Epoxidation of bicyclo[2.2.1]hept-5-ene-2,3-endo- and exodicarboxylic acid N-arylimides

Article abstract of DOI:10.1023/A:1015573902465

Epoxidation of endo- and exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid N-arylimides with a solution of peracetic acid in anhydrous dioxane affords 5,6-exo-epoxybicycloheptanedicarboxylic acid N-arylimides. The epoxidation reaction is not sensitive to

Full text of DOI:10.1023/A:1015573902465

Russian Journal of Organic Chemistry, Vol. 38, No. 2, 2002, pp. 244 247. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 2, 2002,
pp. 265 268.
Original Russian Text Copyright
2002 by Salakhov, Bagmanova.
Epoxidation of Bicyclo[2.2.1]hept-5-ene-2,3-endo-
and Exodicarboxylic Acid N-Arylimides
M. S. Salakhov and M. I. Bagmanova
Institute of Polymer Materials, Azerbaidzhanian National Academy of Sciences, Sumgait, 373204 Azerbaidzhan
Received November 22, 2000
Abstract Epoxidation of endo- and exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid N-arylimides with a
solution of peracetic acid in anhydrous dioxane affords 5,6-exo-epoxybicycloheptanedicarboxylic acid
N-arylimides. The epoxidation reaction is not sensitive to the configuration of the imide fragment, to the
character and position of the substituent in the aromatic ring. The reaction is determined only by oxidation
conditions.
The epoxidation of unsaturated cyclic dicarboxylic
acids is commonly performed as oxidation of the
unsaturated bonds with peroxy acids [1]. The oxida-
tion of the double bond in the anhydride of bicyclo-
[2.2.1]hept-5-ene-2,3-dicarboxylic acid with peracetic
acid is known [2, 3] to occur exactly stereospecifical-
ly affording 5,6-exo-epoxyanhydride from the
exo-anhydride, and endo- -lactone [4, 5] from the
endo-anhydride.
of the imide ring, and on the character and position
of the substituent in the aromatic ring. The oxidation
of the double bond in N-arylimides I XIV was
carried out with a solution of peracetic acid in an
anhydrous dioxane. The solution of peracetic acid had
been preliminary prepared from acetic acid and a
60% solution of hydrogen peroxide in dioxane.
We hoped to obtain epoxides XV XXVIII stable
under the reaction conditions for the presence of
carbonyl groups in the imide ring should have
stabilized the oxide cycle. The alteration in the
negative inductive effect of the N-arylimide moiety
was performed by means of electron-donor and
electron-withdrawing groups introduces in ortho,
meta, and para positions of the aromatic ring.
The present study concerns the behavior of the
double bond in the endo- (I VII) and exo-
(VIII XIV) isomers of bicyclo[2.2.1]hept-5-ene-2,3-
dicarboxylic acid N-arylimides in the course of oxid-
ation depending on the endo or exo configuration
As a result of the investigation performed we
revealed that irrespective of the character and position
of substituents, and also of the imide ring configura-
tion the oxidation of N-arylimides I XIV with
peracetic acid in anhydrous dioxane at room tempera-
ture occurred exactly stereospecifically and afforded
highly heat-resistant epoxy compounds XV XXVIII
with the exo-configuration of the epoxy ring in nearly
quantitative yield (95 98%). The oxygen attack
occurred from the side of endo-methylene bridge
notwithstanding endo- or exo-configuration of the
imide fragment.
The presence of the epoxy ring in compounds
XV XXVIII is proved by IR spectra where is
1
observed an absorption band in 851 860 cm region
characteristic of the epoxy ring, and absorption bands
1
of C=O groups at 1704 1720 cm [6, 7]. The exo-
R = H (I, VIII, XV, XXII), o-, m-, p-OCH3 (II IV,
IX XI, XVI XVIII, XXIII XXV), o-, m-, p-COOH
(V VII, XII XIV, XIX XXI, XXVI XXVIII).
configuration of the epoxy ring in compounds XV
XXVIII follows from the H NMR spectra where the
1
1070-4280/01/3802-244$27.00 2002 MAIK Nauka/Interperiodica

EPOXIDATION OF BICYCLO[2.2.1]HEPT-5-ENE-2,3-ENDO-...
245
signals of protons H8s and H8an appear as AB-quartet
with the geminal coupling constant J 11 Hz
demonstrating their nonequivalence. The assignment
of signals belonging to the protons was done taking
into account magnetically anisotropic effect of the
oxirane ring resulting in the downfield shift of the H8s
resonance [8].
Hydrolysis of endo-isomers XXIX XXXVI with
10% sulfuric acid (or 10% alkali) affords lactone
XLIII, and hydrolysis of isomers XXXVII XLII
affords trans-5,6-dihydroxydicarboxylic acid XLIV.
The trans-configuration of hydroxy groups in the
hydroxyacid XLIV is confirmed by IR spectrum
where appears only the absorption band of free hydr-
1
oxy groups in the region 3465 3480 cm . In the IR
The exo-configuration of imide ring in compounds
XXII XXVIII is proved by nonequivalence of H5 and
H7 protons characteristic of all epoxy compounds in
this series [9]. In the spectra of endo-isomers
XV XXI coupling constants of the endo-atoms H5 and
H7 with the protons H1 and H4 (J 0 2 Hz) are smaller
than in the spectra of exo-isomers XXII XXVIII
(J 2 4 Hz). The chemical shift of signal from H8s is
0.9 ppm for exo-isomers and 1.15 for endo-isomers
[8].
spectrum of lactone XLIII are present absorption
bands at (OH) 3420 and (C=O) 1752 cm 1 [10].
EXPERIMENTAL
1H NMR spectra were recorded on spectrometer
Tesla BS-487 at operating frequency 80 MHz in
CDCl3 solutions, internal reference HMDS. IR
spectra were measured on UR-20 instrument in
1
400 3800 cm range from samples as mulls in
It should be noted that epoxidation carried out
under similar conditions but in the presence of
sulfuric acid as catalyst instead of exo-epoxyimides
XV XXVIII arise trans-5,6-diacetoxy-endo- (XXIX
XXXVI) and exo- (XXXVII XLII) dicarboxylic
acids N-arylimides. Compounds XV XXVIII on
boiling with excess acetic acid in the presence of
sulfuric acid also give rise to trans-5,6-diacetoxy-
imides XXIX XLII that are colorless crystalline
substances well soluble in acetone.
mineral oil [6, 7].
The purity of compounds was checked by TLC,
sorbent silica gel L 5/40 [11], development by UV
irradiation.
Bicyclo[2.2.1]hept-5-ene-2,3-endo- and exo-di-
carboxylic acid N-arylimides were prepared along
procedure [12].
Peracetic acid. Hydrogen peroxide of 33% con-
centration was concentrated to 60% concentration by
vacuum distillation, and the peroxide was extracted
into ether. At 45 50 C the ether was distilled off with
simultaneous addition of dioxane. Into the flask was
charged 72 g (1.2 mol) of acetic acid, 22.6 g of 30%
dioxane solution of hydrogen peroxide [6.8 g
(0.2 mol) of H2O2], and 9.5 g (10% of overall
weight) of cation-exchanger KU-2 in the H-form. The
reaction was carried out at 30 C till complete con-
sumption of hydrogen peroxide (within 3 h), then
KU-2 was filtered off, and we obtained 89.7 g of
solution containing 58.8 g of acetic acid, 15.2 g of
peracetic acid, and 15.7 g of dioxane. The yield of
peracetic acid with respect to the charged hydrogen
peroxide was 99%. Concentration of peracetic acid in
the mixture was 17%.
Oxidation of bicyclo[2.2.1]hept-5-ene-2,3-endo-
and exo-dicarboxylic acid N-arylimides with per-
acetic acid. To a mixture of 0.01 mol of N-arylimide
I XIV and 15 ml of dioxane was added dropwise
10 ml of dioxane solution of peracetic acid maintain-
ing the temperature of the reaction mixture on 10 C
level. On complete consumption of peracetic acid
dioxane was distilled off from the reaction mixture,
and the remaining crystalline product was recrystal-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 2 2002

246
SALAKHOV, BAGMANOVA
Table 1. Yields, melting points, Rf values, elemental analyses, and molecular weight of epoxides (XV XXVIII)
mp,
(solvent for
crystallization)
C
Found, %
H
Calculated, %
M
Compd. Yield,
Rf
Formula
no.
%
C
N
C
H
N
found calc.
XV
XVI
XVII
XVIII
XIX
86
90
87
87
88
90
86
89
87
90
89
88
90
90
185 (ethanol)
168 (benzene)
175 (ethanol)
155 (benzene)
208 (benzene)
242 (ethanol)
220 (ethanol)
197 (ethanol)
161 (benzene)
175 (benzene)
158 (benzene)
202 (benzene)
235 (benzene)
241 (benzene)
0.59
0.61
0.60
0.54
0.82
0.78
0.78
0.58
0.60
0.62
0.58
0.87
0.71
0.67
75.01 4.87 5.29
67.17 5.16 4.80
67.16 5.30 5.00
66.81 5.19 5.02
63.62 4.17 4.62
64.60 3.75 4.52
64.13 4.33 4.20
74.82 4.97 5.39
67.17 5.16 4.80
67.07 5.28 5.00
67.40 5.25 4.38
64.10 4.02 4.66
63.88 4.02 4.33
63.92 3.89 4.06
C15H13NO3 74.90 4.87 5.49
C16H15NO4 67.37 5.26 4.91
C16H15NO4 67.37 5.26 4.91
C16H15NO4 67.37 5.26 4.91
C16H13NO5 64.21 4.34 4.68
C16H13NO5 64.21 4.34 4.68
C16H13NO5 64.21 4.34 4.68
C15H15NO3 74.90 5.09 5.49
C16H15NO4 67.37 5.26 4.91
C16H15NO4 67.37 5.26 4.91
C16H15NO4 67.37 5.26 4.91
C16H13NO5 64.21 4.34 4.68
C16H13NO5 64.21 4.34 4.68
C16H13NO5 64.21 4.34 4.68
253
284
287
285
293
296
294
254
287
286
285
296
293
292
255
286
286
286
295
295
295
255
286
286
286
295
295
295
XX
XXI
XXII
XXIII
XXIV
XXV
XXVI
XXVII
XXVIII
Table 2. Yields, melting points, Rf values, elemental analyses, and molecular weight of
trans-5,6-diacetoxybicyclo[2.2.1]heptane-2,3-dicarboxylic acid N-arylimides XXIX XLII
mp,
(solvent for
crystallization)
C
Found, %
H
Calculated, %
M
Compd. Yield,
Rf
Formula
no.
%
C
N
C
H
N
found calc.
XXIX
XXX
XXXI
72
78
80
85
81
72
73
70
69
175 (benzene) 0.66 63.02 4.92 4.00
163 (benzene) 0.65 62.01 5.29 3.60
160 (benzene) 0.61 62.06 5.59 4.00
133 (benzene) 0.60 61.85 5.27 3.98
186 (benzene) 0.77 59.02 4.81 3.12
195 (benzene) 0.71 59.66 4.68 3.65
187 (benzene) 0.74 59.66 4.65 3.12
176 (benzene) 0.73 63.29 4.98 3.42
164 (benzene) 0.77 61.75 5.33 3.47
141 (benzene) 0.67 61.90 4.99 3.59
164 (benzene) 0.71 62.00 5.60 3.17
C19H19NO6 63.86 5.32 3.90 356.0 357.0
C20H21NO7 62.02 5.69 3.62 385.5 387.0
C20H21NO7 62.02 5.69 3.62 388.0 387.0
C20H21NO7 62.02 5.69 3.62 386.6 387.0
C20H19NO8 59.99 4.79 3.49 400.2 401.0
C20H19NO8 59.99 4.79 3.49 400.8 401.0
C20H19NO8 59.99 4.79 3.49 401.2 401.0
C19H19NO6 63.86 5.32 3.90 355.8 357.0
C20H21NO7 62.02 5.69 3.62 387.5 387.0
C20H21NO7 62.02 5.69 3.62 385.7 387.0
C20H21NO7 62.02 5.69 3.62 386.0 387.0
C20H19NO8 59.99 4.79 3.49 400.4 401.0
C20H19NO8 59.99 4.79 3.49 400.6 401.0
C20H19NO8 59.99 4.79 3.49 400.8 401.0
XXXII
XXXIII
XXXIV
XXXV
XXXVI
XXXVII
XXXVIII 71
XXXIX
XL
70
72
73
70
172 (ethanol)
211 (ethanol)
201 (ethanol)
0.74 59.60 4.63 3.31
0.78 59.68 4.68 3.48
0.76 59.57 4.70 3.42
XLI
XLII
lized from benzene. The characteristics of epoxy-
imides obtained are given in Table 1.
wise within 1 h a mixture of 15 ml of 60% H2O2 and
15 ml of acetic acid. Due to heat evolution the reac-
tion mixture warmed to 50 60 C, and after finishing
the addition the reaction mixture was heated for 2 h
to 70 C. On cooling the mixture precipitated crystals
of compounds XXIX XLIII that were filtered off and
recrystallized from benzene. The characteristics of
the reaction products are presented in Table 2.
trans-5,6-Diacetoxy endo- and exo-bicyclo-
[2.2.1] heptane-2,3-dicarboxylic acid N-arylimides
(XXIX XLII). (a) To a solution of 0.01 mol of aryl-
imides I XIV in 10-fold excess of acetic acid with
2 3 ml of concn. sulfuric acid added thereto at room
temperature and vigorous stirring was added drop-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 2 2002

EPOXIDATION OF BICYCLO[2.2.1]HEPT-5-ENE-2,3-ENDO-...
(b) To a mixture of 0.01 mol of 5,6-exo-epoxy- REFERENCES
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bicyclo[2.2.1]heptane-2,3-dicarboxylic acid N-aryl-
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anhydride and 2 3 ml of concn.H2SO4 as catalyst.
The mixture was heated for 6 h, then the reaction
mixture was cooled, the precipitated crystalline
reaction product XXIX XLII was filtered off,
washed with distilled water, and recrystallized from
benzene.
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30ml of 10% H2SO4 was added 0.01 mol of endo-iso-
mer XXIX XXXVI or exo-isomer XXXVII XLII,
and the mixture was left standing for 2 h. Then the
mixture was heated to 35 C for 2 h, and on cooling
precipitated a crystalline substance that was filtered
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XXIX XXXVI was obtained lactone XLIII, and
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(b) A mixture of 0.01 mol of endo-isomer XXIX
XXXVI or exo-isomer XXXVII XLII and 30 ml of
10% aqueous alkali was boiled for 6 h at 120 140 C
and left for 12 h at room temperature. The separated
crystalline product was filtered off, washed with
distilled water, and recrystallized from ethanol or
benzene. Yield of compound XLIII 77%, of com-
pound XLIV 60%.
2-exo-Hydroxy-5-oxo-4-oxatricyclo[4.2.1.03,7]-
nonane-9-carboxylic acid (XLIII). mp 110 C. Rf
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C 50.00; H 4.44.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 2 2002