Trimethylsilyldiazomethane → Methyl 4-(4-aminophenyl)-4-oxobutanoate

HRID 1168468Notes

Reaction equation

HRID 1168468 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:14])[CH2:9][CH2:10][C:11]([OH:13])=[O:12])=[CH:4][CH:3]=1.[CH3:15][Si](C=[N+]=[N-])(C)C>C1(C)C=CC=CC=1.CO.O1CCCC1.ClCCl>[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([C:8](=[O:14])[CH2:9][CH2:10][C:11]([O:13][CH3:15])=[O:12])=[CH:6][CH:7]=1

Participants

7

Reactant 2

HCID 167693Trimethylsilyldiazomethane3×HCID 2432904-(4-Aminophenyl)-4-oxobutanoic acid

Product 1

HCID 12016833Methyl 4-(4-aminophenyl)-4-oxobutanoate

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred, partial solution of 4-(4-amino-phenyl)-4-oxo-butyric acid (6.96 g, 0.0360 mol) in toluene (240 mL) and methanol (240 mL) at room temperature under nitrogen was added dropwise over 30 minutes a 2.0 M solution of trimethylsilyldiazomethane in hexanes (18 mL, 0.036 mol), and the mixture was stirred for 22 hours. Additional 2.0 M solution of trimethylsilyldiazomethane in hexanes (12 mL, 0.024 mol) was added dropwise, and the mixture was stirred overnight. Additional 2.0 M solution of trimethylsilyldiazomethane in hexanes (19 mL, 0.038 mol) was added dropwise, and the mixture was stirred overnight. After a total of 3 days, the mixture was rotary evaporated, and the residue was suspended in tetrahydrofuran (200 mL) and dichloromethane (100 mL). The mixture was washed with 0.1 M aqueous sodium hydroxide, water, brine, and dried (Na2SO4). The solution was rotary evaporated to give a solid, which was crystallized from chloroform to give 5.13 g of 4-(4-amino-phenyl)-4-oxo-butyric acid, methyl ester as a tan solid; mp 160-162° C.

Workup

  1. stirringthe mixture was stirred overnight
  2. stirringthe mixture was stirred overnight
  3. customAfter a total of 3 days
  4. washThe mixture was washed with 0.1 M aqueous sodium hydroxide, water, brine
  5. dry with materialdried (Na2SO4)
  6. customThe solution was rotary evaporated
  7. customto give a solid, which
  8. customwas crystallized from chloroform

Sources & evidence

ORD record
ord-b4ef71fefa5947d0b6b1a0b5da0e1963
Source dataset
uspto-grants-2003_09
Patent number
US06624196B2

Reaction notes

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