Allyl bromide → (R)-N-(2-(allyloxy)-1-phenylethyl)-2,2,2-trifluoroacetamide

HRID 501679ノート

反応式

HRID 501679 の反応式
[F:1][C:2]([F:16])([F:15])[C:3]([NH:5][C@H:6]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[CH2:7][OH:8])=[O:4].[Li][CH2:18][CH2:19][CH2:20]C.CN1C(=O)N(C)CCC1.C(Br)C=C>C1COCC1>[CH2:20]([O:8][CH2:7][C@H:6]([NH:5][C:3](=[O:4])[C:2]([F:15])([F:16])[F:1])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[CH:19]=[CH2:18]

参加物

6

反応物 4

HCID 7841Allyl bromideHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 15653812(R)-2,2,2-Trifluoro-N-(2-hydroxy-1-phenylethyl)acetamideHCID 178418339Butyllithium

生成物 1

HCID 86622318(R)-N-(2-(allyloxy)-1-phenylethyl)-2,2,2-trifluoroacetamide収率 73.7%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

Step Q (2): (R)-2,2,2-Trifluoro-N-(2-hydroxy-1-phenylethyl)acetamide from step Q (1) (3.34 g, 14.3 mmol) was dissolved in THF (30 mL) and chilled to −78° C. n-BuLi (12 mL, 29 mmol, 2.5 M in hexanes) and DMPU (3.45 mL, 29 mmol) were added to the mixture. After 10 min, allyl bromide (12 mL, 143 mmol) was added. The mixture was warmed to rt and then heated to reflux for 16 h. The mixture was quenched with saturated NH4Cl, diluted with 1 N NaOH, and extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. Purification by silica-gel column chromatography (0-25% EtOAc/Hexanes) afforded 2.88 g (73% yield) of (R)-N-(2-(allyloxy)-1-phenylethyl)-2,2,2-trifluoroacetamide as a yellow residue. LC-MS (M+H)+=274.06. 1H NMR (300 MHz, CDCl3) δ ppm 3.66-3.79 (m, 2H) 3.95-4.01 (m, 2H) 5.07-5.26 (m, 3H) 5.73-5.89 (m, 1H) 6.95-7.06 (m, 1H) 7.24-7.37 (m, 4H).

後処理

  1. additionwere added to the mixture
  2. temperatureheated
  3. temperatureto reflux for 16 h
  4. customThe mixture was quenched with saturated NH4Cl
  5. additiondiluted with 1 N NaOH
  6. extractionextracted with EtOAc
  7. dry with materialThe combined organic layers were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customPurification by silica-gel column chromatography (0-25% EtOAc/Hexanes)

出典と根拠

ORDレコード
ord-9176b7cff35c410baa4f606736e5fa49
出典データセット
uspto-grants-2010_08
特許番号
US07772221B2

反応ノート

読み込み中…