Naphthalene Benkeser reduction

By proper choice of reaction conditions (metal, solvent, the order of addition of reagent and reactant), fused polycyclic aromatics can be converted to different partially reduced derivatives with high selectivity. When the red complex of naphthalene, for example, formed in the Na-NH3 solution, is quenched with aqueous ammonium chloride solution, 1,4-dihydronaphthalene is formed209 [Eq. (11.58)]. Reaction in the presence of an alcohol yields 1,4,5,8-tetrahydronaphthalene210 [Eq. (11.59)]. The Benkeser reduction affords further saturation to the isomeric octalins211 [Eq. (11.60)] or even to decalin212 [Eq. (11.61)] ... 

The preeminence of lithium and sodium in metal reductions has been challenged by the use of calcium in amines, developed by Benkeser. In the initial work, naphthalene was reduced to an 80 20 mixture of A -octalin (522) and A ( )-octalin (523) with lithium in diethylamine-dimethylamine. Replacing lithium with calcium gave a 77 23 mixture of 522 and 523 in 92% yield. This method has come to be called the Benkeser reduction. This has become an important modification because Birch reductions with sodium are... 

A9-Octalin (10) is readily prepared according to R. A. Benkeser (1955) by reduction of naphthalene with lithium and ethylamine and isomerization of small amounts of the All9)-isomer. An Indian group81 converted this hydrocarbon into the... 

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