1-Allyl-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic
Acid
β-N-Tosylhydrazide
(4).
Triethylamine (1.54 ml, 0.011 mol) was added to a solution of hydrazide 3 (2.59 g, 0.01 mol) in dry DMF
(20 ml) followed, with stirring, by p-toluenesulfonyl chloride (2.1 g, 0.011 mol). The product was left for
10-12 h at room temperature and the reaction mixture was then diluted with cold water and acidified with dilute
HCl to pH 5. The precipitated β-N-tosylhydrazide 4 was filtered off, washed with water, and dried. Yield 4.00 g
1
(97%); mp 177-179ºC (DMF-ethanol). H NMR spectrum, δ, ppm (J, Hz): 15.75 (1H, br. s, OH); 11.54 (H, s,
CONH); 10.30 (1H, br. s, SO2NH); 8.06 (1H, dd, J = 7.8 and 1.5, H-5); 7.79 (1H, td, J = 7.9 and 1.5, H-7); 7.73
(2H, d, J = 8.3, H-2',6'); 7.52 (1H, d, J = 8.5, H-8); 7.40 (2H, d, J = 8.3, H-3',5'); 7.36 (1H, t, J = 7.8, H-6); 5.91
(1H, m, CH=CH2); 5.13 (1H, dd, J = 10.6 and 1.1, NCH2CH=CH cis); 4.97 (1H, dd, J = 17.2 and 1.1,
NCH2CH=CH trans); 4.86 (2H, m, NCH2); 2.38 (3H, s, Ar–CH3). Found, %: C 58.25; H 4.76; N 10.05.
C20H19N3O5S. Calculated, %: C 58.10; H 4.63; N 10.16.
1-Allyl-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carbaldehyde (5). Anhydrous Na2CO3 (3.18 g,
0.03 mol) was added in one portion to a solution of β-N-tosylhydrazide 4 (4.13 g, 0.01 mol) in ethylene glycol
(20 ml) heated to 160ºC. (Caution, frothing!) Evolution of gas ceased after several minutes. The reaction
mixture was cooled, diluted with water, and acidified with HCl (1:1) to pH ~ 4. The precipitated aldehyde 5 was
filtered off, washed with cold water, and dried. Yield 2.15 g (94%); mp 84-86ºC (ethanol). 1H NMR spectrum, δ,
ppm (J, Hz): 10.08 (1H, s, CHO); 8.09 (1H, dd, J = 8.0 and 1.3, H-5); 7.78 (1H, td, J = 7.9 and 1.5, H-7); 7.46
(1H, d, J = 8.5, H-8); 7.33 (1H, t, J = 7.6 and 1.1, H-6); 5.92 (1H, m, CH=CH2); 5.13 (1H, dd, J = 10.4 and 1.3,
NCH2CH=CH cis); 5.02 (1H, dd, J = 17.4 and 1.3, NCH2CH=CH trans); 4.85 (2H, m, NCH2). Found, %:
C 68.23; H 4.95; N 5.98. C13H11NO3. Calculated, %: C 68.11; H 4.84; N 6.11.
2-Bromomethyl-5-oxo-1,2-dihydro-5H-oxazolo[3,2-a]quinoline-4-carbaldehyde (8). A solution of
bromine (0.52 ml, 0.01 mol) in glacial acetic acid (5 ml) was added with vigorous stirring to a solution of the
quinoline-2,4-dione 1a (3.68 g, 0.01 mol) in the same solvent (30 ml). The decolorization of the bromine was
virtually instantaneous. The reaction mixture was diluted with cold water and left for 12-14 h at room
temperature. The precipitated oxazoloquinoline 8 was filtered off, washed with water, and dried. Yield 1.87 g
(61%). When using the quinoline-2.4-dione 1b as starting material the yield was 57%. Mp 231-233ºC (ethanol).
1H NMR spectrum,δ, ppm (J, Hz): 10.11 (1H, s, CHO); 8.17 (1H, dd, J = 8.0 and 1.4, H-6); 7.74 (1H, td, J = 7.8
and 1.6, H-8); 7.48 (1H, d, J = 8.1, H-9); 7.40 (1H, td, J = 7.4 and 1.2, H-7); 5.65 (1H, m, NCH2CHO); 4.60
(1H, dd, J = 9.8 and 9.8, NCH); 4.24 (1H, dd, J = 9.8 and 6.6, NCH); 4.05 (1H, dd, J = 11.0 and 4.4, CHBr);
3.97 (1H, dd, J = 11.0 and 4.0, CHBr). 13C NMR spectrum, δ, ppm: 186.1 (CHO); 177.8 (5-C=O); 162.0 (C-3a);
136.2 (C-9a); 133.6 (C-8); 126.8 (C-6); 124.8 (C-7); 125.6 (C-5a); 116.6 (C-9); 101.6 (C-4); 81.2 (NCH2CH);
48.7 (NCH2); 34.7 (CH2Br). Mass spectrum, m/z (Irel, %): 309/307 [M]+ (7.6/8.2), 281/279 [M-CHO]+
(100.0/79.4), 199 [M-CHO-HBr]+ (5.8). Found, %: C 50.33; H 3.39; N 4.66. C13H10BrNO3. Calculated, %:
C 50.67; H 3.27; N 4.55.
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