Bromine → Methyl [7-bromo-4-(3,4-dimethylphenyl)-2-methyl-1-oxo-1,2-dihydro-3-isoquinolinyl][(1,1-dimethylethyl)oxy]acetate

HRID 572500ノート

反応式

HRID 572500 の反応式
[C:1]([O:5][CH:6]([C:11]1[N:12]([CH3:30])[C:13](=[O:29])[C:14]2[C:19]([C:20]=1[C:21]1[CH:26]=[CH:25][C:24]([CH3:27])=[C:23]([CH3:28])[CH:22]=1)=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:7]([O:9][CH3:10])=[O:8])([CH3:4])([CH3:3])[CH3:2].[Br:31]Br>CN(C)C=O.ClCCl>[Br:31][C:16]1[CH:15]=[C:14]2[C:19]([C:20]([C:21]3[CH:26]=[CH:25][C:24]([CH3:27])=[C:23]([CH3:28])[CH:22]=3)=[C:11]([CH:6]([O:5][C:1]([CH3:3])([CH3:4])[CH3:2])[C:7]([O:9][CH3:10])=[O:8])[N:12]([CH3:30])[C:13]2=[O:29])=[CH:18][CH:17]=1

参加物

5

反応物 2

HCID 24408BromineHCID 89871507Methyl 2-(tert-butoxy)-2-(4-(3,4-dimethylphenyl)-2-methyl-1-oxo-1,2-dihydroisoquinolin-3-yl)acetate

生成物 1

HCID 68295047Methyl [7-bromo-4-(3,4-dimethylphenyl)-2-methyl-1-oxo-1,2-dihydro-3-isoquinolinyl][(1,1-dimethylethyl)oxy]acetate収率 55.1%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒

実験手順

An ice cold mixture of methyl 2-(tert-butoxy)-2-(4-(3,4-dimethylphenyl)-2-methyl-1-oxo-1,2-dihydroisoquinolin-3-yl)acetate (187 mg, 0.459 mmol) in N,N-Dimethylformamide (DMF) (2.0 mL) was treated with a solution of bromine (0.071 mL, 1.377 mmol) in dichloromethane (DCM) (2.0 mL). The ice bath was removed and the mixture, which was excluded from light by wrapping the reaction vessel with aluminum foil, was allowed to stir at ambient temperature overnight. The mixture was quenched by adding saturated sodium bicarbonate and then extracted with ethyl acetate. The extracts were washed with water, then brine, dried over sodium sulfate, filtered and concentrated. The residue was purified on silica gel to afford the title compound as a thick colorless oil (123 mg, 55%) that solidified upon standing. 1H NMR (400 MHz, CHLOROFORM-d) δ=8.63 (d, J=2.1 Hz, 1 H), 7.56 (ddd, J=2.2, 6.0, 8.6 Hz, 1 H), 7.31-7.22 (m, 1 H), 7.20-6.88 (m, 3 H), 5.20 (s, 1 H), 3.83-3.74 (m, 3 H), 3.69 (m, 3 H), 2.37 (s, 3 H), 2.31 (s, 3 H), 1.01 (m, 9 H); LC/MS (m/z) ES+=486 (M+1).

後処理

  1. customThe ice bath was removed
  2. customThe mixture was quenched
  3. additionby adding saturated sodium bicarbonate
  4. extractionextracted with ethyl acetate
  5. washThe extracts were washed with water
  6. dry with materialbrine, dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified on silica gel

出典と根拠

ORDレコード
ord-b613c975df1344a4898c8f4116a39490
出典データセット
uspto-grants-2015_05
特許番号
US09029391B2

反応ノート

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