Diethyl Ether → Tert-butyl 2-(6-chloro-5-fluoropyridin-3-yl)acetate

HRID 592231

反応式

HRID 592231 の反応式
Br[C:2]1[CH:3]=[C:4]([F:9])[C:5]([Cl:8])=[N:6][CH:7]=1.[Cl-].[C:11]([O:15][C:16](=[O:19])[CH2:17][Zn+])([CH3:14])([CH3:13])[CH3:12].CCOCC>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].C1([C-]2C(C3C=CC=CC=3)=C(C3C=CC=CC=3)C(C3C=CC=CC=3)=C2C2C=CC=CC=2)C=CC=CC=1.C(P(C(C)(C)C)[C-]1C=CC=C1)(C)(C)C.[Fe+2].C1COCC1>[Cl:8][C:5]1[N:6]=[CH:7][C:2]([CH2:17][C:16]([O:15][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:19])=[CH:3][C:4]=1[F:9]

参加物

7

反応物 3

HCID 3283Diethyl EtherHCID 27632855-Bromo-2-chloro-3-fluoropyridineHCID 178451183HCID 178451183、化合物

生成物 1

HCID 58365072Tert-butyl 2-(6-chloro-5-fluoropyridin-3-yl)acetate

試薬・触媒・溶媒 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium触媒HCID 129828017Ditert-butyl(cyclopenta-2,4-dien-1-yl)phosphane;iron(2+);(2,3,4,5-tetraphenylcyclopenta-1,4-dien-1-yl)benzene触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
70 °C

実験手順

In a sealed tube, a mixture of 5-bromo-2-chloro-3-fluoropyridine 205-1 (631 mg, 3 mmol), 0.5 M (2-tert-butoxy-2-oxoethyl) zinc(II) chloride 205-2 in ether (6.6 mL, 3.3 mmol), Pd(dba)2 (87 mg, 0.15 mmol), 1,2,3,4,5-pentaphenyl-1′-(di-t-butylphosphino)ferrocene (Q-phos, 107 mg, 0.15 mmol), and THF (12 mL) under argon was stirred at 70° C. for 18 hours. After cooled to room temperature, the solvents were evaporated and the residue was redissolved in ethyl acetate, washed with water and brine, dried over Na2SO4 and concentrated to dryness by rotary evaporation. The crude product was purified by silica gel flash chromatography, eluted with 30% ethyl acetate in hexane to give tert-butyl 2-(6-chloro-5-fluoropyridin-3-yl)acetate 205-3 as a brown oil. MS m/z 246.1 (M+1).

後処理

  1. temperatureAfter cooled to room temperature
  2. customthe solvents were evaporated
  3. dissolutionthe residue was redissolved in ethyl acetate
  4. washwashed with water and brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated to dryness by rotary evaporation
  7. customThe crude product was purified by silica gel flash chromatography
  8. washeluted with 30% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-c79a005595ae44d6955ce647b9bd477f
出典データセット
uspto-grants-2016_01
特許番号
US09238646B2

関連ノート

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