Phenol → 2-Acetamido-1-acetoxy-4,5-dimethylbenzene
Reaction equation
[C:1]1(O)C=CC=CC=1.[C:8]([O:11][C:12](=O)[CH3:13])(=[O:10])[CH3:9].C([O:18][CH2:19][CH3:20])(=O)C.[N:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>>[C:19]([NH:21][C:26]1[CH:25]=[C:24]([CH3:1])[C:23]([CH3:22])=[CH:13][C:12]=1[O:11][C:8](=[O:10])[CH3:9])(=[O:18])[CH3:20]Participants
Procedure
This phenol compound is acetylated with acetic anhydride in ethyl acetate/pyridine to give 2-acetamido-1-acetoxy-4,5-dimethylbenzene (m.p. 156°-158° C.) which is nitrated in acetic anhydride with 100% nitric acid at 20° C. From the nitration mixture, there is isolated, in a yield of 43% of theory, 2-acetamido-1-acetoxy-4,5-dimethyl-3-nitrobenzene (m.p. 209°-211° C.). After saponification of this compound with 2 N hydrochloric acid, there is obtained 2-amino-4,5-dimethyl-3-nitrophenol (m.p. 176°-178° C.). This compound is then converted into the sodium salt by means of methanolic sodium methylate and then reacted in dioxan/dimethylformamide with excess 3-chloro-1,2-epoxypropane at 75° C. After evaporation of the reaction mixture, the residue is taken up in chloroform, treated with water and active charcoal and freed from solvent. The amorphous residue obtained of 2-amino-4,5-dimethyl-1-(2,3-epoxypropoxy)-3-nitrobenzene is reacted in boiling ethanol with tert.-butylamine to give 2-amino-4,5-dimethyl-1-(2-hydroxy-3-tert.-butylaminopropoxy)-3-nitrobenzene, which is then hydrogenated quantitatively in ethanol in the presence of platinum dioxide to give 2,3-diamino-4,5-dimethyl-1-(2-hydroxy-3-tert.-butylaminopropoxy)-benzene, which is isolated in the form of a trihydrochloride.
Sources & evidence
- ORD record
- ord-622cc28bb9f34b578a2632ef8fe1721c
- Source dataset
- uspto-grants-1983_01
- Patent number
- US04367235
Reaction notes
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