tert-Butanol → Ethyl 1-[[(1,1-dimethylethoxy)carbonyl]amino]-3,3-difluorocyclobutanecarboxylate

HRID 1497910Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1497910
[CH2:1]([O:3][C:4]([C:6]1(C(O)=O)[CH2:9][C:8]([F:11])([F:10])[CH2:7]1)=[O:5])[CH3:2].[C:15]([OH:19])([CH3:18])([CH3:17])[CH3:16].C1C=CC(P([N:34]=[N+]=[N-])(C2C=CC=CC=2)=O)=CC=1.C([O:40][CH2:41]C)(=O)C>O1CCOCC1>[C:15]([O:19][C:41]([NH:34][C:6]1([C:4]([O:3][CH2:1][CH3:2])=[O:5])[CH2:7][C:8]([F:10])([F:11])[CH2:9]1)=[O:40])([CH3:18])([CH3:17])[CH3:16]

Komponenten

6

Edukt 4

HCID 6386tert-ButanolHCID 8857Ethyl AcetateHCID 199401P,P-Diphenylphosphinic azideHCID 672304401-Ethyl 3,3-difluoro-1,1-cyclobutanedicarboxylate

Produkt 1

HCID 67231098Ethyl 1-[[(1,1-dimethylethoxy)carbonyl]amino]-3,3-difluorocyclobutanecarboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

To a solution of 1-(ethoxycarbonyl)-3,3-difluorocyclobutanecarboxylic acid (162) (1 g, 4.8 mmol) in dry dioxane (18 mL) was added tert-butanol (0.4 mL, 4.3 mmol), DPPA (1.03 mL, 4.8 mmol) and TEA (0.7 mL, 4.9 mmol) and the mixture was refluxed overnight. Ethyl acetate was added and the organic layer was washed twice with 5% citric acid and saturated sodium hydrogen carbonate. The solution was dried and evaporated under reduced pressure. The product was purified using silica gel chromatography using hexanes/ethyl acetate to yield ethyl 1-((tert-butoxycarbonyl)amino)-3,3-difluorocyclobutanecarboxylate (163). 1H NMR (400 MHz, CD2Cl2) δ 4.12 (q, J=6.8 Hz, 2H), 3.18-3.08 (m, 2H), 2.73-2.55 (m, 2H), 1.34 (s, 9H), 1.19 (t, J=6.8 Hz, 4H). MS m/z 280.1 (M+1)+.

Aufarbeitung

  1. temperaturethe mixture was refluxed overnight
  2. washthe organic layer was washed twice with 5% citric acid and saturated sodium hydrogen carbonate
  3. customThe solution was dried
  4. customevaporated under reduced pressure
  5. customThe product was purified

Quellen und Nachweise

ORD-Eintrag
ord-1ec7563febcd4ddfba16a5f0cc5ae487
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09199981B2

Notizen zur Reaktion

Wird geladen…