Triphenylphosphine → tert-Butyl (2-((5-bromopyridin-3-yl)oxy)ethyl)carbamate

HRID 1774732ノート

反応式

HRID 1774732 の反応式
[Br:1][C:2]1[CH:3]=[C:4]([OH:8])[CH:5]=[N:6][CH:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O[CH2:29][CH2:30][NH:31][C:32](=[O:38])[O:33][C:34]([CH3:37])([CH3:36])[CH3:35].C1C(COC(/N=N\C(OCC2C=CC(Cl)=CC=2)=O)=O)=CC=C(Cl)C=1.C([O-])(O)=O.[Na+]>C1COCC1.CCOC(C)=O>[C:34]([O:33][C:32](=[O:38])[NH:31][CH2:30][CH2:29][O:8][C:4]1[CH:5]=[N:6][CH:7]=[C:2]([Br:1])[CH:3]=1)([CH3:37])([CH3:36])[CH3:35]

参加物

8

反応物 5

HCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 5995293-Bromo-5-hydroxypyridineHCID 2733206tert-butyl N-(2-hydroxyethyl)carbamateHCID 16218364(4-chlorophenyl)methyl (NZ)-N-[(4-chlorophenyl)methoxycarbonylimino]carbamate

生成物 1

HCID 71627051tert-Butyl (2-((5-bromopyridin-3-yl)oxy)ethyl)carbamate収率 63%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of 5-bromopyridin-3-ol (0.5 g, 2.87 mmol) in THF (30 mL) cooled to 0° C. were added triphenylphosphine (0.829 g, 3.16 mmol) and tert-butyl 2-hydroxyethylcarbamate (0.51 g, 3.16 mmol) in THF (5 mL) followed by di-(4-chlorobenzyl)azodicarboxylate (1.16 g, 3.16 mmol), added portionwise, and the reaction mixture was then stirred at room temperature over night. The mixture was diluted with EtOAc, poured into aq. NaHCO3 (50 mL) and the aqueous layer was extracted with EtOAc (2×100 mL). Combined organics were washed with brine, dried over Na2SO4, filtered and evaporated. The residue was taken up in diethyl ether (50 mL) and left to stand in the fridge for 2 h. After this time, the solid precipitate was filtered off and the resulting filtrate evaporated to dryness. The residue was purified by silica gel flash chromatography eluting with a 0 to 30% EtOAc-heptane gradient to give the title compound (0.57 g, 63%) as a white solid. MS: 317.0 and 319.0 (M+H+).

後処理

  1. additionadded portionwise
  2. extractionthe aqueous layer was extracted with EtOAc (2×100 mL)
  3. washCombined organics were washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. customevaporated
  7. waitleft
  8. filtrationAfter this time, the solid precipitate was filtered off
  9. customthe resulting filtrate evaporated to dryness
  10. customThe residue was purified by silica gel flash chromatography
  11. washeluting with a 0 to 30% EtOAc-heptane gradient

出典と根拠

ORDレコード
ord-748fa926b8eb4ec6be88caec406fe14d
出典データセット
uspto-grants-2016_02
特許番号
US09260408B2

反応ノート

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