The present report describes the preparation and use of some dimethyl terephthalate derivatives in transition metal-catalyzed coupling reactions to produce new reactive flame retardants. Dimethyl iodoterephthalate and dimethyl 2,5-diiodoterephthalate were successfully employed in the preparation of phosphonic and boronic esters and acids. The latter were tested for heat release with a microcombustion calorimeter (ASTM D7309) to determine the potential for heat release reduction of these flame retardant molecules. The results showed that the addition of boronic or phosphonic acids greatly lowered the heat release, due to a condensed phase (char formation) mechanism. Adding ester groups to the boronic acids or phosphonic acids could either completely remove all flame retardant effects or make the molecule act more like a vapor phase flame retardant. Finally, the various potential flame retardants were solvent blended with a thermoplastic polyurethane to assess their flammability reduction effects by microcombustion calorimetry. The results of these experiments found that the molecules that reduced heat release the most by themselves showed the greatest reduction in heat release in a polyurethane as well, with the boronic acids yielding the greatest reduction in heat release.

The present report describes the X‐ray structural and theoretical studies of some new pinacolboronate esters, and it also outlines the use of the target structures in Suzuki coupling reactions to produce new aromatic or heteroaromatic esters and amides. X‐ray structural analysis of the studied compounds revealed that the pinacolborane ring's position with respect to the benzene ring varies, depending on the particular environment. An ortho‐positioned carboxylic ester (methyl ester) causes a nearly perpendicular orientation of the pinacolborane unit with respect to the benzene ring, whereas an ortho‐positioned amide (N,N‐dimethylamide) causes the pinacolborane unit to orient itself nearly coplanar. A plausible explanation has been provided, based on both steric and electronic factors.