OXIDATION OF AROMATIC COMPOUNDS: XI.
861
EXPERIMENTAL
Coordinates of nonhydrogen atoms and factors of
equivalent isotropic displacement for compound (E-II)
1H and 13C NMR spectra (the latter with and
without decoupling from protons) were registered on
spectrometer Bruker AM-500 at operating frequencies
00 and 125.76 MHz respectively from solutions in
CDCl . As internal references were used the signals
of solvent ( of residual protons at 7.25 and
7.0 ppm). Mass spectra were measured on MKh-
321 instrument. IR spectra were recorded on
spectrophotometer Specord 75 IR from solutions in
CHCl3.
Atom
x
y
z
B
eq
1
5
C
0.6724(8) 0.170(2)
0.6253(7) 0.020(2)
0.6807(8) 0.190(2)
0.7837(7) 0.249(2)
0.8315(7) 0.102(2)
0.7787(7) 0.109(2)
0.4635(8) 0.279(2)
0.9403(8) 0.175(2)
1.0071(8) 0.008(2)
1.0989(7) 0.141(2)
1.1626(8) 0.268(2)
0.5232(5) 0.0606(13)
0.5758(6)
0.6250(6)
0.6623(7)
0.6483(6)
0.5983(6)
0.5642(6)
0.6121(8)
0.5858(6)
0.5455(6)
0.6202(6)
0.7815(6)
0.6410(4)
3.7(2)
3.1(2)
3.5(2)
3.1(2)
2.8(2)
3.2(2)
4.9(3)
3.2(2)
3.5(2)
3.5(2)
4.8(3)
4.5(2)
4.7(2)
4.3(2)
4.5(2)
2
3
4
5
6
7
8
9
1
1
1
C
C
C
C
C
C
C
C
C
C
3
at
C
7
1
Methyl 3-(4-methoxyphenyl)propynoate (I) was
obtained by methylation with dimethyl sulfate of
-(4-methoxyphenyl)propynoic acid along procedures
3, 12]. Yield 70%, mp 44 46 C (from hexane)
0
1
3
[
(
(
O
O
O
O
1
2
3
4
publ.: 45 47 C [3]). IR spectrum, , cm : 1710
0.9869(6) 0.3585(13) 0.6137(5)
1.0828(5) 0.1333(11)
1.1751(5) 0.2471(13)
1
C=O), 2220 (C C). H NMR spectrum, , ppm:
0.7026(4)
0.6056(4)
3
.80 s (3H, OCH ), 3.81 s (3H, OCH ), 6.86 d
3 3
(
8
2H arom, J 8.7 Hz), 7.51 d (2H arom, J
.7 Hz). 13C NMR spectrum, , ppm: 52.7 q (CH3
from COOCH , J 148 Hz), 55.4 q (OCH , J 144 Hz),
COOCH , J 4.2 Hz), 164.3 m (C arom, para-),
3
3
3
1
89.6 t [C=O (ketone), J 4.2 Hz]. Mass spectrum,
7
9.8 s (Csp
[
q C=O]), 87.4 t (C [ q C=O],
sp
+
+
m/z (I , %): 412 (12) M , 381 (5) [M OCH ] ,
J 5.1 Hz), 111.3 t [C arom, ipso- (ipso- q C C)],
J 8.3 Hz), 114.4 d.d (C arom, meta-, J 162, 4.8 Hz),
rel
3
+
3
1
9
53 (6) [M COOCH ] , 289 (4), 261 (3), 159 (4),
35 (100) [CH OC H CO] , 107 (15) [CH OC H ] ,
3
+
+
1
35.0 d.d (C arom, ortho-, J 163, 7.0 Hz), 154.8 m
3
6
4
3
6
4
2 (20). Found, %: C 63.84; H 5.02. C H O . Cal-
(
C arom, para-), 161.6 q (C=O, J 5.0 Hz).
22 20
8
culated, %: C 64.07; H 4.89. M 412.39.
Preparation procedure for dimethyl 2,3-bis-(4-
methoxyphenylcarbonyl)but-2-ene-1,4-dicarboxy-
late (E-II). In a cooled to 0 2 C mixture of 4 ml of
X-ray diffraction study of compound (E-II).
Parameters of unit cell and reflections intensities were
measured on an automatic four-circle diffractometer
Syntex P21 (( MoK , graphite monochromator,
CH Cl and 0.76 ml (10 mmol) of CF COOH was
2
2
3
dissolved at stirring 0.4 g (2.1 mmol) of ester I. To
this solution was added 0.5 g (2.1 mmol) of PbO2,
and the dispersion obtained was stirred at 0 2 C for
-
scanning). The structure of compound under study
was solved by the direct method and refined by
full-matrix least-squares method in anisotropic
approximation for nonhydrogen atoms. The hydrogen
atoms positions were determined geometrically and
were refined in isotropic approximation. All calcula-
tions were carried out on IBM PC/AT along CSD
software [9]. The crystals of compound (E-II) fit for
X-ray study were obtained by slow evaporation of
acetone solution within several days at room tempera-
ture. The main crystallographic data are as follows:
C H O (crystallographically independent is a half
2
2
h. Then the reaction mixture was poured into
00 ml of CHCl . The chloroform solution was
3
washed with water (2 30 ml), with saturated water
solution of NaHCO (2 30 ml), with water (3
3
3
0 ml), dried with sodium sulfate, and the solvent
was distilled off. The solid residue was first washed
on glass frit filter with ethyl ether (2 1 ml), and then
recrystallized from 1 ml of acetone. Yield of product
II 0.22 g (55%), mp 175 177 C. IR spectrum,
,
2
2
20
8
1
cm : 1715 (C=O from COOCH ), 1670 (C=O).
3
of the molecule), M 412.39; at 25 C a 12.198(5), b
1
3
H NMR spectrum, , ppm: 3.56 s (6H, 2COOCH3),
5.838(4), c 14.944(6)
,
111.75(3) , V 988(2)
,
3
3
7
.88 s (6H, 2OCH ), 6.98 d (4H arom, J 8.8 Hz),
.95 d (4H arom, J 8.8 Hz). C NMR spectrum, ,
d 1.386(2) g cm , Z 4 (for the crystallographically
3
C
1
3
independent fragment), space group P21/n. In total
ppm: 53.2 q (CH from COOCH , J 148 Hz), 55.6 q
1119 reflections were measured (at
30 ). The
3
3
max
(
OCH , J 145 Hz), 114.2 d.d (C arom, meta-,
final divergence factor RF 0.0456 for 1083
independent reflections with F(hkl) > 4.0sig(F). The
(E-II) molecule is shown on the figure, the atomic
coordinates are given in the table.
3
J 162, 4.6 Hz), 128.7 t [C arom, ipso- (ipso- q
C=O), J 7.2 Hz], 131.2 d.d (C arom, ortho-, J 161,
7
.0 Hz), 142.0 s (C=C), 163.1 q (C=O from
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003