Ammonium Chloride → HCID 24823963, compound

HRID 1852537Notes

Reaction equation

HRID 1852537 reaction equation
[N:1]1([C:10]2[CH:15]=[CH:14][N:13]=[C:12]([NH:16][CH:17]3[CH2:22][CH2:21][C:20](=[O:23])[CH2:19][CH2:18]3)[N:11]=2)[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[N:3]=[N:2]1.[CH3:24][Mg]Cl.[NH4+].[Cl-]>C1COCC1>[N:1]1([C:10]2[CH:15]=[CH:14][N:13]=[C:12]([NH:16][CH:17]3[CH2:18][CH2:19][C:20]([CH3:24])([OH:23])[CH2:21][CH2:22]3)[N:11]=2)[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[N:3]=[N:2]1

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 59718950HCID 59718950, compoundHCID 178418332HCID 178418332, compound2×

Product 1

HCID 24823963HCID 24823963, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4-(4-benzotriazol-1-yl-pyrimidin-2-ylamino)-cyclohexanone (764 mg, 2.5 mmol) in 80 mL of THF, cooled at −78° C., was added dropwise methylmagnesium chloride (3.5 mL, 3.0 M in THF, 10.5 mmol). The reaction mixture immediately turned bright yellow in color; it was then allowed to warm to RT. The reaction did not reach completion, so it was re-cooled to −78° C. and an additional aliquot of MeMgCl (3 mL, 9 mmol) was added. The resulting mixture was warmed to RT and then poured onto an aqueous solution of NH4Cl; it was extracted with EtOAc. The organic layer was separated, dried over Na2SO4 and filtered; the solvent was evaporated under reduced pressure. The crude residue was purified by column chromatography (1-5/99-95 MeOH/CH2Cl2) to give: a less polar trans-isomer (130 mg, 16% yield, mp=193.0-195.4° C.; MS=325 (M+H)+), and the more polar cis-isomer (360 mg, 45% yield, mp=202.1-205.6° C.; MS=325 (M+H)+) as white crystalline solids.

Workup

  1. temperatureso it was re-cooled to −78° C.
  2. temperatureThe resulting mixture was warmed to RT
  3. extractionit was extracted with EtOAc
  4. customThe organic layer was separated
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customthe solvent was evaporated under reduced pressure
  8. customThe crude residue was purified by column chromatography (1-5/99-95 MeOH/CH2Cl2)
  9. customto give

Sources & evidence

ORD record
ord-331f61a3f6f540509f1d401e2503092f
Source dataset
uspto-grants-2015_02
Patent number
US08962622B2

Reaction notes

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