Synthesis and properties of main chain discotic liquid crystalline polyethers based on rufigallol

Two series of thermotropic main chain discotic liquid crystalline polyethers, PR4m-n, based on rufigallol were prepared starting from the symmetric tetraethers of rufigallol, R4m; m and n represent the number of carbon atoms in the side chain and spacer segment, respectively. The symmetric tetraethers were in turn readily prepared by selective alkylation of rufigallol under controlled phase-transfer conditions. GPC analysis of the polymers suggested that they were all of moderate molecular weights, with M-n varying between 5400 and 17 000. The length of the spacer segment n in these polyethers was systematically varied, and its effect on the phase transition temperatures and the mesophase structure was examined using DSC, polarized light microscopy, and X-ray diffraction. It is noticed that when the spacer lengths are relatively long(n greater than or equal to 2m), the isotropization temperature (TD-i) decreases as the spacer length n increases, an observation that is in accordance with those previously made. However, when the spacer lengths are relatively small (n < 2m), the dependence of TD-i is quite the opposite; TD-i actually increases with an increase in spacer length. Furthermore, X-ray diffraction studies indicate that, in the discotic columnar mesophases that are formed, the columns pack in a hexagonal manner when n greater than or equal to 2m, while they do so in a rectangular lattice when n < 2m, leading to the formation of Dh and Dr mesophases, respectively. Finally, comparison of the discotic polyethers with their low molar mass analogues confirms the role of polymerization in stabilizing the mesophase; while all the polymers exhibit columnar mesophases, some of their low molar mass analogues are not liquid crystalline.

Intermolecular charge-transfer complexes of macrocyclic polyethers with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

The interactions of benzo-15-crown-5, dibenzo-18-crown-6, and dibenzo-24-crown-8 with 2,3-dichloro-5,6-dicyano- 1,4-benzoquinone have been studied in methylene chloride by using spectroscopic methods. These crown ethers from 1:l molecular complexes with the acceptor. The magnitudes of association constants and thermodynamic parameters of complexation are indicative of cooperative interaction of oxygens with the acceptor.

Molecular complexes of macrocyclic polyethers with 1, 3, 5-trinitrobenzene

The interaction of six macrocyclic polyethers with 1, 3, 5-trinitrobenzene has been studied by spectroscopic methods. The association constants have been evaluated by1HMR chemical shift method. There is evidence that major contribution to the interaction isvia n andπ electrons. The donor strengths of the polyethers have been evaluated.

Single-step synthesis of internally functionalizable hyperbranched polyethers

Radical catalyzed thiol-ene reaction has become a useful alternative to the Huisgen-type azide-yne click reaction as it helps expand the variability in reaction conditions as well as the range of clickable entities. In this study, the direct generation of a hyperbranched polyether (HBPE) having decyl units at the periphery and a pendant allyl group on every repeat unit of the polymer backbone is described; the allyl groups serve as a reactive handle for postpolymerization modifications and permits the generation of a variety of internally functionalized HBPEs. In this design, the AB(2) monomer carries two decylbenzyl ether units (B-functionality), an aliphatic OH (A-functionality) and a pendant allyl group within the spacer segment; polymerization of the monomer readily occurs at 150 degrees C via melt transetherification process by continuous removal of 1-decanol under reduced pressure. The resulting HBPE has a hydrophobic periphery due to the presence of numerous decyl chains, while the allyl groups that remain unaffected during the melt polymerization provides an opportunity to install a variety of functional groups within the interior; thiol-ene click reaction with two different thiols, namely 3-mercaptopropionic acid and mercaptosuccinic acid, generated interesting amphiphilic structures. Preliminary field emission scanning electron microscope (FESEM) and Atomic Force Microscopy (AFM) imaging studies reveal the formation of fairly uniform spherical aggregates in water with sizes ranging from 200 to 400 nm; this suggests that these amphiphilic HBPs is able to reconfigure to generate jellyfish-like conformations that subsequently aggregate in an alkaline medium. The internal allyl functional groups were also used to generate intramolecularly core-crosslinked HBPEs, by the use of dithiol crosslinkers; gel permeation chromatography traces provided clear evidence for reduction in the size after crosslinking. In summary, we have developed a simple route to prepare core-clickable HBPEs and have demonstrated the quantitative reaction of the allyl groups present within the interior of the polymers; such HB polymeric systems that carry numerous functional groups within the core could have interesting applications in analyte sequestration and possibly sensing, especially from organic media. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4125-4135

Complexes of lanthanide perchlorates with N,N,N′,N′-tetramethyl-α-carboxamido-O-anisamide and N,N′-di-t-butyl-α-carboxamido-O-anisamide

A survey of the literature on lanthanide coordination compounds reveals that ligands involving ether oxygens as donor atoms have received very little attention [ 11. Only recently have the complexes of lanthanides with cyclic polyethers been characterized [l-3]. We report in this communication that interaction of rareearth perchlorates with two new ligands namely N,N,N’,N’-tetramethyl-u-carboxamido-Oanisamide (TMCA) and N,N’-di-t-butyl-crcarboxamido- 0-anisamide (DTBCA). The two ligands are potentially tridentate possessing two amide moieties and an ether linkage in between. The isolated complexes have been characterized by analysis, electrolytic conductance, infrared and electronic spectra. The ‘H and “C NMR spectra for the diamagnetic La3+ and Y3+ complexes are also discussed.

AB2 + A Type Copolymerization Approach for the Preparation of Thermosensitive PEGylated Hyperbranched Polymers

Hyperbranched polyethers having poly(ethylene glycol) (PEG) segments at their molecular periphery were prepared by a simple procedure wherein an AB2 type monomer was melt-polycondensed with an A-type monomer, namely, heptaethylene glycol monomethyl ether. The presence of a large number of PEG units at the termini rendered a lower critical solution temperature (LCST) to these copolymers, above which they precipitated out of an aqueous solution. In an effort to understand the effect of various molecular structural parameters on their LCST, the length of the hydrophobic spacer segment within the hyperbranched core and the extent of PEGylation were varied. Additionally, linear analogues that incorporates pendant PEG segments were also prepared and comparison of their LCST with that of the hyperbranched analogue clearly revealed that hyperbranched topology leads to a substantial increase in the LCST, highlighting the importance of the peripheral placement of the PEG units.

Reaction of polyperoxides with triphenylphosphine

The triphenylphosphine deoxygenation of the polyperoxides, poly(styrene peroxide), poly(methyl methacrylate peroxide), and poly(alpha-methylstyrene peroxide) proceed via the phosphorane intermediates, which in the presence of moisture hydrolyze to give the respective diols. At higher temperatures and under dry conditions the phosphorane decomposes into epoxide and triphenylphosphine oxide. The reaction has been studied by H-1-, C-13-, and P-31-NMR spectroscopy. The results obtained are consistent with a concerted insertion of the biphile, triphenylphosphine, into the peroxy bond and this reaction pathway seems to be new as far as the chemistry of polyperoxides is concerned. Though the aim of this investigation was to test the selective deoxygenation of polyperoxide by triphenylphosphine as a method of preparing polyethers, it turned out to be a fruitful method of synthesis of stereospecific diols. (C) 1997 John Wiley & Sons, Inc.