Synthesis and characterization of a novel 3D copper(I) coordination polymer with a ligand generated in situ

Hydrothermal reaction of CuCl₂ · 2H₂O, NaN₃ with 1,4-dicyanobenzene in water/ethanol yielded a novel Cu(I)-tetrazolate, {Cu(cptz)}_n, (1) (Hcptz is 5-(4-cyanophenyl)-tetrazole). The cptz ligand in the complex was generated in situ through the [2 + 3] cycloaddition reaction involving one of the two cyano-groups of the precursor 1,4-dicyanobenzene. The structure characterization shows that 1 possesses a 3D 4-connected SrAl₂ topological network. Additionally, complex 1 exhibits strong yellow fluorescence at room temperature in the solid state.     

New method for controlled synthesis of polylactide block copolymers: organoborane/p-quinone system and reversible-deactivation radical polymerization

We developed a new approach to obtain polylactide hybrid block copolymers with vinyl monomers (styrene, methyl methacrylate, methyl acrylate) through the realization of a reaction sequence using triethylborane and various p-quinones. The method offered includes two stages. In the first stage, a chain-transfer agent was obtained by borylation of the terminal hydroxyl groups of polylactide. The second stage was vinyl monomer radical polymerization in the presence of p-quinone accompanied by S_H2-substitution at the boron atom.1,4-Naphthoquinone, 2,3-dimethyl-1,4-benzoquinone, duroquinone and 2,5-di-tert-butyl-1,4-benzoquinone were used as synthetic polymer chain growth mediators. It is shown that 1,4-naphthoquinone and 2,3-dimethyl-1,4-benzoquinone, similar in their characteristics, are effective agents providing the realization of reversible-deactivation radical polymerization. Realization of reversible-deactivation radical polymerization was proved with the analysis of the kinetics of block copolymerization, molecular weight characteristics and compositional homogeneity of block copolymers as well as its further capability to elongate the polymer chain. Synthesized block copolymers have a high thermal stability compared to the initial borylated polylactide. © 2021 Society of Industrial Chemistry.     

Precipitation polymerization of ε-caprolactone in water using metal triflates as catalysts

The precipitation polymerization of ε-caprolactone has been assessed in water using various commercial metal triflates as catalysts. The reaction is quantitative at 70 and 100?°C, leading to number-average molecular weights up to 5,400?g/mol and dispersities around 1.5–2.0. A polycondensation mechanism operating from in situ generated 6-hydroxyhexanoic acid is proposed. Among various salts, aluminum and tin(II) triflates lead to the higher molecular weight after 24?h reaction at 70?°C.     

Palladium-catalyzed coupling of sp(2)-hybridized tellurides

Vinylic tellurides are of importance due to their useful behavior as synthons and intermediates. Recently, the use of these compounds in place of vinylic halides or triflates in the palladium-catalyzed cross-coupling reaction has emerged as a powerful tool in the preparation of conjugated enyne and enediyne. In this way, vinylic tellurides can behave as aryl or vinyl carbocation equivalents. This review focuses on methods that involve the use of vinylic tellurides in palladium-catalyzed cross coupling reaction.     

Synthesis of 1‐Amino‐3‐(trimethylsilyl)allenes by Organocuprate Addition to 3‐(Trimethylsilyl)propyne Iminium Salts

1‐Dialkylamino‐3‐(trimethylsilyl)allenes 2a—q were obtained by conjugate addition of alkyl, vinyl, aryl, hetaryl, and silyl groups, via the respective organocuprates, to 3‐(trimethylsilyl)propyne iminium triflates 1a—d . Similarly, 2‐vinylidene‐2,3‐dihydro‐1,3‐benzothiazoles 4a,b were synthesized from semicyclic propyne iminium triflates 3a,b and a di‐tert‐butyl cuprate.     

用分子动力学模拟研究丁二烯微观结构对丁腈橡胶物理机械性能的影响

采用分子动力学模拟的方法对基于3种不同丁二烯键合结构建立的丁腈橡胶模型(A、B、C模型)进行了模拟计算,以考察丁二烯微观结构对丁腈橡胶物理机械性能的影响.采用恒定应变法计算模型的物理机械性能,然后将模型与铁原子层结合建立摩擦副模型,利用剪切模拟分析丁腈橡胶摩擦过程的磨损机理.结果表明,与A模型和C模型相比,B模型分子链...     

Novel carbon‐nanotube‐based organogels as candidates for oil recovery

A simple method for synthesis of novel organogels based on multiwalled carbon nanotubes (MWCNTs) is reported. Three classes of organogels were synthesized by crosslinking polymerization of dodecyl methacrylate with various weight percentages of 1,4‐butanediol dimethacrylate, vinyl‐group‐modified MWCNTs or pristine MWCNTs in the presence of 2,2‐azoisobutyronitrile as initiator. In this reaction, the carbon nanotubes (CNTs) served simultaneously as an adsorbent, a comonomer and a crosslinking agent. The oil‐absorbent containing CNTs showed much higher swelling capacity in oil and organic solvents compared with that without CNTs. Therefore, CNT‐based organogels can be introduced as a promising candidate for environmental protection and oil recovery. © 2012 Society of Chemical Industry     

Zur Synthese und Funktionalisierung neuer Poly[(silylen)‐2,5‐thiophene]

Treatment of 2,5‐dilithiothiophene with (dimethylamino) methylsilylbis(triflates) gave poly[(dimethylamino‐silylene)‐2,5‐thiophene] 4 in high yield. The amino–silyl bond was cleaved selectively by triflic acid leading to triflate substituted poly[(silylene)‐2,5‐thiophene] 5 . Conversions of this polymers with nucleophiles gave other functionalized derivatives 6 – 9 . Hydrosilylation reaction between silicon–vinyl and silicon–hydrogen derivatives results in polymer networks which may serve as interesting preceramic materials. The structures of the polymers were proven by NMR spectroscopy (²⁹Si, ¹³C, ¹H).     

Pd-Catalyzed C−C,C−N,and C−O Bond-Forming Difunctionalization Reactions of Alkenes Bearing Tethered Aryl/Alkenyl Triflates

Over the past few years our group has described a new type of alkene difunctionalization reaction in which aryl or alkenyl triflates bearing tethered alkenes are coupled with various nucleophiles to afford carbocyclic products. The products are formed in moderate to good chemical yield, with generally high levels of stereoselectivity. Our progress to date in this area, which includes reactions of amine, alcohol, enolate, and indole nucleophiles, is described in this review.     

Hydrogenation of Low Molecular Weight Polymers in Ionic Liquids and the Effects of Added Salt

The biphasic hydrogenations of a number of polymeric materials, polybutadiene (PBD), nitrile‐butadiene rubber (NBR) and styrene‐butadiene rubber (SBR), were investigated in a toluene/N,N′‐butylmethylimidazolium tetrafluoroborate, (BMI⁺BF₄⁻) system with a water‐soluble analogue of Wilkinson's catalyst, RhCl(TPPTS)₃ (TPPTS=triphenylphosphine, trisulfonated) at 100 °C and 3.1 MPa. The catalyst shows reasonable activity within ionic liquids with PBD although it was necessary in the case of NBR and SBR to add water as a co‐solvent to solubilize the catalyst within the ionic media. Both the extent of hydrogenation and the ratio of the internal 1,4‐olefins to vinyl 1,2‐olefins were monitored. A clear preference for the external olefins was observed even within NBR and SBR where functionalization on the polymer might enhance the degree of hydrogenation of the internal olefins. The effect of adding NaCl to the PBD system was also investigated. The addition of salt decreases the activity of the catalyst but has no effect on the preference for the hydrogenation of vinyl olefins.     

Synthesis of vinyl substitute poly(silphenylene‐siloxane) via silyl hydride‐dialkoxysilane process

The synthesis of vinyl‐substituted silphenylene‐siloxane polymer through B(C₆F₅)₃ catalyzed polycondensation of 1,4‐bis(dimethylsilyl)benzene and vinylmethyldimethoxysilane is described. ¹H‐NMR, ²⁹Si‐NMR, and UV spectroscopy indicate that the vinyl groups remain undamaged during the polycondensation reaction. No hydrosilylation side reaction is observed under the reaction conditions. The microstructure of the polymer is not perfectly alternating with a randomization of 20%. The temperature for 5% mass loss is 430°C in inert atmosphere and 417°C in oxidative atmosphere with a residue of 56% at 700°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

氯乙烯-醋酸乙烯酯共聚物的后功能化研究

通过将氯乙烯－醋酸乙烯酯－丙烯酸羟乙醋共聚物（VAGF）与马来酸酐酯化接枝，制得带羟基的氯醋三元共聚物。探索了原料配比、催化剂用量、反应时间及反应温度对酯化接枝反应的影响，并用红外光谱进行表征。得到酯化反应的最佳条件为：催化剂用量为VAGF质量的0．8％，VAGF质量分数为15％，温度100℃，时间9h。氯乙烯－醋酸乙烯酯－丙烯酸羟乙酯三元共聚物的马来酸酐酯化活性高于氯乙烯－醋酸乙烯酯－乙烯醇三元共聚物。     

Fourier transform near‐infrared and electron spin resonance studies on the crosslinking reaction of liquid carboxylated poly(acrylonitrile‐co‐butadiene) rubber with dicumyl peroxide in dioxane

The crosslinking reaction of liquid carboxylated poly(acrylonitrile‐co‐butadiene) [or nitrile rubber (NBR); acrylonitrile = 10 wt %] with dicumyl peroxide (DCPO) was studied in dioxane by means of Fourier transform near‐infrared spectroscopy (FT‐NIR) and electron spin resonance spectroscopy (ESR). Among the three butadiene units (1,2, cis‐1,4, and trans‐1,4 units) of NBR, only the pendant vinyl group of the 1,2 unit showed an absorption at 6110 cm^?1 from the FT‐NIR examination of dioxane solutions of NBR, 1‐octene, 3,3‐dimethyl‐1‐butene, trans‐2‐octene, cis‐5‐octen‐1‐ol, poly‐cis‐1,4‐butadiene, and poly‐1,2‐butadiene. The crosslinking reaction was followed in situ in dioxane by the monitoring of the disappearance of the pendant vinyl double bond with FT‐NIR. The initial disappearance rate (R₀) of the vinyl group was expressed by R₀ = k[DCPO]^0.9[NBR]^?0.2 (120°C). The overall activation energy of the reaction was calculated to be 20.7 kcal/mol. This unusual rate equation suggests unimolecular termination due to degradative chain transfer and depressed reactivity of the vinyl group caused by crosslinking. ESR study of the reaction mixture revealed that an allyl‐type polymer radical was formed in the reaction, and its concentration increased with time and was then saturated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2095–2101, 2003     

From α-arylation of olefins to acylation with aldehydes: a journey in regiocontrol of the Heck reaction

The Pd-catalyzed Mizoroki-Heck reaction of olefins with aryl halides, more often simply called the Heck reaction, was recently recognized with the 2010 Nobel Prize in chemistry. Although highly selective with electron-deficient olefins, which generally yield the linear β-arylated product exclusively, the Heck reaction is less satisfactory with electron-rich olefins. This substrate typically generates a mixture of both α- and β-arylated regioisomeric products, hampering wider application of the reaction in chemical synthesis. Pioneering studies by a number of researchers revealed that high α-regioselectivity could be obtained under Pd-diphosphine catalysis either through (i) the substitution of aryl triflates for halides or (ii) the addition of stoichiometric silver or thallium salts when aryl halides are used. Under these conditions, the arylation is believed to proceed via an ionic pathway. However, silver introduces added cost, thallium salts are toxic, and triflates are generally commercially unavailable, base sensitive, and thermally labile. Believing that the ionic pathway would be promoted in an ionic medium, in the early 2000s, we attempted the Pd-catalyzed arylation of the benchmark electron-rich olefin butyl vinyl ether with aryl bromides in an imidazolium ionic liquid. We were delighted to observe that highly regioselective α-arylation could readily be accomplished, with no need for silver additives, thallium additives, or aryl triflates. A range of other electron-rich olefins has since been shown to be viable as well. The high α-selectivity probably results from the high ionic strength of the medium, which facilitates the dissociation of halide anions from the [L(2)Pd(Ar)X] intermediate, channeling the arylation into the ionic pathway. Hydrogen bonding interactions may also play a role, however. We subsequently discovered that the α-arylation can indeed be significantly accelerated by a hydrogen bond donor salt, in both ionic liquids and common solvents. Evidence shows that the concentration of the cationic Pd(II)-olefin species along the ionic pathway is increased as a result of hydrogen bonding between the hydrogen bond donor and the halide anion. More recently, we reported that cheaper and greener alcohols allow the Heck arylation of electron-rich olefins to proceed in a much faster, productive, and totally α-regioselective manner, circumventing the need for an ionic medium or hydrogen bond donor salt. In particular, aryl chlorides with diverse properties have been demonstrated to be viable substrates for the first time. Significantly, it appears that ethylene glycol facilitates both the oxidative addition of ArCl to Pd(0) and the subsequent dissociation of chloride from Pd(II). A closely related reaction, acylation of aryl halides with aldehydes, was also developed. Proceeding via the intermediacy of an electron-rich enamine, this Pd-pyrrolidine cooperative catalysis affords alkyl aryl ketones in a straightforward manner, extending the Heck reaction from olefins to aldehydes.     

The Reaction of Acid Chlorides with Magnesium Enolates Resulting from the Reaction of Vinylmagnesium Chloride and Carboxylic Acid

This note describes a new preparative method of vinyl esters and diketones. Vinyl-magnesium chloride was added to benzoic acid in tetrahydrofuran to give a magnesium enolate. Without decomposition of the reaction mixture, propionyl chloride was added to give a mixture of 1-phenyl-1,4-pentadienyl propionate and 2-allyl-1-phenyl-pentane-1,3-dione.     

Copolymerization of vinyl chloride with 1-olefins. III. An investigation of the copolymerization reaction of vinyl chloride with 1-butene and 1-pentene

Series of suspension copolymerization of vinyl chloride with various contents of 1-butene and 1-pentene (5–30 mass%) were carried out under the same reaction conditions. By applying a method which utilizes periodic sampling of heterogeneous reaction mixture from the reactor during the reaction and a gas chromatographic determination of unreacted vinyl chloride in the sample, the conversion curves of vinyl chloride were determined and the initial reaction rates were compared.     

A mechanistic study: Nucleophile dependence in glucosylations with glucosyl bromides

Glycosylations using glucosyl bromides and various promoters (Et₄NBr, HgBr₂, or AgOTf) were investigated, competitively and kinetically. The reactions were found to be dependent in both glucosyl bromide and nucleophilic concentration, indicating a S_N2-type rate, determining step. For the AgOTf promoted reaction an ion pair mechanism involving glucosyl triflates is suggested.     

Lithium-mediated ring opening of 1,4-dioxane and structural characterization of a Li12O12 truncated octahedron

The equimolar reaction of ^tBuLi with 4-Cl-2,6-Me₂-C₆H₂OH (ArOH) in 1,4-dioxane led to the unexpected formation of the mixed-anion, 1D polymer [(ArO)₂(RO)₄Li₆ · (diox)]_∞, 1 (where RO = H₂CC(H)OCH₂CH₂O⁻). Incorporation of the alkoxy vinyl ether is due to cleavage of 1,4-dioxane by ^tBuLi. Compound 1 can also be prepared rationally by the reaction of ⁿBuLi with ethylene glycol vinyl ether and ArOH in 1,4-dioxane solution. Direct lithiation of ethylene glycol vinyl ether results in the formation of the alkoxide [ROLi]₁₂, 2. The crystal structure of 2 reveals an unusual truncated octahedral arrangement in the solid state, where each metal is chelated by a vinyl ether subunit.     

偶氮苯改性聚乙烯醇的研究

通过三聚氯氰的氯原子和聚乙烯醇的羟基之间脱氯化氢的反应,用含有2个偶氮苯的三聚氯氰衍生物改性聚乙烯醇（PVA）1788。红外光谱和核磁共振分析表明,在二氧六环和水混合溶剂中可以将偶氮苯成功接枝到PVA上,PVA中约每12个羟基就有1个发生反应。含有偶氮苯的PVA可以溶解在水和二甲亚砜中。其紫外可见吸收光谱与偶氮苯相似,并表现出偶氮苯的典型光致异构现象。