| In the first part of the following study we investigated two possible application of alkali metal complexing agents in organic synthesis: their use with alkali metals to carry out reductions of organic compounds; their use to complex with, and thereby increase the base strength of alkyl lithium reagents.; Formaldehyde was reduced by HMHCY complexed NaK alloy. The reactions were quenched with D{dollar}sb2{dollar}O and gave methanol-OD and dideuteromethanol in 11{dollar}sim{dollar}81% yield. The dideuteromethanol is believed to arise from reaction of a carbanion-like C-O synthon with the D{dollar}sb2{dollar}O and accounts for 0.5{dollar}sim{dollar}10% of the reaction yield. Attempts were also made to reduce 2,2-dimethylpropanal and 2-cyclohexenone using HMHCY complexed NaK alloy. 2,2-Dimethylpropanal dimerized to give 2,2,5,5-tetramethyl-3,4-hexanediol. The reduction of 2-cyclohexenone gave over 35 separate compounds that were not identified.; In the second part we report the design and synthesis of two new complexing agents and several improvements to the methodology used to form polyazamacrocycles. It was found that by carefully controlling temperature, time, and the concentration of sulfuric acid used it was possible to limit the acid hydrolysis of the sulfonyl amide bonds of 1,4,7-tritosyl-1,4,7-triazacyclononane so that one, two or all three tosyl protecting groups were removed. This technique allows a convenient method for synthesizing polyazamacrocycles that have a unique pendant arm on one or two of the available nitrogen atoms. The methodology was used as a key step in the synthesis of the two novel tertiary polyazamacrocycles 1,2-bis(4,7-dimethyl-1,4,7-triazacyclononyl)ethane and 4,7-dimethyl-1-(3-dimethylaminopropyl)-1,4,7-triazacyclononane. In addition we report some improvements for the Richman-Atkins synthesis of polyazamacrocyclic compounds. It was discovered that the use of a catalytic amount of tert--butyl alcohol allowed the use of only a modest excess of a hydride base in the cyclization step without decreasing the yield. |
