Ammonium Chloride → HCID 86653595, compound

HRID 1891998Notes

Reaction equation

HRID 1891998 reaction equation
[CH3:1][Li].[Cl:3][C:4]1[CH:5]=[C:6]([C:11]2([CH3:31])[C:16]([C:17]([O:19][CH3:20])=[O:18])=[C:15](OP(OCC)(OCC)=O)[CH2:14][CH:13]([CH3:30])[CH2:12]2)[CH:7]=[CH:8][C:9]=1[Cl:10].[Cl-].[NH4+]>C(OCC)C.[Cu]I>[Cl:3][C:4]1[CH:5]=[C:6]([C:11]2([CH3:31])[C:16]([C:17]([O:19][CH3:20])=[O:18])=[C:15]([CH3:1])[CH2:14][CH:13]([CH3:30])[CH2:12]2)[CH:7]=[CH:8][C:9]=1[Cl:10]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 67158781HCID 67158781, compoundHCID 178418348HCID 178418348, compound2×

Product 1

HCID 86653595HCID 86653595, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

A stirred suspension of copper (I) iodide (213 mg) in diethyl ether (10 mL) at 0° C. was treated with methyllithium (1.6 M, 1 equivalent), forming a cloudy yellow mixture. Additional methyllithium (1.6 M, 1 equivalent) was added, forming a cloudy grey mixture. This cloudy grey mixture was stirred at 0° C. for 15 min, and then treated with a solution of methyl (4RS,6SR)-6-(3,4-dichlorophenyl)-2-(diethoxyphosphoryloxy)-4,6-dimethylcyclohexen-1-carboxylate (130 mg) in diethyl ether (5 mL). A deep red color formed over 30 min. Stirring was continued while warming to rt for 2 h more. At the conclusion of this period, the resulting mixture was treated with 3:1 saturated aqueous ammonium chloride/concentrated ammonium hydroxide, and stirred for 10 min. The mixture was then extracted three times with diethyl ether, and the combined organic layers were washed with saturated aqueous ammonium chloride and saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated under vacuum. The resulting residue was purified by column chromatography on silica gel, eluting with 15% ethyl acetate/hexanes, to provide methyl (4RS,6RS)-6-(3,4-dichlorophenyl)-2,4,6-trimethylcyclohex-1-enecarboxylate (57 mg). Mass spectrum m/z 349.17 (M+Na+).

Workup

  1. customforming a cloudy yellow mixture
  2. customforming a cloudy grey mixture
  3. customA deep red color formed over 30 min
  4. stirringStirring
  5. temperaturewhile warming to rt for 2 h more
  6. stirringstirred for 10 min
  7. extractionThe mixture was then extracted three times with diethyl ether
  8. washthe combined organic layers were washed with saturated aqueous ammonium chloride and saturated aqueous sodium chloride
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated under vacuum
  11. customThe resulting residue was purified by column chromatography on silica gel
  12. washeluting with 15% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-a190a861bbc842c0a6b86deeb541486e
Source dataset
uspto-grants-2013_08
Patent number
US08507559B2

Reaction notes

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