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Roshchin et al.
K2CO3 (55.2 g, 0.4 mol), PdCl2(MeCN)2 (0.26 g, 1 mmol,
0.5 mol.%), Ph3P (0.52 g, 2 mmol, 1 mol.%), DMF (200 mL),
and water (150 mL) was gently refluxed with stirring for 12 h
under argon, during which the yellow solution with little preꢀ
cipitate was formed. The reaction mixture was concentrated
in vacuo, the solid residue was washed with EtOAc, dissolved in
minimum water, and acidified with HCl to the pH value of 1.
The precipitate of (2ꢀmethoxyphenyl)maleic acid that liberated
was filtered off, washed with a small amount of water, and dried
in the open air. The crude acid was placed into a sublimation
apparatus and slowly heated up to 300—350 °C in vacuo (2 Torr).
Anhydride 4a was condensed as yellow crystals, the yield was
23.8 g (58%), m.p. 134—136 °C (toluene—hexane) (cf. Ref. 10:
m.p. 135—136 °C).
(CDCl3), δ: 23.59, 28.89 (CH2); 47.16 (OC—CH—Ar); 50.67
(OC—C—Ar); 55.36 (OMe); 111.51, 121.11, 126.35, 126.95,
127.55, 128.05, 129.64 (CAr, =CH); 156.21 (CAr—OMe); 174.20,
175.91 (C=O).
(1R*,2S*)ꢀ1ꢀ(4ꢀMethoxyphenyl)cyclohexꢀ4ꢀeneꢀ1,2ꢀdicarbꢀ
oxylic acid anhydride (6b). Yellow oil was obtained under condiꢀ
tions of experiment 11 (see Table 1) after evaporation of the
solvent, which contained ~90% of the main product (1H NMR
data). The prolong storage in the open air transforms the oilꢀlike
anhydride into the corresponding acid, causing its solidificaꢀ
tion. MS (electrospray, MeCN—HCO2H (0.5%), 2.6 kV,
1.5 µL min–1), found: m/z 277.10718, [M + H2O + H]+,
C
15H17O5; 259.09641 [M + H]+, C15H15O4. Calculated:
[M + H2O + H]+, 277.10705 Da; [M + H]+ 259.09649 Da.
(1R*,2S*,3R*,4S*)ꢀ2ꢀ(2ꢀMethoxyphenyl)bicyclo[2.2.1]ꢀ
heptꢀ5ꢀeneꢀ2,3ꢀdicarboxylic acid imide (7). A mixture of anꢀ
hydride 5a (0.20 g, 0.74 mmol), NH4OAc (0.07 g, 0.91 mmol),
and THF (0.8 mL) was kept under pressure of 10 kbar and
145 °C for 5 h. The solvent was evaporated, the residue was
recrystallized from AcOH—H2O. The yield was 0.18 g (90%),
m.p. 237 °C (EtOAc—PriOH).
(4ꢀMethoxyphenyl)maleic anhydride (4b) was obtained simiꢀ
larly from 4ꢀiodoanisole, the duration of heating was 4 h, the
yield was 79%. Yellow crystals, m.p. 145 °C (from toluene; with
partial subl.) (cf. Refs 5 and 10: m.p. 142—143.5 °C).
Investigation of reactions of arylmaleic anhydrides 4a,b with
cyclopentadiene and sulfolene under high pressure. A solution of
anhydride 4a or 4b (0.12 g, 0.6 mmol) and cyclopentadiene
(0.06 mL, 0.72 mmol) or sulfolene (0.08 g, 0.68 mmol) in THF
or CH2Cl2 (0.8 mL) was kept under listed in Table 1 conditions.
The presence of the unreacted anhydride was controlled by TLC
(Silufol, acetone—hexane (1 : 3)). The workꢀup methods of the
reaction mixtures are given below while describing syntheses of
adducts 5a,b and 6a,b, their yields are summarized in Table 1.
(1R*,2S*,3R*,4S*)ꢀ2ꢀ(2ꢀMethoxyphenyl)bicyclo[2.2.1]ꢀ
heptꢀ5ꢀeneꢀ2,3ꢀdicarboxylic acid anhydride (5a). A solution of
anhydride 4a (0.45 g, 2.2 mmol) and freshly distilled cycloꢀ
pentadiene (0.22 mL, 2.67 mmol) in anhydrous THF (3.5 mL)
was kept under pressure of 6.5 kbar and 18 °C for 72 h. The
solvent was evaporated and Et2O (2 mL) was added to the resiꢀ
due. The formed colorless crystals of the adduct were washed
with Et2O—hexane mixture and dried in vacuo. The yield was
0.50 g (84% calculated from anhydride 4a); concentrating the
mother liquor gave additional crop of the product 5a (0.03 g, 5%),
m.p. 133—135 °C (Et2O).
(1R*,2S*)ꢀ1ꢀ(2ꢀMethoxyphenyl)cyclohexꢀ4ꢀeneꢀ1,2ꢀdicarbꢀ
oxylic acid imide (8) was obtained similarly from anhydride 6a in
68% yield, m.p. 203.5—204.5 °C (AcOH—H2O (or EtOAc)).
References
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(1R*,2S*,3R*,4S*)ꢀ2ꢀ(4ꢀMethoxyphenyl)bicyclo[2.2.1]ꢀ
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tained in experiments 9 and 10 (see Table 1) after evaporating
the solvent, which contained 80% of the main product (1H NMR
data). The only considerable impurity (15%) is characterized by
1H NMR signals at δ: 6.03, 6.31 (both dd, =CH—, J = 5.6 Hz,
J = 3.3 Hz), 6.88, 7.25 (both d, J = 9.2 Hz, Ar), which enables
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zene—hexane).
(1R*,2S*)ꢀ1ꢀ(2ꢀMethoxyphenyl)cyclohexꢀ4ꢀeneꢀ1,2ꢀdicarbꢀ
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5.0 mmol) and 3ꢀsulfolene (0.68 g, 5.75 mmol) in CH2Cl2 (3 mL)
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solvent was evaporated and Et2O (3 mL) was added to the resiꢀ
due. The formed colorless crystals of the adduct were washed
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1.11 g (86% calculated from anhydride 4a), m.p. 122—124 °C
(crude), m.p. 124.5—125.5 °C (benzene—hexane). 13C NMR
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(Engl. Transl.)].
Received January 25, 2006;
in revised form March 1, 2007