Hydrochloric Acid → 3-Acetyl-5-(1,1-dioxo-1lambda6-[1,2]thiazinan-2-yl)-benzoic acid methyl ester

HRID 1454200ノート

反応式

HRID 1454200 の反応式
[CH3:1][O:2][C:3](=[O:19])[C:4]1[CH:9]=[C:8]([N:10]2[CH2:15][CH2:14][CH2:13][CH2:12][S:11]2(=[O:17])=[O:16])[CH:7]=[C:6](Br)[CH:5]=1.[CH:20]([O:22]CCCC)=[CH2:21].C1C=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>[CH3:1][O:2][C:3](=[O:19])[C:4]1[CH:9]=[C:8]([N:10]2[CH2:15][CH2:14][CH2:13][CH2:12][S:11]2(=[O:17])=[O:16])[CH:7]=[C:6]([C:20](=[O:22])[CH3:21])[CH:5]=1

参加物

9

反応物 5

HCID 313Hydrochloric AcidHCID 8108Butyl vinyl etherHCID 11430Potassium CarbonateHCID 812191,3-Bis(diphenylphosphino)propaneHCID 575293223-Bromo-5-(1,1-dioxo-1lambda6-[1,2]thiazinan-2-yl)-benzoic acid methyl ester

生成物 1

HCID 575293353-Acetyl-5-(1,1-dioxo-1lambda6-[1,2]thiazinan-2-yl)-benzoic acid methyl ester収率 44.6%

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 3-bromo-5-(1,1-dioxo-1λ6-[1,2]thiazinan-2-yl)-benzoic acid methyl ester (500 mg, 1.44 mmol), 1-(vinyloxy)butane (288.6 mg, 0.37 mL, 2.88 mmol), palladium acetate (9.6 mg, 0.043 mmol), DPPP (39.2 mg, 0.095 mmol) and potassium carbonate (238.5 mg, 1.73 mmol) in DMF (3.8 mL) and H2O (0.45 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 (6 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 (200 mg): 1H NMR (CD3OD, 500 MHz) δ ppm 1.93-2.01 (2H, m), 2.31-2.37 (2H, m), 2.67 (3H, s), 3.27-3.30 (2H, m), 3.83 (2H, t, J=5 Hz), 3.98 (3H, s), 8.14 (1H, m), 8.19 (1H, m), 8.51 (1H, m). HPLC retention time: 1.448 min (method A). MS (ESI) (M+H)+ 312.13.

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-ab7ede4c4f10486babbe1709374c16ed
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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