Triphenylphosphine → Tert-butyl 3-(2-(4-bromo-2-(trifluoromethyl)phenoxy)ethyl)azetidine-1-carboxylate

HRID 517980ノート

反応式

HRID 517980 の反応式
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([C:9]([F:12])([F:11])[F:10])[CH:3]=1.O[CH2:14][CH2:15][CH:16]1[CH2:19][N:18]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:17]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:14][CH2:15][CH:16]2[CH2:19][N:18]([C:20]([O:22][C:23]([CH3:24])([CH3:26])[CH3:25])=[O:21])[CH2:17]2)=[C:4]([C:9]([F:10])([F:11])[F:12])[CH:3]=1

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 142784o-Cresol, 4-bromo-alpha,alpha,alpha-trifluoro-HCID 5363146Diisopropyl azodicarboxylateHCID 22594530tert-Butyl 3-(2-hydroxyethyl)azetidine-1-carboxylate

生成物 1

HCID 67297795Tert-butyl 3-(2-(4-bromo-2-(trifluoromethyl)phenoxy)ethyl)azetidine-1-carboxylate収率 52.6%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

4-Bromo-2-(trifluoromethyl)phenol (3 g), tert-butyl 3-(2-hydroxyethyl)azetidine-1-carboxylate (2.81 g) and triphenylphosphine (3.92 g) were dissolved in DCM (25 ml). The reaction mixture was placed under a nitrogen atmosphere and cooled to 0° C. then DIAD (2.94 ml) was added dropwise. The mixture was stirred at room temperature for 16 hours then solvent evaporated under reduced pressure. The resulting residue was dissolved in ether (10 ml), heptane (15 mL) was then added and the suspension stirred for 45 minutes. The mixture was filtered (solid was washed with 3:2 heptane/ether) and the filtrate washed with NaOH (1M, 2×40 mL). Organics were dried over sodium sulphate and solvent evaporated under reduced pressure to yield crude product as a clear oil (6.05 g). Purification by flash chromatography (100 g silica column, 10% to 25% EtOAc in heptane gradient) afforded tert-butyl 3-(2-(4-bromo-2-(trifluoromethyl)phenoxy)ethyl)azetidine-1-carboxylate (52.6% yield) as a clear oil.

後処理

  1. customsolvent evaporated under reduced pressure
  2. dissolutionThe resulting residue was dissolved in ether (10 ml)
  3. additionheptane (15 mL) was then added
  4. stirringthe suspension stirred for 45 minutes
  5. filtrationThe mixture was filtered
  6. wash(solid was washed with 3:2 heptane/ether)
  7. washthe filtrate washed with NaOH (1M, 2×40 mL)
  8. dry with materialOrganics were dried over sodium sulphate and solvent
  9. customevaporated under reduced pressure
  10. customto yield crude product as a clear oil (6.05 g)
  11. customPurification by flash chromatography (100 g silica column, 10% to 25% EtOAc in heptane gradient)

出典と根拠

ORDレコード
ord-df6f59ee9c9745baa947f2f825f08bf0
出典データセット
uspto-grants-2015_08
特許番号
US09115126B2

反応ノート

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