Hydrochloric Acid → HCID 69076367, compound

HRID 1516691Notes

Reaction equation

HRID 1516691 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[C:15]2[C:10]([C:11](=[O:19])[CH2:12][C:13]([CH3:18])([CH3:17])[O:14]2)=[C:9]([OH:20])[CH:8]=1)(=O)=O.[Cl-].[Li+].[CH:25]([Zn]C(C)C)([CH3:27])[CH3:26].Cl>CN(C)C=O.C1(C)C=CC=CC=1.O>[OH:20][C:9]1[CH:8]=[C:7]([CH2:26][CH2:25][CH3:27])[CH:16]=[C:15]2[C:10]=1[C:11](=[O:19])[CH2:12][C:13]([CH3:18])([CH3:17])[O:14]2

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 433294Lithium ChlorideHCID 58003014HCID 58003014, compoundHCID 178461828HCID 178461828, compound

Product 1

HCID 69076367HCID 69076367, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

At 0° C., 450 mg (550 μmol) of bis(diphenylphosphino)ferrocenepalladium(II) chloride/dichloromethane complex are added to a solution of 4.25 g (12.5 mmol) of 5-hydroxy-2,2-dimethyl-4-oxo-3,4-dihydro-2H-chromen-7-yl trifluoromethanesulfonate (Example 16A) and 1.59 g (37.5 mmol) of lithium chloride in 80 ml of degassed dimethylformamide. 24.98 ml (24.98 mmol) of a 1 M solution of diisopropylzinc in toluene are then slowly added dropwise. After 10 min of stirring at 0° C., the mixture is warmed to room temperature and stirred at this temperature for a further 5 h. The reaction solution is hydrolyzed carefully with water, acidified with 1 M hydrochloric acid, diluted with 500 ml of water and extracted twice with in each case 500 ml of ethyl acetate. After washing with 100 ml of water and 50 ml of saturated sodium chloride solution, the combined organic phases are dried over magnesium sulfate and concentrated under reduced pressure. Chromatography of the residue on silica gel (mobile phase: cyclohexane/ethyl acetate 10:1) gives the target product as a 2:1 mixture with the isomer 5-hydroxy-2,2-dimethyl-7-propyl-2,3-dihydro-4H-chromen-4-one.

Workup

  1. temperaturethe mixture is warmed to room temperature
  2. stirringstirred at this temperature for a further 5 h
  3. extractionextracted twice with in each case 500 ml of ethyl acetate
  4. washAfter washing with 100 ml of water and 50 ml of saturated sodium chloride solution
  5. dry with materialthe combined organic phases are dried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-1c639f8307094f4081c67ea86f7b2d4c
Source dataset
uspto-grants-2012_07
Patent number
US08227511B2

Reaction notes

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