Hydrazine hydrate (1:1) → 1-(7-Amino-3,4-dihydroisoquinolin-2(1H)-yl)ethan-1-one

HRID 729234ノート

反応式

HRID 729234 の反応式
[C:1]([N:4]1[CH2:13][CH2:12][C:11]2[C:6](=[CH:7][C:8]([N+:14]([O-])=O)=[CH:9][CH:10]=2)[CH2:5]1)(=[O:3])[CH3:2].O.NN>CO>[C:1]([N:4]1[CH2:13][CH2:12][C:11]2[C:6](=[CH:7][C:8]([NH2:14])=[CH:9][CH:10]=2)[CH2:5]1)(=[O:3])[CH3:2]

参加物

4

反応物 2

HCID 24654Hydrazine hydrate (1:1)HCID 64254731-(7-Nitro-3,4-dihydroisoquinolin-2(1H)-yl)ethanone

生成物 1

HCID 128113521-(7-Amino-3,4-dihydroisoquinolin-2(1H)-yl)ethan-1-one収率 86.8%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

A mixture of 13 (5.1 g, 23 mmol), activated carbon (4.2 g), ferric chloride hexahydrate (2.1 g, 7.6 mmol) and methanol (140 ml) is stirred under refluxing for 20 minutes. To the boiling mixture is added hydrazine hydrate (8.5 g, 265 mmol) dropwise, and the mixture is refluxed for an additional 4 h, cooled and filtered and the residue washed with methanol. The filtrate is concentrated in vacuo and the residue recrystallized from EtOAc to give compound 14 (3.8 g, 85% yield). 1H NMR [300 MHz, (CD3)2SO], a 3:2 mixture of amide conformers doubling most signals, δ 6.80 (1H, d, H-5), 6.40 (1H, d, H-6), 6.33 (1H, s, H-7), 4.89 (2H, br s, NH2), 4.46 (0.8H, s, ArCH2N), 4.41 (1.2H, s, ArCH2N), 3.57 (2H, t, ArCH2CH2N), 2.66 (1.2H, t, ArCH2CH2N), 2.55 (0.8H, t, ArCH2CH2N), 2.06 (1.2H, s, COCH3), 2.05 (1.8H, s COCH3).

後処理

  1. temperatureunder refluxing for 20 minutes
  2. temperaturethe mixture is refluxed for an additional 4 h
  3. temperaturecooled
  4. filtrationfiltered
  5. washthe residue washed with methanol
  6. concentrationThe filtrate is concentrated in vacuo
  7. customthe residue recrystallized from EtOAc

出典と根拠

ORDレコード
ord-10052024dbfd4794a38efb33a52ab770
出典データセット
uspto-grants-2009_09
特許番号
US07582616B2

反応ノート

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