HCID 58061055, compound → HCID 66678882, compound

HRID 537687Notes

Reaction equation

HRID 537687 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH:20]2[CH2:22][CH2:21]2)=[C:6]([CH:8]2[C:10]3([C:14](=[O:15])[C:13]([CH3:17])([CH3:16])[O:12][C:11]3([CH3:19])[CH3:18])[O:9]2)[CH:7]=1>ClCCl.[Fe](Cl)(Cl)Cl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH:20]2[CH2:21][CH2:22]2)=[C:6]([CH:8]2[C:14](=[O:15])[C:13]([CH3:16])([CH3:17])[O:12][C:11]([CH3:18])([CH3:19])[C:10]2=[O:9])[CH:7]=1

Participants

4

Reactant 1

HCID 58061055HCID 58061055, compound

Product 1

HCID 66678882HCID 66678882, compound

Reagents, catalysts & solvents 2

HCID 24380Iron chloride (FeCl3)CatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a suspension of iron (III) chloride (53.0 g, 327 mmol) in anhydrous dichloromethane (1000 ml) at 5° C. is added a second solution of 2-(5-bromo-2-cyclopropylphenyl)-4,4,6,6-tetramethyl-1,5-dioxaspiro[2.4]heptan-7-one (119.1 g, 326 mmol) in anhydrous dichloromethane (400 ml), at such a rate as to maintain an internal temperature below 10° C. After stirring for 15 minutes the reaction is quenched with distilled water (900 ml) and the mixture is allowed to warm to room temperature. The two phases are separated and the aqueous phase is extracted with dichloromethane (×2). Organics are combined and the crude product is extracted into 1M aqueous potassium carbonate, followed by acidification to pH0 with concentrated hydrochloric acid and re-extraction with dichloromethane. All organics are combined then washed with brine and dried over anhydrous magnesium sulfate. Concentration in vacuo then affords 4-(5-bromo-2-cyclopropylphenyl)-2,2,6,6-tetramethylpyran-3,5-dione as a white solid.

Workup

  1. temperatureat such a rate as to maintain an internal temperature below 10° C
  2. customis quenched with distilled water (900 ml)
  3. customThe two phases are separated
  4. extractionthe aqueous phase is extracted with dichloromethane (×2)
  5. extractionthe crude product is extracted into 1M aqueous potassium carbonate
  6. extractionfollowed by acidification to pH0 with concentrated hydrochloric acid and re-extraction with dichloromethane
  7. washAll organics are combined then washed with brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationConcentration in vacuo

Sources & evidence

ORD record
ord-32a4b5cf7c2349c7a51427b0a63582af
Source dataset
uspto-grants-2014_10
Patent number
US08865623B2

Reaction notes

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