alcohol, if present, or by ammonia in the absence of an alcohol. Anions thatare singly allylic or benzylic are protonated rapidly by ammonia. Examplesinclude the reduction of styrene, stilbene, and phenanthrene. However, doublybenzylic anions, which are formed from anthracene, for example, appear to bepersistent. Borderline basicity is provided by the dihydronaphthalenemonoanion, formed as an intermediate in the reduction of naphthalene. Thelithium salt is protonated in ammonia, especially at reflux temperature,whereas the sodium salt is considerably more resistant to protonation,especially at
. (11)Aromatic compounds may be considered to fall into three classes with respectto their Birch reduction behavior.
: Benzene and its unactivatedderivatives, including alkylbenzenes, aryl ethers, and aminobenzenes, followthe pathway described by Eq.2a. Alcohols are necessary for reduction tooccur, and alkylation of anionic intermediates is not possible.
:Activated benzenes such as benzoates and biphenyls, and many polynucleararomatics with two, three, and four rings; these systems follow Eq.2b.Alcohols are not necessary for the reduction of Class 2 systems, and, in fact,should generally be avoided since if present in amounts exceeding oneequivalent, they usually cause overreduction. Alkylation of the finalmonoanions is possible in these cases, and unless an equivalent of an alcoholis added to prevent the amide formation which occurs when the dianion isprotonated by ammonia, additional alkylation may take place. This result is dueto a second deprotonation/alkylation step occurring after the initial alkylation.Complications may arise when the monoanion is itself protonated by ammonia;phenanthrene is an example. The dihydrophenanthrene monoanion isprotonated by ammonia (Eq.3a) and the resulting neutral compound, which isa biphenyl, is highly reactive under the reduction conditions. Compounds ofthis type are difficult to reduce without overreduction.
: Systems whichform dianions resistant to protonation by ammonia. This result is to beexpected only for large polynuclear compounds or compounds that involve
Class 1 Systems