Acetic Anhydride → 2-Acetamido-1-acetoxy-4,5-dimethylbenzene
반응식
[NH2:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([CH3:9])=[CH:4][C:3]=1[OH:10].Cl.CC1[CH:14]=[C:15]([O:24]CC(O)CNC(C)(C)C)C2NC(=S)NC=2C=1C.[C:34](OC(=O)C)(=[O:36])[CH3:35]>C(OCC)(=O)C.N1C=CC=CC=1>[C:15]([NH:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([CH3:9])=[CH:4][C:3]=1[O:10][C:34](=[O:36])[CH3:35])(=[O:24])[CH3:14]참가 물질
실험 절차
The diamino compound required as intermediate is synthesised in the following manner from 2-amino-4,5-dimethylphenol (see E. Diepolder, Chem. Ber., 42, 2916/1909). 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 in acetic anhydride at 20° C. From the nitration mixture there is isolated, in 43% yield, 2-acetamido-1-acetoxy-4,5-dimethyl-3-nitrobenzene; m.p. 209°-211° C. After saponification of this compound in 2 N hydrochloric acid, there is isolated 2-amino-4,5-dimethyl-3-nitrophenol; m.p. 176°-178° C. This compound is converted into the sodium salt with a methanolic solution of sodium methylate. This salt is reacted in dioxan/dimethylformamide with excess 3-chloro-1,2-epoxypropane at 75° C. After evaporation, the residue is taken up in chloroform, treated with water and active charcoal and freed from solvent. The amorphous residue 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. This compound is then quantitatively hydrogenated in ethanol over platinum dioxide to give 2,3-diamino-4,5-dimethyl-1-(2-hydroxy-3-tert.-butylaminopropoxy)-benzene, which is isolated as its trihydrochloride.
출처 및 근거
- ORD 기록
- ord-b05f24fbd7994ebba44a6c1a3602a223
- 출처 데이터셋
- uspto-grants-1980_07
- 특허 번호
- US04215134
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