Spatial arrangement of norbornanedicarboxylic acids N-arylimides

Article abstract of DOI:10.1134/S1070428010110023

The effect of substituents on the spatial arrangement of norbornane compounds was investigated. Norbornanedicarboxylic acids N-arylimides with OCH₃, Cl, NO₂ groups in the ortho-position of the aromatic ring form as conformational iso

Full text of DOI:10.1134/S1070428010110023

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 11, pp. 1622−1628. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.S. Salakhov, B.T. Bagmanov, N.S. Nabiev, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 11, pp. 1618−1623.
Spatial Arrangement of Norbornanedicarboxylic Acids
N-Arylimides
M. S. Salakhova, B. T. Bagmanova, and N. S. Nabievb
aInstitute of Polymeric Materials, Azerbaijan National Academy of Sciences, Sumgait, 5004 Azerbaijan
e-mail: salahov_mustafa@mail.ru
bBaku State University, Baku, Azerbaijan
Received March 5, 2009
Abstract—The effect of substituents on the spatial arrangement of norbornane compounds was investigated.
Norbornanedicarboxylic acids N-arylimides with OCH3, Cl, NO2 groups in the ortho-position of the aromatic
ring form as conformational isomers with hindered rotation. The specific spatial isomerism is confirmed by the
quantum-chemical calculations.
DOI: 10.1134/S1070428010110023
The oxidation of bicyclo[2.2.2]oct-2-ene with per-
formic acid is known to afford bicyclo[2.2.2]-octane-
trans-2,3-diol, whereas the oxidation of bicyclo[2.2.1]-
hept-2-ene under the same conditions is accompanied
by Wagner–Meerwein rearrangement and 1,3-hydride
shift [1–3].
meta, or para-positions in the N-arylimide fragment only
stereoisomeric epoxy or dihydroxy derivatives formed,
and no lactonization and Wagner–Meerwein rearrange-
ment was observed [14, 15]. The strong electron-acceptor
imide moiety decreases the electron density of the π-bond
of norbornene and diminishes the ionization of the C–O
bond which is the first stage in the Wagner–Meerwein
rearrangement, and the low strain of the five-membered
imide ring and its chemical inertness prevents the lac-
tonization (Scheme 2).
The introduction into the norbornene ring of electron-
acceptor substituents act as a stabilizing factor fixing
the boat-like conformation of the cyclohexene fragment
and thus prevents the hydride shifts and rearrangements
[4, 5]. In the oxidation of norbornenes containing reac-
tive groups in the endo-position forms as a rule a new
lactone ring, whereas the presence of these groups in the
exo-position of the norbornene results in normal oxida-
tion products [6, 7]. This rule is conserved in the oxida-
tion of norbornene dicarboxylic acids, their anhydrides
I, II, and the nitrogen-containing derivatives with the
endo- and exo-configuration [8–10]. The epoxidation
of exo-compounds proceeds stereoselectively with the
formation of an oxirane ring of exo-configuration, a lac-
tone is formed from the corresponding endo-derivatives
[11–13] (Scheme 1).
The role of electronic and sterical effects and the
positions (ortho-, meta-, para-) of substituents in the
formation of the conformational structure of norbornane
N-arylimides remains unclear.
Our quantum-chemical calculations, spectral analysis,
and the consideration of model structures of N-arylimides
III–LXVI of bicyclo[2.2.1]hept-5-ene-endo- and -exo-
2,3-dicarboxylic acid showed that when in the ortho-
position of the aromatic ring were located OCH3, Cl,
NO2 groups the large bulk of the substituents hampered
the free rotation, and as a result a stable conformational
isomer of N-arylimide formed where the benzene ring at
the nitrogen atom was perpendicular to the plane of the
five-membered heterocycle, and the N–C bond suffered
elongation compared to its average length [16].
Our investigation of the oxidation of norbornenedicar-
boxylic acids N-arylimides showed that independent of
the endo- or exo-configuration of the imide ring and also
of the electronic nature of the substituents in the ortho-,
This fact is confirmed by the presence of two
1622

SPATIAL ARRANGEMENT OF NORBORNANEDICARBOXYLIC ACIDS
1623
Scheme 1.
HO
COOH
O
CO
C
H
3
H
3
+
H
H
+
2 O
O
,
H
C
H
2
+
,
H
O
3
O
C
3
,
O
2
H
H
O
2
,
H
H
C
+
H
H2O, H+
CH3CO3H
dioxane
O
CH3CO3H
dioxane
O
CO
СO
COOH
COOH
COOH
COOH
OC
O
OC
O
I
Δ
decaline
O
O
O
H2O, H+
CH3CO3H
CH3CO3H
dioxane
COOH
COOH
C
C
O
COOH
COOH
O
O
dioxane
C
C
O
O
II
H
2
+
H2O, H+ CH3CO3H H2O, H+
O
H
CH3CO3H
,
,
H
+
O
H 2
HO
HO
COOH
COOH
1
unequal signals from the OCH3 group in the H NMR
spectra of compounds VIIa, VIIb, XXIIIa, XXIIIb,
XXXIXa, XXXIXb etc. For instance, the protons
of methoxy groups in the spectra of N-arylimides of
5,6-dihydroxybicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic
acid XXXIXa, XXXIXb give rise to a double singlet at
3.75 and 3.80 ppm indicating the different poitions of the
methoxy group in the ring. Double signals from OCH3
group are lacking in the spectra of the corresponding
meta- and para-isomers VIII, IX, XXIV, XXV, XL,
XLI, LVI, LVII; in the 1H NMR spectra of N-arylimides
IV–VI, XX–XXII, XXXVI–XXXVIII, LII–LIV no two
signals from the methyl groups are observed even in the
ortho-isomers.
C=O group, whereas in the interconvertible conforma-
tions C and D the methoxy group protons are partially
screened by the carbonyl groups of the imide ring, and
therefore the more intense signal corresponding to forms
C and D is slightly shifted upfield (δ 3.80 ppm).
In keeping with the integral intensity of the signals
the ratio of syn-form B to anti-forms C and D equals 25
to 75%, but the separation of stereoisomers XXXIXa,
XXXIXb is materially impossible. (Scheme 3)
The experimental and calculation data show that the
radius of the OCH3 group (0.145 nm) is insufficient for the
complete overlapping with the ortho-substituent therefore
compounds VIIa, VIIb, XXIIIa, XXIIIb, XXXIXa,
XXXIXb, LVa, LVb are conformationally labile.
The consideration of the models of possible isomeric
forms of the molecule shows that in the syn-isomer due
to the steric interaction exists prevailingly only B con-
formation, whereas the anti-isomer can exist in both C
and D conformations.
In order to confirm the experimentally found fact of the
conformational isomerism we attempted to find a relation
between the structure and quantum-chemical descrip-
tion of N-arylimides of bicycloheptene-endo- and exo-
dicarboxylic acids containing in the aryl ring substituents
of various electronic and steric character III–XVIII. The
analysis of the results of the quantum-chemical calcula-
tions shows that although the other parameters also vary
consistently, in this case the most appropriate parameter
1
In the H NMR spectra of compounds XXXIXa,
XXXIXb the less strong singlet of the methoxy group (δ
3.75 ppm) corresponds to form B where the OCH3 group
is relatively distant from the magnetically anisotropic
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

SALAKHOV et al.
1624
Scheme 2.
R
O
CO
N
H
2 O
,
+
H
CO
XIXa_XXXIVa
HO
HO
R
HO
HO
R
H
3
CO
CO
O
N
N
C
3
CO
LIa_LXVIa
CO
XXXVa_La
K
M
H
n
H
C
O
O3
O
C
,
4
R
H
H+
H3
C
2 O
,
CO
H2
CH2
N
O
C
H 2
H
CO
,
3 C
O 4
O
n
H
IIIa_XVIIIa (endo)
IIIb_XVIIIb (exo)
3 H
M
2 O
,
K
H
+
R
R
HO
HO
HO
HO
O
O
C
C
H
3
N
N
O
C
O
3
O
C
C
H
XXXVb_Lb
R
LIb_LXVIb
H+
C
,
O
H2
O
C
O
N
O
C
XIXb_XXXVIb
R = H (III, XIX, XXXV, LI), o-CH3 (IV, XX, XXVI, LII), m-CH3 (V, XXI, XXXVII, LIII), p-CH3 (VI, XXII, XXXVIII,
LIV), o-OCH3 (VII, XXIII, XXXIX, LV), m-OCH3 (VIII, XXIV, XL, LVI), p-OCH3 (IX, XXV, XLI, LVII), o-Cl (X,
XXVI, XLII, LVIII), m-Cl (XI, XXVII, XLIII, LIX), p-Cl (XII, XXVIII, XLIV, LX), o-PO2 (XIII, XXIX, XLV, LXI),
m-PO2 (XIV, XXX, XLVI, LXII), p-PO2 (XV, XXXI, XLVII, LXIII), o-COOH (XVI, XXXII, XLVIII, LXIV), m-COOH
(XVII, XXXIII, XLIX, LXV), p-COOH (XVIII, XXXIV, L, LXVI).
Scheme 3.
HO
HO
HO
HO
HO
HO
HO
HO
C O
O
O
O
C
N
C
N
O
C
N
O
C
O
C
H
C
O
C
N
H
H
H
C
H
C H
C
H
C
H
O
H
H
O
O
O
H
H
B
A
D
C
anti-forms
syn-forms
for establishing the relation between the structure and
property is the heat of formation (Qform). The conforma-
tional isomers are stable at room temperature when the
value of the free activation enthalpy ΔG* is no less than
65–85 kJ mol–1 [17].
The heat of formation is known [18] to include the sum
of energy of all chemical bonds and separate structural
fragments of the molecule. Therefore it is expectable
that the changes in the composition and structure would
affect the Qform values. This conclusion is confirmed
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

SPATIAL ARRANGEMENT OF NORBORNANEDICARBOXYLIC ACIDS
1625
by the calculations. Qform of anhydrides I,II (60.61 and
ent, and the latter prevails.
EXPERIMENTAL
61.91 kcal mol–1) is lower than Qform of endo- and exo-
N-phenylimides IIIa, IIIb (72.72 and 73.39 kcal mol–1,
respectively). In going to N-arylimides containing
electron-donor and electron-acceptor substituents Qform
regularly changes: in the N-arylimides with the electron-
donor substituents in the benzene ring (IVa, IVb, VIIa,
VIIb, Xa, Xb) it decreases, and in the N-arylimides
with the electron-acceptor substituents (XIIIa, XIIIb) it
increases. The value Qform of the ortho-isomers as a rule
is twice as large as that of meta- and para-isomers of the
same molecules notwithstanding the electronic character
of the substituent. The reason of this large difference
between the isomeric N-arylimides is the large barrier to
the rotation around the N–C bond in the ortho-isomers
arising from the steric effect and increased or decreased
by additional factors.
NMR spectra were registered on a spectrometer Tesla
BS-487 at operating frequency 80 MHz in CDCl3, inter-
nal reference HMDS [19]. IR spectra were recorded on
a spectrophotometer UR-20 in the region 400–3800 cm–1
from mulls in mineral oil. UV spectra were measured on
a spectrophotometer Specord M-40 [20].
The purity of compounds was checked by TLC, sor-
bent silica L 5/40μ, development under UV irradiation
[21].
Quantum-chemical calculations were performed along
Schroedinger equation, for multielectron systems with the
use of the method of Hartree–Fock–Roothaan [22, 23].
Multicenter integrals were calculated using semiempirical
methods of Pariser–Parr–Pople [24]. In the calculations
the information was used on the system under consid-
eration (serial number of the atom, its position in the
Periodic Table, bond lengths, bond and dihedral angles)
and on the basis.
The results of the quantum-chemical calculations per-
mit a conclusion that in all ortho-substituted endo- and
exo-isomers of N-arylimide IVa, IVb, VIIa, VIIb, Xa,
Xb, XIIIa, XIIIb the hindered rotation exists; however if
in N-o-methoxyphenylimides VIIa, VIIb a fast racemi-
zation occurs (Qform 89.54 and 88.78 kcal mol–1 respec-
tively), the data for o-chlorophenylimides Xa, Xb (Qform
137.95 and 137.48 kcal mol–1) and for o-nitrophenyl-
imides XIIIa, XIIIb (Qform 148.86 and 150.49 kcal mol–1)
allow a statement that in these events arise stable spatial
conformers. The consideration of the models of the struc-
ture of norbornenedicarboxylic acids N-arylimides shows
that besides the dimensions of these groups a significant
role in the formation of the spatial arrangement plays
the unshared electron pair which increases the stability
of the spatial isomer through the conjugation. (Complete
data of quantum-chemical calculations of anhydrides and
N-arylimides of bicyclo[2.2.1]hept-5-ene- endo- and
exo-2,3-dicarboxylic acid are available from the authors
by e-mail: salahov_mustafa@mail.ru).
N-Arylimides of bicyclo[2.2.1]hept-5-ene-endo- and
-exo-2,3-dicarboxylic acids IIIa, IIIb–XVIIIa, XVIIIb
were obtained as described in [15].
N-Arylimides of 5,6-exo-epoxybicyclo[2.2.1]-
heptane-endo- and -exo-2,3-dicarboxylic acid XIXa,
XIXb–XXXIVa, XXXIVb. In 15 ml of dioxane was
dissolved 0.01 mol of N-arylimide IIIa, IIIb–XVIIIa,
XVIIIb, and at 8–10°C 10 ml of peracetic acid solution in
anhydrous dioxane was added at constant cooling (10°C).
After complete consumtion of peracetic acid (3.5–4 h)
the acetic acid was distilled off in a vacuum of a water-
jet pump, and the reaction product was crystallized from
anhydrous benzene.
N-Phenylimide XIXa. Yield 80%, mp 185–187°C
(from ethanol), Rf 0.59. Found, %: C 75.01; H 5.00;
N 4.79; C15H13NO3. Calculated, %: C 74.90; H 5.09;
N 5.49.
It is possible to conclude from the theoretical con-
siderations that in formation of one of individual syn- or
anti-isomers the governing importance belongs to the
intermediate complex of one or another configuration. In
the first stage in the forming amidoacid the nitrogen atom
has a pyramidal configuration, and the hydrogen atom
of NH group is involved in an intramolecular hydrogen
bond with the oxygen atom of the carbonyl group. This
arrangement determines the configuration of the obtained
intermediate product. The second stage of the reaction
consists in water elimination and in the formation of flat
imide ring with the syn- or anti-orientation of the substitu-
N-(o-Methoxyphenyl)imide XXIIIa. Yield 87%,
mp 160°C (from ethanol), Rf 0.60. Found, %: C 67.17;
H 5.16; N 4.80; C16H15NO4. Calculated, %: C 67.37;
H 5.26; N 4.91.
N-(m-Methoxyphenyl)imide XXIVa. Yield 90%,
mp 154°C (from ethanol), Rf 0.60. Found, %: C 67.07;
H 5.30; N 5.19. C16H15NO4. Calculated, %: C 67.37;
H 5.26; N 4.91.
N-(p-Methoxyphenyl)imide XXVa. Yield 87%,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

SALAKHOV et al.
1626
mp 164–165°C (from ethanol), Rf 0.54. Found, %:
C 66.81; H 5.19; N 5.10. C16H15NO4. Calculated, %:
C 67.37; H 5.26; N 4.91.
spectrum, δ, ppm: 1.10 m (H7an), 1.65 m (H7s), 2.10 s
(H1,4), 3.15 br.m (H2,3), 3.32 br.m (H5,6), 3.36 s (OH),
7.10–7.70 m (MeOC6H4), 3.75–3.80 s (3H, MeO). Found,
%: C 64.22; H 5.91; N 4.83. C16H17NO5. Calculated, %:
C 63.66; H 5.61; N 4.60.
N-(o-Chlorophenyl)imide XXVIa. Yield 90%,
mp 190–192°C (from ethanol), Rf 0.56. Found, %:
C 62.43; H 4.10; Cl 12.53; N 4.67. C15H12ClNO3. Cal-
culated, %: C 62.18; H 4.14; Cl 12.26; N 4.48.
N-(m-Methoxyphenyl)imide XLa. Yield 85%,
mp 163–164°C (from ethanol), Rf 0.72. 1H NMR
spectrum, δ, ppm: 1.12 m (H7an), 1.73 m (H7s), 2.00 s
(H1,4), 3.13 br.m (H2,3), 3.27 br.m (H5,6), 3.30 s (OH),
7.00–7.50 m (MeOC6H4), 3.70–3.77 s (3H, MeO). Found,
%: C 64.22; H 5.91; N 4.83. C16H17NO5. Calculated, %:
C 63.66; H 5.61; N 4.60.
N-(m-Chlorophenyl)imide XXVIIa. Yield 91%,
mp 174–175°C (from ethanol), Rf 0.66. Found, %:
C 62.12; H 3.76; Cl 12.12; N 4.19. C15H12ClNO3. Cal-
culated, %: C 62.18; H 4.14; Cl 12.26; N 4.48.
N-(p-Chlorophenyl)imide XXVIIIa. Yield 89%,
mp 190–191°C (from ethanol), Rf 0.69. Found, %:
C 61.12; H 4.11; Cl 12.30; N 4.89. C15H12ClNO3. Cal-
culated, %: C 62.18; H 4.14; Cl 12.26; N 4.48.
N-(p-Methoxyphenyl)imide XLIa. Yield 91%,
mp 184–185°C (from ethanol), Rf 0.60. 1H NMR
spectrum, δ, ppm: 1.10 m (H7an), 1.70 m (H7s), 2.05 s
(H1,4), 3.15 br.m (H2,3), 3.25 br.m (H5,6), 3.34 s (OH),
7.10–7.55 m (MeOC6H4), 3.85 s (3H, MeO). Found, %:
C 64.22; H 5.91; N 4.83. C16H17NO5. Calculated, %:
C 63.66; H 5.61; N 4.60.
N-(o-Carboxyphenyl)imide XXXIIa. Yield 87%,
mp 207–208°C (from ethanol), Rf 0.82. Found, %:
C 63.62; H 4.17; N 5.02. C16H13NO5. Calculated, %:
C 64.21; H 4.34; N 4.68.
N-(o-Chlorophenyl)imide XLIIa. Yield 93%,
mp 201–202°C (from ethanol), Rf 0.75. Found, %:
C 59.01; H 4.61; Cl 12.01; N 4.72. C15H14Cl NO4. Cal-
culated, %: C 58.53; H 4.55; Cl 11.54; N 4.55.
N-(m-Carboxyphenyl)imide XXXIIIa. Yield 90%,
mp 241–242°C (from ethanol), Rf 0.78. Found, %:
C 64.60; H 3.75; N 4.79. C16H13NO5. Calculated, %:
C 64.21; H 4.34; N 4.68.
N-(m-Chlorophenyl)imide XLIIIa. Yield 95%,
mp 227–228°C (from ethanol), Rf 0.76. Found, %:
C 59.42; H 4.47; Cl 11.17; N 4.92. C15H14ClNO4. Cal-
culated, %: C 58.53; H 4.55; Cl 11.54; N 4.55.
N-(p-Carboxyphenyl)imide XXXIVa. Yield 86%, mp
219–220°C (from ethanol), Rf 0.80. Found, %: C 64.13;
H 4.33; N 4.19. C16H13NO5. Calculated, %: C 64.21;
H 4.34; N 4.68.
N-(p-Chlorophenyl)imide XLIVa. Yield 90%,
mp 202–203°C (from ethanol), Rf 0.70. Found, %:
C 59.13; H 5.11; Cl 12.03; N 4.52. C15H14ClNO4. Cal-
culated, %: C 58.53; H 4.55; Cl 11.54; N 4.55.
N-Arylimides of trans-5,6-dihydroxybicyclo-[2.2.1]
heptane-endo- and -exo-2,3-dicarboxylic acid (XXX-
Va, XXXVb–La, Lb. a. In 30 ml of acetic acid was
dissolved 0.01 mol of N-arylimide IIIa, IIIb–XVIIIa,
XVIIIb, 1–2 drops of concn. H2SO4 was added, and at
constant stirring a mixture of 10 ml of 30% H2O2 in
10 ml of acetic acid was added to the above solution.
The mixture was heated for 2 h at 70°C. Then the reaction
mixture was diluted with 15 ml of water, and the heating
was continued for 1 h. On completion of the reaction the
separated crystals were filtered off, washed with water,
and recrystallized from ethanol.
N-(o-Carboxyphenyl)amandд XLVIIIa. Yield 83%,
mp 225–226°C (from ethanol), Rf 0.86. Found, %:
C 60.47; H 4.57; N 4.77. C16H15NO6. Calculated, %:
C 60.56; H 4.73; N 4.41.
N-(m-Carboxyphenyl)imide XLIXa. Yield 91%,
mp 285–287°C (from ethanol), Rf 0.83. Found, %:
C 60.60; H 5.19; N 4.76. C16H15NO6. Calculated, %:
C 60.56; H 4.73; N 4.41.
N-Phenylimide (XXXVa). Yield 91%, mp 199–
200°C (from ethanol), Rf 0.69. 1H NMR spectrum, δ,
ppm: 1.15 m (H7an), 1.75 m (H7s), 1.95 s (H1,4), 3.15 br.m
(H2,3), 3.30 br.m (H5,6), 3.35 s (OH), 7.30–7.60 m (Harom).
Found, %: C 66.31; H 5.05; N 6.05; C15H15NO4. Calcu-
lated, %: C 66.42; H 4.79; N 5.17.
N-(p-Carboxyphenyl)imide La. Yield 94%, mp 260–
261°C (from ethanol), Rf 0.81. Found, %: C 60.79;
H 4.82; N 4.53. C16H15NO6. Calculated, %: C 60.56;
H 4.73; N 4.41.
b. In 30 ml of 5 H2SO4 % 0.01 mol of N-arylimides
of 5,6-exo-epoxybicyclo-[2.2.1]heptane-endo- (XIXa–
XXXIVa) or -exo-(XIXb–XXXIVb)-2,3-dicarboxylic
acids was heated for 4 h at 60°C. The reaction product was
N-(o-Methoxyphenyl)imide XXXIXa. Yield 83%,
mp 169–170°C (from ethanol), Rf 0.79. 1H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

SPATIAL ARRANGEMENT OF NORBORNANEDICARBOXYLIC ACIDS
1627
filtered off, washed with dilstilled water, and dried. Yield
of trans-imidodiols XXXVa, XXXVb–La, Lb 78–90%.
H 4.29; N 4.27. C16H15NO6. Calculated, %: C 60.56;
H 4.73; N 4.41.
N-Arylimides of exo-cis-5,6-dihydroxybicyc-
lo-[2.2.1]heptane-endo-2,3-dicarboxylic acid (LIa–
LXVIa). To a solution of 0.01 mol of N-arylimide
IIIa–XVIIIa in 100 ml of acetone at room temperature
while vigorous stirring was added dropwise a solution of
1.6 g of potassium permanganate in 250 ml of distilled
water. After the complete consumption of the potassium
permanganate (disappearance of pink color) a dark brown
precipitate separated that after treatment with dilute hy-
drochloric acid turned colorless. The reaction mixture
was left standing for 12 h. The separated crystals were
filtered off and recrystallized from methanol.
N-(p-Carboxyphenyl)imide LXVIa. Yield 61%,
mp 265°C (from ethanol), Rf 0.80. Found, %: C 60.10;
H 4.24; N 4.18. C16H15NO6. Calculated, %: C 60.56;
H 4.73; N 4.41.
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N-Phenylimide LIa. Yield 70%, mp 207°C (from
ethanol), Rf 0.71. Found, %: C 66.0; H 5.42; N 5.07.
C15H15NO4. Calculated, %: C 65.93; H 5.49; N 5.13.
N-(o-Methoxyphenyl)imide LVa. Yield 60%,
mp 239°C (from ethanol), Rf 0.73. Found, %: C 63.14;
H 5.25; N 4.21. C16H17NO5. Calculated, %: C 63.37;
H 5.61; N 4.62.
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N-(m-Methoxyphenyl)imide LVIa. Yield 68%,
mp 252°C (from ethanol), Rf 0.70. Found, %: C 63.50;
H 5.37; N 4.12. C16H17NO5. Calculated, %: C 63.37;
H 5.61; N 4.62.
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N-(p-Methoxyphenyl)imide LVIIa. Yield 63%,
mp 255°C (from ethanol), Rf 0.68. Found, %: C 63.16;
H 5.39; N 4.20. C16H17NO5. Calculated, %: C 63.37;
H 5.61; N 4.62.
N-(o-Chlorophenyl)imide LVIIIa. Yield 75%,
mp 196°C (from ethanol), Rf 0.75. Found, %: C 58.40;
H 4.25; Cl 11.14; N 4.31. C15H14ClNO4. Calculated, %:
C 58.53; H 4.55; Cl 11.54; N 4.55.
N-(m-Chlorophenyl)imide LIXa. Yield 75%,
mp 237°C (from ethanol), Rf 0.71. Found, %: C 58.13;
H 4.09; Cl 11.06; N 4.15. C15H14ClNO4. Calculated, %:
C 58.53; H 4.55; Cl 11.54; N 4.55.
N-(p-Chlorophenyl)imide LXa. Yield 73%,
mp 218°C (from ethanol), Rf 0.74. Found, %: C 58.11;
H 4.15; Cl 11.12; N 4.18. C15H14ClNO4. Calculated, %:
C 58.53; H 4.55; Cl 11.54; N 4.55.
N-(o-Carboxyphenyl)imide LXIVa. Yield 61%,
mp 236°C (from ethanol), Rf 0.68. Found, %: C 60.12;
H 4.51; N 4.37. C16H15NO6. Calculated, %: C 60.56;
H 4.73; N 4.41.
N-(m-Carboxyphenyl)imide LXVa. Yield 61%, mp
255°C (from ethanol), Rf 0.70. Found, %: C 68.18;
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