Pyridine → tert-Butyl 5-(4-(4-bromophenyl)butanamido)-2-(ethylthio)benzyl(methyl)carbamate

HRID 735530ノート

反応式

HRID 735530 の反応式
C(Cl)(=O)[C:2](Cl)=[O:3].[Br:7][C:8]1[CH:13]=[CH:12][C:11]([CH:14]([CH2:18][CH3:19])C(O)=O)=[CH:10][CH:9]=1.[NH2:20][C:21]1[CH:22]=[CH:23][C:24]([S:37][CH2:38][CH3:39])=[C:25]([CH:36]=1)[CH2:26][N:27]([CH3:35])[C:28](=[O:34])[O:29][C:30]([CH3:33])([CH3:32])[CH3:31].N1C=CC=CC=1>C(Cl)Cl.CN(C=O)C.CN(C1C=CN=CC=1)C>[Br:7][C:8]1[CH:9]=[CH:10][C:11]([CH2:14][CH2:18][CH2:19][C:2]([NH:20][C:21]2[CH:22]=[CH:23][C:24]([S:37][CH2:38][CH3:39])=[C:25]([CH:36]=2)[CH2:26][N:27]([CH3:35])[C:28](=[O:34])[O:29][C:30]([CH3:31])([CH3:32])[CH3:33])=[O:3])=[CH:12][CH:13]=1

参加物

8

反応物 4

HCID 1049PyridineHCID 574722-(4-Bromophenyl)butanoic acidHCID 65578Oxalyl chlorideHCID 57956368tert-Butyl 5-amino-2-(ethylthio)benzyl(methyl)carbamate

生成物 1

HCID 57956370tert-Butyl 5-(4-(4-bromophenyl)butanamido)-2-(ethylthio)benzyl(methyl)carbamate収率 88%

試薬・触媒・溶媒 3

HCID 6228Dimethylformamide触媒HCID 142844-(Dimethylamino)pyridine触媒HCID 6344Dichloromethane溶媒2 回

実験手順

Oxalyl chloride (0.180 mL, 2.06 mmol) was added dropwise to a suspension of 4-bromophenylbutanoic acid (0.250 g, 1.03 mmol) in DCM (3 mL) containing DMF (1 drop) at rt. After 4 h, the reaction mixture was concentrated in vacuo and coevaporated with toluene. The residue was dissolved in DCM (2 mL) and added dropwise to a solution of 17A (0.300 g, 1.01 mmol), DMAP (0.025 g, 0.2 mmol)and pyridine (1.0 mL, 12.3 mmol) in DCM (2 mL) at rt. The reaction mixture was stirred overnight at rt. The reaction mixture was concentrated in vacuo and the residue was triturated with water and then purified by silica gel chromatography (gradient from 0 to 20% ethyl acetate in hexanes) to give 17B (0.46 g, 88%) as a clear oil that solidified on standing. 1H NMR (400 MHz, CDCl3) δ ppm 1.26 (t, J=7.03 Hz, 3 H) 1.33-1.58 (m, 9 H) 1.96-2.04 (m, 2 H) 2.33 (t, J=7.47 Hz, 2 H) 2.63 (t, J=7.47 Hz, 2 H) 2.63 (t, J=7.47 Hz, 2 H) 2.74-2.93 (m, 3 H) 4.56 (br. s., 2 H) 6.96-7.02 (m, 0.5 H) 7.05 (d, J=8.35 Hz, 2 H) 7.13 (br. s., 0.4 H) 7.28-7.36 (m, 0.8 H) 7.38 (d, J=8.35 Hz, 2 H) 7.60-7.72 (m, 0.4 H) 7.81-7.98 (m, 0.9 H) 8.33 (br. s., 1 H).

後処理

  1. concentrationthe reaction mixture was concentrated in vacuo
  2. dissolutionThe residue was dissolved in DCM (2 mL)
  3. concentrationThe reaction mixture was concentrated in vacuo
  4. customthe residue was triturated with water
  5. custompurified by silica gel chromatography (gradient from 0 to 20% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-299951a814644dfe8887de927b87117a
出典データセット
uspto-grants-2009_09
特許番号
US07592331B2

反応ノート

読み込み中…