Acetic Acid → 5-bromo-6-chloro-2-(ethoxycarbonyl)-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid

HRID 523253

反応式

HRID 523253 の反応式
Cl.[Br:2][C:3]1[C:11]([Cl:12])=[CH:10][C:6]([C:7]([OH:9])=[O:8])=[C:5]([NH:13]N)[CH:4]=1.O=[C:16]1[CH2:21][CH2:20][CH2:19][CH:18]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH2:17]1.C(O)(=O)C>C1(C)C=CC=CC=1>[Br:2][C:3]1[C:11]([Cl:12])=[CH:10][C:6]([C:7]([OH:9])=[O:8])=[C:5]2[C:4]=1[C:21]1[CH2:20][CH2:19][CH:18]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH2:17][C:16]=1[NH:13]2

参加物

5

反応物 3

HCID 176Acetic Acid2 回HCID 118096Ethyl 3-oxocyclohexanecarboxylate2 回HCID 1177609814-Bromo-5-chloro-2-hydrazinylbenzoic acid hydrochloride

生成物 1

HCID 1177612715-bromo-6-chloro-2-(ethoxycarbonyl)-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid収率 73%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
105 °C

実験手順

A suspension of 4-bromo-5-chloro-2-hydrazinylbenzoic acid hydrochloride (12.89 g, 37.6 mmol), ethyl 3-oxocyclohexanecarboxylate (7.03 g, 41.3 mmol), and acetic acid (6.45 mL, 113 mmol) in toluene (188 mL) was heated at 105° C. overnight. After 16 h, more acetic acid (6 mL) and ethyl 3-oxocyclohexanecarboxylate (2.00 g) were added and the mixture was heated at 110° C. for 4.5 h. The mixture was concentrated, and the residue was combined with toluene (100 mL) and TFA (20 mL). The suspension was heated at 90° C. overnight. The cooled mixture was concentrated and the residue was suspended in EtOAc. The resulting solid was collected by filtration, washed with EtOAc and air-dried to give 5-bromo-6-chloro-2-(ethoxycarbonyl)-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid as a yellow solid (11.0 g, 73% yield). Mass spectrum m/z 400, 402 (M+H)+. 1H NMR (400 MHz, DMSO-d6) δ 13.44 (br. s., 1H), 11.24 (s, 1H), 7.69 (s, 1H), 4.12 (qd, J=7.1, 2.3 Hz, 2H), 3.23-2.81 (m, 5H), 2.23-2.09 (m, 1H), 1.91-1.75 (m, 1H), 1.22 (t, J=7.0 Hz, 3H).

後処理

  1. temperaturethe mixture was heated at 110° C. for 4.5 h
  2. concentrationThe mixture was concentrated
  3. temperatureThe suspension was heated at 90° C. overnight
  4. concentrationThe cooled mixture was concentrated
  5. filtrationThe resulting solid was collected by filtration
  6. washwashed with EtOAc
  7. customair-dried

出典と根拠

ORDレコード
ord-84c073b235094b888f44b75a8138c41f
出典データセット
uspto-grants-2016_05
特許番号
US09334290B2

関連ノート

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