Facile synthesis of graft copolymers containing rigid poly(dialkyl fumarate) branches by macromonomer method

Graft copolymers show microphase separated structure as seen in block copolymers and have lower intrinsic viscosity than block copolymers because of a branching structure. Therefore, considering molding processability, especially for polymers containing rigid segments, graft copolymers are useful architectures. In this work, graft copolymers containing rigid poly(diisopropyl fumarate) (PDiPF) branches were synthesized by full free‐radical polymerization process. First, synthesis of PDiPF macromonomers by addition‐fragmentation chain transfer (AFCT) was investigated. 2,2‐Dimethyl‐4‐methylene‐pentanedioic acid dimethyl ester was found to be an efficient AFCT agent for diisopropyl fumarate (DiPF) polymerization because of the suppression of undesired primary radical termination, which significantly took place when common AFCT agent, methyl 2‐(bromomethyl)acrylate, was used. Copolymerization of PDiPF macromonomer with ethyl acrylate accomplished the generation of the graft copolymer having flexible poly(ethyl acrylate) backbone and rigid PDiPF branches. The graft copolymer showed a microphase separated structure, high transparency, and characteristic thermal properties to PDiPF and poly(ethyl acrylate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2474–2480     

Synthetic studies toward swinhoeisterol A,a novel steroid with an unusual carbon skeleton

Swinhoeisterol A is a novel steroid with unusual 6/6/5/7 tetracyclic skeleton. The model compound with BCD rings is constructed by Friedel–Crafts acylation and an oxidative dearomatization as key steps.     

An Anti CuO2‐type Metal Hydride Square Net Structure in Ln2M2As2Hx (Ln=La or Sm,M=Ti,V, Cr,or Mn)

Using a high pressure technique and the strong donating nature of H⁻, a new series of tetragonal La₂Fe₂Se₂O₃‐type layered mixed‐anion arsenides, Ln₂M₂As₂H_x, was synthesized (Ln=La or Sm, M=Ti, V, Cr, or Mn; x≈3). In these compounds, an unusual M₂H square net, which has anti CuO₂ square net structures accompanying two As³⁻ ions, is sandwiched by (LaH)₂ fluorite layers. Notably, strong metal–metal bonding with a distance of 2.80 Å was confirmed in La₂Ti₂As₂H_2.3, which has metallic properties. In fact, these compounds are situated near the boundary between salt‐like ionic hydrides and transition‐metal hydrides with metallic characters.     

Two dimensional inorganic electride-promoted electron transfer efficiency in transfer hydrogenation of alkynes and alkenes

A simple and highly efficient transfer hydrogenation of alkynes and alkenes by using a two-dimensional electride, dicalcium nitride ([Ca₂N]⁺·e^–), as an electron transfer agent is disclosed. Excellent yields in the transformation are attributed to the remarkable electron transfer efficiency in the electride-mediated reactions. It is clarified that an effective discharge of electrons from the [Ca₂N]⁺·e^– electride in alcoholic solvents is achieved by the decomposition of the electride via alcoholysis and the generation of ammonia and Ca(OⁱPr)₂. We found that the choice of solvent was crucial for enhancing the electron transfer efficiency, and a maximum efficiency of 80% was achieved by using a DMF mixed isopropanol co-solvent system. This is the highest value reported to date among single electron transfer agents in the reduction of C–C multiple bonds. The observed reactivity and efficiency establish that electrides with a high density of anionic electrons can readily participate in the reduction of organic functional groups.     

Shape and structure recovery of an LCP droplet under a large step strain: observation and stress calculation

Shape recovery of a droplet of liquid crystalline polymer (LCP) hydroxypropylcellulose in a matrix of poly(dimethyl siloxane) subjected to a step shear strain has been studied via optical microscopy. Just after application of a large strain, the LCP droplet shape is flat ellipsoid, and then the droplet takes cylindrical shape and band texture perpendicular to the flow direction appears. The band texture fades away before emergence of poly-domain structure. In the final process with the shape of spheroid, poly-domain structure recovers very slowly. Except for the final process, the shape change is identical with that of isotropic droplet at strains smaller than 3, when the LCP viscosity in Region II is taken as an equivalent viscosity for normalization. For a 20:80 blend, the excess relaxation modulus is calculated based on the Doi-Ohta theory, taking account of the distribution of droplet size and compared with experimental modulus data.     

Excess enthalpies of binary mixtures of butylamines + propanols at 298.15 K

The molar excess enthalpies of eight systems of butylamines + propanols were determined at 298.15 K using a twin-microcalorimeter. All excess enthalpies were exothermic and large. An equilibrium constant K ₁ expressed in terms of mole fractions and standard thermodynamic properties of formation (Δ_f H, Δ_f G, Δ_f S) of 1:1 complex were evaluated by ideal mixtures of monomeric molecules and their associated complexes. Concentration dependence of the FT-Raman spectrum showed systematic changes of bands. Spectroscopic considerations based on this and ab initio calculations on molecules were performed at the Mp2/6-311G(d,p) level of theory. Interaction energies between butylamine and propanol were calculated by the supermolecular and NBO methods. The results were discussed with previous results to clarify the steric and positional effect of the amino and hydroxyl group.     

Synthesis of Telechelic Polystyrene by Radical Polymerization Using 1,4-Bis(p-tert-Butylphenylseleno-Methyl)benzene as a Photoiniferter

Abstract

1,4-Bis(p-tert-butylphenylselenomethyl) benzene was synthesized, and used as a bifunctional photoiniferter for the polymerization of styrene. Both the polymer yields and the number average of molecular weights (_n) of polymers increased with the polymerization. The polymerization of styrene by this iniferter permitted telechelic polystyrene containing arylseleno groups at both chain ends, and the degree of functionality was 1.9. The seleno groups of both chain ends of polystyrene were reduced quantitatively by tri-n-butyltin hydride. These seleno groups in polystyrene were also eliminated by treatment with hydrogen peroxide to give telechelic polystyrene with carbon-carbon double bond at both chain ends. Further, polystyrene with double bonds was converted to telechelic polystyrene carrying terminal functional groups as epoxy, hydroxy, and iodide group, respectively.

     

MAO‐free and extremely active catalytic system for ethylene tetramerization

The original Sasol catalytic system for ethylene tetramerization is composed of a Cr source, a PNP ligand, and MAO (methylaluminoxane). The use of expensive MAO in excess has been a critical concern in commercial operation. Many efforts have been made to replace MAO with non‐coordinating anions (e.g., [B(C₆F₅)₄]^?); however, most of such attempts were unsuccessful. Herein, an extremely active catalytic system that avoids the use of MAO is presented. The successive addition of two equivalent [H(OEt₂)₂]⁺[B(C₆F₅)₄]^? and one equivalent CrCl₃(THF)₃ to (acac)AlEt₂ and subsequent treatment with a PNP ligand [CH₃(CH₂)₁₆]₂C(H)N(PPh₂)₂ ( 1 ) yielded a complex presumably formulated as [ 1 ‐CrAl (acac)Cl₃(THF)]²⁺[B(C₆F₅)₄]^?₂, which exhibited high activity when combined with iBu₃Al (1120 kg/g‐Cr/h; ~4 times that of the original Sasol system composed of Cr (acac)₃, iPrN(PPh₂)₂, and MAO). Via the introduction of bulky trialkylsilyl substituents such as –SiMe₃, –Si(nBu)₃, or –SiMe₂(CH₂)₇CH₃ at the para‐position of phenyl groups in 1 (i.e., by using [CH₃(CH₂)₁₆]₂C(H)N[P(C₆H₄‐p‐SiR₃)₂]₂ instead of 1 ), the activities were dramatically improved, i.e., tripled (2960–3340 kg/g‐Cr/h; more than 10 times that of the original Sasol system). The generation of significantly less PE (<0.2 wt%) even at a high temperature is another advantage achieved by the introduction of bulky trialkylsilyl substituents. NMR studies and DFT calculations suggest that increase of the steric bulkiness on the alkyl‐N and P‐aryl moieties restrict the free rotation around (alkyl)N–P (aryl) bonds, which may cause the generation of more robust active species in higher proportion, leading to extremely high activity along with the generation of a smaller amount of PE.     

Functional Fluorescence Labeling of Carbohydrates and Its Use for Preparation of Neoglycoconjugates

Abstract

New bifunctional reagents, 2-amino-6-carboxyethylpyridine and 2-amino-6-cyanoethylpyridine, were designed and synthesized in order to provide a novel procedure for preparation of neoglycoconjugates from fluorescence-labeled and purified sugar chains. Labeling of model sugar chains with these reagents was effected by reductive amination using BH₃.Me₂NH to give corresponding 6-carboxyethylpyridylaminated (CEPA-) and 6-cyanoethylpyridylaminated (CNEPA-) derivatives, which were readily purified by reversed phase HPLC. The reagent parts of the labeled products possess the functional groups which then serve as linkers for coupling with matrices such as proteins and polymers. A CEPA-derivative of glucose was directly coupled with the ε-amino group of a Lys derivative to give a neoglycoprotein model. CNEPA-sugars were hydrogenated to give 6-aminopropylpyridylaminated (APPA-) derivatives, which can then be readily used for the preparation of various types of neoglycoconjugates by use of appropriate spacers as exemplified by the coupling of APPA-maltotriose with bovine serum albumin (BSA), biotin, and acrylic acid. The reaction of APPA-maltotriose with succinimidyl 3-(3-nitro-2-pyridyldithio)propionate gave the corresponding amide to be used for a disulfide formation with BSA. Condensation with biotin was effected by use of N-hydroxysuccinimidobiotin. The conjugation of APPA-maltotriose with acrylic acid was carried out by use of 4-acryloyloxyphenyldimethylsulfonium methylsulfate to give the corresponding acrylamide, which can be used for the preparation of sugar-acrylamide copolymers.