Potassium Iodide → Tert-butyl 3-(1-ethoxycarbonyl-3-cyclohexylpropyl)amino-4-oxo-2,3,4,5-tetrahydro-1,5-benzoxazepine-5-acetate

HRID 464865

反応式

HRID 464865 の反応式
Cl.N[C@@H]1C(=O)NC2C=CC=CC=2OC1.C([O-])(=O)C.[Na+].C1(CCC(=O)C(OCC)=O)CCCCC1.[CH2:35]([O:37][C:38]([CH:40]([NH:49][CH:50]1[C:56](=[O:57])[NH:55][C:54]2[CH:58]=[CH:59][CH:60]=[CH:61][C:53]=2[O:52][CH2:51]1)[CH2:41][CH2:42][CH:43]1[CH2:48][CH2:47][CH2:46][CH2:45][CH2:44]1)=[O:39])[CH3:36].C(=O)([O-])[O-].[K+].[K+].Cl[CH2:69][C:70]([O:72][C:73]([CH3:76])([CH3:75])[CH3:74])=[O:71].[I-].[K+]>[Ni].O.C(OCC)(=O)C.CN(C)C=O.C(O)(=O)C.C(O)C>[CH2:35]([O:37][C:38]([CH:40]([NH:49][CH:50]1[C:56](=[O:57])[N:55]([CH2:69][C:70]([O:72][C:73]([CH3:76])([CH3:75])[CH3:74])=[O:71])[C:54]2[CH:58]=[CH:59][CH:60]=[CH:61][C:53]=2[O:52][CH2:51]1)[CH2:41][CH2:42][CH:43]1[CH2:48][CH2:47][CH2:46][CH2:45][CH2:44]1)=[O:39])[CH3:36]

参加物

14

反応物 7

HCID 4875Potassium IodideHCID 11430Potassium CarbonateHCID 66052tert-Butyl chloroacetateHCID 517045Sodium AcetateHCID 13454680Ethyl 4-cyclohexyl-2-oxobutanoateHCID 18599716(S)-7-Amino-6,7-dihydro-9H-5-oxa-9-aza-benzocyclohepten-8-one hydrochlorideHCID 233200213-(1-Ethoxycarbonyl-3-cyclohexylpropyl)amino-2,3,4,5-tetrahydro-1,5-benzoxazepine-4-one

生成物 1

HCID 23320010Tert-butyl 3-(1-ethoxycarbonyl-3-cyclohexylpropyl)amino-4-oxo-2,3,4,5-tetrahydro-1,5-benzoxazepine-5-acetate

試薬・触媒・溶媒 6

HCID 935Nickel触媒HCID 176Acetic Acid溶媒HCID 702Ethanol溶媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A mixture of 3(S)-amino-2,3,4,5-tetrahydro-1,5-benzoxazepine-4-one hydrochloride (2 g), ethanol (100 ml), sodium acetate (0.8 g), acetic acid (0.6 g), molecular sieves 4A (5 g) and ethyl 4-cyclohexyl-2-oxo-butyrate (5 g) is catalytically hydrogenated over Raney nickel at room temperature under atmospheric pressure. After the absorption of hydrogen ceases, the catalyst is removed by filtration and the filtrate is evaporated in vacuo. To the residue are added water (50 ml) and ethyl acetate (200 ml), and the mixture is agitated thoroughly. The ethyl acetate layer is dried over anhydrous magnesium sulfate and evaporated in vacuo to yield an oily residue containing 3-(1-ethoxycarbonyl-3-cyclohexylpropyl)amino-2,3,4,5-tetrahydro-1,5-benzoxazepine-4-one. A mixture of this oil, potassium carbonate (4 g), tert-butyl chloroacetate (3 g), potassium iodide (0.2 g) and N,N-dimethylformamide (20 ml) is stirred overnight at room temperature, and then diluted with a mixture of water (300 ml) and ethyl acetate (200 ml). The organic layer is separated, dried over anhydrous magnesium sulfate and evaporated in vacuo to yield an oil, which is purified by silica gel column chromatography using hexaneethyl acetate (4:1) as an eluant to yield tert-butyl 3-(1-ethoxycarbonyl-3-cyclohexylpropyl)amino-4-oxo-2,3,4,5-tetrahydro-1,5-benzoxazepine-5-acetate (1 g) as a colorless oil.

後処理

  1. customAfter the absorption of hydrogen ceases
  2. customthe catalyst is removed by filtration
  3. customthe filtrate is evaporated in vacuo
  4. additionTo the residue are added water (50 ml) and ethyl acetate (200 ml)
  5. dry with materialThe ethyl acetate layer is dried over anhydrous magnesium sulfate
  6. customevaporated in vacuo
  7. customto yield an oily residue
  8. stirringis stirred overnight at room temperature
  9. customThe organic layer is separated
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customevaporated in vacuo
  12. customto yield an oil, which
  13. customis purified by silica gel column chromatography

出典と根拠

ORDレコード
ord-8fb58d5fd0f240138c03f62b9c7de446
出典データセット
uspto-grants-1985_10
特許番号
US04548932

関連ノート

読み込み中…