Methane, dichloromethoxy- → HCID 58003024, compound

HRID 1516692Notes

Reaction equation

HRID 1516692 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]([CH:12]([CH3:14])[CH3:13])[CH:9]=[C:8]2[C:3]=1[C:4](=[O:17])[CH2:5][C:6]([CH3:16])([CH3:15])[O:7]2.[CH3:18][O:19]C(Cl)Cl>ClCCl.C(OCC)(=O)C.Cl.[Ti](Cl)(Cl)(Cl)Cl>[OH:1][C:2]1[C:11]([CH:18]=[O:19])=[C:10]([CH:12]([CH3:13])[CH3:14])[CH:9]=[C:8]2[C:3]=1[C:4](=[O:17])[CH2:5][C:6]([CH3:15])([CH3:16])[O:7]2

Participants

7

Reactant 2

HCID 21004Methane, dichloromethoxy-HCID 58002983HCID 58002983, compound

Product 1

HCID 58003024HCID 58003024, compound

Reagents, catalysts & solvents 4

HCID 24193Titanium TetrachlorideCatalystHCID 313Hydrochloric AcidSolventHCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

At −50° C., 13.19 ml (13.19 mmol) of a 1 M solution of titanium(IV) chloride in dichloromethane are added dropwise to a solution of 1.03 g (4.40 mmol) of 5-hydroxy-7-isopropyl-2,2-dimethyl-2,3-dihydro-4H-chromen-4-one (Example 17A) in 50 ml of dichloromethane, and the mixture is stirred at this temperature for 5 min. 437 μl (4.84 mmol) of dichloromethyl methyl ether are then slowly added dropwise. Over a period of 2.5 h, the mixture is allowed to thaw to −25° C. The mixture is then diluted with ethyl acetate and 1 M hydrochloric acid, the aqueous phase is extracted with ethyl acetate and the combined organic phases are dried over sodium sulfate. The solvent is removed under reduced pressure and the residue is purified by column chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 16:1).

Workup

  1. waitOver a period of 2.5 h
  2. customthaw to −25° C
  3. extractionthe aqueous phase is extracted with ethyl acetate
  4. dry with materialthe combined organic phases are dried over sodium sulfate
  5. customThe solvent is removed under reduced pressure
  6. customthe residue is purified by column chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 16:1)

Sources & evidence

ORD record
ord-b206c70973004eaca8d1a44bdb854a62
Source dataset
uspto-grants-2012_07
Patent number
US08227511B2

Reaction notes

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