Sodium hydride → Carbonic acid, 3-cyclopropyl-3-oxetanyl 2-pyridinyl ester

HRID 1852162ノート

反応式

HRID 1852162 の反応式
[H-].[Na+].[CH:3]1([C:6]2([OH:10])[CH2:9][O:8][CH2:7]2)[CH2:5][CH2:4]1.[N:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[O:17][C:18](=O)[O:19]C1C=CC=CN=1>C1COCC1.CCOC(C)=O.[Cl-].[Na+].O>[C:18](=[O:19])([O:17][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][N:11]=1)[O:10][C:6]1([CH:3]2[CH2:5][CH2:4]2)[CH2:9][O:8][CH2:7]1

参加物

7

反応物 3

HCID 24758Sodium hydrideHCID 2757370Carbonic acid di-2-pyridyl esterHCID 717427063-Cyclopropyloxetan-3-ol

生成物 1

HCID 70979138Carbonic acid, 3-cyclopropyl-3-oxetanyl 2-pyridinyl ester収率 18.8%

試薬・触媒・溶媒 3

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒HCID 57417360Sodium chloride; water溶媒

実験手順

To a suspension of sodium hydride, 60% in mineral oil (315 mg, 7.88 mmol) in THF (20 mL) was added 3-cyclopropyloxetan-3-ol (750 mg, 6.57 mmol) at 0° C. After stirring 30 min, the solution was transferred to a solution of di(pyridin-2-yl)carbonate (1421 mg, 6.57 mmol) in THF (20 mL) through a cannula. The formed slurry was stirred at 0° C. for 30 min. The slurry was warmed to rt and stirred for 2 h. The reaction was diluted with EtOAc followed by brine. The organic layer was collected, dried over MgSO4, filtered and evaporated to give the crude material. The crude material was purified via biotage (40 g column, 5-40% EtOAc:Hex) to give the expected product 3-cyclopropyloxetan-3-yl pyridin-2-yl carbonate (290 mg, 18.76% yield) as a clear thick oil. 1H NMR (400 MHz, CHLOROFORM-d) d 8.54-8.36 (m, 1H), 7.89-7.77 (m, 1H), 7.34-7.25 (m, 1H), 7.17 (d, J=8.3 Hz, 1H), 4.84 (d, J=8.5 Hz, 2H), 4.42 (d, J=8.3 Hz, 2H), 1.67-1.56 (m, 1H), 0.81-0.72 (m, 2H), 0.72-0.63 (m, 2H).

後処理

  1. stirringThe formed slurry was stirred at 0° C. for 30 min
  2. stirringstirred for 2 h
  3. customThe organic layer was collected
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. customevaporated
  7. customto give the crude material
  8. customThe crude material was purified via biotage (40 g column, 5-40% EtOAc:Hex)

出典と根拠

ORDレコード
ord-206f36f88ed14c05a1f080ffb013d0db
出典データセット
uspto-grants-2015_02
特許番号
US08957203B2

反応ノート

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