Synthesis of polyamides from diols and diamines with liberation of H2

  title={Synthesis of polyamides from diols and diamines with liberation of H2},
  author={Boopathy Gnanaprakasam and Ekambaram Balaraman and Chidambaram Gunanathan and David Milstein},
  journal={Journal of Polymer Science Part A},
The amidation reaction based on catalytic coupling of alcohols with amines previously reported by us, using the pincer complexes 1 and 2 as catalysts, was applied to the generation of polyamides from nonactivated diols and diamines. A range of polymers was prepared, with Mn up to 26.9 kDa. Unlike the traditional syntheses of polyamides based on carboxylic acid derivatives, which require the use of toxic reagents and generate stoichiometric amounts of waste, this process generates only molecular… 

Figures and Tables from this paper

An efficient N-heterocyclic carbene-ruthenium complex: application towards the synthesis of polyesters and polyamides.
The ruthenium benzimidazolylidene-based N-heterocyclic carbene (NHC) complex 4 catalyzes the direct dehydrogenative condensation of primary alcohols into esters and primary alcohols in the presence
Manganese Catalysed Dehydrogenative Synthesis of Urea Derivatives and Polyureas
Urea derivatives are prevalent intermediates in the synthesis of resin precursors, dyes, agrochemicals, and pharmaceutical drugs. Furthermore, polyureas are useful plastics with applications in
A Diaminopropane Diolefin Ru(0) Complex Catalyzes Hydrogenation and Dehydrogenation Reactions
New ruthenium (0) complexes with a cooperative diolefin diaminopropane (DAP) or the dehydrogenated iminopropenamide ligand (IPA) were synthesized for comparison with their diaminoethane (DAE)/
Iridium-catalyzed dehydrogenative decarbonylation of primary alcohols with the liberation of syngas.
A new iridium-catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed and gives rise to products in good to excellent yields.
Direct synthesis of polyureas from the dehydrogenative coupling of diamines and methanol.
The present methodology replaces the use of toxic diisocyanates, conventionally used for the production of polyureas, with methanol, which is renewable, less toxic, and cheaper, making the overall process safer and more sustainable.
Catalysis by Pincer Complexes: Synthesis of Esters, Amides, and Peptides
Esters, amides, amines, acetals, and peptides are important industrial chemicals. Production of these chemicals is based onmultistep processes using stoichiometric amounts of acid or base promoters
Tunable Dehydrogenative Amidation versus Amination Using a Single Ruthenium-NHC Catalyst
Mixed N-heterocyclic carbene (NHC)/phosphine complexes of the type [RuCl(p-cymene)(bimy)(PPh3)]PF6 (bimy = benzimidazolin-2-ylidene) have been synthesized and fully characterized. Complex 1 bearing
Hydrogenative Depolymerization of Nylons
The first example of hydrogenative depolymerization of conventional, widely used nylons and polyamides, in general, is reported, and a catalytic cycle for the process that is facilitated by metal–ligand cooperativity is proposed.
Ruthenium-Catalyzed Amide-Bond Formation
The amide functionality is one of the most important functional groups in organic and biological chemistry. Classical synthetic strategies of amides involve the stoichiometric, and poor atom
Direct Synthesis of Amides by Acceptorless Dehydrogenative Coupling of Benzyl Alcohols and Ammonia Catalyzed by a Manganese Pincer Complex: Unexpected Crucial Role of Base.
The reaction is catalyzed by a pincer complex of earth-abundant manganese in the presence of stoichiometric base, making the overall process economical, efficient and sustainable.


Direct synthesis of polyamides via catalytic dehydrogenation of diols and diamines.
Compared with conventional condensation method, this catalytic system avoids the requirement of stoichiometric preactivation or in situ activation reagents and provides a much cleaner process with high atomic economy.
Direct Synthesis of Amides from Alcohols and Amines with Liberation of H2
A reaction in which primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen in high yields and high turnover numbers is reported.
Direct synthesis of imines from alcohols and amines with liberation of H2.
A general, efficient, and environmentally benign method for the direct synthesis of imines by the reaction of alcohols with amines is reported, which occurs with liberation of H2 gas and water, high turnover numbers, and no waste products.
Synthesis of Sequential Polyamide by Direct Polycondensation
A convenient method for the synthesis of sequential polyamide (head-to-head, or tail-to-tail) has been developed. This polymer was prepared by the direct polycondensation of symmetric monomer (YccY),
Direct dehydrogenative amide synthesis from alcohols and amines catalyzed by gamma-alumina supported silver cluster.
The first example of a heterogeneously catalyzed reaction of alcohols with amines to form amides and H2 using the easily prepared and inexpensive heterogeneous catalyst, Ag/Al2O3 is demonstrated.
Discovery of Environmentally Benign Catalytic Reactions of Alcohols Catalyzed by Pyridine-Based Pincer Ru Complexes, Based on Metal–Ligand Cooperation
We have developed a new mode of metal–ligand cooperation, based on aromatization–dearomatization of pyridine-based pincer-type ligands, and have demonstrated it in the activation of H2 and C–H bonds
Amide synthesis from alcohols and amines by the extrusion of dihydrogen.
An environmentally friendly method for synthesis of amides is presented where a simple ruthenium catalyst mediates the direct coupling between an alcohol and an amine with the liberation of two
Direct conversion of alcohols to acetals and H(2) catalyzed by an acridine-based ruthenium pincer complex.
Ruthenium complex RuHCl(A-(i)Pr-PNP)(CO) (1) catalyzes the dehydrogenative coupling of alcohols to form esters and may involve hemiacetal dehydration to form an enol ether followed by alcohol addition to the double bond.
Facile Conversion of Alcohols into Esters and Dihydrogen Catalyzed by New Ruthenium Complexes
An efficient, environmentally benign method for the preparation of esters from alcohols under mild, neutral conditions without the need for carboxylic acid derivatives and condensing agents was
Direct Amide Synthesis from Alcohols and Amines by Phosphine‐Free Ruthenium Catalyst Systems
Amides are synthesized directly from alcohols and amines in high yields using an in situ generated catalyst from easily available ruthenium complexes such as the (p-cymene)ruthenium dichloride dimer,