HCID 57733272、化合物 → HCID 67132488、化合物

HRID 1920735ノート

反応式

HRID 1920735 の反応式
[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[C:10]([N+:15]([O-])=O)[CH:11]=[CH:12][CH:13]=2)[C:8](=[O:18])[N:7]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:6]=1[CH3:25])=[O:4]>C1COCC1.Cl.[Zn]>[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[C:10]([NH2:15])[CH:11]=[CH:12][CH:13]=2)[C:8](=[O:18])[N:7]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:6]=1[CH3:25])=[O:4]

参加物

5

反応物 1

HCID 57733272HCID 57733272、化合物

生成物 1

HCID 67132488HCID 67132488、化合物収率 69%

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 313Hydrochloric Acid溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

A suspension of 3-methyl-8-nitro-1-oxo-2-phenyl-1,2-dihydro-isoquinoline-4-carboxylic acid methyl ester (320 mg, 0.95 mmol) and Zn (898 mg, 13.8 mmol) in THF (4.5 ml) and 2M aq. HCl (4.5 ml) was stirred for 10 min, filtered and partitioned between ethyl acetate (3×150 ml) and sat. aq. NaHCO3 (100 ml). The combined organic solution was dried (MgSO4) and evaporated to give 8-amino-3-methyl-1-oxo-2-phenyl-1,2-dihydro-isoquinoline-4-carboxylic acid methyl ester as a dark oil (200 mg, 0.645 mmol, 69% yield. LC-MS (m/z) 309.4 (MH+); tR=1.2. It was dissolved in conc. aq. HCl (0.4 ml) and H2O (3.25 ml). To the obtained solution NaNO2 (46.3 mg, 0.645 mmol, in 0.12 ml H2O) was added dropwise at 0° C. After 15 min it was neutralized (pH=6-7) with sat. aq. NaHCO3 to give diazonium salt solution. To a solution of KCN (202 mg, 3 mmol) in water (0.4 ml) solution of CuSO4×5H2O (197 mg, 0.774 mmol) in water (0.8 ml) was added dropwise at 0° C. After addition completion benzene (2 ml) was added and the mixture was warmed to +60° C. To this mixture diazonium salt solution was added dropwise during 15 min then kept at 70° C. for 85 min. It was allowed to cool to r.t., diluted with ethyl acetate (10 ml) and filtered via plug of cellite. The organic layer was washed with brine (10 ml), dried (MgSO4) and evaporated to give 97.9 mg of the title compound (48% yield). LC-MS (m/z) 319.2 (MH+); tR=1.15.

後処理

  1. filtrationfiltered
  2. custompartitioned between ethyl acetate (3×150 ml) and sat. aq. NaHCO3 (100 ml)
  3. dry with materialThe combined organic solution was dried (MgSO4)
  4. customevaporated

出典と根拠

ORDレコード
ord-efd87835158347849eaacb884950393c
出典データセット
uspto-grants-2012_05
特許番号
US08173639B2

反応ノート

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