Bond interchange reactions in functionalized triglyceride oil/poly(ethylene terephthalate) compositions

Naturally functionalized triglyceride oils are renewable resources which contain reactive chemical groups, hydroxyl in the case of castor oil, and epoxide in the case of vernonia oil. In this article, the reaction of these groups, and the ester linkages between the glycerol and acid residue portions of the oil molecule with poly(ethylene terephthalate) (PET) is investigated through a variety of means. Multiple reactions are possible in the triglyceride–PET system, some of which form a copolymer that increases miscibility, and if allowed to continue, forms a completely random copolymer mixture. Among the numerous reactions possible, PET–ester exchange with the hydroxyl or epoxide functionality of the triglyceride oils is found to be the most significant, and the effects of these and other reactions are observed and structural implications discussed. © 1993 John Wiley & Sons, Inc.     

Easy α- to β-migration of an enol moiety on a pyrrole ring

Functionalized pyrrolic enols, 2-(2,2-dicyano-1-hydroxyethenyl)-1-methylpyrroles, synthesized from 2-ethenylpyrroles by a nucleophilic SEt-OH exchange, upon heating (75-142 °C) are readily rearranged to their 3-isomers in near to quantitative yield. The inter or intramolecular auto-protonation of a pyrrole ring by the acidic enol hydroxyl to form a mesomeric pyrrolium cation or zwitterion is suggested to be a key step in the rearrangement.     

A practical approach to the fused β-carboline system. Asymmetric synthesis of indolo[2,3-a]indolizidinones via a diastereoselective intramolecular α-amidoalkylation reaction

Fused β-carboline systems, as indolo[2,3-a]indolizidinones, indolo[2,3-a]quinolizidinones, their 2-oxa analogues, and benzo[a]indolo[2,3-a]indolizidinones are prepared efficiently via an RLi addition-N-acyliminium ion cyclisation sequence on readily available imides. In an enantioselective variant of these α-amidoalkylation reactions, the addition of MeLi to a chiral non-racemic imide derived from tryptophan yielded an oxo amide, which was cyclised diastereoselectively upon treatment with BF₃·OEt₂, to afford 5,11b-trans-indoloindolizidinone in moderate yield and high ee (99%).     

Improved detection of multi-phosphorylated peptides in the presence of phosphoric acid in liquid chromatography/mass spectrometry

In contrast to lower phosphorylation states (e.g. the tryptic monophosphopeptide FQpSEEQQQTEDELQDK from bovine beta-casein), the specific detection of multi-phosphorylated peptides (e.g. the tetraphosphopeptide RELEELNVPGEIVEpSLpSpSpSEESITR from tryptic digestion of bovine beta-casein) has often been problematic for liquid chromatographic mass spectrometric (LC/MS) analysis owing to their high affinity for adsorption to exposed surfaces. We observed an enhancement in the overall detection of phosphopeptides on addition of phosphoric acid (0.1-1.0%) to the sample solution; a 10-fold increase in sensitivity was determined for the detection of two tryptic phosphopeptides and also a significant improvement in the detection of the tetraphosphopeptide. Using capillary LC with ion trap tandem MS for detection and identification, the achievable detection limits were 50 fmol and 50 pmol for the monophosphopeptide and the tetraphosphopeptide, respectively. Phosphoric acid is believed to act as a blocking agent to available silanol groups on both the silica capillary surface and the C(18)-bonded stationary phase silica surface.     

Generation and reactions of novel oxiranyl ‘Remote’ anions

Deprotonation of an oxiranyl β-proton takes place in a stereoselective manner providing the corresponding oxiranyl ‘remote’ anion. The anion is stabilized by chelation between the lithium and the carbonyl moiety of an ester, lactone, imide, or keto-group in the form of a five-membered cyclic intermediate. Certain ester-stabilized oxiranyl anions are stable and can be left in THF solution at −78°C for several hours. The generated anions undergo a stereoselective alkylation reaction to provide products, which could be useful intermediates in the synthesis of bioactive naturally occurring α-methylene bis-γ-butyrolactones.     

Novel polymer blends based on poly(ether-urethane) ionomer and ion-containing styrene copolymer

The structure-property relationships of thermoplastic polymer blends based on poly(ether-urethane) ionomer (PEUI) and ion-containing styrene-acrylic acid copolymer (S-co-AA(K)) have been investigated by using DMTA, DSC and TGA, as well as tensile tests. Convergence of the glass transition temperature (T_g) values of the PEUI and the S-co-AA(K) components in the blends studied, as compared to the individual polymers, was found and explained by improving compatibility of the components due to increasing effective density of physical networks formed by ion-dipole and ion-ion interactions of ionic groups of the components. Character of E'=f(T) and E'=f(T) dependencies confirms the increase of the effective density of physical networks in the compositions studied compared to individual PEUI and S-co-AA(K). Improvement of end-use properties, i.e. thermal stability and tensile properties has been found for the PEUI/S-co-AA(K) compositions with lower content of S-co-AA(K) (i.e. <10 mass%) and explained by formation of additional network of intermolecular ionic bonds between the functional groups of PEUI and S-co-AA(K).     

Crosslinked poly(ethylene oxide) modified with tetraalkylammonium salts as phase transfer catalyst

Radiation crosslinked poly(ethylene oxide)s (PEO) modified with two tetraalkylammonium salts: allyldimethyldodecylammonium bromide and ethylmethacrylate dimethyldodecylammonium bromide were prepared. They have been characterized by elemental analysis, IR, ¹H-NMR spectra, and DSC measurements. Their activity as phase transfer catalysts (PTC) in the model displacement reaction of 1-bromooctane with aqueous sodium cyanide were studied. The reaction kinetics were followed under pseudo-first-order conditions. Small amounts of onium salt inserted into the PEO network gave rise to a five time increase in the rate constant. The recovered catalysts could be re-used without loss of activity. © 1995 John Wiley & Sons, Inc.     

VIB金属蝎型配合物(Scorpionate)的研究进展

综述了VIB金属(Mo、W)多吡唑硼配合物近年来的研究进展。详细地叙述了第二代多吡唑硼配体的合成与表征。     

Novel selenium-containing non-natural diamino acids

The general synthesis of a new class of non-natural diamino acids, 2-amino-3-[(2′-aminoalkyl)seleno]propanoic acids, or Se-(aminoalkyl)selenocysteines, is reported. Under the conditions devised, enantiopure N-Boc-protected β-l-iodoamines, which are readily generated from proteinogenic α-amino acids, were treated with the selenolate anion obtained from NaBH₄ splitting of the Se-Se bond in commercial l-selenocystine. The Se-alkylation products were enantiomerically pure and the reaction is high yielding (92-98%), without any detectable traces of accompanying by-products.     

Trifluoromethyl- and difluoromethyl-β-lactams as useful building blocks for the synthesis of fluorinated amino acids, dipeptides, and fluoro-taxoids

Enantiopure 1-acyl-3-hydroxyl-4-CF₂H-azetidin-2-ones and 1-acyl-3-hydroxy-4-CF₃-azetidin-2-ones serve as versatile intermediates for the syntheses of CF₂- and CF₃-containing α-hydroxy-β-amino acids, dipeptides, and taxoid anticancer agents. Both enantiomers of 3-hydroxy-4-CF₂H-β-lactams can be obtained in high yields through the diethylaminosulfur trifluoride (DAST) reaction of the corresponding enantiopure 4-formyl-β-lactam that is prepared through [2+2] cycloaddition of acetoxyketene to a 3-methyl-2-butenaldimine, followed by enzymatic optical resolution and ozonolysis. (+)-3-Hydroxy-4-CF₃-β-lactams and (−)-3-hydroxy-4-CF₃-β-lactams can also be readily obtained in enantiopure form through [2+2] cycloaddition of a CF₃-imine with a ketene, followed by enzymatic optical resolution. Practical processes for the preparations of these enantiopure 3-hydroxy-4-R_f-β-lactams as well as their synthetic applications are described.