Studies on the Willgerodt Reaction. II. The Mechanism of the Reaction

Reactions of Benzylamine with Sulfur

“…This should be according to [15]. However, it is first necessary to correct for the differing sulfur chain lengths, i.e., eq.…”

“…6, the benzylamine produced now reacts exclusively with the benzylidenimine polysulfides according to [15]. The latter must be modified (added to [16]) to correct the sulfur chain length and may then be added to [6] to give (after dividing out a common factor of 2) eq.…”

“…Most of the proposed mechanisms (1,2,9,(13)(14)(15)(16)(17) have considered the first step to be attack either by the amine at the carbonyl carbon or by sulfur at the u-carbon to the carbonyl group. This step is generally thought ried out in the presence of a hydrogen sulfide scavenger (25,27).…”

“…4 through 8 to eliminate all to eliminate benzylidenimine (twice [8] added to intermediates. Benzylamine polysulfides may be [7]) to give [15]. Finally, it should be noted that eliminated by adding eq.…”

Sulfur Oxidation of Olefins to Ketones

“…T he aqueous ammonium polysulfide oxidation of aryl methyl ketones to form terminal carboxyamides was discovered by Willgerodt in 1887 (Carmack and Spielman, 1946;Pryor, 1962;Willgerodt, 1887). Compounds other than aryl alkyl ketones were subsequently reported to undergo a similar type of oxidation-e.g., aliphatic ketones (Cavalieri and Pattison, 1945; King and McMillan, 1946), aromatic (Carmack and Detar, 1946;Detar and Carmack, 1946;King and McMillan, 1946;McMillan and King, 1948), and aliphatic olefins (King and McMillan, 1946; Naylor and Anderson, 1953;Pattison and Carmack, 1946), and alkyl aryl hydrocarbons (Naylor and Anderson, 1953; ' Toland et al, 1958). Terminal carboxylic acids and amides and thioamides were the major products.…”