Hydrochloric Acid → HCID 14842724, compound

HRID 326637Notes

Reaction equation

HRID 326637 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([CH:7]=[CH:8][CH:9]=1)[NH2:6])#[N:2].C[O:11][C:12]([C:14]#[C:15][C:16](OC)=[O:17])=[O:13].[OH-].[Na+].Cl>CO.C1(OC2C=CC=CC=2)C=CC=CC=1.O>[C:1]([C:3]1[CH:9]=[CH:8][CH:7]=[C:5]2[C:4]=1[C:16](=[O:17])[CH:15]=[C:14]([C:12]([OH:13])=[O:11])[NH:6]2)#[N:2]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 12980Dimethyl acetylenedicarboxylateHCID 14798Sodium HydroxideHCID 167023-Aminobenzonitrile

Product 1

HCID 14842724HCID 14842724, compoundYield 0.5%

Reagents, catalysts & solvents 3

HCID 887MethanolSolvent2×HCID 962WaterSolventHCID 7583Diphenyl EtherSolvent

Procedure

3-Cyanoaniline (21.3 g, 0.18 mol) and dimethylacetylene dicarboxylate (10.9 ml, 0.12 mol) were dissolved in dry methanol and heated at reflux for 14 h. After cooling, the solvent was removed in vacuo and the residue partitioned between diethyl ether and 1N hydrochloric acid. The organic layer was dried (Na2SO4), filtered and concentrated in vacuo to leave an oil which was heated in diphenyl ether (100 ml) at 250° C. for 15 minutes. On cooling, a solid precipated which was collected and recrystallised successively from acetic acid/diethyl ether, then from pyridine, to give a pure material by t.l.c. (0.165 g). This was dissolved in water (20 ml) and methanol (10 ml) with sodium hydroxide (0.13 g) and the solution heated at 100° C. for 2 h. Addition of 1N hydrochloric acid caused precipitation of a white solid which was collected by filtration and washed successively with water, ethanol and diethyl ether to give 5-cyano-4-oxo-1,4-dihydroquinoline-2-carboxylic acid (0.14 g) m.p. 278°-279° C., δ (360 MHz, NAOD) 6.96 (1H, s, 3-H), 7.64 (1H, dd, 7-H), 7.83 (1H, dd, 6-H) and 8.05 (1H, dd, 8-H). (Found: C, 60.23; H, 3.03; N, 12.46%. C11H6N2O3. 0.3H2O requires C, 60.17; H, 3.03; N, 12.78%).

Workup

  1. temperatureheated
  2. temperatureat reflux for 14 h
  3. temperatureAfter cooling
  4. customthe solvent was removed in vacuo
  5. customthe residue partitioned between diethyl ether and 1N hydrochloric acid
  6. dry with materialThe organic layer was dried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto leave an oil which
  10. temperatureOn cooling
  11. customa solid precipated which was collected
  12. customrecrystallised successively from acetic acid/diethyl ether
  13. customfrom pyridine, to give a pure material by t.l.c
  14. customprecipitation of a white solid which
  15. filtrationwas collected by filtration
  16. washwashed successively with water, ethanol and diethyl ether

Sources & evidence

ORD record
ord-107dbd248f484d74a9d08301d3e8600c
Source dataset
uspto-grants-1993_12
Patent number
US05270309

Reaction notes

Loading…