A 4,4’ MDA (methylenedianiline) derivative was synthesized using a three-step route. Industrially, MDA has 3 regioisomers which consist of 2,2’, 4,4’, and 2,4’ configurations. Here, a direct route for the synthesis of the 4,4’ isomer was exhibited. First, nitrobenzyl bromide and nitrophenyl boronic acid were reacted via a Suzuki reaction. This utilizes microwave irradiation in its key step to produce 4,4’ MDN (bis(4-nitrophenyl)methane). Homocoupling can cause some concern within Suzuki reactions because boronic acids can react with themselves. Incidence of homocoupling was combated by adjusting the equivalences of the nitrobenzyl bromide and boronic acid. Subsequently, 4,4’ MDN is hydrogenated to yield 4,4’ MDA. 4,4’ MDA is then converted to 4,4’ MDC (methylenedicarbamate) upon being treated with methyl chloroformate. This process was employed in the synthesis of a deuterated version of this compound, which will be developed into a set of 4,4’ isomer standards. In addition to the quantification of the residual 4,4’ MDI (methylene diphenyl diisocyanate) in commercial samples, these standards can later be administered in testing for the presence of potential carcinogenic extractables and leachables in consumer products. Examples of these products include nylon spatulas, insulation, and adhesives.

Three step synthesis of a 4,4’ methylenedianiline derivative

2019 Spring National Meeting

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