4-Chlorobenzylamine → HCID 178522933, compound

HRID 2289934Notes

Reaction equation

HRID 2289934 reaction equation
[OH:1][C:2]1[C:11]2[C:6](=[C:7]([OH:12])[CH:8]=[CH:9][CH:10]=2)[N:5]=[CH:4][C:3]=1[C:13]([O:15]CC)=O.[Cl:18][C:19]1[CH:26]=[CH:25][C:22]([CH2:23][NH2:24])=[CH:21][CH:20]=1>C(Cl)Cl>[Cl:18][C:19]1[CH:26]=[CH:25][C:22]([CH2:23][NH:24][C:13]([C:3]2[CH:4]=[N:5][C:6]3[C:11]([C:2]=2[OH:1])=[CH:10][CH:9]=[CH:8][C:7]=3[OH:12])=[O:15])=[CH:21][CH:20]=1

Participants

4

Reactant 2

HCID 660364-ChlorobenzylamineHCID 178469673HCID 178469673, compound

Product 1

HCID 178522933HCID 178522933, compoundYield 49.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
180 °C

Procedure

A mixture of 2-aminophenol (5.457 g) and diethyl ethoxymethylenemalonate (10.81 g) is heated to 130° C. for 2 h with removal of ethanol by a Dean-Stark trap. The reaction is cooled to room temperature. Diphenyl ether (50 mL) is added and the mixture is heated to 240° C. for 90 min with removal of ethanol by a Dean-Stark trap. The solution is cooled to room temperature and the resulting solid is collected and washed with hexanes. The crude solid is recrystallized from acetone to yield 0.650 g of ethyl 4,8-dihydroxyquinoline-3-carboxylate. A mixture of this ester (0.500 g) and 4-chlorobenzylamine (1.518 g) are heated to 180° C. for 1 h. The solution is cooled to room temperature and diluted with CH2Cl2. The resulting solid is collected and chromatographed on silica, eluting with 3% MeOH/CH2Cl2. Fractions homogeneous by TLC are combined and concentrated in vacuo. The residue is sonicated with CH2Cl2 /hexanes. The resulting solid is collected and dried to afford 0.349 g of the desired product as an off-white solid.

Workup

  1. temperatureThe solution is cooled to room temperature
  2. customThe resulting solid is collected
  3. customchromatographed on silica
  4. washeluting with 3% MeOH/CH2Cl2
  5. concentrationconcentrated in vacuo
  6. customThe residue is sonicated with CH2Cl2 /hexanes
  7. customThe resulting solid is collected
  8. customdried

Sources & evidence

ORD record
ord-9ee35062bde94afeadd06f3afc35c428
Source dataset
uspto-grants-2000_07
Patent number
US06093732

Reaction notes

Loading…