Development of chlorotriazine polymer dehydrocondensing reagents (Poly-Trzs)

• Published in: Tetrahedron Vol. 63; no. 12; pp. 2604 - 2612
• Main Authors: Kunishima, Munetaka, Yamamoto, Kazuyoshi, Hioki, Kazuhito, Kondo, Tomohito, Hasegawa, Masumi, Tani, Shohei
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 19.03.2007
• Subjects: Dehydrocondensing reagent; Immobilized reagent; Polymer; Triazine; Triazine; Polymer; Dehydrocondensing reagent; Immobilized reagent
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2007.01.034

Polymer-type dehydrocondensing reagents comprising of a triazine dehydrocondensing reagent, itself in a polymerized form (Poly-Trz—MMs'), have been developed by exploiting the chemical properties of cyanuric chloride that readily binds to alcohol or amines. A chlorotriazine polymer bearing two alkoxy substituents at the 4- and 6- positions (Poly- O-Trz–Cl) was prepared by alternating copolymerization between cyanuric chloride and tetra(ethylene glycol). Similarly, polymers bearing both alkoxy and amino substituents (Poly- N-Trz–Cl) were synthesized from tetra(ethylene glycol) bis(4,6-dichlorotriazin-2-yl) ether 6 and tris(2-aminoethyl)amine 7 and/or ethylenediamine 8. All the polymers were shown to be good reagents for dehydrocondensation of carboxylic acids and amines in the presence of NMM, compared to the corresponding monomeric dehydrocondensing reagent (DMT–MM). The advantages of the polymeric reagents are as follows: (1) both the reaction and isolation procedure of dehydrocondensation can be greatly simplified, (2) the dehydrocondensation can be conducted in protic solvents as well as in common organic solvents, (3) the reagents can be efficiently prepared at a low cost, and (4) these reagents are considered eco-friendly, generating a lower amount of waste compared to conventionally related reagents because of high loading of the dehydrocondensing activity (ca. 3 mequiv/g). [Display omitted]