Hydrogen Peroxide → 3-(2-Acetoxymethyl-6-methyl-pyridin-4-yl)-benzoic acid methyl ester

HRID 498253Notes

Reaction equation

HRID 498253 reaction equation
[CH3:1][O:2][C:3](=[O:18])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:10]2[CH:15]=[C:14]([CH3:16])[N:13]=[C:12]([CH3:17])[CH:11]=2)[CH:5]=1.[C:19]([C:22]1C=C(B(O)O)C=CC=1)([OH:21])=[O:20].BrC1C=C(C)N=C(C)C=1.COC(=O)C1C=CC=C(C2C=CN=C(C)C=2)C=1.OO>C(O)(=O)C.C(OC(=O)C)(=O)C>[CH3:1][O:2][C:3](=[O:18])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:10]2[CH:15]=[C:14]([CH3:16])[N:13]=[C:12]([CH2:17][O:21][C:19](=[O:20])[CH3:22])[CH:11]=2)[CH:5]=1

Participants

8

Reactant 5

HCID 784Hydrogen PeroxideHCID 27339573-Carboxyphenylboronic acidHCID 130817354-Bromo-2,6-dimethylpyridineHCID 694867793-(2,6-Dimethyl-pyridin-4-yl)-benzoic acid methyl esterHCID 694891453-(2-Methyl-pyridin-4-yl)-benzoic acid methyl ester

Product 1

HCID 694898713-(2-Acetoxymethyl-6-methyl-pyridin-4-yl)-benzoic acid methyl esterYield 82%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 7918Acetic AnhydrideSolvent

Procedure

Oxidation of 3-(2,6-dimethyl-pyridin-4-yl)-benzoic acid methyl ester (28.8 g, 0.12 mol; prepared from commercially available 3-carboxyphenylboronic acid [CAS-No. 25487-66-5] and 4-bromo-2,6-dimethylpyridine [Chem. Pharm. Bull. 38 (1990) 2446 and J. Org. Chem. 27 (1962) 1665] as described for 3-(2-methyl-pyridin-4-yl)-benzoic acid methyl ester in example K12) with H2O2 (30%, 36.5 ml, 0.36 mol) in acetic acid (117 ml) at 70° C. for 27 h and subsequent reaction of the N-oxide in acetic acid anhydride (31 ml) at 135° C. for 30 min yielded after aqueous work-up 3-(2-acetoxymethyl-6-methyl-pyridin-4-yl)-benzoic acid methyl ester (29.2 g, 82%) as a brown oil.

Workup

  1. customat 70° C.
  2. customfor 27 h

Sources & evidence

ORD record
ord-2413d1419fb84dfcb4e17b67b1ca3732
Source dataset
uspto-grants-2005_09
Patent number
US06949542B2

Reaction notes

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