Ethyl 2-methylacetoacetate → HCID 178432194, compound

HRID 1361459Notes

Reaction equation

HRID 1361459 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[C:9](=[O:17])[C:10]1[CH:15]=[CH:14][C:13]([Cl:16])=[CH:12][CH:11]=1)[NH2:5].[CH3:18][CH:19]([C:25]([CH3:27])=O)[C:20](OCC)=[O:21].C1(C)C=CC(S(O)(=O)=O)=CC=1.ClC1C(C(=O)C2C=CC(Cl)=CC=2)=CC=C2C=1C(O)=C(C)C(C)=N2>C1(C)C(C)=CC=CC=1>[Cl:1][C:2]1[CH:3]=[C:4]2[C:6]([C:20]([OH:21])=[C:19]([CH3:18])[C:25]([CH3:27])=[N:5]2)=[CH:7][C:8]=1[C:9](=[O:17])[C:10]1[CH:15]=[CH:14][C:13]([Cl:16])=[CH:12][CH:11]=1

Participants

6

Reactant 4

HCID 701Ethyl 2-methylacetoacetateHCID 6101p-Toluenesulfonic acidHCID 30165104-Amino-2,4'-dichlorobenzophenoneHCID 178432175HCID 178432175, compound

Product 1

HCID 178432194HCID 178432194, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Procedure

A solution of 2.7 g of 3-chloro-4-(4-chlorobenzoyl)aniline, 2.4 g of ethyl 2-methylacetoacetate, and 0.3 g of p-toluenesulfonic acid dissolved in 100 mL of xylene was heated under reflux for 31 hr. This reaction solution was cooled, and the precipitated crystals were collected by filtration and were washed with n-hexane to give 2.68 g of a mixture of 5-chloro-6-(4-chlorobenzoyl)-4-hydroxy-2,3-dimethyl-quinoline with 7-chloro-6-(4-chlorobenzoyl)-4-hydroxy-2,3-dimethyl-quinoline (yield 77%). The crystals of the mixture thus obtained were stirred in 40 mL of acetic anhydride with heating at 120 to 125° C. for one hr. The reaction solution was concentrated, and the crude product was then purified by column chromatography on silica gel (BW300, manufactured by Fuji Sylysia Chemical Ltd., solvent: n-hexane/ethyl acetate) to give 1.0 g of 4-acetoxy-5-chloro-6-(4-chlorobenzoyl)-2,3-dimethyl-quinoline (yield 32.6%) and 0.47 g of 4-acetoxy-7-chloro-6-(4-chlorobenzoyl)-2,3-dimethyl-quinoline (yield 15.6%).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 31 hr
  3. temperatureThis reaction solution was cooled
  4. filtrationthe precipitated crystals were collected by filtration
  5. washwere washed with n-hexane

Sources & evidence

ORD record
ord-45ff7f3812634f8f814fa60441d29692
Source dataset
uspto-grants-2011_02
Patent number
US07880006B2

Reaction notes

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