Diethyl Ether → Methyl 3,7-dimethyl-4-oxo-6-octenoate

HRID 27648

Reaction equation

HRID 27648 reaction equation
[CH3:1][CH:2]([CH:8]([N+]([O-])=O)[CH2:9][CH:10]=[C:11]([CH3:13])[CH3:12])[CH2:3][C:4]([O:6][CH3:7])=[O:5].C[O-].[Na+].[OH:20]P([O-])(O)=O.[K+].[OH-].[Na+].CCOCC>CO.[Cl-].[Cl-].[Ti+2]>[CH3:1][CH:2]([C:8](=[O:20])[CH2:9][CH:10]=[C:11]([CH3:13])[CH3:12])[CH2:3][C:4]([O:6][CH3:7])=[O:5]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 10942334Sodium MethoxideHCID 23341447Methyl 3,7-dimethyl-4-nitro-6-octenoateHCID 24942486NaOH KH2PO4

Product 1

HCID 15340230Methyl 3,7-dimethyl-4-oxo-6-octenoateYield 35%

Reagents, catalysts & solvents 2

HCID 10290777Titanium(2+);dichlorideCatalystHCID 887MethanolSolvent2×

Procedure

A solution of methyl 3,7-dimethyl-4-nitro-6-octenoate (24.55 g, 0.107 m) in methanol (10 ml) is added dropwise to a solution of sodium methoxide (6.37 g, 0.118 m) in methanol (250 ml) at room temperature under nitrogen. The mixture is stirred for 1 hour, added to a mixture of 20% titanous chloride (170 ml, 0.267 m) and pH 7 buffer (potassium phosphate monobasic-sodium hydroxide buffer) solution (340 ml). The resulting mixture is stirred for 30 minutes after which it is treated with ether (1 l). The organic phase is separated, dried (Na2SO4) and evaporated in vacuo to give the crude product (15.4 g). This material is purified by column chromatography on silica gel (300 g, 2% ethyl acetate in hexane) to give methyl 3,7-dimethyl-4-oxo-6-octenoate as a colorless liquid (6.8 g, 35%).

Workup

  1. stirringThe resulting mixture is stirred for 30 minutes after which it
  2. customThe organic phase is separated
  3. dry with materialdried (Na2SO4)
  4. customevaporated in vacuo
  5. customto give the crude product (15.4 g)
  6. customThis material is purified by column chromatography on silica gel (300 g, 2% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-aa5477c2625d4b8b8d317708dc0a77ff
Source dataset
uspto-grants-1980_09
Patent number
US04222937

Linked notes

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