Dichloromethane → 3-Acetoxy-2-(methoxycarbonyl)methoxypyridine

HRID 1862246Notes

Reaction equation

HRID 1862246 reaction equation
B(F)(F)F.[CH3:5][CH2:6][O:7][CH2:8][CH3:9].NC1[C:12]([O:17][CH2:18][C:19]([O:21][CH3:22])=[O:20])=[N:13][CH:14]=[CH:15]C=1.ClCCl.N(OC(C)(C)C)=[O:27]>COCCOC.C(OC(=O)C)(=O)C.CCCCC>[C:6]([O:7][C:8]1[C:12]([O:17][CH2:18][C:19]([O:21][CH3:22])=[O:20])=[N:13][CH:14]=[CH:15][CH:9]=1)(=[O:27])[CH3:5]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 8000Boron trifluoride etherateHCID 10906Tert-Butyl nitriteHCID 121155123-Amino-2-(methoxycarbonyl)methoxypyridine

Product 1

HCID 121155133-Acetoxy-2-(methoxycarbonyl)methoxypyridineYield 36.4%

Reagents, catalysts & solvents 3

HCID 7918Acetic AnhydrideSolventHCID 8003PentaneSolventHCID 80711,2-DimethoxyethaneSolvent2×

Procedure

1.6 g of boron trifluoride diethyl etherate was added to a mixture of 1.0 g of 3-amino-2-(methoxycarbonyl)methoxypyridine, 3 ml of 1,2-dimethoxyethane and 1 ml of dichloromethane dropwise at −10° C. The mixture was stirred for 10 minutes at the same temperature, then, to the reaction solution was added a solution of 0.68 g of t-butyl nitrite in 1 ml of 1,2-dimethoxyethane dropwise at −5° C. or lower. The mixture was stirred for 30 minutes at the same temperature, then, into the mixture was poured n-pentane. The lower layer of two separated layers was dissolved in 5 ml of acetic anhydride, and the mixture was stirred for 1 hour at 80° C. The solvent was distilled off, then, the resulted residue was subjected to silica gel chromatography to obtain 0.45 g of 3-acetoxy-2-(methoxycarbonyl)methoxypyridine.

Workup

  1. stirringThe mixture was stirred for 30 minutes at the same temperature
  2. stirringthe mixture was stirred for 1 hour at 80° C
  3. distillationThe solvent was distilled off

Sources & evidence

ORD record
ord-4940deffccc8447e857ef24154566f87
Source dataset
uspto-grants-2003_03
Patent number
US06537948B1

Reaction notes

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