1,3-Dibromopropane → Methyl 5-bromo-2-(3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pentanoate

HRID 1930135ノート

反応式

HRID 1930135 の反応式
[H-].[Na+].[Cl:3][C:4]1[CH:5]=[C:6]([CH2:19][C:20]([O:22][CH3:23])=[O:21])[CH:7]=[CH:8][C:9]=1[B:10]1[O:14][C:13]([CH3:16])([CH3:15])[C:12]([CH3:18])([CH3:17])[O:11]1.[Br:24][CH2:25][CH2:26][CH2:27]Br>CN(C=O)C>[Br:24][CH2:25][CH2:26][CH2:27][CH:19]([C:6]1[CH:7]=[CH:8][C:9]([B:10]2[O:14][C:13]([CH3:15])([CH3:16])[C:12]([CH3:17])([CH3:18])[O:11]2)=[C:4]([Cl:3])[CH:5]=1)[C:20]([O:22][CH3:23])=[O:21]

参加物

5

反応物 3

HCID 80011,3-DibromopropaneHCID 24758Sodium hydride2 回HCID 58464478Benzeneacetic acid, 3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-, methyl ester2 回

生成物 1

HCID 59627651Methyl 5-bromo-2-(3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pentanoate収率 24.12%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
0 °C

実験手順

Sodium hydride (0.153 g, 3.83 mmol) was added in one portion to methyl 2-(3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)acetate (Intermediate 2-7; 1.08 g, 3.48 mmol) in DMF (20 mL) cooled to 0° C. under nitrogen. The resulting solution was stirred at 0° C. for 10 minutes. 1,3-Dibromopropane (0.392 mL, 3.83 mmol) was added to the reaction and was stirred at 0° C. for 5 minutes. Sodium hydride (0.153 g, 3.83 mmol) was added in one portion to the reaction and stir at 0° C. for 1 hour. The reaction mixture was quenched with saturated NH4Cl (50 mL). The reaction mixture was diluted with EtOAc (75 mL), and washed sequentially with water (4×50 mL) and saturated brine (50 mL). dried over MgSO4 The organic layer was evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution gradient 0 to 30% EtOAc in isohexane. Pure fractions were evaporated to dryness to afford methyl 5-bromo-2-(3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pentanoate (0.362 g, 24.12%) as a colourless gum.

後処理

  1. stirringwas stirred at 0° C. for 5 minutes
  2. stirringstir at 0° C. for 1 hour
  3. customThe reaction mixture was quenched with saturated NH4Cl (50 mL)
  4. additionThe reaction mixture was diluted with EtOAc (75 mL)
  5. washwashed sequentially with water (4×50 mL) and saturated brine (50 mL)
  6. dry with materialdried over MgSO4 The organic layer
  7. customwas evaporated
  8. customto afford crude product
  9. customThe crude product was purified by flash silica chromatography, elution gradient 0 to 30% EtOAc in isohexane
  10. customPure fractions were evaporated to dryness

出典と根拠

ORDレコード
ord-b7fc5e39f6714b74ba8f022db7bf3fbe
出典データセット
uspto-grants-2012_05
特許番号
US08188092B2

反応ノート

読み込み中…