The mechanism of chemical modification of artificial fibers based on cellulose derivatives

A fabric based on cellulose derivatives has been hydrophobized via coating with oligochloromethylethoxysiloxane and then treated with butyl alcohol, benzyl alcohol, and higher fatty alcohols. With the use of X-ray photoelectron spectroscopy, it has been shown that the reaction of alcohols with the siloxane coating proceeds through the exchange of ethoxysilane groups for higher alkoxy groups, whereas the expected reaction of chloromethyl groups with alcohols (the Williamson reaction) does not occur under the chosen conditions.     

Hypervalent Iodine Reagents Enable Chemoselective Deboronative/Decarboxylative Alkenylation by Photoredox Catalysis

Chemoselective C(sp³)? C(sp²) coupling reactions under mild reaction conditions are useful for synthesizing alkyl‐substituted alkenes having sensitive functional groups. Reported here is a visible‐light‐induced chemoselective alkenylation through a deboronation/decarboxylation sequence under neutral aqueous reaction conditions at room temperature. This reaction represents the first hypervalent‐iodine‐enabled radical decarboxylative alkenylation reaction, and a novel benziodoxole‐vinyl carboxylic acid reaction intermediate was isolated. This C(sp³)? C(sp²) coupling reaction leads to aryl‐and acyl‐substituted alkenes containing various sensitive functional groups. The excellent chemoselectivity, stable reactants, and neutral aqueous reaction conditions of the reaction suggest future biomolecule applications.     

Amino acid end-group in commercial heparin. II. Reaction kinetics of the amino end groups with 2,4,6-trinitrobenzenesulfonic acid

Three different commercial heparins were trinitophenylated with 2,4,6-trinitrobenzenesulfonic acid (TNBS) under aqueous conditions. The reaction kinetics of amino groups in heparin with TNBS showed that the reactivities of amino groups were significantly different for free amino groups on heparin, compared to reactivities in peptides and amino acid residues attached to heparin molecules. With TNBS, unreactive amino groups were always present during the reaction.     

Cationic polyelectrolytes. I. Soluble polymers prepared from reaction of chloromethylated polystyrene with tris(2-hydroxythyl)amine

The reaction of chloromethylated polystyrene with tris(2-hydroxyethyl)amine in N,N-dimethylformamide is described for the conditions to prepare soluble reaction products. The groups of the quaternary ammonium salt, which appear in the first stage of the reaction, transpose to the amino-ether groups. The reaction was followed by elementary analysis, IR and ¹H-NMR spectra, and viscosimetric measurements for nondialyzed and dialyzed samples. The presence of the tertiary amine groups on obtained polymers was also shown by titration. The polymers from the reaction of chloromethylated polystyrene with tris(2-hydroxyethyl)amine reacted easily with benzyl chloride.     

接枝型偕胺肟树脂/SiO_2功能复合微粒的制备

用偶联剂γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH-570)对微米级硅胶进行了表面化学改性,采用溶液聚合法,在改性硅胶微粒表面接枝丙烯腈(AN),制备了接枝微粒PAN/SiO2。用盐酸羟胺对接枝PAN进行偕胺肟(AO)化转变,制得了接枝有偕胺肟树脂(PAO)的复合型功能微粒PAO/SiO2。采用红外光谱(FT-IR)、热失重(TGA)及扫描电子显微镜(SEM)等测试技术,对接枝微粒PAN/SiO2以及功能微粒PAO/SiO2进行了表征,考察了制备条件对AN的接枝聚合过程及对PAN的偕胺肟化转变过程的影响规律。结果表明,适宜的接枝聚合条件为:引发剂质量分数为1.5%,反应温度为75℃。接枝聚合5h可制得接枝度为0.14g/g的接枝微粒PAN/SiO2。受偕胺肟基团空间位阻的影响,PAN的偕胺肟化转变反应不能进行彻底,适宜的PAN/SiO2偕胺肟化转变反应条件为:介质pH值为6～7,温度70℃,反应时间4h。所制得的功能微粒PAO/SiO2腈基转化率约为78%。     

Ruthenium-catalyzed annulation of aromatic ketones with internal alkynes: A reliable route to substituted naphthalene derivatives

We report herein the preparation of polysubstituted naphthalene derivatives by the ruthenium-catalyzed benzannulation reaction of aromatic ketones with internal alkynes. This method (1) forms two new carbon-carbon bonds in one single step, (2) accommodates a variety of functional groups, and (3) undergoes mild reaction conditions.     

Lithium trifluoromethanesulfonate (LiOTf) as a recyclable catalyst for highly efficient acetylation of alcohols and diacetylation of aldehydes under mild and neutral reaction conditions

A variety of alcohols and aldehydes were reacted with acetic anhydride at room temperature in the presence of a catalytic amount of lithium triflate (LiOTf) to produce the corresponding esters and 1,1-diacetates, respectively, in good to excellent yields under essentially neutral reaction conditions. Sensitive functional groups such as PhCO(2)-, OMe, and OTBDMS ethers survived intact under the described reaction conditions.     

Catalytic synthesis of 1,4-dihydropyridine derivatives using scandium(III) triflate

Scandium(III) triflate smoothly catalyzed the reaction of imines with ethyl propiolate (2.5 equiv) to produce the corresponding N-substituted 1,4-dihydropyridines in good yields in toluene or BTF under reflux conditions. It also catalyzed the reaction of aniline and ethyl propiolate (3.2 equiv) to give another 1,4-dihydropyridine bearing three ester groups in moderate yield under the same conditions.     

Trans-hydrometalation of alkynes by a combination of InCl3 and DIBAL-H: one-pot access to functionalized (Z)-alkenes

[reaction: see text] Triethylborane-induced hydrometalation of alkynes proceeds in an anti manner to afford the corresponding (Z)-alkenylmetal compounds stereoselectively, where dichloroindium hydride would play a key role. A variety of functional groups including hydroxy, carbonyl, and carboxy groups were tolerant under the reaction conditions. Following iodolysis and cross-coupling reaction of the (Z)-alkenylmetal species show the usefulness of this strategy.     

Thermal and environmental stability of poly(4-ethynyl-p-xylylene-co-p-xylylene) thin films

The aim of this paper was to test the thermal and environmental stability of poly(4-ethynyl-p-xylyleneco-p-xylylene) thin films prepared by chemical vapor deposition(CVD) and to optimize the reaction conditions of the polymer.Fourier transformed infrared spectroscopy(FTIR),thermogravimetric analysis(TGA) and fluorescence microscopy were employed to investigate the stability of the reactive polymer coatings in various environmental conditions.Chemical reactivity of the thin films were then tested by Huisgen 1,3-dipolar cycloaddition reaction(‘‘click' reaction).The alkyne functional groups on poly(4-ethynyl-p-xylylene-co-p-xylylene) thin films were found to be stable under ambient storage conditions and thermally stable up to 100 8C when annealed at 0.08 Torr in argon.We also optimized the click reaction conditions of azide-functionalized molecules with poly(4-ethynyl-p-xylylene-co-p-xylylene).The best reaction result was achieved,when copper concentration was 0.5 mmol/L,sodium ascorbate concentration to copper concentration was 5:1.In contrast,the azide concentration and temperature had no obvious effect on the surface reaction.     

N,O-羧甲基化羟丙基壳聚糖的制备及结构表征

用NaOH作为催化剂, 在异丙醇悬浮体系中环氧丙烷(PO)与壳聚糖(CS)在60 ℃下反应8 h, 制备取代度超过0.8的羟丙基壳聚糖(HPCS). HPCS在水溶液中与氯乙酸反应, 制备了一种结构新颖的两性聚合物N,O-羧甲基化羟丙基壳聚糖(HPCMS), 羧甲基取代度可控制在0.42～1.38之间. 采用NMR和FTIR对产物结构进行表征. 结果表明, 在壳聚糖的羟丙基化改性过程中, C6位羟基首先与环氧丙烷反应, 生成HPCS; 在与氯乙酸反应过程中, HPCS上的羟基和氨基同时与氯乙酸发生取代反应.     

Synthesis of Furoxans (1,2,5‐oxadiazole 2‐oxides) from Styrenes and Nitrosonium Tetrafluoroborate in Non‐Acidic Media and Mechanistic Study

Diverse furoxans (1,2,5‐oxadiazole 2‐oxides) were synthesized from the corresponding styrenes using nitrosonium tetrafluoroborate as the nitrosation reagent in pyridine (basic media) or dichloromethane (neutral media). Acid‐sensitive functional groups were tolerated under these conditions. The probable reaction mechanism was elucidated. The experimental results support an ionic reaction pathway in contrast to the conventional acidic conditions with a radical mechanism.     

Copper-mediated trifluoromethylation of arylboronic acids by trifluoromethyl sulfonium salts

The ligand-free trifluoromethylation of arylboronic acids with a [Ph(2)SCF(3)](+)[OTf](-)/Cu(0) system has been carefully investigated. Aryl-, alkenyl- and heteroarylboronic acids with a variety of functional groups were suitable substrates for this reaction. It is suggested that a CuCF(3) species is formed under the reaction conditions.     

Synthesis of Functionalized Polynorbornanes Employing 2,5‐Bis(trifluoromethyl)‐1,3,4‐oxadiazole

Cycloaddition reaction of 2,5‐bis(trifluoromethyl)‐1,3,4‐oxadiazole with strained olefinic bonds of norbornenes was used to synthetize functionalized polynorbornanes. This simple, one step procedure was more effective when reaction was carried out by classical heating, in comparison to microwave‐assisted reactions. Various functional groups were stable in the reaction conditions (ester, imide, phthalimide, piperidyl, and carboxylic acid), whereas anhydride, N‐Boc, or TMS functionalities do not withstand reaction conditions.     

Studies on formaldehyde condensation resins. XIII. Gelation of acetoguanamine–formaldehyde resin

The gelation reaction of acetoguanamine with formaldehyde was investigated in the light of the gelation theory for tetrafunctional amino resins described in the previous paper. The gel time and extents of reaction of formaldehyde, amino groups, and imino groups varied with the molar ratio in the feed, but values of K (the ratio of the rate constant for condensation to that for addition) and k (the ratio of the rate constant for addition of the imino group to that of the amino group) were nearly constant. When the catalyst concentration was increased, the gel time, extents of reaction of each functional group, and the values of K and k varied; in particular K increased markedly. From the results of varying the molar ratio and concentration of acidic catalyst, it was found that the number of methylol groups per molecule of acetoguanamine at the gel point was influenced by the reaction conditions but the number of methylene linkages per molecular of acetoguanamine was nearly constant at about 0.6, regardless of reaction conditions. The number-average molecular weights up to the gel point varied with the reaction conditions, but at the gel point they were all nearly constant at about 385.     

Basic Catalytic Performance of Amino and Acylamide Functionalized Metal-organic Framework in the Synthesis of Chloropropene Carbonate from CO2 Under Atmospheric Pressure

In this work, a metal-organic framework with free standing basic groups(e. g., amino and acylamide groups) decorated in the pore wall was utilized to catalyze the CO₂ cycloaddition reaction and its basic properties were tested in Knoevenagel condensation reactions. The results reveal that the metal-organic framework(MOF) material has excellent catalytic activity and high repeatability for the synthesis of chloropropene carbonate from CO₂ and epichlorohydrin with no co-catalyst under mild reaction conditions, suggesting that it is a promising heteroge-neous catalyst for CO₂ cycloaddition reaction.     

Synthesis of polycyclic aromatics and heteroaromatics via electrophilic cyclization

[reaction: see text] A variety of substituted polycyclic aromatics are readily prepared in good to excellent yields under very mild reaction conditions by the reaction of 2-(1-alkynyl)biphenyls with ICl, I(2), NBS, and p-O(2)NC(6)H(4)SCl. This methodology readily accommodates various functional groups and has been successfully extended to systems containing a variety of polycyclic and heterocyclic rings.     

Stereoselective iodocyclization of (S)-allylalanine derivatives: gamma-lactone vs cyclic carbamate formation

An efficient procedure for highly chemo- and stereoselective cyclization of (S)-allylalanine derivatives is reported (diastereomeric ratios up to 96:4) where the reaction course can be completely controlled by switching from gamma-lactones to cyclic carbamates simply with the proper choice of the amino acid protecting groups. Both processes are stereoconvergent and afford the (S,S)-products in high yields, short reaction times, and mild reaction conditions.     

Preparation of Poly(N‐isopropylacrylamide) Microgels using Different Initiators Under Various pH Values

Ammonium persulfate (APS), 2,2′‐azobis(amidinopropane) dihydrochloride (V50) and 4,4′‐azobis(4‐cyanovaleric acid) (ACVA) were utilized to prepare temperature‐sensitive poly(N‐isopropylacrylamide) (PNIPAM) microgels by precipitation polymerization under various reaction pH conditions. Their particle sizes and swelling ratios depended on the reaction pH due to the pH dependence on the ionization degree of the decomposed fragments originating from the initiators and their hydrophilicity‐hydrophobicity. The more hydrophobic initiator, under the reaction pH conditions used, could be partitioned to a greater extent into the microgel particles due to the hydrophobicity of PNIPAM chains at the reaction temperature, which led to a more cross‐linked structure inside the microgels resulting in their smaller swelling ratio. pH dependence of surface charge density of the microgels with amidino groups or carboxylic acid groups on their surfaces was evidenced by the variation of their zeta potentials as a function of pH.     

Efficient synthesis of meso-substituted corroles in a H2O-MeOH mixture

New and efficient conditions for the synthesis of meso-substituted corroles were developed. The first step, involving the reaction of aldehydes with pyrrole, was carried out in a water-methanol mixture in the presence of HCl. A relatively narrow distribution of aldehyde-pyrrole oligocondensates was obtained through careful control of their solubility in the reaction medium. After thorough optimization of various reaction parameters (cosolvent, reagent, and acid concentration), high yields of bilanes were obtained. Additionally, the bilane derived from 4-cyanobenzaldehyde was isolated, and the oxidative macrocyclization reaction was performed under various reaction conditions (different solvents, different concentrations, and various oxidants). As a result, triphenylcorrole was obtained in the highest yield (32%) reported to date. The scope and limitations studied showed that this method was particularly efficient for moderately reactive aldehydes and those bearing electron-donating groups (yields 14-27%). Using these conditions, corroles bearing strongly electron-donating groups were obtained for the first time. In addition, it was found that the reaction of unhindered dipyrromethanes with aldehydes under analogous conditions afforded trans-A2B-corroles in very high yields (45-56%; 8-fold higher than previously reported) without scrambling. The fact that scrambling was not observed in this reaction despite a very high HCl concentration (0.3 M) is unprecedented. Detailed studies on the oxidation of bilane, derived from sterically hindered dipyrromethane, allowed us to unequivocally establish that the yield of macrocyclization is insensitive to the concentration. It was found the 1H NMR spectra of corroles in deuterated TFA gave very sharp signals.