4-Chlorobenzylamine → HCID 178522871, compound

HRID 2289928Notes

Reaction equation

HRID 2289928 reaction equation
[OH:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][C:10]=2[OH:12])[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>>[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])=[C:10]([OH:12])[CH:9]=[CH:8][CH:7]=3)=[O:15])=[CH:21][CH:20]=1

Participants

3

Reactant 2

HCID 660364-ChlorobenzylamineHCID 178469547HCID 178469547, compound

Product 1

HCID 178522871HCID 178522871, compoundYield 28.4%

Conditions

Temperature
180 °C

Procedure

A mixture of 3-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 80° C. and 50 ml of diphenyl ether is added. The mixture is heated to 250° C. for 30 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. A portion of this solid is adsorbed onto silica and chromatographed, eluting with 5% MeOH/CH2Cl2. Fractions homogeneous by TLC are combined and concentrated in vacuo to yield ethyl 4,5-dihydroxyquinoline-3-carboxylate as a gold solid. A mixture of this ester (0.125 g) and 4-chlorobenzylamine (0.379 g) are heated to 180° C. for 1 h. The solution is cooled to room temperature. The crude reaction is chromatographed on silica, eluting with 2% 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 yield 0.050 g of the desired product as a pale-yellow solid.

Workup

  1. temperatureThe solution is cooled to room temperature
  2. customThe crude reaction
  3. customis chromatographed on silica
  4. washeluting with 2% 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-b688047cf8cf4d9f9b00f72b3b41e09f
Source dataset
uspto-grants-2000_07
Patent number
US06093732

Reaction notes

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