Dipropylamine → (1E,4E)-2-amino-8-bromo-N,N-dipropyl-3H-benzo[b]azepine-4-carboxamide

HRID 38025

反応式

HRID 38025 の反応式
[CH2:1]([NH:4][CH2:5][CH2:6][CH3:7])[CH2:2][CH3:3].C[Al](C)C.[NH2:12][C:13]1[CH2:14][C:15]([C:25]([O:27]CC)=O)=[CH:16][C:17]2[CH:23]=[CH:22][C:21]([Br:24])=[CH:20][C:18]=2[N:19]=1.[C@H](O)(C([O-])=O)[C@@H](O)C([O-])=O.[Na+].[K+]>C1(C)C=CC=CC=1>[NH2:12][C:13]1[CH2:14][C:15]([C:25]([N:4]([CH2:5][CH2:6][CH3:7])[CH2:1][CH2:2][CH3:3])=[O:27])=[CH:16][C:17]2[CH:23]=[CH:22][C:21]([Br:24])=[CH:20][C:18]=2[N:19]=1

参加物

6

反応物 4

HCID 8902DipropylamineHCID 9357Potassium Sodium TartrateHCID 16682925TrimethylaluminumHCID 58228535ethyl 2-amino-8-bromo-3H-benzo[b]azepine-4-carboxylate

生成物 1

HCID 66961446(1E,4E)-2-amino-8-bromo-N,N-dipropyl-3H-benzo[b]azepine-4-carboxamide収率 34.1%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
0 °C

実験手順

A 50 ml round bottom flask equipped with a stir bar and nitrogen inlet was charged with 15 mls of dry toluene and dipropylamine (0.44 ml, 3.24 mmol). This was chilled to 0° C. and AlMe3 (4.04 mls, 8.09 mmol, 2M in toluene) was then added. Once the addition was complete, the mixture was allowed to warm to room temperature (˜20-30 minutes). (1E,4E)-ethyl 2-amino-8-bromo-3H-benzo[b]azepine-4-carboxylate (0.5 g, 1.62 mmol) was then added portionwise resulting in a dark solution. This mixture was warmed to 100° C. for about 16 hours, and then allowed to cool to room temperature. This mixture was then poured into 50 mls of a 30% aq. solution of Rochelle's salt and vigorously stirred for 20 minutes, then extracted with EtOAc (2×), extracts dried over sodium sulfate and concentrated under reduced pressure. Flash 40 Biotage (40M cartridge, 5% MeOH/DCM) afforded 201 mgs (32%) of (1E,4E)-2-amino-8-bromo-N,N-dipropyl-3H-benzo[b]azepine-4-carboxamide. m/z (APCI-pos) M+1=364.2, 366.2.

後処理

  1. customA 50 ml round bottom flask equipped with a stir bar and nitrogen inlet
  2. additionOnce the addition
  3. temperatureto warm to room temperature (˜20-30 minutes)
  4. customresulting in a dark solution
  5. temperatureThis mixture was warmed to 100° C. for about 16 hours
  6. temperatureto cool to room temperature
  7. extractionextracted with EtOAc (2×)
  8. dry with materialextracts dried over sodium sulfate
  9. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-febcc2bbf55a49ebae7f0dc6f20e7b7e
出典データセット
uspto-grants-2013_09
特許番号
US08524702B2

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