Methanol → tert-Butyl 3-[2-(tert-butyldiphenylsilanyloxy)ethyl]-6-(3-isobutylcyclobutyl)-4-methoxyimino-5-hexynoate

HRID 1912052Notes

Reaction equation

HRID 1912052 reaction equation
[Si:1]([O:18][CH2:19][CH2:20][CH:21]([C:30](=O)[C:31]#[C:32][CH:33]1[CH2:36][CH:35]([CH2:37][CH:38]([CH3:40])[CH3:39])[CH2:34]1)[CH2:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CO.S([O-])([O-])(=O)=O.[Na+].[Na+].[Cl-].[CH3:52][O:53][NH3+:54]>N1C=CC=CC=1>[Si:1]([O:18][CH2:19][CH2:20][CH:21]([C:30](=[N:54][O:53][CH3:52])[C:31]#[C:32][CH:33]1[CH2:36][CH:35]([CH2:37][CH:38]([CH3:39])[CH3:40])[CH2:34]1)[CH2:22][C:23]([O:25][C:26]([CH3:27])([CH3:29])[CH3:28])=[O:24])([C:14]([CH3:17])([CH3:15])[CH3:16])([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 11639O-methylhydroxylammonium chlorideHCID 24436Sodium SulfateHCID 71127321tert-Butyl 3-[2-(tert-butyldiphenylsilanyloxy)ethyl]-6-(3-isobutylcyclobutyl)-4-oxo-5-hexynoate

Product 1

HCID 86675035tert-Butyl 3-[2-(tert-butyldiphenylsilanyloxy)ethyl]-6-(3-isobutylcyclobutyl)-4-methoxyimino-5-hexynoateYield 91%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

tert-Butyl 3-[2-(tert-butyldiphenylsilanyloxy)ethyl]-6-(3-isobutylcyclobutyl)-4-oxo-5-hexynoate (58.1 g) and methanol (300 mL) were mixed. To the mixture were added sodium sulfate (21.55 g), pyridine (30 mL) and O-methylhydroxylammonium chloride (12.67 g) at ice temperature. The mixture was stirred at RT overnight and the resultant precipitate was removed by filtration. After concentration of the filtrate in vacuo, toluene (350 mL) was poured into the residue. The mixture was washed with 1 N hydrochloric acid (300 mL), water (300 mL) and brine (150 mL), then dried over sodium sulfate. The sodium sulfate was filtered off and the filtrate was concentrated in vacuo. After an addition of silica gel (80 g) and ethyl acetate/hexane=1/20 (600 mL) to the residue, the mixture was stirred at RT for 1 hr. The silica gel was filtered off and the filtrate was concentrated in vacuo to give the title compound (55.54 g) as a crude product.

Workup

  1. customthe resultant precipitate was removed by filtration
  2. additionAfter concentration of the filtrate in vacuo, toluene (350 mL) was poured into the residue
  3. washThe mixture was washed with 1 N hydrochloric acid (300 mL), water (300 mL) and brine (150 mL)
  4. dry with materialdried over sodium sulfate
  5. filtrationThe sodium sulfate was filtered off
  6. concentrationthe filtrate was concentrated in vacuo
  7. additionAfter an addition of silica gel (80 g) and ethyl acetate/hexane=1/20 (600 mL) to the residue
  8. stirringthe mixture was stirred at RT for 1 hr
  9. filtrationThe silica gel was filtered off
  10. concentrationthe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-e85de78ceef64079b566aaf6a05b0ad3
Source dataset
uspto-grants-2013_12
Patent number
US08604069B2

Reaction notes

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