtered off and dried at room temperature.
endo,exo,exo-1,8,11,12-Tetrachlorotricyclo-
[6.2.2.02,7]dodec-11-ene-4,5:9,10-tetracarboxylic
anhydride (XId) and imides XIe and XIf were
synthesized in a similar way from anhydride IIIa and
imides VIb and VIc.
Compound Xa. Yield 96%, mp 260–263°C (from
methanol), Rf 0.98. Found, %: C 36.98; H 0.89;
Cl 36.29. M 385.0. C12H4Cl4O6. Calculated, %: C 37.30;
H 1.04; Cl 36.79. M 386.0.
Compound XId. Yield 90%, mp 173–175°C (from
diethyl ether), Rf 0.78. Found, %: C 43.10; H 1.89;
Cl 31.88. M 439.0. C16H10Cl4O6. Calculated, %:
C 43.64; H 2.27; Cl 32.27. M 440.0.
Compound Xb. Yield 97%, mp 184–185°C (from
chloroform–hexane), Rf 0.96. Found, %: C 40.19;
H 3.08; Cl 30.00; N 11.37. M 469.0. C16H16Cl4N4O4.
Calculated, %: C 40.85; H 3.40; Cl 30.41; N 11.91.
M 470.0.
Compound XIe. Yield 90%, mp 166–168°C (from
chloroform–hexane), Rf 0.80. Found, %: C 43.91;
H 3.00; Cl 28.33; N 11.92. M 523.0. C20H22Cl4N4O4.
Calculated, %: C 43.72; H 3.24; Cl 28.74; N 12.21.
M 524.0.
Compound Xc. Yield 98%, mp 201–202°C (from
chloroform–hexane), Rf 0.97. Found, %: C 58.01;
H 4.07; Cl 16.00; N 14.04. M 865.0. C42H36Cl4N4O8.
Calculated, %: C 58.20; H 4.15; Cl 16.40; N 14.78.
M 866.0.
Compound XIf. Yield 91%, mp 116–118°C (from
diethyl ether), Rf 0.81. Found, %: C 59.68; H 4.00;
Cl 14.98; N 13.71. M 918.0. C46H42Cl4N4O8. Calculat-
ed, %: C 60.00; H 4.56; Cl 15.43; N 13.91. M 920.0.
endo,exo,exo,endo-1,8,15,16-Tetrachlorotetra-
cyclo[6.6.2.02,7.09,14]hexadec-15-ene-4,5:11,12-tetra-
carboxylic dianhydride (XIIa) and imides XIIb and
XIIc. A solution of 0.01 mol of compound IIIb, VIIb
or VIIc and 0.01 mol of anhydride IXa or imide IXb
or IXc, respectively, in 20 ml of benzene was heated
for 2 h under reflux. The mixture was then treated as
described above.
exo,exo,endo-1,8,11,12-Tetrachlorotricyclo-
[6.2.2.02,7]dodec-11-ene-4,5:9,10-tetracarboxylic
dianhydride (XIa) and diimides XIb and XIc
(general procedure). a. A mixture of 0.01 mol of anhy-
dride IIIb or imide VIIb or VIIc and 0.01 mol of
maleic anhydride (VIIIa) or maleimide VIIIb or
VIIIc, respectively, was dissolved in 20 ml of acetone.
The solution spontaneously warmed up to 38°C and
was left to stand for 12 h. The precipitate was filtered
off and dried.
Compound XIIa. Yield 90%, mp 162–164°C (from
chloroform–hexane), Rf 0.81. Found, %: C 48.04;
H 2.88; Cl 28.21. M 493.0. C20H16Cl4O6. Calculated,
%: C 48.58; H 3.24; Cl 28.74. M 494.0.
Compound XIa. Yield 91%, mp 225°C (from
diethyl ether), Rf 0.80. Found, %: C 43.00; H 1.97;
Cl 31.87. M 439.0. C16H10Cl4O6. Calculated, %:
C 43.64; H 2.27; Cl 32.27. M 440.0.
Compound XIIb. Yield 91%, mp 80–82°C (from
chloroform–hexane), Rf 0.88. Found, %: C 44.04;
H 4.01; Cl 21.91; N 8.18. M 641.0. C24H28Cl4N4O4.
Calculated, %: C 44.41; H 4.34; Cl 22.11; N 8.72.
M 642.0.
Compound XIb. Yield 90%, mp 88–90°C (from
chloroform–hexane), Rf 0.81. Found, %: C 44.48;
H 4.01; Cl 26.90; N 12.00. M 522.0. C20H22Cl4N4O4.
Calculated, %: C 43.72; H 3.24; Cl 28.74; N 12.21.
M 524.0.
Compound XIIc. Yield 88%, mp 160–162°C (from
chloroform–hexane), Rf 0.90. Found, %: C 61.05;
H 4.43; Cl 14.02; N 12.98. M 973.5. C50H48Cl4N4O8.
Calculated, %: C 61.60; H 4.93; Cl 14.58; N 13.14.
M 974.5.
Compound XIc. Yield 90%, mp 125–127°C (from
diethyl ether), Rf 0.80. Found, %: C 59.80; H 4.21;
Cl 15.04; N 13.21. M 919.0. C46H42Cl4N4O8. Calculat-
ed, %: C 60.00; H 4.56; Cl 15.43; N 13.91. M 920.0.
REFERENCES
b. A solution of 0.01 mol of anhydride IIIa or imide
VIb or VIc and 0.01 mol of 1,2,3,6-tetrahydrophthalic
1. Korshak, V.V., Rusanov, A.L., Margalitadze, Yu.N., and
Tabidze, R.S., Plast. Massy, 1987, no. 5, p. 5.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008

SYNTHESIS OF POLYCHLORINATED UNSATURATED CYCLIC ...
1443
2. Salakhov, M.S. and Guseinov, M.M., J. Chem. Tech.,
9. Zul’faliev, Sh.R., Salakhov, M.S., Pirgulieva, M.S., and
1978, p. 44.
Efendiev, A.A., Azerb. Khim. Zh., 1998, no. 4, p. 10.
3. Salakhov, M.S., Zul’faliev, Sh.R., and Efendiev, A.A.,
Abstracts of Papers, III Mezhdunarodnaya Mamedaliev-
skaya Neftekhimicheskaya konferentsiya (IIIrd Mameda-
liev Int. Conf. on Petroleum Chemistry), 1998, p. 281.
10. Salakhov, M.S., Treivus, E.M., and Salakhova, R.S.,
Vopr. Stereokhim., 1977, no. 6, p. 50.
11. Odinokov, V.N., Galeeva, R.I., and Tolstikov, G.A.,
Zh. Org. Khim., 1977, vol. 13, p. 1195.
4. Salakhov, M.S., Guseinov, M.M., and Magomedo-
12. Akhrem, A.A. and Kuznetsova, A.I., Tonkosloinaya
va, E.M., Osn. Org. Sint. Neftekhim., 1976, no. 6, p. 60.
khromatografiya
(Thin-Layer
Chromatography),
5. Salakhov, M.S., Guseinov, M.M., Musaeva, N.E., and
Alekperov, N.A., USSR Inventor’s Certificate
no. 467070; Byull. Izobret., 1975, no. 14.
6. Salakhov, M.S., Salakhova, R.S., Musaeva, N.E., Alek-
perov, N.A., Vereshchagin, A.N., Timosheva, A.L., and
Vul’fson, S.R., Izv. Akad. Nauk SSSR, Ser. Khim., 1975,
p. 869.
Moscow: Nauka, 1964.
13. Kretov, A.E. and Kul’chitskaya, N.E., Zh. Obshch.
Khim., 1956, vol. 26, p. 208.
14. Salakhov, M.S., Guseinov, M.M., and Kyazimova, T.G.,
Dokl. Akad. Nauk Azerb. SSR, 1966, vol. 22, no. 2,
p. 31.
15. Solntsev, A.P., Maistrov, I.I., Krutko, E.P., Volo-
zhin, A.I., and Paushkin, Ya.M., Vestn. Akad. Nauk
BSSR, Ser. Khim., 1974, p. 87.
7. Salakhov, M.S., Alekperov, N.A., Poladov, P.M., Sala-
khova, Ya.S., Guseinov, M.M., and Kucherov, V.F.,
Zh. Org. Khim., 1973, vol. 9, p. 942.
16. Simonov, V.D., Antonov, L.T., Nedel’chenko, B.M., and
Sklyar, S.Ya., USSR Inventor’s Certificate no. 363079;
Byull. Izobret., 1973, no. 8.
8. Salakhov, M.S., Alekperov, N.A., Ismailov, S.A., and
Khudaverdieva, E.F., Zh. Org. Khim., 1978, vol. 14,
p. 1234.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 10 2008