Acetic Acid → p-Nitrobenzyl 2-(4-tert-butylthio-2-oxo-1-azetidinyl)-4,4-dimethyl-3-oxopentanoate

HRID 1031043Notes

Reaction equation

HRID 1031043 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[C:11]([S:15][CH:16]1[N:19]([CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=2)=[O:22])[C:18](=[O:34])[CH2:17]1)([CH3:14])([CH3:13])[CH3:12].[C:35](Cl)(=[O:40])[C:36]([CH3:39])([CH3:38])[CH3:37].C(O)(=O)C>C1COCC1.C1(C)C=CC=CC=1>[C:11]([S:15][CH:16]1[N:19]([CH:20]([C:35](=[O:40])[C:36]([CH3:39])([CH3:38])[CH3:37])[C:21]([O:23][CH2:24][C:25]2[CH:26]=[CH:27][C:28]([N+:31]([O-:33])=[O:32])=[CH:29][CH:30]=2)=[O:22])[C:18](=[O:34])[CH2:17]1)([CH3:14])([CH3:12])[CH3:13]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 62493Pivaloyl chlorideHCID 2733832Lithium HexamethyldisilazideHCID 14460289HCID 14460289, compound

Product 1

HCID 14460290p-Nitrobenzyl 2-(4-tert-butylthio-2-oxo-1-azetidinyl)-4,4-dimethyl-3-oxopentanoateYield 60.7%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

6 ml of a freshly prepared 1 M solution of lithium bis-trimethylsilylamide in THF are added dropwise at -70° C. to a solution of 1.059 mg (3 mmol) of p-nitro-benzyl (4-tert-butylthio-2-oxo-1-azetidinyl)-acetate in 7 ml of dry THF and then a solution of 382 mg of pivaloyl chloride in 1 ml of THF is added dropwise at -70° C. and the reaction mixture is further stirred at the same temperature during the course of 30 minutes. The mixture is diluted with 200 ml of toluene and a little aqueous acetic acid is added. Washing the organic phase with 100 ml of 2 N aqueous hydrochloric acid and washing twice with saturated sodium chloride solution (100 ml), drying the organic phase with MgSO4 and evaporating the solvent in vacuo yields a dark red oil. Purification of the crude product on 40 g of silica gel using toluene/ethyl acetate (9:1) yields 795 mg of a non-crystalline solid. IR spectrum in methylene chloride: 2970, 1770, 1760, 1715, 1610, 1530, 1350, 1315, 1180, 995, 845 cm-1.

Workup

  1. washWashing the organic phase with 100 ml of 2 N aqueous hydrochloric acid
  2. washwashing twice with saturated sodium chloride solution (100 ml)
  3. dry with materialdrying the organic phase with MgSO4
  4. customevaporating the solvent in vacuo
  5. customyields a dark red oil
  6. customPurification of the crude product on 40 g of silica gel

Sources & evidence

ORD record
ord-734862309cb142fab118ab8f5c20e146
Source dataset
uspto-grants-1992_04
Patent number
US05108747

Reaction notes

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