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

HRID 62750노트

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HRID 62750 반응식
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]

참가 물질

6

반응물 3

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

생성물 1

HCID 67041833Methyl 4-chloro-3,5-diisopropoxybenzoate수율 36%

시약·촉매·용매 2

HCID 62652Cuprous chloride촉매HCID 6342Acetonitrile용매2회

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온도
65 °C

실험 절차

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+).

후처리

  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)

출처 및 근거

ORD 기록
ord-ee66a503bb9b42dabd090455d8b78dc4
출처 데이터셋
uspto-grants-2016_09
특허 번호
US09447028B2

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