1-Bromo-1-methylcyclohexane → ethyl (2Z)-2-(1-methylcyclohexyl)oxyimino-3-oxobutanoate

HRID 1194878Notes

Reaction equation

HRID 1194878 reaction equation
[OH:1]/[N:2]=[C:3](/[C:9](=[O:11])[CH3:10])\[C:4]([O:6][CH2:7][CH3:8])=[O:5].Br[C:13]1([CH3:19])[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1>O1CCOCC1.FC(F)(F)S([O-])(=O)=O.[Ag+]>[CH3:19][C:13]1([O:1]/[N:2]=[C:3](/[C:9](=[O:11])[CH3:10])\[C:4]([O:6][CH2:7][CH3:8])=[O:5])[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1

Participants

5

Reactant 2

HCID 125021291-Bromo-1-methylcyclohexaneHCID 178472876HCID 178472876, compound

Product 1

HCID 14864970ethyl (2Z)-2-(1-methylcyclohexyl)oxyimino-3-oxobutanoateYield 69%

Reagents, catalysts & solvents 2

HCID 76223Silver(I) trifluoromethanesulfonateCatalystHCID 312751,4-DioxaneSolvent

Procedure

Ethyl (Z)-2-hydroxyimino-3-oxobutyrate (3.18 g, 20 mmol) and 1-bromo-1-methylcyclohexane (3.54 g, 20 mmol) in dry dioxane (15 ml) were stirred together in the dark and silver trifluoromethanesulphonate (5.13 g, 20 mmol) was added portionwise over 4 h. After a total of 100 h the mixture was filtered through Kieselguhr and the residue was washed well with dioxane. The filtrate was evaporated in vacuo, toluene was added and evaporated in vacuo and the residual oil was dissolved in ethyl acetate and washed with dilute aqueous NaHCO3, followed by water and brine. Ater drying (MgS4) the ethyl acetate was evaporated in vacuo and the residual oil was chromatographed on silica gel, to give the title compound as a yellow oil (3.49 g; 69%); νmax (CH2Cl2) 2945, 1740, 1685, 1370, 1320, 1235, 1070 and 1005 cm-1 ; δH (60 MHz, CDCl3) 1.35 (6H, s superimposed on t), 1.4-2.0 (10H, m), 2.37 (3H, s), 4.55 (2H, q, J 7 Hz).

Workup

  1. additionwas added portionwise over 4 h
  2. filtrationAfter a total of 100 h the mixture was filtered through Kieselguhr
  3. washthe residue was washed well with dioxane
  4. customThe filtrate was evaporated in vacuo, toluene
  5. additionwas added
  6. customevaporated in vacuo
  7. dissolutionthe residual oil was dissolved in ethyl acetate
  8. washwashed with dilute aqueous NaHCO3
  9. dry with materialAter drying (MgS4) the ethyl acetate
  10. customwas evaporated in vacuo
  11. customthe residual oil was chromatographed on silica gel

Sources & evidence

ORD record
ord-40b1f18248e34153bba737bc69091074
Source dataset
uspto-grants-1989_03
Patent number
US04816452

Reaction notes

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