Diethyl Ether → HCID 23459836, compound

HRID 2287274Notes

Reaction equation

HRID 2287274 reaction equation
[O:1]=[C:2]1[N:9]2[C:4]([CH3:12])([CH2:5][CH2:6][O:7][C:8]2([CH3:11])[CH3:10])[C:3]1([CH3:15])[CH2:13][OH:14].[OH-:16].[K+].ClC(O[CH2:22][C:23]1[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=1)=O.CC[O:34][CH2:35]C>>[O:1]=[C:2]1[N:9]2[C:4]([CH3:12])([CH2:5][CH2:6][O:7][C:8]2([CH3:10])[CH3:11])[C:3]1([CH3:15])[CH2:13][O:14][O:16][C:35]([CH2:22][C:23]1[CH:24]=[CH:25][C:26]([N+:29]([O-:31])=[O:30])=[CH:27][CH:28]=1)=[O:34]

Participants

5

Reactant 4

HCID 3283Diethyl EtherHCID 14797Potassium HydroxideHCID 782054-Nitrobenzyl chloroformateHCID 13018397HCID 13018397, compound

Product 1

HCID 23459836HCID 23459836, compound

Procedure

Under anhydrous conditions at 0° C. a solution of 8-oxo-2,2,6,7-tetramethyl-7-(hydroxymethyl)-3-oxa-1-azabicyclo[4.2.0]octane (0.302 mmole) in 0.6 ml ether is treated with powdered potassium hydroxide (19 mg, 0.332 mmole). After a period of 15 minutes, p-nitrobenzyl chloroformate (65 mg, 0.302 mmole) is added to the reaction mixture. Stirring is continued at 25° C. for an additional 15 hours. The mixture is partitioned between 1 M pH 7 phosphate buffer and more ether. The ether phase is washed with water and brine, dried over magnesium sulfate and filtered. Evaporation of the filtrate under reduced pressure, followed by purification by preparative thick layer chromatography on silica gel developing with 1:9 ethyl acetate/benzene gives 8-oxo-2,2,6,7-tetramethyl-7-(p-nitrobenzylcarbonyldioxymethyl)-3-oxa-1-azabicyclo[4.2.0]octane.

Workup

  1. waitis continued at 25° C. for an additional 15 hours
  2. customThe mixture is partitioned between 1 M pH 7 phosphate buffer and more ether
  3. washThe ether phase is washed with water and brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. customEvaporation of the filtrate under reduced pressure
  7. customfollowed by purification by preparative thick layer chromatography on silica gel developing with 1:9 ethyl acetate/benzene

Sources & evidence

ORD record
ord-38efed6db9a44c56977287e17b4862c4
Source dataset
uspto-grants-1981_05
Patent number
US04269873

Reaction notes

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