Vacuum ultraviolet optical analysis of spin‐cast chitosan films modified by succinic anhydride and glycidyl phenyl ether

Optical properties of spin‐cast chitosan films were determined in the vacuum ultraviolet (VUV) through visible regions of the spectrum using spectroscopic ellipsometry. The onset of absorption in the ultraviolet was determined for chitosan films modified with succinic anhydride (SA) and glycidyl phenyl ether (GPE). This absorption was accounted for by including Gaussian and Tauc–Lorentz shaped oscillators in the optical model. VUV through visible optical constants were determined for these modified films, as well as for immunoglobulin G (IgG) attached to GPE‐modified samples. Several resonant oscillator structures exhibit greatly differing oscillator parameters for the as‐deposited, as well as SA‐ and GPE‐modified films. These in‐plane and out‐of‐plane oscillator strengths, energy positions, and broadening were determined and tabulated, and their chemical origins identified. A phenyl resonant π‐bond at approximately 6.3 eV was observed for the GPE‐modified sample. This was not present in the bare chitosan data. GPE contains a phenyl group in the molecule and absorption due to it is clearly identified. Clarity of data after surface chemical modification is due to the high surface sensitivity of VUV ellipsometry. Copyright © 2007 John Wiley & Sons, Ltd.     

Reaction of diphenylcarbodiimide with phenyl glycidyl ether

Conclusions The reaction of diphenylcarbodiimide with phenyl glycidyl ether gives 3-phenyl-5-phenoxymethyl-2-N-phenyliminooxazolidine, which, in contrast to a number of substituted iminooxazolidines, does not isomerize to the corresponding imidazolidinone when heated to 250°.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 474–476, February, 1983.     

Reaction of phenylbenzoxazole with phenyl glycidyl ether

Conclusions The reaction of phenyibenzoxazole with phenyl glycidyl ether is not limited to the addition of the -oxide ring to the C=N bond of phenyibenzoxazole, but is followed by addition of a second molecule of phenyl glycidyl ether with the formation of an N derivative of hydroxyaniline.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1356–1359, June, 1987.     

Reactions of 2-aminobenzothiazoles with phenyl glycidyl ether

In acidic media 2-aminobenzothiazole and its derivatives react with phenyl glycidyl ether at the ring nitrogen atom, while in alkaline media they react at the exocyclic nitrogen atom. The structures of the compounds were proved by spectral methods and alternative synthesis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 685–691, May, 1991.     

Reaction of phenyl glycidyl ether with triphenyl isocyanurate

Conclusions On the example of the reaction of triphenyl isocyanurate with phenyl glycidyl ether it was shown that oxirane rings when heated can react with the isocyanurate ring to give oxazolidone fragments.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1645–1646, July, 1981.     

Anionic graft polymerization and homopolymerization of phenyl glycidyl ether

Phenyl glycidyl ether was found to react with potassium starch alkoxide in dimethyl sulfoxide (DMSO) to give graft polymers in almost quantitative yields, both the monomer and the starch being incorporated completely into the graft polymer. No transfer reactions to monomer or solvent leading to homopolymerization was found. For this reason this system was used as a model for the study of the rate of the graft polymerization of alkylene oxides on starch and other carbohydrates. Comparison of the rates of the graft polymerization of phenyl glycidyl ether on starch alkoxide with that of the homopolymerization by potassium naphthalene in DMSO under comparable conditions showed that the former reaction was much slower. Rates of the graft polymerizations on dextrin and sucrose under comparable conditions, were similar to those obtained with starch. On the other hand, the rates of polymerization on poly(ethylene oxide) alkoxides of different molecular weights were similar to those obtained in the corresponding homopolymerization by potassium naphthalene, showing that neither the molecular weight of the initiator nor the viscosity of the reaction medium were the governing factors. This suggested that the lower rates obtained by using the carbohydrate alkoxides as initiators were connected with the heterogeneity of these reaction systems, the polymeric alkoxide being insoluble in DMSO. The systematic study carried out on the homopolymerization by potassium naphthalene in DMSO showed that the effective initiator was dimsyl anion obtained by interaction of potassium naphthalene with DMSO. The reaction was bimolecular, being first order to monomer and to initiator. The molecular weights increased with increasing monomer concentration and decreasing catalyst concentration, in accordance with a “living” polymerization system.     

Reaction of phenyl glycidyl ether with N-trimethylsilylaniline and trimethylsiloxybenzene

Conclusions It was shown by the IR spectroscopy method that the reaction of phenyl glycidyl ether with trimethylsiloxybenzene and N-trimethylsilylaniline proceeds via insertion of the opened epoxide ring between the Si-O and Si-N atoms.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 454–458, February, 1978.     

Reaction of phenyl glycidyl ether with some heterocycles

The respective hydroxypropyl phenyl ethers were obtained by the reaction of 5,5-dimethylhydantoin, morpholine, benzotriazole, benzimidazole, pyrrolidone, and phthalimide with phenyl glycidyl ether. 8-(2-Hydroxy-3-phenoxy) quinoline was synthesized by O-alkylation. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 817–820, June, 2008.     

Thermokinetics of the reaction of phenyl glycidyl ether with aniline

The thermokinetic curves in the reaction of phenyl glycidyl ether with aniline were calculated for various compositions of the reaction mixture and temperatures. In addition to the main exothermic effect related to the epoxide ring opening, another exothermic effect of unknown nature was observed. The kinetic data obtained are explained in terms of structural changes caused by the self-aggregation of the reaction product molecules. The “kinetic investigation” approach provides a quantitative analysis of calorimetric data.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 371–375, February, 2005     

Single Crystals of Poly(phenyl glycidyl ether)

Abstract

The Watson-Crick model for DNA has been modified to account for observed physical phenomena associated with DNA. The viscosity data obtained on both partially denatured DNA and on undenatured DNA in various aqueous salt solutions give rise to acidic-type cationic sequences. These results can only be explained if there exist additional bonds other than the hydrogen bonds between base pairs. Considering the experimental data, the only possible type of bond that could exist is an ionic bond between the negatively charged phosphate group and the polar or positively charged nitrogen atom attached to the C'-1 position of the deoxyribose unit. The formation of such an ionic bond produces a natural twist in the DNA strand. The model is also applicable to RNA, although steric factors affect the stability and structure of such an RNA. Values of ΔH for the formation of the DNA and RNA double helix substantiate the proposed models. The most plausible structure for the double-stranded DNA helix is a model where the base pairs are on the surface rather than on the interior of the helix. Hydrophobic bonds do not exist except possibly in the altered structure produced during preparation of the DNA for X-ray analyses. The viscosity results on undenatured DNA in various salt solutions are caused by two factors: a destruction of the ionic bond and a reversal of charge effect on the DNA. The results show that the charge on DNA must change from a negative to a positive charge with addition of salt. The proposed model is applied to replication of DNA and formation of RNA from DNA and associated phenomena.     

Influence of solvent on conformational equilibrium in phenyl glycidyl ether

The conformational equilibrium in phenyl glycidyl ether in aprotic solvents was studied by the PMR method over a broad range of changes in the values of the dielectric constant. It was shown that the parameters of the multiplet of noncyclic methylene protons in the PMR spectrum of phenyl glycidyl ether are a sensitive indicator of the position of the conformational equilibrium in the glycidyl fragment. The specific interaction of the molecules of aromatic solvents with the epoxide ring has been discovered.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 21, No. 2, pp. 245–247, March–April, 1985.     

Mechanism of reaction of phenyl glycidyl ether with phenyl benzoate in the presence of water

The reaction of phenyl glycidyl ether with phenyl benzoate in the presence of water was investigated by adsorption liquid chromatography.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 131–133, January, 1990.     

Epoxy compounds. VIII. Stereoregular and stereorandom polymerization of phenyl glycidyl ether with tertiary amines,and infrared spectra of poly(phenyl glycidyl ether)

Crystalline and amorphous polymers have been obtained from the polymerization of phenyl glycidyl ether in the presence of tertiary amines. The crystalline fraction is high melting and insoluble at room temperature. The amorphous fractions are soluble at room temperature and their molecular weights are found to be ～950 in benzene at 30°C. The yields of the crystalline fraction and the amorphous paste fraction decreased considerably with increasing the catalyst concentration and reaction temperature above 50°C. The yield of the liquid fraction, however, increased with increasing concentration of the catalyst and the reaction temperature. The x-ray diffraction analysis of the crystalline fraction shows that the fraction has 47–50% crystallinity and that its diffraction pattern is similar to that of poly(phenyl glycidyl ether) obtained by Noshay and Price. The infrared spectra of these fractions have been obtained in the region of 650–4000 cm.^?1. These data are compared with those of polystyrene and poly(styrene oxide) and are used to make an assignment of the normal modes of the poly(phenyl glycidyl ether) molecule. On the basis of analyses of polystyrene and poly(styrene oxide), and a study of the combination bands, it has been possible to make a fairly satisfactory assignment of all of the benzene ring fundamentals of the CH₂, CH, and skeletal modes.     

Polymerization and crosslinking of epoxides: Base-catalyzed polymerization of phenyl glycidyl ether

The anionic polymerization of 2,3-epoxypropyl phenyl ether initiated by sodium methoxide and dimsyl sodium in dioxane and in dimethyl sulfoxide has been studied. Kinetic and dielectric constant measurements have been recorded, and a mechanism for the initiation reaction with dimsyl sodium has been put forward. Polymerization initiated with dimsyl sodium revealed almost total absence of sulfur in the polymer by endgroup analysis. The reaction was shown to be inhibited by oxygen. Molecular weight determinations have indicated a reaction involving transfer to give polymers of lower than calculated M?_n and a ratio of k_p/k_tr ratio of approximately 73. Gel-permeation chromatography suggests a narrow molecular weight distribution in the polymers prepared.     

Novel lipase-catalyzed ring-opening copolymerization of oxiranes and succinic anhydride forming polyesters bearing functional groups

Oxiranes, such as glycidyl phenyl ether (GPE) and benzyl glycidate (BG), were copolymerized with succinic anhydride (SA) by lipase at a temperature between 60 and 80°C to yield the corresponding polyesters bearing carboxyl or phenyl groups. Bulk polymerization, especially at the temperature of 80°C, and preferably using porcine pancreatic lipase gave biodegradable polyesters with a molecular weight greater than 5000.     

Composition and reactivity of aminolysis products of phenyl glycidyl ether with benzylamine

Composition of aminolysis products of phenyl glycidyl ether with benzylamine in various conditions was studied. The ratio of 1-(benzylamino)-3-phenoxypropan-2-ol and 1,1'-(benzylazanediyl)bis(3-phenoxypropan-2-ol) does not considerably depend on the nature of the solvent and is basically determined by ratio of initial reagents. 2,6-Bis(phenoxymethyl)morpholine was obtained by dehydration of aminodiol in conditions of Mitsunobu reaction with subsequent reductive debenzylation.