Cyclohexanone Oxime → Benzyl 2-oxa-3-azabicyclo[2.2.1]hept-5-ene-3-carboxylate

HRID 1523227ノート

反応式

HRID 1523227 の反応式
[C:1]1(=[N:7][OH:8])[CH2:6][CH2:5][CH2:4][CH2:3]C1.ClCl.C([O-])([O-])=O.[Na+].[Na+].Cl[C:18]([O:20][CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)=[O:19].C1CC=CC=1>O.C(OC)(C)(C)C>[CH:4]12[CH2:3][CH:1]([CH:6]=[CH:5]1)[N:7]([C:18]([O:20][CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)=[O:19])[O:8]2

参加物

8

反応物 5

HCID 7517Cyclohexanone OximeHCID 7612CyclopentadieneHCID 10340Sodium Carbonate2 回HCID 10387Benzyl chloroformateHCID 24526Chlorine

生成物 1

HCID 15817097Benzyl 2-oxa-3-azabicyclo[2.2.1]hept-5-ene-3-carboxylate

試薬・触媒・溶媒 2

HCID 962Water溶媒2 回HCID 15413tert-Butyl methyl ether溶媒

反応条件

温度
-10 °C

実験手順

Cyclohexanone oxime (20.04 g, 171.8 mmol) and methyl t-butyl ether (110 mL) were added to a reactor at 25° C. and stirred under N2 (g). The solution was cooled to −10° C. and Cl2 (g) was added during 15 min until a deep blue, clear solution was obtained. Vacuum was applied to remove remaining Cl2 and possible HCl from the reaction mixture. The temperature was set to −2° C., and a solution of Na2CO3 (11.03 g, 103 mmol) in water (90 mL) was slowly added during 30 min. The phases were separated and the organic phase transferred to a solution of Na2CO3 (19.3 g, 180.3 mmol) in water (126 mL) at 15° C. Benzyl chloroformate (32.3 g, 179.87 mmol) was added and the reaction mixture stirred for 10 min after which cyclopentadiene (25.2 g, 362.16 mmol) was added and the reaction mixture stirred for 3 h. Vacuum was applied and the remaining cyclopentadiene was removed. The phases were separated and the organic phase containing the title product was taken further directly to Example 2 as below.

後処理

  1. customwas obtained
  2. customto remove
  3. customwas set to −2° C.
  4. customThe phases were separated
  5. additionwas added
  6. stirringthe reaction mixture stirred for 3 h
  7. customthe remaining cyclopentadiene was removed
  8. customThe phases were separated
  9. additionthe organic phase containing the title product

出典と根拠

ORDレコード
ord-5577c84a0d6e4961a8d6789555c6aa31
出典データセット
uspto-grants-2015_07
特許番号
US09079873B2

反応ノート

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