Trimethylsilyldiazomethane → methyl 2-amino-4,5-dimethylbenzoate

HRID 1814995Notes

Reaction equation

[CH3:1][C:2]1[C:10]([CH3:11])=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[C:4]([NH2:12])[CH:3]=1.[CH3:13][Si](C=[N+]=[N-])(C)C>>[CH3:1][C:2]1[C:10]([CH3:11])=[CH:9][C:5]([C:6]([O:8][CH3:13])=[O:7])=[C:4]([NH2:12])[CH:3]=1

Participants

Reactant 2

HCID 167693Trimethylsilyldiazomethane

HCID 2665342-amino-4,5-dimethylbenzoic acid

Product 1

HCID 267386methyl 2-amino-4,5-dimethylbenzoate

Procedure

0.41 g Sodium nitrite in water is added to 1 g 4,5-dimethyl-2-nitroaniline in 3 mL conc. HCl and stirred for 1 hour at +4° C. This solution is added to a mixture of 0.67 g copper (I) cyanide, 0.98 g sodium cyanide, 0.32 g sodium carbonate, 25 mL of water and 3 mL toluene. The mixture is stirred for 12 hours at room temperature and worked up to give 0.45 g 4,5-dimethyl-2-nitrobenzonitrile. 4,5-Dimethyl-2-nitrobenzonitrile is reduced with iron powder in acetic acid to yield 4,5-dimethyl-2-aminobenzonitrile. 4,5-Dimethyl-2-aminobenzonitrile is heated at reflux for 12 hours in conc. HCl to give 4,5-dimethyl-2-aminobenzoic acid. 4,5-Dimethyl-2-aminobenzoic acid is reacted with trimethylsilyl diazomethane to yield methyl 4,5-dimethyl-2-aminobenzoate (Chem. Pharm. Bull. Vol. 29, 1475 (1981)).

Sources & evidence

ORD record: ord-98dcc449662e437aa2ac84cb0b794457
Source dataset: uspto-grants-2005_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06878720B2

Reaction notes

Loading…