Methyl iodide → HCID 86754811, compound

HRID 1603265Notes

Reaction equation

HRID 1603265 reaction equation
[Br:1]/[C:2](=[C:6](/[CH3:18])\[CH:7]=[CH:8]\[C:9]1[C:14]([CH3:16])([CH3:15])[CH2:13][CH2:12][CH2:11][C:10]=1[CH3:17])/[C:3]([OH:5])=[O:4].[H-].[Na+].[H][H].[CH3:23]I>CN(C)C=O.O1CCCC1>[Br:1]/[C:2](=[C:6](/[CH3:18])\[CH:7]=[CH:8]\[C:9]1[C:14]([CH3:16])([CH3:15])[CH2:13][CH2:12][CH2:11][C:10]=1[CH3:17])/[C:3]([O:5][CH3:23])=[O:4].[Br:1]/[C:2](=[C:6](\[CH3:18])/[CH:7]=[CH:8]/[C:9]1[C:14]([CH3:16])([CH3:15])[CH2:13][CH2:12][CH2:11][C:10]=1[CH3:17])/[C:3]([O:5][CH3:23])=[O:4]

Participants

8

Reactant 4

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 86754813HCID 86754813, compoundHCID 178418361HCID 178418361, compound

Product 2

HCID 86754811HCID 86754811, compoundHCID 86754812HCID 86754812, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
55 °C

Procedure

A mixture of (2E,4E) and (2Z,4E)-2-bromo-3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienoic acid (75 g) was dissolved in dimethylformamide (500 ml) and slowly added to a suspension of sodium hydride (10.5 g; 65% in oil) in tetrahydrofuran (1100 ml) at 10° C. and then stirred until all hydrogen evolution ceased. Methyl iodide (50 g) was then added and the resulting mixture was heated for 2 hours at 50-60° C., poured onto an ice-water mixture and extracted with hexane. The hexane extracts were washed with water, dried (magnesium sulphate) and concentrated. The mixture of methyl esters was then separated by HPLC (2.5% ether/hexane) to give pure methyl (2Z,4E)-2-bromo-3-methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4-pentadienoate (20 g) and methyl (2E,4E)-2-bromo-3-methyl-5-(2,6,6-trimethyl-cyclohexen-1-yl)-2,4-pentadienoate (37 g).

Workup

  1. extractionextracted with hexane
  2. washThe hexane extracts were washed with water
  3. dry with materialdried (magnesium sulphate)
  4. concentrationconcentrated
  5. additionThe mixture of methyl esters
  6. customwas then separated by HPLC (2.5% ether/hexane)

Sources & evidence

ORD record
ord-67bfa909b27e432a9a84564699337504
Source dataset
uspto-grants-1999_11
Patent number
US05986131

Reaction notes

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