Water → 4-Benzyl-7-methoxy-1,3,4,5-tetrahydro-benzo[e][1,4]diazepin-2-one

HRID 1041594ノート

反応式

HRID 1041594 の反応式
[CH2:1]([N:8]1[CH2:17][C:16](=[O:18])[C:15]2[C:10](=[CH:11][C:12]([O:19][CH3:20])=[CH:13][CH:14]=2)[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N-:21]=[N+]=[N-].[Na+].O.[OH-].[Na+]>CS(O)(=O)=O>[CH2:1]([N:8]1[CH2:9][C:10]2[CH:11]=[C:12]([O:19][CH3:20])[CH:13]=[CH:14][C:15]=2[NH:21][C:16](=[O:18])[CH2:17]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

6

反応物 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 33557Sodium AzideHCID 13760255N-benzyl-7-methoxy-1,2-dihydroisoquinolin-4(3H)-one

生成物 1

HCID 578538974-Benzyl-7-methoxy-1,3,4,5-tetrahydro-benzo[e][1,4]diazepin-2-one収率 73%

試薬・触媒・溶媒 1

HCID 6395Methanesulfonic Acid溶媒

反応条件

温度
65 °C

実験手順

To a solution of 2-benzyl-7-methoxy-2,3-dihydro-1H-isoquinolin-4-one (7.0 g, 26.2 mmol) in methanesulfonic acid (50 mL) was added sodium azide (3.4 g, 52.4 mmol) portionwise with stirring (Caution: mild exotherm, gas evolution). The mixture was heated to 65° C. for two hours before being cooled to ambient temperature. Water (100 mL) was added, the mixture was cooled in an ice-water bath, and the pH was adjusted to 7-8 (10N NaOH). The gummy precipitate was extracted (DCM), the organic phase was washed with brine, dried over magnesium sulfate, filtered and concentrated. Further purification by flash chromatography over silica gel (DCM/MeOH) gave 4-benzyl-7-methoxy-1,3,4,5-tetrahydro-benzo[e][1,4]diazepin-2-one (5.4 g, 73%) as a tan solid; 1H NMR (400 MHz, DMSO-d6) δ 9.80 (s, 1H), 7.33 (m, 5H), 6.97 (d, J=8 Hz, 1H), 6.87 (d, J=8 Hz, 1H), 6.82 (s, 1H), 3.73 (s, 3H), 3.67 (s, 4H), 3.09 (s, 2H); MS (m/e) 283 (M+1); mp 134° C.

後処理

  1. temperaturebefore being cooled to ambient temperature
  2. temperaturethe mixture was cooled in an ice-water bath
  3. extractionThe gummy precipitate was extracted (DCM)
  4. washthe organic phase was washed with brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customFurther purification by flash chromatography over silica gel (DCM/MeOH)

出典と根拠

ORDレコード
ord-ea0b874834e647f882f89daaf046f4de
出典データセット
uspto-grants-2013_10
特許番号
US08552186B2

反応ノート

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