Renewable Rigid Diamines: Efficient, Stereospecific Synthesis of High Purity Isohexide Diamines

Abstract

We report an efficient three-step strategy for synthesizing rigid, chiral isohexide diamines derived from 1,4:3,6-dianhydrohexitols. These biobased chiral building blocks are presently the subject of several investigations (in our and several other groups) because of their application in high-performance biobased polymers, such as polyamides and polyurethanes. Among the three possible stereo-isomers, dideoxy-diamino isoidide and dideoxy-diamino isosorbide can be synthesized from isomannide and isosorbide respectively in high yield with absolute stereo control. Furthermore, by using this methodology dideoxy-amino isomannide-a tricyclic adduct-was obtained starting from isoidide in high yield. Our improved synthetic route is a valuable advance towards meeting scale and purity demands for evaluating the properties of new biobased performance materials, which will benefit the development of these plastics.

Poly(hydroxy urethane)s based on renewable diglycerol dicarbonate

“…was obtained from Merck. Isoidide diamine (IIDA, P95%) was kindly provided by Wageningen UR Food and Biobased Research [33,34]. Priamine™ 1075 (FDA, 98.7 wt% diamine, 1 wt% triamine) was kindly provided by Croda.…”

Bio-based, amorphous polyamides with tunable thermal properties

“…Pripol™ 1009 (FAD, 98.7% dicarboxylic acid, 1% tricarboxylic acid) was kindly supplied by Croda. 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol (isoidide diamine, IIDA, P95%) was synthesized by Wageningen UR Food and Biobased Research [17,18]. Solvents were obtained from Biosolve in AR grade.…”

From the Synthesis of Biobased Cyclic Carbonate to Polyhydroxyurethanes: A Promising Route towards Renewable Non‐Isocyanate Polyurethanes

“…Van Es et al. realized nucleophilic substitution on tosylated ISO with benzylamine followed by catalytic hydrogenolysis . Other ISO bifunctional amine derivatives were also developed.…”