HCID 57733272, 화합물 → HCID 67132488, 화합물

HRID 1920735노트

반응식

HRID 1920735 반응식
[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]

참가 물질

5

반응물 1

HCID 57733272HCID 57733272, 화합물

생성물 1

HCID 67132488HCID 67132488, 화합물수율 69%

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 313Hydrochloric Acid용매HCID 8028Tetrahydrofuran용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-efd87835158347849eaacb884950393c
출처 데이터셋
uspto-grants-2012_05
특허 번호
US08173639B2

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