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

HRID 501679Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 501679
[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]

Komponenten

6

Edukt 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

Produkt 1

HCID 86622318(R)-N-(2-(allyloxy)-1-phenylethyl)-2,2,2-trifluoroacetamideAusbeute 73,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-9176b7cff35c410baa4f606736e5fa49
Quelldatensatz
uspto-grants-2010_08
Patentnummer
US07772221B2

Notizen zur Reaktion

Wird geladen…