Methane, dichloromethoxy- → methyl (R)-7-(4-fluorophenyl)-7-(3-formyl-6-hydroxy-2,4,5-trimethylphenyl)heptanoate

HRID 37721Notes

Reaction equation

HRID 37721 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C@H:8]([C:18]2[C:23]([CH3:24])=[CH:22][C:21]([CH3:25])=[C:20]([CH3:26])[C:19]=2[OH:27])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][C:14]([O:16][CH3:17])=[O:15])=[CH:4][CH:3]=1.[CH3:28][O:29]C(Cl)Cl>ClCCl.[Ti](Cl)(Cl)(Cl)Cl>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C@H:8]([C:18]2[C:19]([OH:27])=[C:20]([CH3:26])[C:21]([CH3:25])=[C:22]([CH:28]=[O:29])[C:23]=2[CH3:24])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][C:14]([O:16][CH3:17])=[O:15])=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 21004Methane, dichloromethoxy-HCID 10714337methyl (R)-7-(4-fluorophenyl)-7-(2-hydroxy-3,4,6-trimethylphenyl)heptanoate

Product 1

HCID 10644683methyl (R)-7-(4-fluorophenyl)-7-(3-formyl-6-hydroxy-2,4,5-trimethylphenyl)heptanoate

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of methyl (R)-7-(4-fluorophenyl)-7-(2-hydroxy-3,4,6-trimethylphenyl)heptanoate (0.8 g, 2.1 mmol) and dichloromethyl methyl ether (0.62 ml) in dichloromethane (10 ml) was added dropwise a solution of titanium tetrachloride (0.76 ml) in dichloromethane (3 ml) under argon atmosphere while maintaining the temperatures of the reaction mixture at a range from -10 ° C. to -12° C. The reaction mixture was then stirred for 30 minutes at the same temperature range. The reaction mixture was then added to ice-water, which was subjected to extraction with ethyl acetate. The organic layer was washed with water, an aqueous solution of sodium hydrogencarbonate, water and a saturated aqueous saline solution, successively, followed by drying over magnesium sulfate. The solvent was distilled off under reduced pressure. The residue was recrystallized from chloroform/hexane to afford 0.63 g of methyl (R)-7-(4-fluorophenyl)-7-(3-formyl-6-hydroxy-2,4,5-trimethylphenyl)heptanoate. Physico-chemical properties and spectral data of the product were shown in [Table 4].

Workup

  1. temperaturewhile maintaining the temperatures of the reaction mixture at a range from -10 ° C. to -12° C
  2. extractionwas subjected to extraction with ethyl acetate
  3. washThe organic layer was washed with water
  4. dry with materialby drying over magnesium sulfate
  5. distillationThe solvent was distilled off under reduced pressure
  6. customThe residue was recrystallized from chloroform/hexane

Sources & evidence

ORD record
ord-1022d4f1471345869688f0cbe79aa6a2
Source dataset
uspto-grants-1995_05
Patent number
US05420363

Reaction notes

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