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

HRID 978834ノート

反応式

HRID 978834 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]([CH3:34])(=[O:33])=[O:32])[NH:29][C:28]1=[O:35].C1OC1C>C(Cl)Cl.CC(N(C)C)=O.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]([CH3:34])(=[O:33])=[O:32])[NH:29][C:28]2=[O:35])=[O:22])[N:18]=1)=[O:12]

参加物

9

反応物 4

HCID 6378Propylene OxideHCID 10426DiphosgeneHCID 581157C8H8ClN3O4SHCID 53637648(3R,4R)-3-amino-4-methylsulfonyl-2-oxoazetidine

生成物 1

HCID 53860321(3R,4R)-3-[2-(2-chloroacetamidothiazol-4-yl)-2-methoxyiminoacetamido]-4-methylsulfonyl-2-oxoazetidine収率 70.2%

試薬・触媒・溶媒 4

HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒2 回HCID 8471Triethylamine溶媒2 回HCID 31374Dimethylacetamide溶媒

実験手順

To a solution of 0.122 g of DMF in 5 ml of methylene chloride is added 0.10 ml of diphosgene at -10° C. The mixture is stirred for 30 minutes at room temperature, then cooled to a temperature of -70° C., followed by dropwise addition of 10 ml of methylene chloride solution containing 0.427 g of 2-(2-chloroacetamidothiazol-4-yl)-2-methoxyiminoacetic acid and 0.17 g of triethylamine. The mixture is stirred for 2 hours at a temperature ranging from -25° to -20° C., which is cooled to a temperature of -70° C., to which are added 0.17 g of triethylamine, a solution of 0.229 g of (3R,4R)-3-amino-4-methylsulfonyl-2-oxoazetidine in 3 ml of DMA, and 2 ml of propylene oxide, successively. The temperature of the mixture is raised up to room temperature in the course of 1.5 hours. The reaction mixture is concentrated under reduced pressure, and the residue is purified on a silica-gel column (ethyl acetate:n-hexane=1:1) to give 0.415 g of (3R,4R)-3-[2-(2-chloroacetamidothiazol-4-yl)-2-methoxyiminoacetamido]-4-methylsulfonyl-2-oxoazetidine. This is in agreement with the compound (syn-isomer) obtained in Reference Example 15B in IR and NMR.

後処理

  1. temperaturecooled to a temperature of -70° C.
  2. stirringThe mixture is stirred for 2 hours at a temperature
  3. customranging from -25° to -20° C.
  4. temperaturewhich is cooled to a temperature of -70° C., to which
  5. temperatureThe temperature of the mixture is raised up to room temperature in the course of 1.5 hours
  6. concentrationThe reaction mixture is concentrated under reduced pressure
  7. customthe residue is purified on a silica-gel column (ethyl acetate:n-hexane=1:1)

出典と根拠

ORDレコード
ord-3dd6a1574cc8439db1cc5d1a0210f61c
出典データセット
uspto-grants-1987_05
特許番号
US04665067

反応ノート

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