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

HRID 1497910ノート

反応式

HRID 1497910 の反応式
[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]

参加物

6

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

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)+.

後処理

  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

出典と根拠

ORDレコード
ord-1ec7563febcd4ddfba16a5f0cc5ae487
出典データセット
uspto-grants-2015_12
特許番号
US09199981B2

反応ノート

読み込み中…