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THE GREEN SYNTHESIS AND MATERIAL AND ORGANIC APPLICATIONS OF BORANE-AMINES

thesis
posted on 2024-04-15, 20:02 authored by Randy L LinRandy L Lin

Reported herein is a brief summary regarding the previous syntheses of borane-amines, newly developed protocols to synthesize borane-amines, and the material and synthetic applications utilizing borane-amines. Methods to generate borane-amines typically relied on a metathesis-dehydrogenation reaction between ammonium salts and metal borohydrides in organic solvent, typically hazardous tetrahydrofuran (THF). However, due to the poor solubility of inorganic salts in organic solvent, stirring of the reaction mixture becomes difficult and, in turn, scalability is made challenging. We report two new methods to generate borane-amines that both rely on the hydroboration of sodium borohydride and a carbonyl activator, followed by the SN2-type reaction with the amine to form the requisite borane-amine. The activator for our procedures are either 1) gaseous carbon dioxide or 2) water/ethyl acetate system. The CO2 mediated protocol was applied to a variety of 1°-, 2°-, 3°-, and heteroaromatic amines as well as phosphines to form the corresponding borane adducts (73-99%). Water was also found to be a green, compatible activator. Interestingly, we had swapped environmentally and health hazardous THF with ethyl acetate (EtOAc) and found the reaction had still proceeded with competitive conversion of amines to the borane-amines (72-97%). The robustness of this reaction was demonstrated with a 1.1 mol scale synthesis of borane pyridine with 87% yield. With increased accessibility of borane-amines established, we sought to investigate their potential applications, including testing their hypergolic properties. Additionally, we utilized borane-ammonia for a sequential reduction/Friedel-Crafts alkylation of benzyl carbonyls. Traditionally an alkyl halide, the scope of the electrophilic aromatic substitution reaction has widened to include alcohols and carbonyls as potential Friedel-Crafts reactants. Few reports exist for the arylation of aldehydes and ketones, while no precedence exists for the arylation of carboxylic acids and esters. Our group previously reported that TiCl4 is capable of eliminating oxygen from benzyl alcohols, forming a carbocation intermediate. Theoretically, the carbocation formed from TiCl4 and benzyl alcohols would be vulnerable from attacks from other nucleophiles, including pi bonds from arenes. This was indeed proven to be the case when benzyl alcohol was reacted in 1 equiv. TiCl4 with benzene as the solvent and diphenylmethane was obtained as the sole product. By including borane-ammonia as a hydride source, various aryl carbonyls and aryl carbinols were also reduced to the corresponding alcohol in situ, enabling these substrates to participate in Friedel-Crafts alkylation.

History

Degree Type

  • Doctor of Philosophy

Department

  • Chemistry

Campus location

  • West Lafayette

Advisor/Supervisor/Committee Chair

Padinjaremadhom Ramachandran

Additional Committee Member 2

Herman O. Sintim

Additional Committee Member 3

Chittaranjan Das

Additional Committee Member 4

Davin G. Piercey

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