Hydrochloric Acid → HCID 19747565, compound

HRID 484420Notes

Reaction equation

HRID 484420 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:6]=[C:7]([Cl:9])[CH:8]=1)[NH2:5].[CH2:10]([O:12][C:13](=[O:22])[CH:14]=[CH:15][CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH3:11].C(OCC)C.Cl>ClCCl>[Cl:1][C:2]1[CH:8]=[C:7]([Cl:9])[CH:6]=[C:4]2[C:3]=1[C:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:15][C:14]([C:13]([O:12][CH2:10][CH3:11])=[O:22])=[N:5]2

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 3283Diethyl EtherHCID 122813,5-DichloroanilineHCID 748981,5-Diethyl pent-2-enedioate

Product 1

HCID 19747565HCID 19747565, compoundYield 10.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

3.5-Dichloraniline (10.95 g) and diethylglutaconate (13.5 g) were dissolved in dry dichloromethane and heated at reflux for 14 h. Diethyl ether, saturated with hydrogen chloride (10 ml) was added and the reaction mixture was heated at reflux for a further 24 h. After this time the solution was filtered and the filtrate was washed with saturated sodium hydrogen carbonate solution, dried (Na2SO4), filtered and concentrated in vacuo to give an oily residue which was purified by silica gel chromatography using 15% ethyl acetate in hexane as the eluent to give as a colourless solid, 5,7-dichloro-2,4-diethoxycarbonylquinoline (2.4 g, m.p. 104°-106° C.); δ (360 MHz, CDCl3), 1.44 (3H, t, J=7.2 Hz, CH3CH2), 1.49 (3H, t, J=7.2 Hz, CH3CH2), 4.51 (2H, q, J=7.2 Hz, CH3CH2), 4.56 (2H, q, J=7.2 Hz, CH3CH2), 7.77 (1H, d, J=1.9 Hz, 6-H or 8-H), 8.17 (1H, s, 3-H) and 8.32 (1H, d, J=1.9 Hz, 6-H or 8-H); m/z 342 (M+1), 269 (100%, M+1 -CO2Et); Found: C, 52.58; H, 3.87; N, 4.04. C15H13Cl2NO4 requires C, 52.65; H, 3.83; N, 4.09% and 5,7-dichloro-4-(3,5-dichloroanilino)-2,4-diethoxycarbonyl-1,2,3,4-tetrahydro-quinoline (0.23 g, m.p. 153°-154° C.; δ (360 MHz, CDCl3) 1.29 (6H, t, J=7.2 Hz, CH3CH2 ×2), 2.34 (1H, dd, J=14.4 and 2.9 Hz, CHAHB -CHC), 2.65 (1H, dd, J=14.4 and 12.3 Hz, CHAHB -CHC), 4.27 (5H, m, CH3CH2 ×2 and HC), 4.91 (1H, br, NH), 5.54 (1H, br, NH), 6.28 (2H, d, J=1.8 Hz, ortho anilino protons), 6.60 (1H, t, J=1.8 Hz, para anilino proton), 6.64 (1H, d, J=2.1 Hz, 6-H or 8-H), 6.68 (1H, d, J=2.1 Hz, 6-H or 8-H); m/z 506 and 504 (M+), 433 (100%, M-CO2Et); Found: C, 49.95; H, 4.07; N, 5.51. C21H20Cl4N2O4 requires C, 49.83; H, 3.98; N, 5.53%).

Workup

  1. temperatureheated
  2. temperatureat reflux for 14 h
  3. temperaturethe reaction mixture was heated
  4. temperatureat reflux for a further 24 h
  5. filtrationAfter this time the solution was filtered
  6. washthe filtrate was washed with saturated sodium hydrogen carbonate solution
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto give an oily residue which
  11. customwas purified by silica gel chromatography

Sources & evidence

ORD record
ord-c20eb9acdab74a7b820d72a0f80f4c58
Source dataset
uspto-grants-1993_07
Patent number
US05231102

Reaction notes

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