4-Chlorobenzylamine → HCID 178522884, compound

HRID 2289932Notes

Reaction equation

HRID 2289932 reaction equation
[OH:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([OH:12])[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][C:9]([OH:12])=[CH:8][CH:7]=3)=[O:15])=[CH:21][CH:20]=1

Participants

4

Reactant 2

HCID 660364-ChlorobenzylamineHCID 178469585HCID 178469585, compound

Product 1

HCID 178522884HCID 178522884, compoundYield 52.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
180 °C

Procedure

A mixture of 4-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 250° C. for 45 min with removal of ethanol by a Dean-Stark trap. The solution is cooled to 80° C. and the resulting solid is collected and washed with hexanes. The solid is suspended in 250 mL MeOH and brought to a boil. The insoluble material is filtered and the filtrate is adsorbed onto silica and chromatographed, eluting with 5% MeOH/CH2Cl2 then with 10% MeOH/CH2Cl2. Fractions homogeneous by TLC are combined and concentrated in vacuo to yield 0.644 g of ethyl 4,6-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 0.372 g of the desired product as a 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-5b36f00a6881473e9542d46a719ca04d
Source dataset
uspto-grants-2000_07
Patent number
US06093732

Reaction notes

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