Heptane → (tert-Butyl) 6-bromonicotinate

HRID 602077

反応式

HRID 602077 の反応式
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([OH:10])=[O:9])=[CH:4][N:3]=1.C(Br)(=O)C(Br)=O.CCCCCCC.[CH3:24][C:25]([O-])([CH3:27])[CH3:26].[K+]>C(Cl)Cl.CN(C=O)C.C1COCC1.CCOC(C)=O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([O:10][C:25]([CH3:27])([CH3:26])[CH3:24])=[O:9])=[CH:4][N:3]=1

参加物

9

反応物 4

HCID 8900HeptaneHCID 84841Ethanedioyl dibromideHCID 2389326-Bromonicotinic acidHCID 23665647Potassium tert-butoxide

生成物 1

HCID 26369925(tert-Butyl) 6-bromonicotinate収率 36%

試薬・触媒・溶媒 4

HCID 6228Dimethylformamide触媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a round bottom flask containing 2-bromo-5-pyridinecarboxylic acid (10.0 g, 49 mmol) in DCM (500 mL) was added oxalyl bromide (7.4 mL) and 5 drops of DMF. After some gas evolution, the reaction mixture was stirred at reflux ca 6 h, then cooled to rt and heptane 100 mL was added, followed by concentration of the mixture. The mixture was then suspended in THF 400 mL, cooled to 0° C. t-BuOK (5.8 g, 52 mmol) was then added and the r×n allowed to warm to rt and stirred for 2 h. The mixture poured into EtOAc, washed with 1 N NaOH, water, brine, dried MgSO4 filtered and concentrated. The residue was purified by silica gel chromatography Biotage 40S Heptane EtOAc 0-80% 3 L to afford the title compound 4.2 g (36%) of as a white solid. 1H NMR (400 MHz, DMSO-d6) □ ppm 8.78-8.86 (1H, m), 8.14 (1H, dd, J=8.4, 2.4 Hz), 7.81 (1H d, J=8.4 Hz), 1.56 (9H, s).

後処理

  1. temperatureat reflux ca 6 h
  2. additionwas then added
  3. temperatureto warm to rt
  4. stirringstirred for 2 h
  5. washwashed with 1 N NaOH, water, brine, dried MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by silica gel chromatography Biotage 40S Heptane EtOAc 0-80% 3 L

出典と根拠

ORDレコード
ord-095c96c71dcd440692571a81ff1a332e
出典データセット
uspto-grants-2011_03
特許番号
US07902373B2

関連ノート

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