One-Step Synthesis and Structure of an Oligo(spiro-orthocarbonate)

Abstract

The reaction of pentaerythritol and tetraethylorthocarbonate at 260 degrees C for 12 h yields a white crystalline material that was characterized by 13C CPMAS NMR, CHN analysis, FT-IR, electron and X-ray powder diffraction, and Rietveld analysis. The white crystalline material was found to have the formula C6H8O4 and a crystal structure with a monoclinic cell [a = 9.167 A, b = 5.681 A, c = 5.880 A, beta = 90.0 degrees , space group I2] of hexagonally arranged spiro-oligomeric chains.

Cross-Linked Poly(orthocarbonate)s as Organic Solvent Sorbents

“…Poly-(orthocarbonate)s were synthesized by condensation of dichlorodiphenoxymethane with diphenols, resulting in an extremely thick gel. 10 In this paper, we present a simple method for the synthesis of cross-linked polymers using tetraethyl orthocarbonate 13 and different diol and triol monomers.…”

Efficient synthesis and properties of soluble aliphatic oligo(spiroorthocarbonate)s from pentaerythritol derivatives

“…The polycondensation of 1a with TEOC gave the corresponding OSOC 2a . As has been reported, it was insoluble in common organic solvents and thus its molecular weight of the oligomer could not be measured by SEC. The structure of OSOC 2a was confirmed by solid state 13 C NMR (CPMAS).…”

“…Spiropolymers are a subclass of ladder polymers consisted of double‐stranded main chains, which are expected to be thermally and mechanically more stable than polymers with a single main chain. Poly(spiroketal)s and poly(spiroorthocarbonate)s (PSOCs) have been two major spiropolymers because of the simplicity of their syntheses . Previously, we reported the synthesis of aromatic poly(spiroorthocarbonate)s (PSOCs) by the polycondensation of 1,2,4,5‐tetrahydroxybenzene (THB) with 2,2,6,6‐tetrachlorobenzo [1,2‐d;4,5‐d’]bis[1,3]dioxol (TCBBD) .…”

“…Aliphatic PSOCs are also attractive as candidate high‐performance materials because of the absence of UV absorbable moieties that allow the potential high UV‐resistance of PSOCs. Yaghi et al have reported a oligo(spiroorthocarbonate) (OSOC) that can be synthesized by the polycondensation of pentaerythritol and tetraethylorthocarbonate (TEOC) . The OSOC thus obtained was insoluble in common organic solvents due to the high crystallinity, which was arisen by the spontaneous alignment of the rigid rod‐like oligomer chains into a bundle, preventing adequate structural analyses.…”

Unusual cationic ring‐opening behavior of a novel six‐membered ring spiro‐orthocarbonate bearing adamantane backbones

“…Spiro compounds are of interest because of their fascinating structure and unique properties, and many studies on the synthesis and utilization of various types of organic compounds and polymers bearing spiro structure(s) have been conducted 1–4. In various types of spiro structures, we have mainly given attention to spiro‐orthocarbonates ( SOCs ), and the ring‐opening behavior of various‐membered ring SOCs with a cationic initiator has been revealed 5–13.…”