Bertold Berrang

Nickel boride reduction of aryl nitro compounds

Abstract Nickel boride smoothly reduces aryl nitro compounds to the corresponding anilines in the presence of iodo and ortho carboalkoxy groups in contrast to the problematic reductions by other methods.

Synthesis of [1-3H]morphine-6-β-D-glucuronide

Tritiated morphine of high specific activity was protected at the 3-position by acetylation and subjected to glucuronidation by Koenigs-Knorr procedure with methyl 2,3,4-tri-0-acetyl-1-bromo-1-deoxy-D-glucopyranuronate and silver carbonate. Fully protected morphine-6-glucuronide was obtained in 42% yield and 95% radiochemical purity as determined by TLC-RAM. Alkali catalyzed solvolysis in two steps furnished [1-3H]morphine-6-β-D-glucuronide in 23% overall radiochemical yield and 99% radio-chemical purity determined by HPLC-liquid scintillation counting and TLC-RAM. Copyright

Synthesis of 4-alkyl- and 4-(.beta.-alkylvinyl) derivatives of primaquine as potential antimalarials

4(beta-Alkylvinyl)-6-methoxy-8-nitroquinolines (6) were prepared from 6-methoxy-8-nitroquinoline-4-carboxaldehyde (5) via a Wittig reaction. Stannous chloride reduction of 6 gave 4-(beta-alkylvinyl)-8-amino-6-methoxyquinolines (8), whereas catalytic reduction of 6 using Raney nickel catalyst gave 4-alkyl-8-amino-6-methoxyquinolines (7). Alkylation of 7 and 8 with 4-iodo-1-phthalimidopentane, followed by removal of the phthaloyl-protecting group with hydrazine, gave 4-alkyl and 4-(beta-alkylvinyl) derivatives of primiquine, respectively. These compounds were evaluated for antimalarial activity against P. berghei and P. berghei yoelii in mice and against P. cynomolgi in rhesus monkeys. Several of the compounds were active in the P. bergheii yoelii screen. None of the compounds showed significant activity in the other two screens.

Preparation of carbon-14 labeled hair dyes: Disperse blue 1

Friedel-Crafts acylation of [U- 14 C]p-dichlorobenzene with 3,6-dichlorophthalic anhydride in aluminum bromide melt followed by oleum cyclization afforded [U- 14 C]-1,4,5,8-tetrachloroanthraquinone. Potassium fluoride mediated amidosulfonation followed by hydrolysis gave [U- 14 C]-1,4,5,8-tetraaminoanthraquinone with specific activity 39.7 mCi/mmol in 5.6% radiochemical yield.