Hexamethylenetetramine → ethyl 2-[(1R)-1-(2-tert-butoxy-2-oxoethyl)-4-cyclohexylbutyl]-1,3-oxazole-4-carboxylate

HRID 2084498ノート

反応式

HRID 2084498 の反応式
C1N2CN3CN(C2)CN1C3.C1CCN2C(=NCCC2)CC1.[C:22]([O:26][C:27](=[O:49])[CH2:28][C@H:29]([C:39]1[O:40][CH2:41][C@@H:42]([C:44]([O:46][CH2:47][CH3:48])=[O:45])[N:43]=1)[CH2:30][CH2:31][CH2:32][CH:33]1[CH2:38][CH2:37][CH2:36][CH2:35][CH2:34]1)([CH3:25])([CH3:24])[CH3:23]>C(Cl)Cl>[C:22]([O:26][C:27](=[O:49])[CH2:28][C@H:29]([C:39]1[O:40][CH:41]=[C:42]([C:44]([O:46][CH2:47][CH3:48])=[O:45])[N:43]=1)[CH2:30][CH2:31][CH2:32][CH:33]1[CH2:38][CH2:37][CH2:36][CH2:35][CH2:34]1)([CH3:25])([CH3:24])[CH3:23]

参加物

5

反応物 3

HCID 4101HexamethylenetetramineHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 59909855Ethyl (4S)-2-{(1R)-1-[2-(tert-butoxy)-2-oxoethyl]4-cyclohexylbutyl}-4,5-dihydro-1,3-oxazole-4-carboxylate

生成物 1

HCID 59110691ethyl 2-[(1R)-1-(2-tert-butoxy-2-oxoethyl)-4-cyclohexylbutyl]-1,3-oxazole-4-carboxylate

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

A suspension of CuBr2 (20.88 g, 93.5 mmol) and HMTA (13.1 g, 93.5 mmol) in degassed DCM (250 ml) was treated with DBU (14.0 ml, 93.5 mmol) and the dark solution formed was stirred in a water bath for 5 minutes. A solution of ethyl (4S)-2-[(1R)-1-(2-tert-butoxy-2-oxoethyl)-4-cyclohexylbutyl]-4,5-dihydro-1,3-oxazole-4-carboxylate (preparation 152) (9.24 g, 23.4 mmol) in degassed DCM (30 ml) was added dropwise to the reaction mixture and stirred at room temperature for a further 3 hours. The solvent was removed under reduced pressure. The resdue was dissolved in EtOAc and washed with a 1:1 solution of NH3(aq):NH4Cl. The aqueous extract was washed with EtOAc (2×380 ml). The combined organic extracts were washed with 2M HCl (500 ml), sat. NaHCO3 (500 mL) and brine (500 ml). The organic extracts were dried over anhydrous MgSO4 and filtered. The solvent was removed under reduced pressure. The crude material was purified on a silica column eluting with a solvent gradient of EtOAc:pentane (0:100) gradually changing to (25:75) to afford the title compound as colourless oil which formed needles on standing (7.39 g, 80%).

後処理

  1. customthe dark solution formed
  2. stirringstirred at room temperature for a further 3 hours
  3. customThe solvent was removed under reduced pressure
  4. dissolutionThe resdue was dissolved in EtOAc
  5. washwashed with a 1:1 solution of NH3(aq)
  6. extractionThe aqueous extract
  7. washwas washed with EtOAc (2×380 ml)
  8. washThe combined organic extracts were washed with 2M HCl (500 ml), sat. NaHCO3 (500 mL) and brine (500 ml)
  9. dry with materialThe organic extracts were dried over anhydrous MgSO4
  10. filtrationfiltered
  11. customThe solvent was removed under reduced pressure
  12. customThe crude material was purified on a silica column
  13. washeluting with a solvent gradient of EtOAc:pentane (0:100)

出典と根拠

ORDレコード
ord-69c81f4693f74fa1ac9520eb8bec5cf7
出典データセット
uspto-grants-2004_04
特許番号
US06716861B2

反応ノート

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