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Russ.Chem.Bull., Int.Ed., Vol. 55, No. 1, January, 2006
Chudinov et al.
Table 1. Constants and yields of compounds 2 and 3
thylꢀ2ꢀphenylpropyl)ꢀ1,3ꢀ (5c), 3ꢀbenzylꢀ4ꢀhydroxyꢀ1,3ꢀdꢀ
imethylꢀ5ꢀ(2ꢀmethylꢀ2ꢀphenylpropyl)ꢀ1,3ꢀ (5d), 4ꢀhydroxyꢀ4,5ꢀ
dimethylꢀ5ꢀ(2ꢀmethylꢀ2ꢀphenylpropyl)ꢀ3ꢀphenethylꢀ1,3ꢀ (5e),
and 3ꢀ[2ꢀ(3,4ꢀdimethoxyphenyl)ethyl]ꢀ4ꢀhydroxyꢀ4,5ꢀdimeꢀ
thylꢀ5ꢀ(2ꢀmethylꢀ2ꢀphenylpropyl)ꢀ1,3ꢀoxazolidinꢀ2ꢀones (5f),
1,2ꢀbis[4ꢀhydroxyꢀ4,5ꢀdimethylꢀ5ꢀ(2ꢀmethylꢀ2ꢀphenylpropyl)ꢀ
2ꢀoxoꢀ1,3ꢀoxazolidinꢀ3ꢀyl]ethane (5g), sodium [4ꢀhydroxyꢀ4,5ꢀ
dimethylꢀ5ꢀ(2ꢀmethylꢀ2ꢀphenylpropyl)ꢀ2ꢀoxoꢀ1,3ꢀoxazolidinꢀ
3ꢀyl]acetate (5h), 5ꢀbenzylꢀ3ꢀethylꢀ4ꢀhydroxyꢀ4,5ꢀdimethylꢀ
1,3ꢀ (6a) and 3,5ꢀdibenzylꢀ4ꢀhydroxyꢀ4,5ꢀdimethylꢀ1,3ꢀoxazoꢀ
lidinꢀ2ꢀones (6b), 1,2ꢀbis(5ꢀbenzylꢀ4ꢀhydroxyꢀ4,5ꢀdimethylꢀ2ꢀ
oxoꢀ1,3ꢀoxazolidinꢀ3ꢀyl)ethane (6c), sodium (5ꢀbenzylꢀ4ꢀ
hydroxyꢀ4,5ꢀdimethylꢀ2ꢀoxoꢀ1,3ꢀoxazolidinꢀ3ꢀyl)acetate (6d),
3ꢀanilinoꢀ5ꢀbenzylꢀ4ꢀhydroxyꢀ4,5ꢀdimethylꢀ1,3ꢀoxazolidinꢀ2ꢀ
one (6e), and 5ꢀ[2ꢀ(2ꢀfuryl)ethyl]ꢀ4ꢀhydroxyꢀ4,5ꢀdimethylꢀ
1,3ꢀ (7a), 5ꢀ[2ꢀ(2ꢀfuryl)ethyl]ꢀ4ꢀhydroxyꢀ3,4,5ꢀtrimethylꢀ
1,3ꢀ (7b), 3ꢀethylꢀ5ꢀ[2ꢀ(2ꢀfuryl)ethyl]ꢀ4ꢀhydroxyꢀ4,5ꢀdimethylꢀ
1,3ꢀ (7c), and 3ꢀbenzylꢀ5ꢀ[2ꢀ(2ꢀfuryl)ethyl]ꢀ4ꢀhydroxyꢀ4,5ꢀdiꢀ
methylꢀ1,3ꢀoxazolidinꢀ2ꢀones (7d).
Oxazolidinones 4i, 5i, 6f, and 8a. An appropriate dioxolaꢀ
none 3 (10 mmol) was dissolved in acetonitrile (10 mL) and
histamine hydrochloride (10 mmol) was added. Triethylamine
(15 mmol) was added at 60 °C to the stirred mixture and stirring
was continued at the same temperature for 1 h. The reaction
mixture was cooled, the resulting precipitate of triethylamine
hydrochloride was filtered off, the solvent was removed, and the
residue was crystallized from MeOBut. The yields of the prodꢀ
ucts were 25—60%.
Following this procedure, we obtained for the first time
4ꢀhydroxyꢀ3ꢀ[2ꢀ(imidazolꢀ5ꢀyl)ethyl]ꢀ4,5ꢀdimethylꢀ5ꢀphenꢀ
ethylꢀ1,3ꢀ (4i), 4ꢀhydroxyꢀ3ꢀ[2ꢀ(imidazolꢀ5ꢀyl)ethyl]ꢀ4,5ꢀdiꢀ
methylꢀ5ꢀ(2ꢀmethylꢀ2ꢀphenylpropyl)ꢀ1,3ꢀ (5i), and 5ꢀbenzylꢀ
4ꢀhydroxyꢀ3ꢀ[2ꢀ(imidazolꢀ5ꢀyl)ethyl]ꢀ4,5ꢀdimethylꢀ1,3ꢀoxazoꢀ
lidinꢀ2ꢀones (6f) and 4ꢀhydroxyꢀ3ꢀ[2ꢀ(imidazolꢀ5ꢀyl)ethyl]ꢀ
4,5,5ꢀtrimethylꢀ1,3ꢀoxazolidinꢀ2ꢀone (8a).
Synthesis of compounds 9—13 (general procedure). Polyꢀ
phosphoric acid (30ꢀfold amount, w/w) was added to oxazolidiꢀ
none 4a—h, 5a—g, or 6c. The reaction mixture was stirred at
80 °C for 30 min, cooled, and diluted with a tenfold volume of
ice water. In the case of compounds 9a—d, 10a,b, and 11, the
resulting precipitate was filtered off and washed with water to
pH 7. In the other cases, the reaction mixture was carefully
neutralized with 40% NaOH so that the temperature did not
increase above 30 °C and the product was extracted three times
with AcOEt (the volume of AcOEt was ~1/3 that of the aqueous
phase). For products 9g,h, 10g, and 12, CHCl3 was used as an
extractant. The extracts were combined, dried with Na2SO4,
and concentrated. The cyclization products were crystallized
from MeOBut or MeOBut—AcOEt.
Comꢀ
pound
B.p./°C
(Torr)
Yield Found
Molecular
formula
(%)
(%)
Calculated
or m.p./°C
C
H
2a
2b
2c
2d
3a
3b
3c
3d
93—95 (1.5)
91—92 (1)
81—83 (1)
78—84 (1)
132 (0.5)
42—43a
72
71
78
86
82
76
80
82.70
82.72
83.13
83.12
82.44
82.46
73.14
73.15
71.53
71.54
73.14
73.15
70.53
70.58
63.46
63.45
8.12
8.10
8.96
8.97
7.57
7.55
7.37
7.37
6.48
6.47
7.37
7.37
5.91
5.92
5.80
5.81
C12H14
C14H18
C11H12
O
O
O
C10H12O2
C13H14O3
C15H18O3
C12H12O3
C11H12O4
86—87b
117—120 (0.5) 75
a From light petroleum.
b From acetone.
CuBr (0.4 g). Carbon dioxide was pumped until the initial presꢀ
sure at 100 °C was 220 atm. The reaction was carried out for
20—30 h; the conversion was 95—98% (GLC). The reaction
mixture was diluted with an equal volume of acetone, the cataꢀ
lyst was filtered off, and the solvent was removed. Compounds
3a,d were purified by distillation in vacuo, while compounds
3b,c, by crystallization (see Table 1).
Following this procedure, we obtained for the first time
4ꢀmethylꢀ5ꢀmethylideneꢀ4ꢀphenethylꢀ1,3ꢀ (3a), 4ꢀmethylꢀ5ꢀ
methylideneꢀ4ꢀ(2ꢀmethylꢀ2ꢀphenylpropyl)ꢀ1,3ꢀ (3b), 4ꢀbenzylꢀ
4ꢀmethylꢀ5ꢀmethylideneꢀ1,3ꢀ (3c), and 4ꢀ[2ꢀ(2ꢀfuryl)ethyl]ꢀ4ꢀ
methylꢀ5ꢀmethylideneꢀ1,3ꢀdioxolanꢀ2ꢀones (3d).
Oxazolidinones 4a—h, 5a—h, 6a—e, and 7a—d. A dioxolaꢀ
none 3 (10 mmol) was dissolved in acetonitrile (7 mL) and an
appropriate amine (10 mmol) was added (ammonia, methylꢀ
amine, ethylamine, and ethylenediamine were used as aqueous
solutions; sodium glycinate was predissolved in a minimum
amount of water). The reaction mixture was left at 45 °C and
then concentrated. Most oxazolidinones were isolated as yellow
oils crystallized from MeOBut—light petroleum. The yields of
the products were 80—100%.
Following this procedure, we obtained for the first time
4ꢀhydroxyꢀ4,5ꢀdimethylꢀ5ꢀphenethylꢀ1,3ꢀ (4a), 4ꢀhydroxyꢀ
3,4,5ꢀtrimethylꢀ5ꢀphenethylꢀ1,3ꢀ (4b), 3ꢀethylꢀ4ꢀhydroxyꢀ4,5ꢀ
dimethylꢀ5ꢀphenethylꢀ1,3ꢀ (4c), 3ꢀbenzylꢀ4ꢀhydroxyꢀ4,5ꢀdiꢀ
methylꢀ5ꢀphenethylꢀ1,3ꢀ (4d), 4ꢀhydroxyꢀ4,5ꢀdimethylꢀ3,5ꢀ
diphenethylꢀ1,3ꢀ (4e), and 3ꢀ[2ꢀ(3,4ꢀdimethoxyphenyl)ethyl]ꢀ
4ꢀhydroxyꢀ4,5ꢀdimethylꢀ5ꢀphenethylꢀ1,3ꢀoxazolidinꢀ2ꢀ
ones (4f), 1,2ꢀbis(4ꢀhydroxyꢀ4,5ꢀdimethylꢀ2ꢀoxoꢀ5ꢀphenethylꢀ
1,3ꢀoxazolidinꢀ3ꢀyl)ethane (4g), sodium (4ꢀhydroxyꢀ4,5ꢀdiꢀ
methylꢀ2ꢀoxoꢀ5ꢀphenethylꢀ1,3ꢀoxazolidinꢀ3ꢀyl)acetate (4h),
4ꢀhydroxyꢀ4,5ꢀdimethylꢀ5ꢀ(2ꢀmethylꢀ2ꢀphenylpropyl)ꢀ
1,3ꢀ (5a), 4ꢀhydroxyꢀ3,4,5ꢀtrimethylꢀ5ꢀ(2ꢀmethylꢀ2ꢀphenylꢀ
propyl)ꢀ1,3ꢀ (5b), 3ꢀethylꢀ4ꢀhydroxyꢀ4,5ꢀdimethylꢀ5ꢀ(2ꢀmeꢀ
Following this procedure, we obtained for the first time
3a,9bꢀdimethylꢀ3a,4,5,9bꢀtetrahydronaphtho[1,2ꢀd][1,3]oxꢀ
azolꢀ2(1H)ꢀone (9a), 1,3a,9bꢀtrimethylꢀ3a,4,5,9bꢀtetrahydroꢀ
naphtho[1,2ꢀd][1,3]oxazolꢀ2(1H)ꢀone (9b), 1ꢀethylꢀ3a,9bꢀdiꢀ
methylꢀ3a,4,5,9bꢀtetrahydronaphtho[1,2ꢀd][1,3]oxazolꢀ
2(1H)ꢀone (9c), 1ꢀbenzylꢀ3a,9bꢀdimethylꢀ3a,4,5,9bꢀtetrahydroꢀ
naphtho[1,2ꢀd][1,3]oxazolꢀ2(1H)ꢀone (9d), 3a,9bꢀdimethylꢀ
1ꢀphenethylꢀ3a,4,5,9bꢀtetrahydronaphtho[1,2ꢀd][1,3]oxazolꢀ
2(1H)ꢀone (9e), 1,2ꢀbis(3a,9bꢀdimethylꢀ2ꢀoxoꢀ3a,4,5,9bꢀ
tetrahydronaphtho[1,2ꢀd][1,3]oxazolꢀ1(2H)ꢀyl)ethane (9g),
(3a,9bꢀdimethylꢀ2ꢀoxoꢀ3a,4,5,9bꢀtetrahydronaphꢀ
tho[1,2ꢀd][1,3]oxazolꢀ1(2H)ꢀyl)acetic acid (9h), 3a,5,5,9bꢀtetꢀ