第13章胺及其他含氮化合物重点.ppt

Questions: Answer to question 1: ????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????? Answer to question 2: ????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????? Answer to question 3: ????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????? Answer to question 4: * Stable diazonium tetrafluoroborate salts may be isolated, and on heating these lose nitrogen to give an arylfluoride product The top reaction with hypophosphorus acid, H3PO2, is noteworthy because it achieves the reductive removal of an amino (or nitro) group. Unlike the nucleophilic substitution reactions, this reduction probably procedes by a radical mechanism. It should be clear that the methyl substituent will eventually be oxidized to a carboxylic acid function. The timing is important, since a methyl substituent is ortho/para-directing and the carboxyl substituent is meta-directing. The cyano group will be introduced by a diazonium intermediate, so a nitration followed by reduction to an amine must precede this step. The hydroxyl group is a strong activating substituent and would direct aromatic ring chlorination to locations ortho para to itself, leading to the wrong product. As an alternative, the nitro group is not only meta-directing, it can be converted to a hydroxyl group by way of a diazonium intermediate. The resulting strategy is self evident. Selective introduction of a fluorine is best achieved by treating a diazonium intermediate with boron tetrafluoride anion. To get the necessary intermediate we need to make p-nitroaniline. Since the nitro substituent on the starting material would direct a new substituent to a meta-location, we must first