No abstract

From a marine sponge Verongia fistularis and related species3 we isolated four compounds: A, mp 195°; B, mp 191°; C, mp 132°; and D, mp 137°. The structure and synthesis of compound A, mp 195°, having a broad antibacterial spectrum, was reported in a recent paper.4 A comparison of the ir, nmr, and mass spectra of compound C, molecular formula C29H50O, mp 132°, [a]20n -38.7, with those of /3-sitosterol5 revealed them to be identical. Now we wish to report the evidence leading to structure 1 for compound B, mp 191°. This compound was analyzed for CkHisNOiBi^and showed infrared bands (8) L. F. Feiser and M. Feiser in "Reagents for Organic Synthesis,"

p‐Methoxyphenylacetaldehyd (I), dargestellt aus der entsprechenden Säure über das Chlorid, Anilid und Reduktion mit Lithiumalanagsetzt sich mit dem nach Arbusov erhaltenen Phosphonsäurediäthylester (II) zu dem trans, trans‐Diencarbonsäureester (IIIa) um, der mit Salzsäure zur Säure (IIIb) verseift wird, welche mit Thionyl= Ch10l′id das Chlorid (IIIc) liefert.

The reduction of ketones t o the corresponding alcohols using 1,2-dihydro-2-phenylpyridyllithium has been studied. Benzophenone is reduced more readily than is acetophenone, which in turn is more readily reduced than cyclohexanone. I t is suggested that the by-product formed in the reduction of benzophenone is 4-diphenylhydroxymethyl-2-phenylpyridine.The reaction of phenyllithium with pyridine and substituted pyridines has been studied extensively in these laboratories (1-4). The reaction is thought to proceed in two stages: the first is the addition leading t o the formation of 1,2-dihydro-2-phenylpyridyllithium, which has been formulated either as Ia or Ib; this, on heating, splits off lithium hydride to give 2-phenylpyridine (11). Alternatively, it may be treated with water and the 1,2-dihydro-2-phenylpyridine formed oxidized in situ to 11. I t occurred to us that the adduct I might well behave as a selective reducing agent and it was proposed to examine the possibility of reducing a number of ketones making use of this intermediate. While this work was in progress Lansbury and Peterson (5) reported the results of their interesting work carried out using the adduct I11 formed between pyridine and lithium aluminum hydride, a reagent similar in many ways t o the one used in the present work.Dihydropyridines play an important role in biological oxidation-reduction systems and many dihydropyridine derivatives have been reported t o reduce a variety of substances non-enzymically: nitro groups (6, 7), olefinic double bonds (7, S), ketones (9), keto acids (lo), quinones (7, 11), and other functional groups. The reduction of hexachloroacetone proceeds readily to give a reasonably good yield (53-60%) of the alcohol (9), but chloral only gives a 3% yield of 2,2,2-trichloroethanol with 1-benzyl-1,4-dihydronicotinamide.