脂肪族ケトンオキシムのポリリン酸,ポリリン酸エステル,およびリン酸エステルによる Beckmann 転位反応-相対転位比の経時変化について-

抄録

The Beckmann rearrangement of aliphatic ketone oximes, R(CHs)C=NOH (R=Et (1); n-Pr (2); iso-Pr (3); iso-Bu (4)), with polyphosphoric acid (PPA), polyphosphate ester (PPE), and ester of phosphoric acid (2 P-5 R) was carried out and migratory ratios ((a)/(b) in eq. (1)) were determined, The results are shown in Fig.1, 2, and 3, respectively.
In Fig.1 and 2, the migratory ratios decrease with reaction time and nearly approach to the ratios of anti-alkyl form/syn-alkylform in benzene(A1) or DMSO(A2)except for (3) (See Table 1). From this fact, it has been found that PPA and PPE are inactive for isomerization of the oximes andanti-alkyl oximes rearrange faster than syn-alkyl ones. ln the case of (3), migratery ratios are smaller than Ai or A2. As acetonitrile is detected by GLC, it is presumed that fission has been occurred simultaneously with rearrangement in anti-alkyl oxime (eq. (3)). In the case of 2 P-5 R, all modes of the reaction arethe same as in above, except that the rate of fission is tnuch faster than that in PPA and PPE.
The reaction of anti-alkyl ketone oximes having a bulky grouphas been greatly influenced by the use of sterically demanding catalysts such asPPA, PPE, and 2 P-5 R.