Cesium carbonate → 4-Tert-butyl-2-(2-chloro-4-fluorophenoxy)benzoic acid

HRID 1625199

反応式

HRID 1625199 の反応式
Br[C:2]1[CH:10]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[Cl:15][C:16]1[CH:21]=[C:20]([F:22])[CH:19]=[CH:18][C:17]=1[OH:23].C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1>[C:11]([C:9]1[CH:8]=[CH:7][C:3]([C:4]([OH:6])=[O:5])=[C:2]([O:23][C:17]2[CH:18]=[CH:19][C:20]([F:22])=[CH:21][C:16]=2[Cl:15])[CH:10]=1)([CH3:14])([CH3:13])[CH3:12]

参加物

5

反応物 3

HCID 10796Cesium carbonateHCID 748142-Chloro-4-fluorophenolHCID 2363522-Bromo-4-tert-butylbenzoic acid

生成物 1

HCID 576877084-Tert-butyl-2-(2-chloro-4-fluorophenoxy)benzoic acid収率 72.2%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
120 °C

実験手順

In a pressure-vessel, a stirring mixture of 2-bromo-4-tert-butylbenzoic acid (1.00 g, 3.89 mmol) and 2-chloro-4-fluorophenol (860 mg, 620 μL, 5.87 mmol) in toluene (20 mL) was added Cs2CO3 (2.53 g, 7.78 mmol) followed by copper(I) triflate benzene complex (98 mg, 0.19 mmol). The sealed vessel was heated to 120° C. for 16 h. After cooling to room temperature, the reaction mixture was partitioned between 50 mL EtOAc and 50 mL H2O. The aqueous layer was acidified using 2.0 N HCl(aq) and re-extracted with EtOAc. The combined organic solution was dried over Na2SO4, filtered, and concentrated. The residue was purified via silica gel chromatography using 0-3% MeOH/CH2Cl2 to give the product, 4-tert-butyl-2-(2-chloro-4-fluorophenoxy)benzoic acid as a white solid (907 mg, 2.81 mmol) in 72% yield. LC/MS: m/z 323.2 (M+H) at 1.99 min (10%-99% CH3CN (0.035% TFA)/H2O (0.05% TFA)).

後処理

  1. temperatureAfter cooling to room temperature
  2. customthe reaction mixture was partitioned between 50 mL EtOAc and 50 mL H2O
  3. extractionre-extracted with EtOAc
  4. dry with materialThe combined organic solution was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified via silica gel chromatography

出典と根拠

ORDレコード
ord-729cbca1987243dba6b471d9c68653b3
出典データセット
uspto-grants-2014_07
特許番号
US08779197B2

関連ノート

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