1484
BUDNIKOVA, RUBINOV
or VIIIa in 30 ml of benzene was added 1.5-fold
excess (0.87 mmol) of an appropriate amine, and the
mixture was left overnight at room temperature. The
benzene solution was washed with 10 ml of 5% hydro-
chloric acid and water, dried with sodium sulfate.
The benzene was distilled off in a vacuum, the
residue was crystallized from ethyl acetate heptane
mixture. Thus were obtained enaminodiketones
IXa, b, Xa c.
3.98 s (2H, CH2S), 4.60 d (2H, NCH2, J 6.0 Hz),
7.20 7.45 m (5H, C6H5), 11.28 br.s (1H, NH).
3-Acetyl-4-(4-methoxyphenylamino)-(5H)-di-
1
hydrothiophene-2-one (Xc). IR spectrum, , cm :
1
3100, 1660, 1625, 1570, 1520. H NMR spectrum,
, ppm: 2.58 s (3H, CH3), 3.87 s (3H, OCH3), 3.90 s
(2H, CH2S), 6.97 d (2H arom, J 9.0 Hz), 7.17 d
(2H arom, J 9.0 Hz), 12.24 br.s (1H, NH).
4-Allylamino-3-acetyl-5-methyl-(5H)dihydrothio-
Enaminodiketones from compounds Ic, e g were
prepared from the ether solution of the enol methyl
ethers mixture obtained by treating along above de-
scribed procedure of 1.5 mmol of the appropriate
triketone with the ether solution of diazomethane.
This ether solution was treated with the 1.5-fold
excess (1.7 mmol, 2.25 ml) of allylamine, and from
the reaction mixture were isolated by column
chromatography on alumina (eluent toluene) enamino-
diketones IXc, Xd g. Yields, melting points, and
elemental analyses of products IXa c, Xa g are listed
in Table 3.
1
phene-2-one (Xd). IR spectrum, , cm : 3100, 1640,
1610, 1590, 1520. 1H NMR spectrum, , ppm:
1.72 d (3H, CH3CHS, J 6.5 Hz), 2.52 s (3H, CH3),
4.16 t (2H, CH2NH, J 6.0 Hz), 4.40 q (1H,
CH3CHS, J 6.5 Hz), 5.25 5.40 m (2H, CH2=),
5.96 m (1H, CH=), 11.26 br.s (1H, NH).
4-Allylamino-3-propanoyl-(5H)-dihydrothioph-
1
ene-2-one (Xe). IR spectrum, , cm : 3200, 3100,
1
1685, 1655, 1620, 1590. H NMR spectrum, , ppm:
1.12 t (3H, CH3, J 7.2 Hz), 2.98 q (2H, CH2CH3, J
7.2 Hz), 3.98 s (2H, CH2S), 4.04 t (2H, NCH2, J
6 Hz), 5.25 5.40 m (2H, CH2=), 5.95 m (1H,
CH=), 11.10 br.s (1H, NH).
2-Allylamino-3-acetyl-(3H)-dihydrothiophene-
1
2-one (IXa). IR spectrum, , cm : 3160, 1650,
1595, 1570. 1H NMR spectrum, , ppm: 2.51 s
(3H, CH3), 3.67 s (2H, CH2S), 4.04 t (2H, NCH2,
J 6.0 Hz), 5.36 m (2H, CH2=), 5.90 m (1H, CH=),
11.18 br.s (1H, NH).
4-Allylamino-3-pentanoyl-(5H)-dihydrothioph-
1
ene-2-one (Xf). IR spectrum, , cm : 3100, 1675,
1
1630, 1590. H NMR spectrum, , ppm: 0.91 t (3H,
CH3CH2, J 7 Hz), 1.36 m (2H, CH2CH3), 1.58 m
(2H, CH2CH2CH3), 2.94 t (2H, CH2CO, J 7 Hz),
3.96 s (2H, CH2S), 4.04 t (2H, NCH2, J 6 Hz),
4.32 q (1H, CHS), 5.30 m and 5.36 m (2H, CH2=),
5.91 m (2H, CH=), 11.15 s (1H, NH).
3-Acetyl-2-(4-methoxyphenylamino)-(3H)-di-
1
hydrothiophene-2-one (IXb). IR spectrum, , cm :
3150, 1635, 1620, 1600, 1580, 1520. 1H NMR
spectrum, , ppm: 2.58 s (3H, CH3), 3.64 s (2H,
CH2S), 3.86 s (3H, OCH3), 7.20 d (2H arom, J
9.0 Hz), 7.28 d (2H arom, J 9.0 Hz), 12.60 br.s
(1H, NH).
4-Allylamino-5-methyl-3-pentanoyl-(5H)di-
1
hydrothiophene-2-one (Xg). IR spectrum, , cm :
1
3100, 1675, 1625, 1590. H NMR spectrum, , ppm:
0.90 t (3H, CH3CH2, J 7.2 Hz), 1.35 m (2H,
CH2CH3), 1.56 m (2H, CH2CH2CH3), 1.67 d (3H,
SCHCH3, J 7.0 Hz), 2.94 t (2H, CH2CO, J 7.2 Hz),
4.09 t (2H, NCH2, J 6.0 Hz), 4.32 q (1H, CHS,
J 7.0 Hz), 5.30 5.36 m (2H, CH2=), 5.91 m (2H,
CH=), 11.35 br.s (1H, NH).
2-Allylamino-3-acetyl-5-methyl-(3H)-dihydro-
1
thiophene-2-one (IXc). IR spectrum, , cm : 3200,
1
1685, 1655, 1620, 1590. H NMR spectrum, , ppm:
1.62 d (3H, CH3CHS, J 6.5 Hz), 2.51 s (3H, CH3),
3.80 q (1H, CH3CHS, J 6.5 Hz), 4.06 t (2H, CH2NH,
J 6.0 Hz), 5.25 5.40 m (2H, CH2=), 5.96 m (1H,
CH=), 11.16 br.s (1H, NH).
3-Acetyl-4-pyrrolidino-(5H)-dihydrothiophene-
2-one (XI). To a solution of 0.12 g (1 mmol) of di-
ketone Va in 15 ml of 5% hydrogen chloride solution
in methanol was added 0.12 ml (1.1 mmol) of tri-
methyl orthoformate, and the mixture was kept at
room temperature under anhydrous conditions for
48 h (TLC monitoring). On completion of the reac-
tion the solvent was removed in a vacuum, and the
residue was diluted with water (20 ml).The methyl
ether was extracted with ethyl ether (2 30 ml), the
extract was washed with 2% solution of sodium
4-Allylamino-3-acetyl-(5H)-dihydrothiophene-2-
1
one (Xa). IR spectrum, , cm : 3195, 1640, 1615,
1
1580. H NMR spectrum, , ppm: 2.51 s (3H, CH3),
3.98 s (2H, CH2S), 4.06 t (2H, NCH2, J 6.0 Hz),
5.32 m (2H, CH2=), 5.90 m (1H, CH=), 11.00 br.s
(1H, NH).
3-Acetyl-4-benzylamino-(5H)-dihydrothiophene-
1
2-one (Xb). IR spectrum, , cm : 3200, 1660, 1610,
1
1500. H NMR spectrum, , ppm: 2.50 s (3H, CH3),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 10 2001