Hydrochloric Acid → Methyl 3-acetyl-5-(methylsulfonyl)benzoic acid

HRID 1454197ノート

反応式

HRID 1454197 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([S:12]([CH3:15])(=[O:14])=[O:13])[CH:11]=1)[C:5]([O:7]C)=[O:6].[CH:16]([O:18]CCCC)=[CH2:17].[CH:23]1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(=O)([O-])[O-].[K+].[K+].Cl>CN(C=O)C.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:23][C:3]1[C:2]([C:16](=[O:18])[CH3:17])=[CH:11][C:10]([S:12]([CH3:15])(=[O:14])=[O:13])=[CH:9][C:4]=1[C:5]([OH:7])=[O:6]

参加物

9

反応物 5

HCID 313Hydrochloric AcidHCID 8108Butyl vinyl etherHCID 11430Potassium CarbonateHCID 812191,3-Bis(diphenylphosphino)propaneHCID 22101072Methyl 3-bromo-5-methanesulfonylbenzoate

生成物 1

HCID 68830431Methyl 3-acetyl-5-(methylsulfonyl)benzoic acid収率 416.2%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
122 °C

実験手順

A mixture of methyl 3-bromo-5-(methylsulfonyl)benzoate (66 mg, 0.226 mmol), 1-(vinyloxy)butane (45.3 mg, 0.06 mL, 0.452 mmol), palladium acetate (1.5 mg, 0.0068 mmol), DPPP (6.1 mg, 0.015 mmol) and potassium carbonate (37.5 mg, 0.27 mmol) in DMF (0.6 mL) and H2O (0.07 mL) in a Smith process vial was heated at 122° C. in microwave for 3 h. The reaction mixture was cooled down to room temperature and hydrolyzed by addition of 5% HCl (1 mL) slowly. The reaction mixture was worked up by extraction with ethyl acetate and concentration under vacuum. The crude mixture was purified by reverse phase prep HPLC to give the title compound (16 mg): 1H NMR (CD3OD, 500 MHz) δ ppm 2.74 (3H, s), 3.24 (3H, s), 8.70 (1H, m), 8.75 (1H, m), 8.87 (1H, m). HPLC retention time: 1.037 min (method A). MS (ESI) (M+H)+ 243.10.

後処理

  1. extractionThe reaction mixture was worked up by extraction with ethyl acetate and concentration under vacuum
  2. customThe crude mixture was purified by reverse phase prep HPLC

出典と根拠

ORDレコード
ord-cf874909ecf14dec9f8a8c08fd3450dd
出典データセット
uspto-grants-2009_01
特許番号
US07476764B2

反応ノート

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