Synthesis and characterization of bigraft copolymers based on grafted type peracid polymer

In this study, a radiation-induced copolymer, namely, polyethylene-g-acrylic acid and EVA-g-acrylic acid, in the form of a membrane, particulate, or tube was used as a substrate. The carboxyl groups of the grafted acrylic chains were oxidized into peracids. Optimal conditions for the oxidation, including the catalyst, reaction time, and temperature were investigated. Novel bigraft copolymers were then synthesized from the grafted polymeric peracid. A third component (e.g., 2-hydroxyethyl methacrylate) was grafted through the decomposition of peracid groups. Abnormality in morphology of the acrylic acid grafted and HEMA bigraft membrane was investigated by SEM and TEM observation, which showed the levelling effect of the third component and manifested a third circular domain generated inside the membrane at high degree of grafting.     

Preparation of new types of temperature-responsive cellulose derivatives

This paper reviews briefly our preliminary results concerning thermoplastic hydrogels and thermotropic aqueous gels from cellulose. Several kinds of thermoplastic hydrogels and thermotropic aqueous gels were prepared from cellulose and their thermal properties were examined. The former aims at preparing water-insoluble cellulose derivatives having a high water absorbency and a thermal flow temperature of approximately 130°C, while the later aims at preparing water-soluble cellulose derivatives which show a solubility behavior similar to that of synthetic polymers with a lower critical solution temperature (LCST) in aqueous solution. The results will be discussed in terms of the chemical structure of the prepared derivatives and their substituent distributions along the cellulose chain.     

Synthesis of methoxy-substituted phenols by peracid oxidation of the aromatic ring

[reaction: see text] A novel benign protocol for the preparation of hydroxy-methoxybenzene derivatives is disclosed. By utilizing this protocol, activated aromatic compounds such as 1,3-dimethoxy-2-methyl-benzene and 1-(2,6-dimethoxyphenyl)ethanone are smoothly converted to the corresponding monohydroxylated compound. The reaction can be considered to be a normal aromatic electrophilic substitution reaction, and the regioselectivity for the reaction thus follows the similar rules as for electrophilic substitutions. The protocol is composed by benign reagents, namely, hydogenperoxide, acetic acid, and p-toluene sulfonic acid, which lead to the production of ethaneperoxoic acid in situ. The ethaneperoxoic acid operates as the hydroxylating reagent. The hydroxylation reaction is completed within a short period and requires moreover only mild experimental conditions, which make this novel protocol a green, cheap, and rapid process leading to hydroxy-methoxybenzene derivatives. The proposed reaction mechanism is supported by density functional theory and NMR spectroscopy experiments. The mechanism is constituted by two discrete steps: (a) addition of OH+ to the most nucleophilic carbon atom of the aromatic ring, which is the rate-determining step, and (b) the loss of the proton from the aromatic ring.     

Synthesis of temperature-responsive anion exchanger via click reaction

The temperature-responsive anion exchanger was synthesized by immobilizing the poly(N-isopropylacrylamide) (PNIPAM), a kind of the temperature-responsive polymer, on the external surface of mesoporous silica via click reaction. The structure of this synthesized composite was characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), elemental analysis, and nitrogen adsorption experiment. The amount of PNIPAM immobilized on the external surface of mesoporous silica, which was calculated from the weight loss measured by thermogravimetry, increased from 5.3 wt.% to 12.9 wt.% (dry) depending on the amount of PNIPAM added in the click reaction. The adsorption-desorption behavior of methyl orange (MO) ions in this synthesized anion exchanger was affected by the temperature of aqueous solution: the MO ions were adsorbed and desorbed reversibly and repeatedly with changing the pH of the solution at 25 °C, while the amount of adsorbed MO ions remained nearly constant at about 0.05 mmol/g independent of the pH of the solution at 40 °C. Also, the amount of PNIPAM immobilized on the mesoporous silica influenced the adsorption rate of MO ions, suggesting that the adsorption rate in this composite is controlled by the diffusion of MO ions through the PNIPAM layer.     

Synthesis of cyclic peroxides containing the Si-gem-bisperoxide fragment. 1,2,4,5,7,8-Hexaoxa-3-silonanes as a new class of peroxides

A method was developed for the synthesis of the previously unknown class of organic peroxides, 1,2,4,5,7,8-hexaoxa-3-silonanes, based on the reaction of dialkyldichlorosilanes with 1,1'-dihydroperoxyperoxides. 1,2,4,5,7,8-Hexaoxa-3-silonanes are rather stable under ambient conditions and were characterized by NMR spectroscopy, X-ray diffraction, and elemental analysis. Their yields are in a range of 59-96%. The attempts were made to prepare 1,2,4,5-tetraoxa-3-silinanes by the reaction of dialkyldichlorosilanes with gem-bishydroperoxides. 1,2,4,5-Tetraoxa-3-silinanes were detected by NMR spectroscopy; these compounds rapidly decompose upon isolation.     

Epoxidation of olefins with a silica-supported peracid

Anhydrous [2-percarboxyethyl] functionalized silica (2a) is an advantageous oxidant for performing the epoxidation of olefins 1. Epoxides 3 do not undergo the ring-opening reactions catalyzed by the acidic silica surface, except for particularly activated cases such as styrene oxide. The hydrophilic and acidic character of the silica surface does not interfere with the directing effects exerted by allylic H-bond acceptor substituents. The alkenes 1 carrying hydroxyl groups react with silica-supported peracid 2a faster than unsubstituted alkenes, thus reversing the trend known for reactions with soluble peracids. These results are attributed to the H-bond interactions of substrate 1 with the silanol and carboxylic acid groups bonded to the silica surface.     

Synthesis of novel calixarenes having a tweezer-type structure

Monobromide was used as the starting material. The [2+2]photocycloaddition of diolefins directly gave all the calix[4]arene regioisomers having chiral and achiral structures in 20-47% yields. They formed a complex with alkali metal ions and extracted large metal picrates rather than small ones.     

Synthesis and characterization of hydroxypropyl cellulose from bacterial cellulose

Bacterial cellulose produced by Acetobacter xylinum has been reacted with propyleneoxide to synthesize hydroxypropyl cellulose(HPC) under different reaction conditions while diluted by toluene. The effects of mass ratio of bacterial cellulose to propyleneoxide, dilutability of toluene, reaction temperature(T) and time(t) were investigated by series of experiments. The degree of substitution(DS), hydroxypropyl content(A) and yield(η) were compared. The optimized product exhibited cold-water solubility and hot-water gelatinization in aqueous medium. Further study was carried out with FTIR, TGA, XRD, SEM and 13C-NMR for characterization. The water/air contact angle measurement reveals that it is a good hydrophobic material with good mechanical properties.     

Synthesis of pyrimidinocyclophanes having a bridging nitrogen atom

Reactions of 1,3-bis(ω-bromoalkyl)-substituted uracils, quinazoline-2,4-dione, and 5-methyl-1,3,5-triazine-2,4,6-trione and 1,3-bis(m-bromomethylbenzyl)-5-bromouracil with amines (aliphatic amines, benzylamines, naphthylmethanamine, and anisidine) gave a series of macrocyclic compounds having one pyrimidine or triazine fragment and an azapolymethylene bridge connecting the N¹ and N³ atoms of the heteroring. The bridging nitrogen atom in some macrocyclic compounds was subjected to quaternization with methyl p-toluenesulfonate.     

Synthesis of beta-cyclopropylalanines by photolysis of diacyl peroxides

[reaction: see text] Photolysis at 254 nm of neat (no solvent) unsymmetrical diacyl peroxides derived from cyclopropane carboxylic acids and l-aspartic acid generates protected beta-cyclopropylalanines in reasonable yields. Orthogonally protected 3-(trans-2-aminocyclopropyl)alanine (21), a key constituent of the antitumor agent belactosin A, as well as protected hypoglycin A (26), a causative agent of Jamaican vomiting sickness, is synthesized by this approach with coupling of the intermediate substituted cyclopropyl radicals proceeding predominantly with retention of configuration (dr >or= 95:5).     

Synthesis and characterization of microcrystalline cellulose produced from bacterial cellulose

In this study, microcrystalline cellulose (MCC) was prepared from the acid hydrolysis of bacterial cellulose (BC) produced in culture medium of static Acetobacter xylinum. The MCC-BC produced an average particle size between 70 and 90 μm and a degree of polymerization (DP) of 250. The characterization of samples was performed by thermogravimetric analysis, X-ray diffraction, and scanning electron microscopy (SEM). The MCC shows a lower thermal stability than the pristine cellulose, which was expected due to the decrease in the DP during the hydrolysis process. In addition, from X-ray diffractograms, we observed a change in the crystalline structure. The images of SEM for the BC and MCC show clear differences with modifications of BC fiber structure and production of particles with characteristics similar to commercial MCC.     

Synthesis and isolation of a monoamine having a thermodynamically stabilized pseudo-chirotopic nitrogen

We have synthesized a tricyclic monoamine, (1S,4R)-(E)-7,3′-heptenylene-2,3:5,6-dibenzo-7-azabicyclo[2.2.1]heptane (1), by applying a ring-closing metathesis reaction in the key step of the synthetic route and by using preparative chiral HPLC for the separation. The X-ray crystallographic analysis of its salt with (1R)-camphor-10-sulfonic acid showed that the geometry and absolute configuration are (E) and (1S,4R), respectively. The theoretical calculations revealed that the inversion of the nitrogen atom at the 7-position of (1S,4R)-(E)-1 thus isolated takes place through a very slow process and that the configuration of the N(7) is highly biased to (R), indicating that (1S,4R)-(E)-1 is a thermodynamically controlled N-pseudo-chirotopic compound ((1S,4R,7R): (1S,4R,7S) = 99.68:0.32 at 120 °C).     

Synthesis of a hemostatic drug from cellulose acetate

Hemostatic resorbent polymeric materials have been synthesized from water-soluble acetylcellulose, lagochilin, and lagohirsin. The substances obtained possess an effective hemostatic action and have a water-soluble form.Tashkent Institute of Chemical Technology. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 238–241, March–April, 1998.     

Convenient synthesis of a glycopeptide analogue having a complex type disialyl-undecasaccharide

Described herein is a convenient synthesis of a glycopeptide analogue having an undecasaccharide and its stability towards peptide:N-glycosidase F (PNGase-F). To obtain the glycopeptide analogue, bromoacetamidyl undecasaccharide and undecapeptide containing a cysteine residue were synthesized and then a coupling reaction between haloacetamide and thiol was performed. The coupling reaction progressed smoothly at pH 7.0 in phosphate buffer and afforded the desired glycopeptide analogue. In addition, stability of the glycopeptide analogue thus obtained towards PNGase-F was investigated. The result indicated that the glycopeptide analogue was resistant to the enzymatic digestion.