Macromolecular synthesis from saccharic lactones. Ring‐opening polyaddition of D‐glucaro‐ and D‐mannaro‐1,4:6,3‐dilactones with alkylenediamines

Abstract

Ring‐opening polyaddition of a saccharic acid dilactone prepared from D‐glucose, D‐glucaro‐1,4 : 6,3‐dilactone, with several alkylenediamines proceeded at room temperature with no catalyst. The resulting new polyamides carrying many pendant hydroxyl groups, poly(alkylene D‐glucaramide)s, were more amorphous and hydrophilic than the corresponding nylons having no hydroxyl groups, and were hydrolyzed more easily than the latter in an acidic condition. The ring‐opening ability of D‐mannaro‐1,4:6,3‐dilactone, which was another saccharic acid dilactone obtained from D‐mannitol, was found to be lower than that of the D‐glucaric analogue. © 1993 John Wiley & Sons, Inc.

Synthetic polyhydroxypolyamides from galactaric, xylaric, D ‐glucaric, and D ‐mannaric acids and alkylenediamine monomers—some comparisons

“…In contrast, the polymerization of dimethyl 11,14 (Scheme 3). D-Mannaryl polyamides (9) were stereoregular in that the mannaryl units had an S configuration at each chiral carbon.…”

“…However, the low solubility of the polymers in the reaction solvent limited their molecular weights. A number of poly-(glucaramide)s reported here also were prepared by Hashimoto et al, 14 who condensed D-glucaro-1,4:6,3-dilactone with alkylenediames in a DMSO solution. As the polyamides were all soluble in this solvent, the higher M n 's they reported were likely due to the chain-length buildup continuing in solution rather then being limited by a low solubility as observed with methanol as the reaction solvent.…”

“…Because the previously observed cutoff between the water-soluble and water-insoluble polymers was either the ethylene or tetramethylene polyamides, only these two additional poly(D-mannaramide)s, 9a and 9b, respectively, were made for comparison (Table IV). The latter polymers, as well as 9c, were synthesized in dimethyl sulfoxide (DMSO) by Hashimoto et al 14 Although the polymerizations in a methanol solution were very efficient and showed little color with the esterified aldaric acids already described, this was not the case with the polymerization of D-mannaro-1,4:6,3-dilactone (8) with diamines. Reaction mixtures became tan to brown in color, and precipitated polymers tended to be 14 reported that the condensation polymerizations of 8 in DMSO with diamines were not efficient.…”

“…PHPAs based on DGlucaric, 9 -14 meso-xylaric, 9,10,15 and D-mannaric acid 11,14 have been described more recently. The primary structural differences between those polymers with alkylenediamine units in common originate from the variable stereochemistry and number of carbon atoms in the diacid monomer units.…”

“…Poly(hexamethylene D-mannaramide) (9c) 11,14 A solution of D-mannaro-1,4;6,3-dilactone (10; 0.870 g, 5.50 mmol) in methanol (20 mL) and triethylamine (0.25 mL) in a 100-mL round-bottom flask was refluxed for 20 min, and a methanol solution of hexamethylenediamine (2c; 1.47 M, 1.72 mL, 5.45 mmol) was added. The reaction mixture became yellow within 5 min but was refluxed for 3 h without any significant increase in the color intensity.…”