1,3-Benzodioxol-5-amine, 4-methyl- synthesis

Yield:-

Reaction Conditions:

with nitric acid;palladium in methanol;chloroform;acetic anhydride;

Steps:

2 Example 2

A solution of 1.42 mL of concentrated nitric acid in 20 mL of acetic anhydride is added dropwise to a stirred solution of 2.90 g of 4-methyl-1,3-benzodioxole in 75 mL of acetic arthydride at -5° C. After 15 minutes the mixture is poured over 100 g of crushed ice and allowed to stir for 30 minutes as a yellow precipitate falls out of solution. The solid is filtered and taken up in chloroform, dried over magnesium sulfate and concentrated under reduced pressure to afford 2.85 g of an inseparable mixture of 5-nitro-4-methyl-1,3-benzodioxole and 6-nitro-4-methyl-1,3-benzodioxole. 5-Amino-4-methyl-1,3-benzodioxole. 2.85 g of the above mixture is mixed with 0.30 g of 5% palladium on carbon in 75 mL of methanol and placed under a 50 psi hydrogen atmosphere. The mixture is shaken for three hours at room temperature. The reaction mixture is filtered through Celite to yield a yellow solution. Concentration under reduced pressure affords an oil, which is purified by chromatography on silica gel to afford 0.62 g of 5-amino-4-methyl-1,3-benzodioxole. 5-Isothiocyanato-4-methyl-1,3-benzodioxole.

References:

US5663189,1997,A