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

HRID 1497910노트

반응식

HRID 1497910 반응식
[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]

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 312751,4-Dioxane용매

실험 절차

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)+.

후처리

  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

출처 및 근거

ORD 기록
ord-1ec7563febcd4ddfba16a5f0cc5ae487
출처 데이터셋
uspto-grants-2015_12
특허 번호
US09199981B2

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