N-oxidation of 1-methyl-(I) and 1-benzyl-phthalazine (II) was attempted at lower than 10° in the mixed solvents of chloroform and ether using monoperphthalic acid. 2-Oxide (I
2) and 3-oxide (I
3) were produced from I in a 1 : 2 ratio and from II 2-oxide (II
2) and 3-Oxide (II
3) in almost a 3 : 1 ratio. The position of N-oxide groups were determined by the following procedures. To I
2 and I
3, phenylmagnesium bromide was reacted respectively and the reaction solution was treated with p-benzoquinone to 2-oxide (III
2) and 3-oxide (III
3) of 1-methyl-4-phenylphthalazine (III). III
2 was confirmed by the synthesis separately carried out in reacting 1-phenylphthalazine 3-oxide (IV
3) with methylmagnesium iodide. Therefore, the structure of I
2 was decided and that of I
3 might be suggested. Similar procedures were made in the determination of the structures of II
2 and II
3. It was reported that only 2-oxide (III
2) was produced from 1-methyl-4-phenylphthalazine (III) and that from 1-isopropyl-4-phenylphthalazine (VII), only 3-oxide (VII
3) was produced (Chart 3). N-oxidation of 1-ethyl-4-phenylphthalazine (IX) was attempted and only 2-oxide (IX
2) was obtained (Chart 4).
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