Cyanoacetic acid → 7-Chloro-1,2-dihydro-2-oxo-3-quinolinecarbonitrile

HRID 2259622Notes

Reaction equation

[NH2:1][C:2]1[CH:9]=[C:8]([Cl:10])[CH:7]=[CH:6][C:3]=1[CH2:4]O.[C:11]([CH2:13][C:14](O)=[O:15])#[N:12]>>[Cl:10][C:8]1[CH:9]=[C:2]2[C:3]([CH:4]=[C:13]([C:11]#[N:12])[C:14](=[O:15])[NH:1]2)=[CH:6][CH:7]=1

Participants

Reactant 2

HCID 9740Cyanoacetic acid

HCID 4134900(2-Amino-4-chlorophenyl)methanol

Product 1

HCID 140265107-Chloro-1,2-dihydro-2-oxo-3-quinolinecarbonitrileYield 16%

Procedure

2-Amino-4-chlorobenzyl alcohol (3 g, 19.29 mmol) and cyanoacetic acid (3.61 g, 42.44 mmol) were reacted in a similar manner as described in Example 1 to give 0.63 g of 7-chloro-3-cyano-2(1H)-quinolone. mp 306°-309° C. This nitrile (0.46 g) was dissolved in 1-methylpyrrolidinone and treated with triethylammonium hydrochloride (0.465 g) and sodium azide (0.44 g). The reaction was heated to 140° C. for 1 h, cooled, acidified (HCl), and extracted with ethyl acetate (2×). The combined organic phases were extracted into dilute sodium hydroxide (2×) and washed with diethyl ether. The aqueous layer was acidified and the precipitate which formed was extracted into ethyl acetate (3×). The combined organic phases were washed with water and then evaporated to give the title compound as a powdered brown solid; mp 327° C. (dec) (DMF, acetone, water). (Found: C, 48.61; H, 2.47.C10H6ClN5O requires C, 48.50; H, 2.44%); δH (360 MHz, DMSO-d6) 7.36 (1H, d, dd, J=8.4 and 2.0 Hz, 6-H), 7.44 (1H, d, J=2.0 Hz), 8.01 (1H, d, J=8.4 Hz, 5-H), 8.98 (1H, s, 4-H), 12.3-12.7 (1H, vbr s, NH); m/z (EI+) 247 (M+).

Sources & evidence

ORD record: ord-25f6e4d712a14cd9884da56f9f203099
Source dataset: uspto-grants-1995_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05475008

Reaction notes

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