Hydrochloric Acid → Methyl 4-chloro-3,5-diisopropoxybenzoate

HRID 62750ノート

反応式

HRID 62750 の反応式
N(OC(C)(C)C)=O.N[C:9]1[C:18]([O:19][CH:20]([CH3:22])[CH3:21])=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][C:10]=1[O:23][CH:24]([CH3:26])[CH3:25].[ClH:27]>CC#N.[Cu]Cl>[Cl:27][C:9]1[C:18]([O:19][CH:20]([CH3:22])[CH3:21])=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][C:10]=1[O:23][CH:24]([CH3:26])[CH3:25]

参加物

6

反応物 3

HCID 313Hydrochloric AcidHCID 10906Tert-Butyl nitriteHCID 67041607Methyl 4-amino-3,5-diisopropoxybenzoate

生成物 1

HCID 67041833Methyl 4-chloro-3,5-diisopropoxybenzoate収率 36%

試薬・触媒・溶媒 2

HCID 62652Cuprous chloride触媒HCID 6342Acetonitrile溶媒2 回

反応条件

温度
65 °C

実験手順

A suspension of copper (I) chloride (129 mg, 1.31 mmol) and tert-butyl nitrite (155 μL, 1.31 mmol) in anhydrous MeCN (2 mL) was stirred at 65° C. A solution of methyl 4-amino-3,5-diisopropoxybenzoate (4) (233 mg, 0.872 mmol) in anhydrous MeCN (1 mL) was added dropwise. Once the addition was complete the mixture was allowed to cool to RT and poured on to 20% HCl (5 mL). The mixture was partitioned between DCM (10 mL) and aq. ammonia (35%, 5 mL), the phases were separated and the organic solution was further washed with ammonia solution (17.5%, 10 mL), and brine (2×20 mL). The solvent was removed in vacuo and the residue was purified by silica gel chromatography (40 g, 0-100% EtOAc in isohexane) to afford methyl 4-chloro-3,5-diisopropoxybenzoate (93 mg, 36% yield) as a colourless oil: m/z 287 [M+H]+ (ES+).

後処理

  1. additionOnce the addition
  2. temperatureto cool to RT
  3. customThe mixture was partitioned between DCM (10 mL) and aq. ammonia (35%, 5 mL)
  4. customthe phases were separated
  5. washthe organic solution was further washed with ammonia solution (17.5%, 10 mL), and brine (2×20 mL)
  6. customThe solvent was removed in vacuo
  7. customthe residue was purified by silica gel chromatography (40 g, 0-100% EtOAc in isohexane)

出典と根拠

ORDレコード
ord-ee66a503bb9b42dabd090455d8b78dc4
出典データセット
uspto-grants-2016_09
特許番号
US09447028B2

反応ノート

読み込み中…