- Photoinduced Isomerization of Radical Ions. 3. Radical Cations of Cyclopentadiene, Dicyclopentadienes, and 1,3-Bishomocubane Produced in γ-Irradiated Freon Matrices
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The radical cations of cyclopentadiene and the three C10H12 systems in the title have been produced in γ-irradiated Freon matrices at 77 K.Electronic and ESR spectroscopy were used to determine the interrelationships among the cations and their photoproducts.The three C10H12+.'s yielded different photoproducts depending upon the wavelength used for photoexcitation.The photoproduct obtained from endo-dicyclopentadiene cation excited to its first excited state was also obtained by a thermal reaction between the neutral molecule of cyclopentadiene and its radical cation.The product is inferred to be the radical cation of a new dicyclopentadiene.Possible mechanisms of obtaining this new C10H12+. isomer are discussed.
- Shida, Tadamasa,Momose, Takamasa,Ono, Noboru
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Read Online
- Time-Resolved Kinetic Energy Releases for Metastable Phenol Ions
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Time-resolved kinetic energy releases (KERs) were determined from metastable ion peak shapes for the reaction C6H5OH+ -> c-C5H6+ + CO in phenol.Ion beam pulsing was combined with an ion trapping device and with an MS/MS technique of
- Lifshitz, C.,Gefen, S.,Arakawa, R.
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Read Online
- Gas-phase identification of (Z)-1,2-ethenediol, a key prebiotic intermediate in the formose reaction
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Prebiotic sugars are thought to be formed on primitive Earth by the formose reaction. However, their formation is not fully understood and it is plausible that key intermediates could have formed in extraterrestrial environments and subsequently delivered
- Alessandrini, Silvia,Barone, Vincenzo,Bizzocchi, Luca,Dore, Luca,Gazzeh, Houda,Guillemin, Jean-Claude,Melosso, Mattia,Puzzarini, Cristina,Rivilla, Víctor M.,Tonolo, Francesca
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supporting information
p. 2750 - 2753
(2022/03/07)
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- Diastereoselective Diboration of Cyclic Alkenes: Application to the Synthesis of Aristeromycin
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The Pt-catalyzed diboration of cyclic alkenes is extended to unsaturated heterocycles and bicyclic compounds and can be accomplished in a diastereoselective fashion. The optimal procedures, substrate scope, and diastereoselectivity were investigated, and examples employing both homogeneous and heterogeneous catalysis were examined. Lastly, application to the construction of the nucleoside analog (±)-aristeromycin was conducted.
- Vendola, Alex J.,Allais, Christophe,Dechert-Schmitt, Anne-Marie R.,Lee, James T.,Singer, Robert A.,Morken, James P.
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supporting information
p. 2863 - 2867
(2021/05/05)
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- Near-Infrared Fluorescent Micelles from Poly(norbornene) Brush Triblock Copolymers for Nanotheranostics
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This contribution describes the design and synthesis of multifunctional micelles based on amphiphilic brush block copolymers (BBCPs) for imaging and selective drug delivery of natural anticancer compounds. Well-defined BBCPs were synthesized via one-pot multi-step sequential grafting-through ring-opening metathesis polymerization (ROMP) of norbornene-based macroinitiators. The norbornenes employed contain a poly(ethylene glycol) methyl ether chain, an alkyl bromide chain, and/or a near-infrared (NIR) fluorescent cyanine dye. After block copolymerization, post-polymerization transformations using bromide-azide substitution, followed by the strain-promoted azide-alkyne cycloaddition (SPAAC) allowed for the functionalization of the BBCPs with the piplartine (PPT) moiety, a natural product with well-documented cytotoxicity against cancer cell lines, via an ester linker between the drug and the polymer side chain. The amphiphilic BBCPs self-assembled in aqueous media into nano-sized spherical micelles with neutral surface charges, as confirmed by dynamic light scattering analysis and transmission electron microscopy. During self-assembly, paclitaxel (PTX) could be effectively encapsulated into the hydrophobic core to form stable PTX-loaded micelles with high loading capacities and encapsulation efficiencies. The NIR fluorescent dye-containing micelles exhibited remarkable photophysical properties, excellent colloidal stability under physiological conditions, and a pH-induced disassembly under slightly acidic conditions, allowing for the release of the drug in a controlled manner. The in vitro studies demonstrated that the micelles without the drug (blank micelles) are biocompatible at concentrations of up to 1 mg mL-1 and present a high cellular internalization capacity toward MCF-7 cancer cells. The drug-functionalized micelles showed in vitro cytotoxicity comparable to free PPT and PTX against MCF-7 and PC3 cancer cells, confirming efficient drug release into the tumor environment upon cellular internalization. Furthermore, the drug-functionalized micelles exhibited higher selectivity than the pristine drugs and preferential cellular uptake in human cancer cell lines (MCF-7 and PC3) when compared to the normal breast cell line (MCF10A). This study provides an efficient strategy for the development of versatile polymeric nanosystems for drug delivery and image-guided diagnostics. Notably, the easy functionalization of BBCP side chains via SPAAC opens up the possibility for the preparation of a library of multifunctional systems containing other drugs or functionalities, such as target groups for recognition.
- Braga, Carolyne B.,Pilli, Ronaldo A.,Ornelas, Catia,Weck, Marcus
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p. 5290 - 5306
(2021/11/30)
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- Cyclohexanedicarboxylic acid derivative with bridge ring and pharmaceutical composition and application thereof
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The invention discloses a cyclohexane dicarboxylic acid derivative with a bridged ring represented by general formula (I). The application of the stereoisomers and the pharmaceutically acceptable salts in the preparation of antitumor drugs has obvious inhibition effects on leukemia, liver cancer, lung cancer, gastric cancer and ovarian cancer. The compound disclosed by the invention has high anti-tumor activity, wide anti-tumor spectrum and low toxicity, and is suitable for preparing anti-cancer drugs.
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Paragraph 0081-0083; 0109-0110
(2021/11/10)
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- Oxathiaborolium-Catalyzed Enantioselective [4 + 2] Cycloaddition and Its Application in Lewis Acid Coordinated and Chiral Lewis Acid Catalyzed [4 + 2] Cycloaddition
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The nascency of second-generation sulfur-stabilized borenium cations by halophilic Lewis acid SnCl4 leads to highly active chiral Lewis acids that are very effective catalysts for [4 + 2] cycloaddition. Oxathiaborolium pentachlorostannate (5-10 mol %) successfully catalyzed cycloaddition of various dienes and dienophiles to afford cycloadducts with excellent enantioselectivity (20 examples, up to 99% ee). This super Lewis acid also exhibited good enantioselectivity for the first Lewis acid coordinated and chiral Lewis acid catalyzed [4 + 2] cycloaddition to α,β-unsaturated mixed ester amide.
- Boobalan, Ramalingam,Chein, Rong-Jie
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supporting information
p. 6760 - 6764
(2021/09/11)
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- Application of hierarchical pore molecular sieve in preparation process of cyclopentadiene and JP-10 aviation fuel
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The invention relates to an application of a hierarchical pore molecular sieve in a the preparation process of cyclopentadiene and JP-10 aviation fuel. The hierarchical pore molecular sieve is one or two or more of an H-ZSM-5 molecular sieve, an H-beta molecular sieve, an H-Y molecular sieve, an H-USY molecular sieve, a La-Y molecular sieve and an H-MOR molecular sieve with a hierarchical pore structure, a sulfonated SBA-15 molecular sieve, a sulfonated MCM-41 molecular sieve, a sulfonated Ti-SBA-15 molecular sieve, a sulfonated MCM-41 molecular sieve, a sulfonated Zr-MCM-41 molecular sieve and a sulfonated Zr-SBA-15 molecular sieve; and the hierarchical pore structure comprises micropores and mesopores. The catalyst and the raw materials used in the method are cheap and easy to obtain, the preparation process is simple, and the hierarchical pore molecular sieve has high activity and selectivity for rearrangement reaction of furfuryl alcohol, hydrogenation reaction of hydroxyl cyclopentenone and dehydration reaction. The invention provides a cheap and efficient synthesis method for synthesizing the JP-10 aviation fuel from a lignocellulose-based platform compound furfuryl alcohol.
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- Production Of Cyclopentadiene From Furfural
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The application relates to processes and systems that use a furfural compound for producing five-membered carbocyclic rings that are unsaturated, such as cyclopentene and cyclopentadiene. Examples methods for conversion of furfural compounds may include converting a furfural compound to at least a five-membered, saturated carbocyclic ring, and converting the five-membered, saturated carbocyclic ring in a presence of a catalyst to at least a five-membered, unsaturated carbocyclic ring.
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Paragraph 0040; 0081-0085
(2021/06/26)
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- Direct Evidence on the Mechanism of Methane Conversion under Non-oxidative Conditions over Iron-modified Silica: The Role of Propargyl Radicals Unveiled
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Radical-mediated gas-phase reactions play an important role in the conversion of methane under non-oxidative conditions into olefins and aromatics over iron-modified silica catalysts. Herein, we use operando photoelectron photoion coincidence spectroscopy to disentangle the elusive C2+ radical intermediates participating in the complex gas-phase reaction network. Our experiments pinpoint different C2-C5 radical species that allow for a stepwise growth of the hydrocarbon chains. Propargyl radicals (H2C?C≡C?H) are identified as essential precursors for the formation of aromatics, which then contribute to the formation of heavier hydrocarbon products via hydrogen abstraction–acetylene addition routes (HACA mechanism). These results provide comprehensive mechanistic insights that are relevant for the development of methane valorization processes.
- ?ot, Petr,Hemberger, Patrick,Pan, Zeyou,Paunovi?, Vladimir,Puente-Urbina, Allen,van Bokhoven, Jeroen Anton
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supporting information
p. 24002 - 24007
(2021/10/01)
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- Method for preparation of high purity cyclopentadiene
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The present invention relates to a method for producing high purity cyclopentadiene. In contrast to the prior art for synthesizing cyclopentadiene by reacting dicyclopentadiene at high temperature, dicyclopentadiene is distilled and purified at low temperature to produce cyclopentadiene, which can be utilized for producing CVD precursors such as semiconductors.
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Paragraph 0027; 0036-0052
(2020/12/01)
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- Preparation method of intermediate prostacyclin (by machine translation)
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The preparation comprises the following steps: preparing,dibromocyclopentene :(1) by adding: to DEG C after BHT, reaction 180 - 200 °C, dissolving 40 - 50 °C-bromophenol, in, a second solvent and, carrying out ;(2) distillation to prepare: the preparation method of A the, cyclopentadiene-prostacyclin intermediate through the post-treatment operation. The preparation method disclosed by, the invention A can, effectively reduce the impurities A, generated in the, process production process 2, 4, 6 - 3,5 - 70, 70 70 to B, B 77700° C. after the reaction. The preparation method, of the invention discloses a preparation method of the preparation method of the penprostacyclin midbody after reacting with a solvent and a preparation method of the present invention. (by machine translation)
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Paragraph 0038-0041
(2020/05/11)
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- Study of all stages of the Diels–Alder reaction of cyclopentadiene with 2,3-dicyano-1,4-benzoquinone and monoadducts: Kinetics, thermochemistry, and high pressure effect
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The kinetic parameters and enthalpies of the Diels–Alder reactions between cyclopentadiene and 2,3-dicyano-1,4-benzoquinone leading to the formation of two different monoadducts and bisadduct were determined. The stability of adducts is compared. Monoadduct appears to be thermodynamically more stable than the bisadduct. Comparison with the other Diels–Alder reactions studied previously allows us to conclude that the heat effects upon formation of the considered Diels–Alder adducts are the lowest in comparison with all the studied dienophiles.
- Kolesnikova, Anastasia O.,Kornilov, Dmitry A.,Gubaidullin, Aidar T.,Kiselev, Vladimir D.
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p. 301 - 309
(2020/03/04)
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- Preorganization: A Powerful Tool in Intermolecular Halogen Bonding in Solution
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Preorganization is a powerful tool in supramolecular chemistry which has been utilized successfully in intra- and intermolecular halogen bonding. In previous work, we had developed a bidentate bis(iodobenzimidazolium)-based halogen bond donor which featured a central trifluoromethyl substituent. This compound showed a markedly increased catalytic activity compared to unsubstituted bis(iodoimidazolium)-based Lewis acids, which could be explained either by electronic effects (the electron withdrawal by the fluorinated substituent) or by preorganization (the hindered rotation of the halogen bonding moieties). Herein, we systematically investigate the origin of this increased Lewis acidity via a comparison of the two types of compounds and their respective derivatives with or without the central trifluoromethyl group. Calorimetric measurements of halide complexations indicated that preorganization is the main reason for the higher halogen bonding strength. The performance of the catalysts in a series of benchmark reactions corroborates this finding.
- Voelkel, Martin H. H.,Wonner, Patrick,Huber, Stefan Matthias
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p. 214 - 224
(2020/03/10)
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- Preparation of a Key Tetraene Precursor for the Synthesis of Long Acenes
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The tetraene 7,7-dimethoxy-2,3,5,6-tetramethylenebicyclo[2.2.1]heptane is a key compound for the preparation of a large variety of acenes protected by a carbonyl bridge. We report herein a medium scale preparation in seven steps of this valuable starting material. Diels–Alder addition between 6,6-dimethtyl fulvene and maleic anhydride, followed by carboxylation, ozonolysis of the double bond, reduction of the four ester groups, then chlorination of the alcohol groups and dehydrochlorination give the target compound in 17 % overall yield.
- ?ámal, Michal,Cisa?ová, Ivana,Gourdon, André,Hung, Nguyen Khanh,Jancarik, Andrej,Levet, Gaspard,Rybá?ek, Ji?í
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- Fast Titanium-Catalyzed Hydroaminomethylation of Alkenes and the Formal Conversion of Methylamine
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The scientific interest in catalytic hydroaminoalkylation reactions of alkenes has vastly increased over the past decade, but these reactions have struggled to become a viable option for general laboratory or industrial use because of reaction times of several days. The titanium-based catalytic system introduced in this work not only reduces the reaction time by several orders of magnitude, into the range of minutes, but the catalyst is also demonstrated to be easily available from common starting materials, at a cost of approximately 1 € per millimole of catalyst. We were also able to formally perform C?H activation of methylamine and achieve coupling to a broad variety of alkenes, through silyl protection of the amine and simple deprotection by water.
- Bielefeld, Jens,Doye, Sven
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supporting information
p. 6138 - 6143
(2020/03/13)
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- Method for preparing titanocene dichloride
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The invention discloses a method for preparing titanocene dichloride. The method comprises the following steps: cracking and rectifying dicyclopentadiene to prepare cyclopentadiene, carrying out a reflux reaction on the prepared cyclopentadiene and a mixed solution containing titanium tetrachloride, tetrahydrofuran and diethylamine, and carrying out post-treatment on the system after the reflux reaction to obtain titanocene dichloride. The post-treatment comprises the following steps: 1, cooling a post-reflux reaction system in an ice bath, filtering, and washing the obtained retentate with tetrahydrofuran and petroleum ether in sequence to obtain a washed retentate; 2, adding the washed retentate into a hydrochloric acid solution, stirring, and filtering to obtain a filtered retentate; and 3, sequentially washing the filtered retentate with ice water and ethanol, and drying to obtain titanocene dichloride. According to the method, the titanocene dichloride is prepared by adopting a cracking-reflux reaction-post-treatment method, so that the influence on the synthesis reaction due to the fusion of cyclopentadiene serving as a raw material can be avoided, and the purity of the titanocene dichloride prepared by adopting the method is 98% or above.
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Paragraph 0024-0026; 0035-0037; 0046-0048; 0057-0059; 0068-
(2020/06/17)
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- Scalable synthesis and polymerisation of a β-angelica lactone derived monomer
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Bio-based levulinic acid is easily ring-closed to α-angelica lactone (α-AL). α-AL can be isomerized to the conjugated β-AL under the influence of base, but since this is an equilibrium mixture it is very hard to devise a scalable process that would give pure β-AL. This problem was circumvented by distilling the equilibrium mixture to obtain a 90?:?10 mixture of β-and α-AL in 88% yield. This mixture was used for Diels-Alder reactions on 3 terpenes and on cyclopentadiene in up to 100 g scale. The latter DA adduct was subjected to a ROMP reaction catalysed by the Grubbs II catalyst. The resulting polymer has some similarities to poly-norbornene but is more polar. The polymer can be processed into films with very good transparency.
- De Vries, Johannes G.,Dell'Acqua, Andrea,Kirchhecker, Sarah,Stadler, Bernhard M.,Tin, Sergey
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p. 5267 - 5273
(2020/09/17)
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- Photo-oxidation of Cyclopentadiene Using Continuous Processing: Application to the Synthesis of (1 R,4 S)-4-Hydroxycyclopent-2-en-1-yl Acetate
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(1R,4S)-4-Hydroxycyclopent-2-en-1-yl acetate is a chiral small building block that was requested to advance several Pfizer programs into the clinic. Pfizer and Syncom partnered to develop a photo-oxidation process of cyclopentadiene using a flow approach followed by subsequent bis-acetylation of the meso diol and final biocatalytic desymmetrization. This continuous process was demonstrated on a 6 g·h-1 input and is amenable to larger scale. The optimization and scale-up of this sequence is described therein.
- Allais, Christophe,Herrero-Gomez, Elena,Huck, Lena,Keene, Nandell F.,Li, Bryan,Pouwer, Kees,Rioz-Martínez, Ana,Van Der Loo, Cornelis H. M.
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p. 2304 - 2310
(2020/11/23)
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- Synthesis method of beraprost sodium intermediate
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The invention relates to a synthesis method of a beraprost sodium intermediate I. Cyclopentene and N-bromosuccinimide (NBS) are subjected to a free radical reaction to obtain dibromocyclopentene, anda safer solvent is used for replacing solvents such as carbon tetrachloride and benzene; during preparation of sodium tribromophenolate, sodium hydroxide and other alkalis are used for replacing sodium hydride; 3, 5-bis (2, 4, 6-tribromophenoxy) cyclopentene is directly prepared from generated dibromocyclopentene and 2, 4, 6-tribromophenol sodium through interaction by a'one-pot boiling 'method. The improved reaction conditions are milder, the environment is more friendly, and industrial production is facilitated.
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Paragraph 0060-0062
(2020/12/14)
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- GROUP 1 METAL ION CONTENT OF MICROPOROUS MOLECULAR SIEVE CATALYSTS
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A catalyst comprising a microporous crystalline aluminosilicate having a Constraint Index less than or equal to 12, a Group 1 alkali metal or a compound thereof and/or a Group 2 alkaline earth metal or a compound thereof, a Group 10 metal or a compound thereof, and optionally a Group 11 metal or a compound thereof; wherein the total amount of Group 1 and/or Group 2 metal is present at a ratio that is optimized for the desirable chemical conversion process.
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Paragraph 0046-0047
(2020/05/28)
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- Enhanced photocatalysis and anticancer activity of green hydrothermal synthesized Ag?TiO2 nanoparticles
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Titanium dioxide (TiO2) nanoparticles (NPs) have been doped with varying amounts (0.005, 0.010 and 0.015 M) of silver nanoparticles (Ag NPs) using hydrothermal method. Further, in this work, a green approach was followed for the formation of Ag?TiO2 NPs using Aloe vera gel as a capping and reducing agent. The structural property confirmed the presence of anatase phase TiO2. Increased peak intensity was observed while increasing the Ag concentration. Further, the morphological and optical properties have been studied, which confirmed the effective photocatalytic behavior of the prepared Ag?TiO2 NPs. The photocatalytic performance of Ag?TiO2 has been considered for the degradation of picric acid in the visible light region. The concentration at 0.010 M of the prepared Ag?TiO2 has achieved higher photocatalytic performance within 50 min, which could be attributed to its morphological behavior. Similarly, anticancer activity against lung cancer cell lines (A549) was also determined. The Ag?TiO2 NPs generated a large quantity of reactive oxygen species (ROS), resulting in complete cancer cell growth suppression after their systemic in vitro administration. Ag?TiO2 NPs was adsorbed visible light that leads to an enhanced anticancer sensitivity by killing and inhibiting cancer cell reproduction through cell viability assay test. It was clear that 0.015 M of Ag?TiO2 NPs were highly effective against human lung cancer cell lines and showed increased production of ROS in cancer cell lines due to the medicinal behavior of the Aloe vera gel.
- Hariharan,Thangamuniyandi,Jegatha Christy,Vasantharaja,Selvakumar,Sagadevan,Pugazhendhi,Nehru
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- An Intramolecular Cycloaddition Approach to the Kauranoid Family of Diterpene Metabolites
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Synthetic studies toward the ent-kauranoid family of diterpene natural products are reported. An intramolecular (4 + 3) cycloaddition allows the direct elaboration of diverse natural product frameworks, encompassing a challenging bicyclo[3.2.1]octane core. The established routes comprise only a few synthetic operations (3-5 steps), transforming a range of simple starting materials into the tetracyclic scaffolds that are commonly found in many ent-kaurene metabolites.
- Callebaut, Brenda,Hullaert, Jan,Van Hecke, Kristof,Winne, Johan M.
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supporting information
p. 310 - 314
(2019/01/10)
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- Rapid Diels-Alder Cross-linking of Cell Encapsulating Hydrogels
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Recent efforts in the design of hydrogel biomaterials have focused on better mimicking the native cellular microenvironment to direct cell fate. To simultaneously control multiple material parameters, several orthogonal chemistries may be needed. However, present strategies to prepare cell-encapsulating hydrogels make use of relatively few chemical reactions. To expand this chemical toolkit, we report the preparation of hydrogels based on a Diels-Alder reaction between fulvenes and maleimides with markedly improved gelation kinetics and hydrolytic stability. Fulvene-maleimide gels cross-link up to 10-times faster than other commonly used DA reaction pairs and remain stable for months under physiological conditions. Furthermore, fulvene-maleimide gels presenting relevant biochemical cues, such as cell-adhesive ligands and proteolytic degradability, support the culture of human mesenchymal stromal cells. Finally, this rapid DA reaction was combined with an orthogonal click reaction to demonstrate how the use of selective chemistries can provide new avenues to incorporate multiple functionalities in hydrogel materials.
- Madl, Christopher M.,Heilshorn, Sarah C.
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p. 8035 - 8043
(2019/10/21)
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- STING MODULATOR COMPOUNDS, AND METHODS OF MAKING AND USING
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The present disclosure provides STING modulators/agonists, and methods of synthesis and methods for using for the prophylaxis or treatment of cancer and other STING-related diseases. The present disclosure relates to a compound represented by the Formula (I): wherein each symbol is as defined in the description, or a pharmaceutically acceptable salt thereof.
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Paragraph 0215
(2019/05/30)
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- Light-Stabilized Dynamic Materials
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The light-responsive adaptation of polymer materials typically requires different wavelengths or additional heat to induce reversible covalent bond formation and dissociation. Here, we bypass the use of invasive triggers by introducing light-stabilized dynamic materials that can undergo a repeatable change in topology from a covalently cross-linked material into a liquid polymer formulation by switching one visible light source on-and-off without the need for any additional triggers. Specifically, we exploit the photo-Diels-Alder reaction of triazolinediones with naphthalenes as a dynamic covalent cross-linking platform that enables green light-induced network formation, while the cross-linked material collapses through spontaneous cycloreversion upon standing in the dark at ambient temperature. Importantly, the covalent cross-links remain stabilized for as long as visible light is present, thereby retaining the material's structural integrity. This enables their potential use in an array of light-directed applications whereby network properties such as stiffness can be tuned by the mildest trigger of all: darkness.
- Houck, Hannes A.,Blasco, Eva,Du Prez, Filip E.,Barner-Kowollik, Christopher
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supporting information
p. 12329 - 12337
(2019/08/27)
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- A synthesis method of the branch stands lactone diol
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The invention discloses a method for the branch stands lactone diol (( -) - Corey lactone diol) synthetic method, synthesis method of the invention is to dicyclopentadiene as raw materials, by depolymerization, cyclization, oxidation, dechlorination, open-loop, split, Prins reaction, hydrolysis reaction to obtain the target product. The invention discloses a synthetic route, raw material economic, high separation efficiency, and is suitable for industrial production.
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Paragraph 0067; 0068
(2019/06/07)
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- Making JP-10 Superfuel Affordable with a Lignocellulosic Platform Compound
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The synthesis of renewable jet fuel from lignocellulosic platform compounds has drawn a lot of attention in recent years. So far, most work has concentrated on the production of conventional jet fuels. JP-10 is an advanced jet fuel currently obtained from fossil energy. Due to its excellent properties, JP-10 has been widely used in military aircraft. However, the high price and low availability limit its application in civil aviation. Here, we report a new strategy for the synthesis of bio-JP-10 fuel from furfuryl alcohol that is produced on an industrial scale from agricultural and forestry residues. Under the optimized conditions, bio-JP-10 fuel was produced with high overall carbon yields (≈65 %). A preliminary economic analysis indicates that the price of bio-JP-10 fuel can be greatly decreased from ≈7091 US$/ton (by fossil route) to less than 5600 US$/ton using our new strategy. This work makes the practical application of bio-JP-10 fuel forseeable.
- Li, Guangyi,Hou, Baolin,Wang, Aiqin,Xin, Xuliang,Cong, Yu,Wang, Xiaodong,Li, Ning,Zhang, Tao
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p. 12154 - 12158
(2019/08/12)
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- X-ray Absorption Spectroscopy and Theoretical Investigation of the Reductive Protonation of Cyclopentadienyl Cobalt Compounds
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Cobalt(III) hydrides, formed via protonation of basic cobalt(I) centers, have long been recognized as key intermediates in the electrocatalytic reduction of protons to hydrogen. An understanding of the structural and electronic factors that govern their formation is key to developing more efficient and potent catalysts. A combination of Co K-edge X-ray absorption spectroscopy, extended X-ray absorption fine structure, density functional theory (DFT), and time-dependent DFT methods have been used to investigate several cyclopentadienyl (Cp) Co(III)L (L = ligand) species and their two-electron reduced Co(I) analogues. The results reveal that when L is strongly π-accepting, the reduced species demonstrates strong backbonding between the electron-rich Co(I) center and the ligand L, resulting in a weakly basic Co center that does not protonate to form a Co(III)-H. In contrast, a weakly π-accepting or σ-donating ligand system results in an electron-rich Co(I) center, which is readily protonated to form a Co(III)-H. This study reveals the strength of a combined X-ray spectroscopy/theory method in understanding the role of ligands in tuning the electronic structure and subsequent reactivity of the metal center.
- McLoughlin, Elizabeth A.,Giles, Logan J.,Waymouth, Robert M.,Sarangi, Ritimukta
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supporting information
p. 1167 - 1176
(2019/01/26)
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- Synthesis method of beraprost sodium intermediate
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The invention relates to a synthesis method of a Beraprost sodium intermediate (III). Cyclopentene and N-bromo-succinimide (NBS) carry out free radical reaction to obtain dibromocyclopentene; and dibromocyclopentene reacts with 2,4,6-tribromophenol to directly generate 3,5-bis(2,4,6-tribromophenoxyl) cyclopentene (compound I) through a one-pot method. Then through Grignard reactions, a compound (I) and a compound (II) are obtained. N-bromo-succinimide and a commercial product namely cyclopentene are taken as the raw materials to synthesize dibromocyclopentene, 170 DEG C cracking and ultralow temperature reactions (-40 to -30 DEG C) are avoided, the using of bromine is also avoided, the reaction conditions are milder, and the synthesis method is more environmentally friendly and is convenient for industrial production.
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Paragraph 0085-0087
(2019/11/28)
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- Decomposition of Picolyl Radicals at High Temperature: A Mass Selective Threshold Photoelectron Spectroscopy Study
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The reaction products of the picolyl radicals at high temperature were characterized by mass-selective threshold photoelectron spectroscopy in the gas phase. Aminomethylpyridines were pyrolyzed to initially produce picolyl radicals (m/z=92). At higher temperatures further thermal reaction products are generated in the pyrolysis reactor. All compounds were identified by mass-selected threshold photoelectron spectroscopy and several hitherto unexplored reactive molecules were characterized. The mechanism for several dissociation pathways was outlined in computations. The spectrum of m/z=91, resulting from hydrogen loss of picolyl, shows four isomers, two ethynyl pyrroles with adiabatic ionization energies (IEad) of 7.99 eV (2-ethynyl-1H-pyrrole) and 8.12 eV (3-ethynyl-1H-pyrrole), and two cyclopentadiene carbonitriles with IE′s of 9.14 eV (cyclopenta-1,3-diene-1-carbonitrile) and 9.25 eV (cyclopenta-1,4-diene-1-carbonitrile). A second consecutive hydrogen loss forms the cyanocyclopentadienyl radical with IE′s of 9.07 eV (T0) and 9.21 eV (S1). This compound dissociates further to acetylene and the cyanopropynyl radical (IE=9.35 eV). Furthermore, the cyclopentadienyl radical, penta-1,3-diyne, cyclopentadiene and propargyl were identified in the spectra. Computations indicate that dissociation of picolyl proceeds initially via a resonance-stabilized seven-membered ring.
- Reusch, Engelbert,Holzmeier, Fabian,Gerlach, Marius,Fischer, Ingo,Hemberger, Patrick
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supporting information
p. 16652 - 16659
(2019/12/24)
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- Palladium-Catalyzed Reductive Coupling Reaction of Terminal Alkynes with Aryl Iodides Utilizing Hafnocene Difluoride as a Hafnium Hydride Precursor Leading to trans-Alkenes
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Herein, we describe a reductive cross-coupling of alkynes and aryl iodides by using a novel catalytic system composed of a catalytic amount of palladium dichloride and a promoter precursor, hafnocene difluoride (Cp2HfF2, Cp=cyclopentadienyl anion), in the presence of a mild reducing reagent, a hydrosilane, leading to a one-pot preparation of trans-alkenes. In this process, a series of coupling reactions efficiently proceeds through the following three steps: (i) an initial formation of hafnocene hydride from hafnocene difluoride and the hydrosilane, (ii) a subsequent hydrohafnation toward alkynes, and (iii) a final transmetalation of the alkenyl hafnium species to a palladium complex. This reductive coupling could be chemoselectively applied to the preparation of trans-alkenes with various functional groups, such as an alkyl group, a halogen, an ester, a nitro group, a heterocycle, a boronic ester, and an internal alkyne.
- Takahashi, Keita,Ogiwara, Yohei,Sakai, Norio
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supporting information
p. 809 - 814
(2018/03/13)
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- Synthesis, structure-activity relationships, and mechanistic studies of 5-arylazo-tropolone derivatives as novel xanthine oxidase (XO) inhibitors
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Xanthine oxidase (XO) is an enzyme that contains molybdenum at the active site and catalyzes the oxidation of purine bases to uric acid. Even though XO inhibitors are widely used for the treatment of hyperuricemia and gout, only very few such compounds are clinically used as drugs for the treatment of these diseases. Given the unique physicochemical properties of tropolone, i.e., its chelating effect and the pKa value that is similar to that of carboxylic acid, we have synthesized 22 5-arylazotropolone derivatives as potential XO inhibitors. In vitro enzyme-inhibitory assays for XO revealed that 3-nitro derivative 1j showed the most potent XO inhibitory activity, which is by one order of magnitude more potent than allopurinol. An enzyme-kinetic study revealed that 1j inhibited the production of uric acid by XO both competitively and non-competitively. A docking-simulation study of 1j with XO suggested that the carbonyl and hydroxyl groups of the tropolone ring interact with the hydroxy group that acts as a ligand for molybdenum and the amino acid residues around the active site of XO.
- Sato, Daisuke,Kisen, Takuya,Kumagai, Mina,Ohta, Kiminori
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p. 536 - 542
(2017/12/29)
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- Synthesis of Main-Chain Ionic Polymers of Chiral Imidazolidinone Organocatalysts and Their Application to Asymmetric Diels–Alder Reactions
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Main-chain ionic polymers incorporating chiral imidazolidinone moieties in the polymer main chain were successfully synthesized by the polyaddition reaction of a chiral imidazolidinone dimer with a disulfonic acid. The organocatalytic activities of these polymers were investigated in the asymmetric Diels–Alder reaction between trans-cinnamaldehyde and 1,3-cyclopentadiene. The catalytic performance of the polymers was found to be sensitive to the chemical structure of the disulfonate units and the imidazolidinone dimer. With the use of these heterogeneous polymeric chiral organocatalysts, enantioselectivities of up to 99% for the endo isomer were obtained. This result was higher than those obtained with corresponding monomeric and dimeric counterparts in a homogeneous solution. The polymeric chiral organocatalyst was recovered and reused several times, maintaining its high enantioselectivity. (Figure presented.).
- Haraguchi, Naoki,Takenaka, Nagisa,Najwa, Aisyah,Takahara, Yuta,Mun, Mah Kar,Itsuno, Shinichi
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supporting information
p. 112 - 123
(2017/12/26)
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- Synthesis of an energetic polynorbornene with pendant bis-azidoacetyloxymethyl groups (PNBAA)
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A novel energetic polynorbornene with pendant bisazidoacetyloxymethyl (named PNBAA) was designed, by combining its intrinsic energetic properties, potential good mechanical properties, its compatibility with a plasticizer and odourless polynorbornene in one polymer. A green synthesis of PNBAA was achieved starting from easily available materials, by using the solvent-free Diels-Alder reaction, chloroacetylation of norbornene dimethanol in water, solvent-free ring opening metathesis polymerization (ROMP), azidation in aqueous 3-pentanone and tandem ROMP and azidation in one pot. In addition, the Nuclear Magnetic Resonance (NMR) technique was utilized to investigate the key ROMP and azidation steps in situ. PNBAA as an energetic polymer was demonstrated by measuring its TG-IR, DSC and mechanical sensitivity. The strategy reported in this paper will lead to the general green synthesis of diverse energetic polymers in the future.
- Jiang, Kun,Deng, Han-Lin,Zhang, Qi,Wang, Shuifeng,Wu, Hao,Liu, Yan,Chai, Chunpeng,Huang, Mu-Hua
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p. 2813 - 2820
(2018/06/29)
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- Probing the electron transfer mechanism of the half-sandwich iron(II)-carbonyl complexes and their catalysis on proton reduction
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The electrochemical behaviors of three half-sandwich iron(II) complexes, [CpFe(CO)2X] (Cp = cyclopentadienyl, 1: X = Cl; 2: X = Br; 3: X = I) were investigated. For the three complexes, two reduction processes at ca. ?1.3 V and ?2.0 V were observed. They are assigned to the reductions of Fe(II) → Fe(I) couple and the reduction of the dimer, [CpFe (μ-CO)(CO)]2 (Fp2), which formed via the dimerization of the neutral intermediate “CpFe(CO)2” (Fp) generated from the first reduction, respectively. Our results ruled out the possibility of two-electron reduction for the first process. Using stop-flow infrared spectroscopic technique (SFIS) allowed us to trace the rapid chemical reactions and the first-order reaction rate constants for the formations of both Fp and Fp2 were derived as 0.27 and 0.43 s?1, respectively. Both complexes 1 and Fp2 could be reduced by LiHBEt3. In the reduction, ligand exchange reaction occurred between the chloride and hydride, which was evidenced by the observation the absorption bands of [CpFe(CO)2H] (FpH). Their reduction reactions abided first-order model for the complex and the reducing agent. By assuming that equal moles of the complex and the reducing agent were used in the reduction, a rate equation was established. Again, the SFIS technique was employed to follow the reductions and linear plots were observed to give the rate constants as 14 and 18 mol?1 L s?1, respectively. The catalysis on proton reduction of the complexes was also examined. Sufficient experimental evidences in our work and the analysis of literature data suggested strongly that the catalytic species was not the neutral species Fp. Instead the anion, FpX?, was responsible for the catalysis. The poor performance in catalysis of these complexes resulted from the competing reaction coupled to the first reduction, loss of the halide upon reduction. The resultant neutral species, Fp dimerized rapidly into Fp2.
- Rong, Bingying,Zhong, Wei,Gu, Erxing,Long, Li,Song, Lijuan,Liu, Xiaoming
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- METHOD FOR PRODUCING NORBORNANE DICARBOXYLIC ACID
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The present invention relates to a method for producing norbornane carboxylic acid, and more specifically, to a method for producing norbornane carboxylic acid, which comprises a step for reacting cyclopentadiene obtained by thermal decomposition of dicyclopentadiene with maleic anhydride. The production method according to the present invention utilizes dicyclopentadiene, has excellent reaction efficiency, and has an industrially useful whole reaction process, and thus it is possible to mass-produce the norbornane dicarboxylic acid with high yield and the norbornane dicarboxylic acid can be applied to various industrial fields.COPYRIGHT KIPO 2018
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Paragraph 0092; 0094; 0095
(2018/07/28)
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- METHOD FOR PRODUCING BICYCLO[2.2.1]HEPTANE-2,3-DIYLDIMETHANOL
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The present invention refers to bicyclo [2. 2. 1] Heptane - 2, 3 - manufacturing method relates to the d methanol which will be a d, more particularly claw pen hit diene between d and reacting maleic anhydride with pen hit diene obtained by pyrolysis cycles including a number bath is formed on the bicyclo [2. 2. 1] Heptane - 2, 3 - to the d methanol which will be a d manufacturing method are disclosed. The present invention according to manufacturing method is that by the claw pen hit diene between d, reaction efficiency is superior, since the whole reaction process industrially useful bicyclo [2. 2. 1] Heptane - 2, 3 - [...] high yield can be mass produced, industrially nephrophathy intensity applications. (by machine translation)
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Paragraph 0103-0104
(2018/07/28)
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- Scalable and Highly Diastereo- and Enantioselective Catalytic Diels-Alder Reaction of α,β-Unsaturated Methyl Esters
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Despite tremendous advances in enantioselective catalysis of the Diels-Alder reaction, the use of simple α,β-unsaturated esters, one of the most abundant and useful class of dienophiles, is still severely limited in scope due to their low reactivity. We report here a catalytic asymmetric Diels-Alder methodology for a large variety of α,β-unsaturated methyl esters and different dienes based on extremely reactive silylium imidodiphosphorimidate (IDPi) Lewis acids. Mechanistic insights from accurate domain-based local pair natural orbital coupled-cluster (DLPNO-CCSD(T)) calculations rationalize the catalyst control and stereochemical outcome.
- Gatzenmeier, Tim,Turberg, Mathias,Yepes, Diana,Xie, Youwei,Neese, Frank,Bistoni, Giovanni,List, Benjamin
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supporting information
p. 12671 - 12676
(2018/10/15)
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- Preparation of (1R,4S)-4-hydroxycyclopent-2-en-1-yl acetate via Novozym-435 catalyzed desymmetrization of cis-3,5-Diacetoxy-1-cyclopentene
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Photooxidation of cyclopentadiene has been carried out in methanol using white light of LED lamp, rose bengal as photo initiator, and compressed air at 0 °C. Under conditions of [thiourea] ? [cyclopentadiene], the consumption of thiourea follows a pseudo-first-order reaction kinetics with half life of 75 ± 10 min; corr. coeff. r = 0.989. Slow addition of the monomer and maintaining excess thiourea concentration in reaction mass improves the yield. cis-3,5-Dihydroxy-1-cyclopentene is acetylated without isolation to obtain cis-3,5-Diacetoxy-1-cyclopentene of high purity (>99%) with overall isolated yield of 30%. Desymmetrization of the diacetate to (1R,4S)-4-hydroxycyclopent-2-en-1-yl acetate has been carried out via enzymatic transesterification with methanol in methyl tert-butyl ether (MTBE) at 5 °C using Novozym-435. The enantiomerically pure monoacetate (e.e. >99%) was obtained in 95% isolated yield. The recovered enzyme was reused for more than 10 times without loss in yield and selectivity. The entire protocol does not require purification of final product by chromatography.
- Putta, Shekhar,Reddy, Annem Mallikarjun,Sheelu, Gurrala,Reddy, B.V. Subba,Kumaraguru, Thenkrishnan
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p. 6673 - 6679
(2018/10/15)
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- Study of Methylidyne Radical (CH and CD) Reaction with 2,5-Dimethylfuran Using Multiplexed Synchrotron Photoionization Mass Spectrometry
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At 298 K the reactions of 2,5-dimethlyfuran + CH(X2Θ) and + CD radicals were investigated using synchrotron radiation coupled with multiplexed photoionization mass spectrometry at the Lawrence Berkeley National Laboratory. Reaction products wer
- Carrasco, Erica,Meloni, Giovanni
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p. 6118 - 6133
(2018/07/09)
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- Stereoselectivity in a series of 7-alkylbicyclo[3.2.0]hept-2-enes: Experimental and computational perspectives
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Rate constants for overall decomposition (kd) for a series of exo-7-alkylbicyclo[3.2.0]hept-2-enes are relatively invariant. For the alkyl substituents ethyl, propyl, butyl, isopropyl, and t-butyl, the ratio of the rate constant for [1,3] sigmatropic rearrangement to the rate constant for fragmentation, k13/kf, is significantly lower than k13/kf?=?150 observed for exo-7-methylbicyclo[3.2.0]hept-2-ene. Regardless of the size and mass of the alkyl group, the stereoselectivity of the [1,3] carbon migration appears to be quite stable at 80% to 89% suprafacial inversion (si), an observation consistent with conservation of angular momentum but not conservation of orbital symmetry. This global result comports with the phenomenon of “dynamic matching” espoused by Carpenter and collaborators for [1,3] sigmatropic rearrangements in general.
- Leber, Phyllis,Kidder, Katherine,Viray, Don,Dietrich-Peterson, Eric,Fang, Yuan,Davis, Alexander
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- Synthesis of Guanine α-Carboxy Nucleoside Phosphonate (G-α-CNP), a Direct Inhibitor of Multiple Viral DNA Polymerases
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The synthesis of guanine α-carboxy nucleoside phosphonate (G-α-CNP) is described. Two routes provide access to racemic G-α-CNP 9, one via base construction and the other utilizing Tsuji-Trost allylic substitution. The latter methodology was also applied to the enantiopure synthesis of both antipodes of G-α-CNP, each of which showing interesting antiviral DNA polymerase activity. Additionally, we report an improved multigram scale preparation of the cyclopentene building block 10, starting material for the preferred Tsuji-Trost route to 9.
- Maguire, Nuala M.,Ford, Alan,Balzarini, Jan,Maguire, Anita R.
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p. 10510 - 10517
(2018/09/06)
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- Method for preparing JP-10 aviation fuel from furfuryl alcohol
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The invention relates to a method for preparing JP-10 aviation fuel from furfuryl alcohol. The method for preparing JP-10 aviation fuel by taking the furfuryl alcohol as a raw material is totally divided into six reactions as follows: a first reaction of carrying out a rearrangement reaction on a furfuryl alcohol solution in the presence of a base catalyst or under the condition that any catalystis not added to prepare hydroxy cyclopentenone; a second reaction of reacting the hydroxy cyclopentenone and hydrogen under catalysis of a hydrogenation catalyst so as to prepare 1,3-cyclopendiol; a third reaction of dehydrating the 1,3-cyclopendiol to prepare cyclopentadiene; a fourth reaction of carrying out a D-A reaction on the cyclopentadiene to produce dicyclopentadiene; a fifth reaction ofhydrogenating the dicyclopentadiene to produce endo-tetrahydrodicyclotadiene; and a sixth reaction of performing isomerization on the endo-tetrahydrodicyclotadiene to produce hanging type tetrahydrodicyclopentadiene, wherein the prepared hanging type tetrahydrodicyclopentadiene can directly serve as the JP-10 aviation fuel. The invention provides a cheap high-efficiency synthetic method for synthesizing the JP-10 aviation fuel from a lignocelluloses-based platform chemical compound, namely furfuryl alcohol.
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- Experimental and Theoretical Studies on the Reactivity of Titanium Chelidamate Complexes: The Significant Role of the Hydroxide Pyridine Moiety
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The reaction of [TiCp2Cl2] with dipotassium chelidamate yields the carboxylate derivative [TiCp2{(OOC)2PyOH}] (2), which is sparsely soluble in water at neutral pH but soluble in basic medium. [TiCp?Cl3/su
- Fandos, Rosa,Hernández, Carolina,Otero, Antonio,Pacheco, Janira,Rodríguez, Ana M.,Ruiz, María José,Organero, Juan ángel
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p. 3515 - 3523
(2018/10/31)
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- BORON-BASED CYCLOADDITION CATALYSTS AND METHODS FOR THE PRODUCTION OF BIO-BASED TEREPHTHALIC ACID, ISOPHTHALIC ACID AND POLY (ETHYLENE TEREPHTHALATE)
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Methods for producing cycloaddition products comprising: reacting a diene with a dienophile in the presence of one or more boron-based catalysts of Formula I or Formula II are provided. In particular, the methods can be used to prepare 4-methyl-3-cyclohexene- 1-carboxylic acid and 3-methyl-3-cyclohexene-l-carboxylic acid, including bio-based versions thereof. The cycloaddition products can be advantageously used in the production of terephthalic acid and isophthalic acid, and ultimately, poly(ethylene terephthalate), and bio-based versions thereof. Formula I Formula II
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Paragraph 00212
(2017/04/11)
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- The organic metal compound, and container therefor (by machine translation)
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PROBLEM TO BE SOLVED: To provide a method for producing an organometallic compound being a solid at normal temperature with high purity and in high yield, and to provide a vessel to be used in the method for producing the organometallic compound.SOLUTION: The vessel 1 includes: a vessel body 10 having relatively higher thermal conductivity; and a bottom wall member 20 which is laid attachably/detachably on the bottom surface of the vessel body 10 and has relatively lower thermal conductivity. At least one of the vapor and molten liquid of the organometallic compound being the solid at normal temperature is introduced into the vessel 1. The organometallic compound introduced in the vessel 1 is cooled and solidified. The solidified organometallic compound is withdrawn from the vessel body 10 together with the bottom wall member 20.
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Paragraph 0041
(2018/01/19)
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- The use of optically active O-alkyl ester hydrochlorides of L-phenylalanine and L-tyrosine as chiral micellar media for the catalysis of diels-alder reactions
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The effect of a range of O-alkyl ester hydrochloride surfactants derived from L-phenylalanine and L-tyrosine as catalysts on the Diels-Alder reaction between cyclopentadiene and methyl acrylate was studied. Both chain lengths (C8-C14) and head groups of the surfactants were found to influence the yield and selectivity of the Diels-Alder product. The C10 derivatives of both phenylalanine and tyrosine surfactants gave the highest yields and selectivity. Phenylalanine ester hydrochlorides showed better catalytic activity than the tyrosine derivatives. Adduct optimum yield was obtained at a concentration relating to their critical micelle concentration (CMC) values. The Diels-Alder reaction was also found to be favored in acidic condition (pH 3) as well as in the presence of lithium chloride (LiCl) as salting out agent.
- Caumul,Koonja,Namooya,Prayag,Joondan,Jhaumeer-Laulloo
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p. 509 - 518
(2018/02/06)
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- Synthesis & antitumor activity of new group 3 Metallocene complexes
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The quest for alternative drugs with respect to the well-known cis-platin and its derivatives, which are still used in more than 50% of the treatment regimens for patients suffering from cancer, is highly needed. In this context, organometallic compounds, which are defined as metal complexes containing at least one direct covalent metal-carbon bond, have recently been found to be promising anticancer drug candidates. A series of new metallocene complexes with scandium, yttrium, and neodymium have been prepared and characterized. Some of these compounds show a very interesting anti-proliferative activity in triple negative breast cancer cell line (MDA.MB231) and the non-hormone sensitive prostate cancer cell line (DU145). Moreover, the interaction of some of them with biological membranes, evaluated using liposomes as bio-membrane mimetic model systems, seems to be relevant. The biological activity of these compounds, particularly those based on yttrium, already effective at low concentrations on both cancer cell lines, should be taken into account with regard to new therapeutic approaches in anticancer therapy.
- Caporale, Angelamaria,Palma, Giuseppe,Mariconda, Annaluisa,Del Vecchio, Vitale,Iacopetta, Domenico,Parisi, Ortensia Ilaria,Sinicropi, Maria Stefania,Puoci, Francesco,Arra, Claudio,Longo, Pasquale,Saturnino, Carmela
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- GROUP 3 METAL COMPOUNDS AND USE THEREOF IN THE TREATMENT OF SOLID TUMORS
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The present invention relates to the compounds of Formula 1 wherein M is Sc or Y, Hal is CI, Br, F or I R is alkyl with 1 - 4 atoms of C X is CI, Br, F or I or a group such as that shown hereinafter wherein R is alkyl with 1 - 4 atoms of C and the use thereof in the treatment of solid tumors.
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Page/Page column 6; 7; 8
(2017/12/14)
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- Synthesis of annulated oxa-triquinanes and oxa-diquinanes via cascade Michael addition-intramolecular alkylation involving α-halodicyclopentadienones
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Base Mediated Michael addition of 1,3-dicarbonyl compounds to α-halodicyclopentadienones followed by cyclization of the intermediate Michael adducts leads to novel annulated dihydrofurans as single diastereomers. Such fused dihydrofurans, which are also oxa-triquinanes and oxa-diquinanes, undergo retro-Diels-Alder reaction to give cyclopentadiene-eliminated products in excellent yield. Certain 1,3-dicarbonyl compounds exhibited a different reactivity profile with α-halodicyclopentadienones leading to spiro-cyclopropanes fused to dicyclopentadiene skeleton.
- Lal, Sohan,Chowdhury, Arindrajit,Namboothiri, Irishi N.N.
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p. 1297 - 1305
(2017/02/15)
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- Process for Conversion of Acyclic C5 Compounds to Cyclic C5 Compounds and Catalyst Composition for Use Therein
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Disclosed is a process for the conversion of acyclic C5 feedstock to a product comprising cyclic C5 compounds, such as for example, cyclopentadiene, and catalyst compositions for use in such process. The process comprising the steps of contacting said feedstock and, optionally, hydrogen under acyclic C5 conversion conditions in the presence of a catalyst composition to form said product. The catalyst composition comprising a microporous crystalline ferrosilicate, a Group 10 metal, and, optionally, a Group 11 metal, in combination with an optional Group 1 alkali metal and/or an optional Group 2 alkaline earth metal.
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Paragraph 0125-0126
(2017/05/19)
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