Ammonium Chloride → HCID 58002934, compound

HRID 1516713Notes

Reaction equation

HRID 1516713 reaction equation
FC(F)(F)S(O[C:7]1[CH:19]=[C:18]2[C:10]([C:11](=[O:20])[CH2:12][C:13]3([O:17]2)[CH2:16][CH2:15][CH2:14]3)=[C:9]([OH:21])[CH:8]=1)(=O)=O.[Cl-].[Li+].[CH:26]([Zn]C(C)C)([CH3:28])[CH3:27].[Cl-].[NH4+]>O.Cl.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].CN(C)C=O>[OH:21][C:9]1[CH:8]=[C:7]([CH:26]([CH3:28])[CH3:27])[CH:19]=[C:18]2[C:10]=1[C:11](=[O:20])[CH2:12][C:13]1([O:17]2)[CH2:16][CH2:15][CH2:14]1

Participants

10

Reactant 4

HCID 25517Ammonium ChlorideHCID 433294Lithium ChlorideHCID 58002968HCID 58002968, compoundHCID 178461828HCID 178461828, compound

Product 1

HCID 58002934HCID 58002934, compound

Reagents, catalysts & solvents 5

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Under argon, 16 g (45.42 mmol) of 5-hydroxy-4-oxo-3,4-dihydrospiro[chromen-2,1′-cyclobutan]-7-yl trifluoromethanesulfonate (Example 44A), 3.71 g (4.54 mmol) of [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) and 5.78 g (136.25 mmol) of lithium chloride are suspended in 400 ml of abs. dimethylformamide. The mixture is cooled to 0° C., 90.8 ml (90.8 mmol) of diisopropylzinc (1 M solution in toluene) are added and the mixture is stirred at this temperature for 4 hours. At 0° C., saturated ammonium chloride solution is then added to the mixture. The mixture is diluted with water, 1 N hydrochloric acid and ethyl acetate, the organic phase is separated off and the aqueous phase is extracted repeatedly with ethyl acetate. The combined organic phases are washed twice with water and once with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. The residue is adsorbed on silica gel and purified on a silica gel column (mobile phase: cyclohexane→cyclohexane/ethyl acetate 20:1). This gives 9.6 g (86% of theory) of the title compound.

Workup

  1. customthe organic phase is separated off
  2. extractionthe aqueous phase is extracted repeatedly with ethyl acetate
  3. washThe combined organic phases are washed twice with water and once with saturated sodium chloride solution
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. custompurified on a silica gel column (mobile phase: cyclohexane→cyclohexane/ethyl acetate 20:1)

Sources & evidence

ORD record
ord-9c4f06bbad0545d58fd82c7073356649
Source dataset
uspto-grants-2012_07
Patent number
US08227511B2

Reaction notes

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