The synthesis of a fluorinated phthalocyanine

The reaction of perfluoroalkylcopper with 4-iodophthalonitrile provides a convenient route to fluorinated phthalonitriles which readily form phthalocyanines in the presence of stannous chloride dihydrate.During the course of preparing 4-perfluoroheptylphthalonitrile $\text{1}$, a secondary reaction was observed when the reaction time was extended beyond two hours. This reaction involves the interaction of the orthodinitrile with copper and/or cuprous iodide to afford the phthalocyanine nucleus. This coaction is portrayed by the appearance of a green color in the reaction media.     

Synthesis of a New Phosphonate Methacrylate Monomer

In this work, a new methacrylate phosphonate monomer synthesis was described according to a two-step reaction. First the monoaddition of thioglycolic acid onto dimethylvinyl phosphonate monomer led to dimethyl–5-carboxymethyl-2-thiaethylphosphonate, a new phosphonate acid compound. This reaction also led to the thioester homologue of dimethyl–5-carboxymethyl-2-thiaethylphosphonate with a 15% yield by reaction of a thioglycolic acid thioester with dimethylvinyl phosphonate. Second, dimethyl carboxy-4-thia-butyl phosphonate reacted with glycidyl methacrylate. This epoxy-acid addition reaction was catalyzed by chromium salt at 70°C and led to the new methacrylate phosphonate monomer. We showed that only the secondary alcohol was obtained via a β addition. The two-step reaction final yield was calculated to be about 85%.     

Novel rearrangement reaction of a 6,14-endoethanomorphinan derivative to a benzomorphan derivative

Treatment of 7α-hydroxymethylendoethenomorphinan derivative with trifluoromethanesulfonic anhydride at rt and subsequent toluene reflux afforded a novel lactone by rearrangement reaction. The skeleton of the lactone is analogous to that of the benzomorphan like pentazocine, which is a useful analgesic. The rearrangement reaction opens the door to a facile synthesis from the 4,5-epoxymorphinans to the benzomorphan derivatives. On the basis of careful examination of the reaction intermediates, a reaction mechanism was proposed.     

Nucleic acid-templated energy transfer leading to a photorelease reaction and its application to a system displaying a nonlinear response

The photocleavage of a nitrobenzyl-type linker (NPPOC) at 405 nm wavelength was enabled by nucleic acid-templated energy transfer from a sensitizer (thioxanthenone) to the linker. This strategy was used to release profluorescent rhodamine, which facilitated monitoring of the reaction via fluorescence measurement in a nonoverlapping window with the sensitizer/photocleavage reaction. The rate acceleration of the templated reaction was greater than 20-fold over the background reaction. The templated reaction was used in conjunction with strand displacement to design four-component systems that responded to an analyte (DNA). Programming a specific hierarchical relationship among the four components enabled the design of a system that responded first positively and then negatively to increasing levels of an analyte.     

Mode change in the self-motion of a benzoquinone disk coupled with a NADPH system

The self-motion of a benzoquinone (BQ) disk on NADPH was investigated as the coupling of an autonomous motor and an enzyme reaction. In the absence of the enzyme reaction, features of motion changed depending on the concentration of NADPH, that is, continuous motion→ intermittent oscillatory motion→ no motion. When the reverse reaction from NADP(+) to NADPH was introduced into the system with the addition of an enzyme reaction, continuous motion changed to intermittent oscillatory motion with small amplitude. The mechanism of this mode change is discussed in relation to the surface tension as a driving force and the time course of UV spectra as a window to the progress of the reaction. Characteristic features of the mode change were qualitatively reproduced by a numerical calculation.     

Plasmonic Enhancement of a Photocycloreversion Reaction of a Diarylethene Derivative Using Individually Dispersed Silver Nanoparticles

The fabrication of silver nanoparticles covered with polymers with a well‐defined core–shell structure and the quantitative evaluation of the plasmonic enhancement effect on a photochemical reaction in the vicinity of these silver nanoparticles individually dispersed in a medium are described. The photocycloreversion reaction of a diarylethene polymer in the vicinity of silver nanoparticles was enhanced by 2–6 times relative to the reaction without the nanoparticles. The promotion of the photocycloreversion reaction is due to enhancement of the electromagnetic field near the surface of the silver core.     

Direct observation of single-molecule generation at a solid-liquid interface

Direct observation of single-molecule generation from a chemical reaction was achieved at a solid-liquid interface. The reaction between fluorescamine and immobilized N'-(3-trimethoxysilylpropyl)diethylenetriamine (DETA) was studied at the single-molecule level. Time-lapse fluorescence images of single-molecule products, excited by the evanescent field generated at a quartz-liquid interface, were recorded to follow the chemical reaction to its completion. The reactions were restricted to the approximately 1 nm thick layer nearest to the interface. Analysis of the photoelectron intensity of the fluorescent product of the reaction and its distribution shows that the reaction kinetics goes through a transition from zeroth-order to first-order as the reaction proceeds. This approach offered a novel means to study single-molecule reactions at the solid-liquid interface. It also enabled the investigation of reaction kinetics and chemical mapping of surface heterogeneity at the single-molecule level.     

Efficient C-C double-bond formation reaction via a new synthetic strategy: a self-sorting tandem reaction

[reaction: see text] A novel and efficient carbon-carbon double-bond formation reaction via coupling of aryl or heteroaryl methyl ketones has been developed. A dimethyl sulfoxide-iodine-CuO system was proven to be efficient for this reaction and afforded the expected products in good yields. A new synthetic strategy, a self-sorting tandem reaction, was involved in this type of reaction and was presented for the first time.     

Oscillatory Reaction of a Pendant Drop in a Liquid–Air System under Microwave Irradiation

A Belousov–Zhabotinsky reaction in a pendant drop under microwave radiation was observed under nonstirring conditions. The period decreased as the irradiation power and time were increased because the droplet temperature increased. Moreover, the color change of the solution during the oscillatory reaction depended on the irradiation power and time although the droplet temperature returned to room temperature quickly. Irradiation at higher powers or longer times suspended the oscillatory reaction. However, for moderate irradiation powers or times, the oscillatory reaction stopped after irradiation because the concentration distribution of the reagents became homogeneous. After a time, the oscillatory reaction restarted because a concentration gradient developed again. Accordingly, the effect of the microwave irradiation history continued because the oscillatory reaction stopped even after the irradiation was stopped. This is because the rotation of the polar molecule caused by the irradiation produced a flat concentration distribution for the reagents through increased molecular diffusion.     

Rheological and thermal behaviours of a hyperbranched polycarbosilane

A hyperbranched polymer, a precursor of silicon carbide (SiC), was successfully synthesized using a hydrosilylation reaction with Karstedt's catalyst. This reaction was optimized with the use of a rheometer coupled with an infrared spectrometer. The polymeric precursor was characterized using NMR and Fourier transform infrared spectroscopies, and dynamic rheology. The polymerization reaction was followed in situ by combined rheological and infrared measurements, indicating a gel‐like behaviour for alkene conversions higher than 0.55. Overall second‐order kinetics was determined for the hydrosilylation reaction. Pyrolysis at 1400 °C led to porous materials with β‐SiC and free carbon.     

Pyrolysis of a tubular aromatic compound

[reaction: see text] In the attempt to close the walls of a small tubular system that is a substructure of a [4,4] armchair nanotube a very unusual rearrangement reaction was observed.     

Addition of a cyclopropyl alkyne to tetramesityldigermene: evidence for a biradical intermediate

The reaction pathway for the addition of alkynes to tetramesityldigermene was examined using a cyclopropyl alkyne mechanistic probe. The results obtained indicate that the reaction is stepwise and involves biradical intermediates.     

Solution-phase parallel synthesis of a pyridinium pyrazol-3-olate inner salt library using a three-component reaction

We present here the discovery of a novel, versatile, multicomponent reaction leading to various 4-[4-(pyridinium-1-yl)-2,5-dioxo-2,5-dihydro-1H-pyrrol-3-yl]-2H-pyrazol-3-olate inner salts. The structure of the unusual zwitterionic inner salts was elucidated, and the scope of the novel reaction was investigated. After rapid optimization, the reaction was adapted to parallel synthesis, and an 800-membered compound library was produced.     

Monitoring the Progress of a Photochemical Reaction Performed in Supercritical Fluid Carbon Dioxide Using a Continuously Stirred Reaction Cell Interfaced to On-Line SFC

A high-pressure photochemical reaction cell operated with a magnetic stir drive has been directly interfaced on-line with either SFC or HPLC. The interface consisted of an oven housing a recirculation pump directly connected to a sample injection valve. The inlet of the recirculation pump and the outlet from the sample injection valve were connected to the stirred reaction cell such that a return flow circuit was established. With this arrangement, a continuous flow of fresh supercritical fluid photochemical reaction mixture was maintained through the sample injection valve. This enabled samples of reaction mixture to be conveniently analyzed at regular intervals to monitor reaction progress using either on-line SFC or HPLC. The photoreduction of benzophenone in the presence of propan-2-ol to produce 1,1,2,2-tetraphenylethane-1,2-diol and 2-methyl-1,1-diphenylpropan-1,2-diol was studied. For this reaction, on-line SFC provided significantly better performance than on-line HPLC and was therefore used to monitor overall reaction progress and the different product yields. Quantitative results for this study demonstrate that highly efficient photochemical reactions proceeded in supercritical fluid carbon dioxide at 13 and 20 MPa.     

Kinetics of Maillard reaction in a chicken meat model system using a multiresponses modeling approach

This research aimed to study the Maillard reaction pathway in chicken meat. Owing to the complexity of real chicken meat, which is composed of many different types of amino acids and reducing sugars, the experiment was initiated with a glucose/lysine model system with the same concentration ratio of reactants as found in chicken meat. By considering glucose as the rate-limiting substrate, a kinetic model of the glucose/lysine model system was developed. Methylglyoxal (MG) was found to be the principal important α-dicarbonyl compound intermediates that further reacted to form melanoidins. Pyridine was a major volatile compound in this model system. The optimized kinetic model was then further validated in a chicken extract, for which the Maillard reaction mechanism has not been elucidated. However, the kinetic model of the glucose/lysine system could not explain the Maillard reaction in the chicken extract, presumably because both types of intermediates and reaction pathway depend on the reactants. Thus, a kinetic model of the Maillard reaction in the chicken extract was developed based on the main types of detected intermediates. Overall, MG was the central intermediate and acted as a substrate for the formation of furfural, volatile compounds, melanoidins, and unknown carbonyl compound(s) (C_n). Pyrazines and aldehydes were the major volatile compounds in the chicken extract.     

The first example of a diastereoselective thio-Ugi reaction: a new synthetic approach to chiral imidazole derivatives

The first example of a diastereoselective thio-Ugi reaction with chiral alpha-methylbenzylamine is described. The reaction results in formation of two diastereomers of thioamides, the major of which was isolated. We have found that under similar conditions stereochemical results of the thio-Ugi reaction are opposite to stereochemical results of the Ugi reaction. Several chiral thioamides were synthesized. The reaction of thioamides with ammonia results in substituted amidines, which can be cyclized to imidazole derivatives in aqueous HCl. The synthesis of chiral imidazole derivatives was elaborated. Using certain approaches, both isomers of a key synthon in the synthesis of SB203386 (an orally bioactive HIV-1 protease inhibitor) were prepared. The scope, limitations, and stereochemistry of the approach are discussed.     

一种四氢苯并吡喃及其衍生物的水相合成

制备了一种以三乙烯二胺(DABCO)为基础的离子液体;在水溶剂中,以该离子液体为催化剂催化三组分一锅法制备四氢苯并吡喃的反应,得到2-氨基-3-氰基-4-芳基-7,7-二甲基-5-氧代-4H-5,6,7,8-四氢苯并[b]吡喃;考察了反应时间、催化剂用量、催化剂加入时间、反应温度对反应收率的影响,确定了最优反应条件;由不同的芳香醛和活性亚甲基化合物制备了一系列四氢苯并吡喃衍生物,并讨论了可能的反应机理.结果表明,所选用的合成反应条件温和、时间短、收率高、后处理简单,且催化剂重复使用4次催化效果变化不大;就反应机理而言,所用催化剂具有双重催化活性.     

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.     

Evolution of Polycopperorganosiloxanes in the Course of a Catalytic Reaction of CCl4Addition to a Multiple Bond

The catalytic activity of linear and network oligomer copperorganosiloxanes immobilized on the surface of Silochrome in a reaction of CCl₄addition to olefins was studied. It is likely that the reduction of Cu(II) ions to Cu(I) is a step in the catalytic radical reaction studied. This process also occurs in the absence of reagents at relatively low temperatures. The reaction occurs more readily in linear polycopperorganosiloxanes than in the network oligomers, which is consistent with the catalytic activity. The studied catalytic reaction is characterized by an unusual dependence of the activity of polycopperorganosiloxanes on metal concentration.     

Electrophoretically mediated reaction of glycosidases at a nanoliter scale

We have investigated electrophoretically mediated microanalysis (EMMA) for the assay of a native glyco-enzyme. As a representative of this class of enzyme, beta-glucosidase was selected, and the reaction was analyzed. Our EMMA was based on the plug-plug interaction of enzyme and substrate plugs, which is essential to reduce quantities of materials. Furthermore, we have addressed the problem of incompatibility of the enzymatic reaction and separation of the reactants. As a result, EMMA of native glycosidase was achieved with a reaction volume of approximately 20 nL and the Michaelis constant was estimated according to the Lineweaver-Burk plot. The current method may have advantages over traditional assay methods, especially in terms of the amount of enzyme (ng order) and substrate (pmol order) required for a reaction.