Sodium hydride → HCID 86746387, compound

HRID 374288Notes

Reaction equation

HRID 374288 reaction equation
[H-].[Na+].[CH3:3][C:4]1[CH:9]=[C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:7]([CH3:18])=[CH:6][C:5]=1[OH:19].[H][H].Br[CH:23]([CH2:31][CH3:32])[C:24]([CH3:30])([CH3:29])[C:25]([O:27][CH3:28])=[O:26].C1([O-])C=CC=CC=1.[Na+]>C1(C)C=CC=CC=1.O.CS(C)=O>[CH3:3][C:4]1[CH:9]=[C:8]([O:10][CH2:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:7]([CH3:18])=[CH:6][C:5]=1[O:19][CH2:32][CH2:31][CH2:23][C:24]([CH3:30])([CH3:29])[C:25]([O:27][CH3:28])=[O:26]

Participants

9

Reactant 5

HCID 24758Sodium hydrideHCID 4445035Phenolate SodiumHCID 19809653HCID 19809653, compoundHCID 53830941HCID 53830941, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 86746387HCID 86746387, compound

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
75 °C

Procedure

A 1 liter, 3 neck round bottom flask fitted with an overhead stirrer is charged with 100 mL of dimethylsulfoxide and 6.0 g of 60% sodium hydride, washed free of mineral oil with toluene (3.6 g contained; 150 mmol), then a solution of 34.2 g 150 mmol) of 2,5-dimethyl-4-(phenylmethoxy)-phenol (Example K) in 200 mL of toluene is added at 20°-25° C. When hydrogen evolution is complete, 40.1 g (1.2×150 mmol) of 5 bromo-2,2 dimethylvaleric acid, methyl ester (U.S. Pat. No. 4,665,226) is added and the temperature is raised to 75° C. When the temperature reaches 55° C., a solid separates (sodium phenolate). After 18 hours overnight the mixture is heated to reflux for 4 hours; then the mixture is cooled and 200 mL of water is added. The aqueous layer is extracted with diethyl ether and the organic layers are combined and the solution is washed with water, dried (magnesium sulfate) and evaporated leaving 65.7 g of a dark brown oil which crystallizes on standing. Recrystallization from hexane in the presence of charcoal affords 39.5 g of the title compound; mp 75.5°-76.5° C.

Workup

  1. customA 1 liter, 3 neck round bottom flask fitted with an overhead stirrer
  2. addition4,665,226) is added
  3. customreaches 55° C.
  4. temperatureAfter 18 hours overnight the mixture is heated
  5. temperatureto reflux for 4 hours
  6. temperaturethen the mixture is cooled
  7. extractionThe aqueous layer is extracted with diethyl ether
  8. washthe solution is washed with water
  9. dry with materialdried (magnesium sulfate)
  10. customevaporated

Sources & evidence

ORD record
ord-bfe97341002049bbac4ca2fb8a1f6897
Source dataset
uspto-grants-1992_11
Patent number
US05166398

Reaction notes

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