Propylene Oxide → (3R,4S)-3-[2-(2-chloroacetamidothiazol-4-yl)-2-methoxyiminoacetamido]-4-methylthio-2-oxoazetidine

HRID 653253ノート

反応式

HRID 653253 の反応式
O=C(Cl)OC(Cl)(Cl)Cl.[Cl:9][CH2:10][C:11]([NH:13][C:14]1[S:15][CH:16]=[C:17]([C:19](=[N:23][O:24][CH3:25])[C:20]([OH:22])=O)[N:18]=1)=[O:12].[NH2:26][C@H:27]1[C@H:30]([S:31][CH3:32])[NH:29][C:28]1=[O:33].C1OC1C>C(Cl)Cl.C(N(CC)CC)C.CN(C=O)C>[Cl:9][CH2:10][C:11]([NH:13][C:14]1[S:15][CH:16]=[C:17]([C:19](=[N:23][O:24][CH3:25])[C:20]([NH:26][C@H:27]2[C@H:30]([S:31][CH3:32])[NH:29][C:28]2=[O:33])=[O:22])[N:18]=1)=[O:12]

参加物

8

反応物 4

HCID 6378Propylene OxideHCID 10426DiphosgeneHCID 581157C8H8ClN3O4SHCID 54083832(3R,4S)-3-amino-4-methylthio-2-oxoazetidine

生成物 1

HCID 54560850(3R,4S)-3-[2-(2-chloroacetamidothiazol-4-yl)-2-methoxyiminoacetamido]-4-methylthio-2-oxoazetidine

試薬・触媒・溶媒 3

HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒2 回HCID 8471Triethylamine溶媒2 回

実験手順

To a solution of 0.228 g of DMF in 5 ml of methylene chloride is added at -10° C. 0.137 ml of diphosgene. The mixture is then stirred for 30 minutes at room temperature, to which is added at a temperature of -70° C. 15 ml of methylene chloride solution containing 0.80 g of 2-(2-chloroacetamidothiazol-4-yl)-2-methoxyiminoacetic acid and 0.316 g of triethylamine. The mixture is stirred for two hours at -25° C., then cooled to -70° C., followed by addition of 0.632 g of triethyl amine, 0.69 g of tosyl salt of (3R,4S)-3-amino-4-methylthio-2-oxoazetidine and 2 ml of propylene oxide. The temperature of the mixture is raised up to 0° C. in the course of one hour, while stirring. The mixture is stirred for further two hours at the same temperature, then concentrated, followed by addition of THF and removal of the resulting insolubles by filtration. The filtrate is concentrated and the residue is purified on a silica-gel column (AcOEt:CHCl3 :CH3OH=3:3:1) to yield 0.461 g of (3R,4S)-3-[2-(2-chloroacetamidothiazol-4-yl)-2-methoxyiminoacetamido]-4-methylthio-2-oxoazetidine.

後処理

  1. additionis added at a temperature of -70° C
  2. stirringThe mixture is stirred for two hours at -25° C.
  3. temperaturecooled to -70° C.
  4. temperatureThe temperature of the mixture is raised up to 0° C. in the course of one hour
  5. stirringwhile stirring
  6. stirringThe mixture is stirred for further two hours at the same temperature
  7. concentrationconcentrated
  8. additionfollowed by addition of THF and removal of the resulting insolubles by filtration
  9. concentrationThe filtrate is concentrated
  10. customthe residue is purified on a silica-gel column (AcOEt:CHCl3 :CH3OH=3:3:1)

出典と根拠

ORDレコード
ord-89b401e5dafb4667b09fdcff156e3b70
出典データセット
uspto-grants-1987_06
特許番号
US04675397

反応ノート

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