Acetone → methyl 2-{(3R,4R)-3-isocyano-3-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-2-oxo-4-allylazetidin-1-yl}-3-methylbut-2-enoate

HRID 851416ノート

反応式

HRID 851416 の反応式
[N+:1]([C@@H:3]1[C@@H:6]([CH2:7][CH:8]=[CH2:9])[N:5]([C:10](=[C:15]([CH3:17])[CH3:16])[C:11]([O:13][CH3:14])=[O:12])[C:4]1=[O:18])#[C-:2].C([Li])CCC.[CH3:24][C:25]([CH3:27])=[O:26].Cl[C:29]([O:31][CH2:32][C:33]1[CH:38]=[CH:37][C:36]([N+:39]([O-:41])=[O:40])=[CH:35][CH:34]=1)=[O:30]>O1CCCC1.C(O)(=O)C>[N+:1]([C@@:3]1([C:25]([CH3:27])([O:26][C:29]([O:31][CH2:32][C:33]2[CH:34]=[CH:35][C:36]([N+:39]([O-:41])=[O:40])=[CH:37][CH:38]=2)=[O:30])[CH3:24])[C@@H:6]([CH2:7][CH:8]=[CH2:9])[N:5]([C:10](=[C:15]([CH3:17])[CH3:16])[C:11]([O:13][CH3:14])=[O:12])[C:4]1=[O:18])#[C-:2]

参加物

7

反応物 4

HCID 180AcetoneHCID 782054-Nitrobenzyl chloroformateHCID 54071546methyl 2-[(3R,4R)-3-isocyano-2-oxo-4-allylazetidin-1-yl]-3-methylbut-2-enoateHCID 178418339Butyllithium

生成物 1

HCID 53687939methyl 2-{(3R,4R)-3-isocyano-3-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-2-oxo-4-allylazetidin-1-yl}-3-methylbut-2-enoate

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
-78 °C

実験手順

To a solution of methyl 2-[(3R,4R)-3-isocyano-2-oxo-4-allylazetidin-1-yl]-3-methylbut-2-enoate (127.6 mg) in tetrahydrofuran (2.55 ml) was added dropwise a solution of n-butyl lithium (0.409 ml of 1.51 M solution in hexane) at -78° C. over a period of 3 minutes. After stirring for 15 minutes at -78° C., the reaction mixture was added dropwise with a solution of acetone (0.0459 ml) in tetrahydrofuran (0.459 ml) at -78° C. over a period of 3 minutes. After stirring for 25 minutes at -78° C., the reaction mixture was added dropwise with a solution of 4-nitrobenzyl chloroformate (124.1 mg) in tetrahydrofuran (1.24 ml) at -78° C. over a period of 3 minutes. The resulting solution was allowed to warm to 0° C. over a period of 40 minutes and added with acetic acid (0.0412 ml) at 0° C. The solvent was distilled off in vacuo at 0° C. and the residue was dissolved in ethyl acetate (30 ml) and washed with brine, aqueous sodium bicarbonate, brine and saturated aqueous sodium chloride. After drying over magnesium sulfate, the ethyl acetate extract was filtered and evaporated in vacuo. The residual oil (285.4 mg) was chromatographed on silica gel (5.7 g) eluting with a mixture of ethyl acetate and hexane (1:5→1:3) to give methyl 2-{(3R, 4R)-3-isocyano-3-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-2-oxo-4-allylazetidin-1-yl}-3-methylbut-2-enoate (211.2 mg) as an oil.

後処理

  1. stirringAfter stirring for 25 minutes at -78° C.
  2. temperatureto warm to 0° C. over a period of 40 minutes
  3. distillationThe solvent was distilled off in vacuo at 0° C.
  4. dissolutionthe residue was dissolved in ethyl acetate (30 ml)
  5. washwashed with brine, aqueous sodium bicarbonate, brine and saturated aqueous sodium chloride
  6. dry with materialAfter drying over magnesium sulfate
  7. extractionthe ethyl acetate extract
  8. filtrationwas filtered
  9. customevaporated in vacuo
  10. customThe residual oil (285.4 mg) was chromatographed on silica gel (5.7 g)
  11. washeluting with a mixture of ethyl acetate and hexane (1:5→1:3)

出典と根拠

ORDレコード
ord-a73cc8f8074d4d6b88213195454f28d6
出典データセット
uspto-grants-1983_05
特許番号
US04383945

反応ノート

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