- COMPOSITES, METHODS AND USES THEREOF
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The present invention relates, in general terms, to methods of catalysing a reaction, including the steps of contacting a chemical entity comprising a sulphide moiety with a composite and an oxidant. The composite acts as a heterogeneous catalyst to oxidise the sulphide moiety. The present invention also relates to composites, methods of synthesising the composites and its use as a catalyst thereof.
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Page/Page column 26
(2021/06/04)
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- Preparation method of p-methylsulfonyl benzaldehyde
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The invention relates to a preparation method of p-methylsulfonyl benzaldehyde, and solves the technical problems that the existing preparation method is unreasonable, high in raw material toxicity, complex in operation, high in cost, high in three-waste yield, low in yield and unsuitable for industrial product. The preparation method of p-methylsulfonyl benzaldehyde takes p-nitroformaldehyde as a raw material and sodium sulfide as a reducing agent, and the preparation method comprises the following steps: carrying out a reduction reaction under an alkaline condition to generate p-aminobenzaldehyde, dropwise adding sodium methyl mercaptide into the p-aminobenzaldehyde in the presence of hydrochloric acid and sodium nitrite, carrying out a diazo reaction and a substitution reaction to generate p-methylthiobenzaldehyde, and oxidizing the p-methylthiobenzaldehyde by using hydrogen peroxide under an acidic condition to obtain the p-methylsulfonyl benzaldehyde. The method can be widely applied to the technical field of veterinary drug and medicine raw material medicine synthesis.
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Paragraph 0014; 0027-0028; 0032-0034; 0038-0040; 0044...
(2021/07/24)
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- Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
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A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
- Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
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supporting information
p. 8691 - 8695
(2021/10/22)
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- Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
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An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
- Amri, Nasser,Wirth, Thomas
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p. 15961 - 15972
(2021/07/20)
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- Synthesis and Biological Evaluation of 1,3,5-Trisubstituted 2-Pyrazolines as Novel Cyclooxygenase-2 Inhibitors with Antiproliferative Activity
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A new series of 1,3,5-trisubstituted 2-pyrazolines for the inhibition of cyclooxygenase-2 (COX-2) were synthesized. The designed structures include a COX-2 pharmacophore SO2CH3 at the para-position of the phenyl ring located at C-5 of a pyrazoline scaffold. The synthesized compounds were tested for in vitro COX-1/COX-2 inhibition and cell toxicity against human colorectal adenocarcinoma cell lines HT-29. The lead compound (4-chlorophenyl){5-[4-(methanesulfonyl)phenyl]-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl}methanone (16) showed significant COX-2 inhibition (IC50=0.05±0.01 μM), and antiproliferative activity (IC50=5.46±4.71 μM). Molecular docking studies showed that new pyrazoline-based compounds interact via multiple hydrophobic and hydrogen-bond interactions with key binding site residues of the COX-2 enzyme.
- Vahedpour, Teymour,Kaur, Jatinder,Hemmati, Salar,Hamzeh-Mivehroud, Maryam,Alizadeh, Ali Akbar,Wuest, Frank,Dastmalchi, Siavoush
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- Synthesis of new Zn (II) complexes for photo decomposition of organic dye pollutants, industrial wastewater and photo-oxidation of methyl arenes under visible-light
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Synthesis of new Schiff's base Zn-complexes for photo-oxidation of methyl arenes and xylenes are reported under visible light irradiation conditions. All the synthesized new ligands and Zn-complexes are thoroughly characterized with various spectral analyses and confirmed as 1:1 ratio of Zn and ligand with distorted octahedral structure. The bandgap energies of the ligands are higher than its Zn-complexes. These synthesized new Zn(II) complexes are used for the photo-fragmentation of organic dye pollutants, photodegradation of food industrial wastewater and oxidation of methyl arenes which are converted into its respective aldehydes with moderate yields under visible light irradiation. The photooxidation reaction dependency on the intensity of the visible light was also studied. With the increase in the dosage of photocatalyst, the methyl groups are oxidized to get aldehydes and mono acid products, which are also identified from LC-MS data. Finally, [Zn(PPMHT)Cl] is with better efficiency than [Zn(PTHMT)Cl] and [Zn(MIMHPT)Cl] for oxidation of methyl arenes is reported under visible-light-driven conditions.
- Ahemed, Jakeer,Bhongiri, Yadagiri,Chetti, Prabhakar,Gade, Ramesh,Kore, Ranjith,Pasha, Jakeer,Pola, Someshwar,Rao D, Venkateshwar
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- One-Pot Direct Oxidation of Primary Amines to Carboxylic Acids through Tandem ortho-Naphthoquinone-Catalyzed and TBHP-Promoted Oxidation Sequence
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Biomimetic oxidation of primary amines to carboxylic acids has been developed where the copper-containing amine oxidase (CuAO)-like o-NQ-catalyzed aerobic oxidation was combined with the aldehyde dehydrogenase (ALDH)-like TBHP-mediated imine oxidation protocol. Notably, the current tandem oxidation strategy provides a new mechanistic insight into the imine intermediate and the seemingly simple TBHP-mediated oxidation pathways of imines. The developed metal-free amine oxidation protocol allows the use of molecular oxygen and TBHP, safe forms of oxidant that may appeal to the industrial application.
- Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
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supporting information
p. 18150 - 18155
(2021/12/09)
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- Preparation method of P-methylsulfonyl benzoic acid
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The invention relates to a preparation method of p-methylsulfonylbenzoic acid, and solves the technical problems of poor selectivity, serious environmental pollution, large wastewater and difficult treatment of solid waste in the traditional process, and comprises the following steps: (1) bromination. (2) Hydrolysis. (3) Alkalization. (4) Acidification and. The method is widely applied to the technical field of flame retardant synthesis.
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Paragraph 0024-0027; 0030-0033; 0036-0039; 0043-0047
(2021/10/13)
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- Palladium-Catalyzed Reductive Carbonylation of (Hetero) Aryl Halides and Triflates Using Cobalt Carbonyl as CO Source
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An efficient protocol for the reductive carbonylation of (hetero) aryl halides and triflates under CO gas-free conditions using Pd/Co2(CO)8 and triethylsilane has been developed. The mild reaction conditions, enhanced chemoselectivity and, easy access to heterocyclic and vinyl carboxaldehydes highlights its importance in organic synthesis.
- Dogga, Bhushanarao,Joseph, Jayan T.,Kumar, C. S. Ananda
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p. 309 - 313
(2020/12/23)
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- 4CzIPN catalyzed photochemical oxidation of benzylic alcohols
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A green photoredox oxidation of benzylic primary and secondary alcohols to aldehydes and ketones with air as an oxidant was reported. The oxidation shows broad substrate scope and excellent selectivity over benzylic alcohols to the aliphatic alcohols. Further mechanistic studies revealed a quinuclidine mediated HAT process, and blue LEDs promoted 4CzlPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene) photoredox cycle were involved in our oxidation.
- Zhang, Heng,Guo, Tianyun,Wu, Mingzhong,Huo, Xing,Tang, Shouchu,Wang, Xiaolei,Liu, Jian
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supporting information
(2021/02/20)
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- Cobalt Single-Atom-Intercalated Molybdenum Disulfide for Sulfide Oxidation with Exceptional Chemoselectivity
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The identification of chemoselective oxidation process en route to fine chemicals and specialty chemicals is a long-standing pursuit in chemical synthesis. A vertically structured, cobalt single atom-intercalated molybdenum disulfide catalyst (Co1-in-MoS2) is developed for the chemoselective transformation of sulfides to sulfone derivatives. The single-atom encapsulation alters the electron structure of catalyst owing to confinement effect and strong metal–substrate interaction, thus enhancing adsorption of sulfides and chemoselective oxidation at the edge sites of MoS2 to achieve excellent yields of up to 99% for 34 examples. The synthetic scopes can be extended to sulfide-bearing alkenes, alkynes, aldehydes, ketones, boronic esters, and amines derivatives as a toolbox for the synthesis of high-value, multifunctional sulfones and late-stage functionalization of pharmaceuticals, e.g., Tamiflu. The synthetic utility of cobalt single atom-intercalated MoS2, together with its reusability, scalability, and simplified purification process, renders it promising for industrial productions.
- Chen, Zhongxin,Liu, Cuibo,Liu, Jia,Li, Jing,Xi, Shibo,Chi, Xiao,Xu, Haisen,Park, In-Hyeok,Peng, Xinwen,Li, Xing,Yu, Wei,Liu, Xiaowang,Zhong, Linxin,Leng, Kai,Huang, Wei,Koh, Ming Joo,Loh, Kian Ping
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- Synthetic method of p-methylsulfonyl benzaldehyde
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The invention relates to a synthetic method of p-methylsulfonyl benzaldehyde. The synthetic method comprises the following steps: 1, adding an aqueous solution of sodium methyl mercaptide, an organicsolvent, p-chlorobenzaldehyde and a phase transfer catalyst, carrying out heating to a temperature of 50-90 DEG C, carrying out a heat-preserved reaction, carrying out standing layering on a reactionproduct after the reaction is finished, taking an organic layer, and removing the organic solvent to obtain p-methylmercaptobenzaldehyde; 2, adding the p-methylmercaptobenzaldehyde obtained in the step 1 and water, controlling a temperature to be 0-20 DEG C, dropwise adding an aqueous peroxyacetic acid solution into a reactor, controlling the temperature to be 0-30 DEG C in the adding process, andcarrying out a heat-preserved reaction at 0-40 DEG C after dropwise adding is finished, then dropwise adding an aqueous sodium hydroxide solution into the reactor to adjust a pH value to 7-12, carrying out suction filtration on a reaction product, taking the obtained solid, rinsing the solid, and drying the solid to obtain an off-white solid which is p-methylsulfonyl benzaldehyde. With the method, product purity can reach 99% or above at a time, secondary refining is not needed, and yield is high.
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Paragraph 0059; 0062; 0063; 0066; 0067; 0070; 0073; 0074
(2020/04/02)
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- A biradical oxo-molybdenum complex containing semiquinone and: o -aminophenol benzoxazole-based ligands
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We report a new mononuclear molybdenum(iv) complex, MoOLBISLSQ, in which LSQ (2,4-di-tert-butyl o-semibenzoquinone ligand) has been prepared from the reaction of the o-iminosemibenzoquinone form of a tridentate non-innocent benzoxazole ligand, LBIS, and MoO2(acac)2. The complex was characterized by X-ray crystallography, elemental analysis, IR and UV-vis spectroscopy and magnetic susceptibility measurements. The crystal structure of MoOLBISLSQ revealed a distorted octahedral geometry around the metal centre, surrounded by one O and two N atoms of LBIS and two O atoms of LSQ. The effective magnetic moment (μeff) of MoOLBISLSQ decreased from 2.36 to 0.2 μB in the temperature range of 290 to 2 K, indicating a singlet ground state caused by antiferromagnetic coupling between the metal and ligand centred unpaired electrons. Also, the latter led to the EPR silence of the complex. Cyclic voltammetry (CV) studies indicate both ligand and metal-centered redox processes. MoOLBISLSQ was applied as a catalyst for the oxidative cleavage of cyclohexene to adipic acid and selective oxidation of sulfides to sulfones with aqueous hydrogen peroxide. This journal is
- Galindo, Agustín,Jagli?i?, Zvonko,Masoumpour, Marzieh Sadat,Nasibipour, Mina,Safaei, Elham,Wojtczak, Andrzej
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p. 40853 - 40866
(2020/11/23)
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- Method for preparing methylsulfonyl benzaldehyde without catalyst
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The invention relates to a novel method for preparing methylsulfonyl benzaldehyde without a catalyst. The method comprises the following steps: taking isobutyraldehyde as a coreduction agent, taking oxygen as an oxidizing agent, and directly oxidizing methylthio benzaldehyde, thereby obtaining the corresponding sulfone. Under the condition that the ratio of n(isobutyraldehyde) to n(methylthio benzaldehyde) is 3.5:1, acetonitrile is selected as a solvent, a reaction is carried out for 40 minutes, the amount of the methylthio benzaldehyde is 1.25*10 mol, the reaction is carried out at a temperature of 50 DEG C and the oxygen flow is 40mL/min, the conversion rate of the methylthio benzaldehyde can reach 99.5%, and the selectivity can reach 98.9%. Compared with other catalytic oxidation methods, the method disclosed by the invention does not need a catalyst and is simple and convenient to operate.
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Paragraph 0012-0026
(2019/10/01)
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- Oxidation of sulfides including DBT using a new vanadyl complex of a non-innocent o-aminophenol benzoxazole based ligand
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Reaction of a non-innocent o-aminophenol benzoxazole based ligand HLBAP with VOCl3 afforded a vanadyl complex, VOLBIS (SQ), in which SQ is a 2,4-di-tert-butylsemiquinone produced from hydrolysis of HLBAP. The crystal structure of VOLBIS (SQ) exhibits an octahedral geometry with the VO2+ center coordinated by two nitrogen and one oxygen atoms of LBAP and two oxygen atoms of SQ. Electrochemical studies showed quasi-reversible metal-centered reduction and ligand-centered oxidation of complex. The magnetic moment of VOLBIS (SQ) is consistent with the spin-only value expected for S?=?1/2 system. The neutral species of VOLBIS (SQ) is EPR active, which is consistent with a paramagnetic electronic ground state (S?=?1/2). This result is in accordance with the vanadyl (IV) moiety surrounded by tridentate iminobenzosemiquinonate anion radical (HLBIS)?- and benzosemiquinone ligand (SQ)?. The theoretical calculations confirm the experimental results. Furthermore, we present the optimal conditions for maximum efficiency of sulfide oxidation for oxidative desulfurization with hydrogen peroxide and 6 times reusability of catalyst for sulfoxidation of dibenzothiophene.
- Saeedi, Roonak,Safaei, Elham,Lee, Yong-Ill,Lu?nik, Janez
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- A Deoximation Method for Deprotection of Ketones and Aldhydes Using a Graphene-Oxide-Based Co-catalysts System
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The deoximation of a wide range of ketoximes and aldoximes to their corresponding carbonyl compounds with high yields has been achieved using graphene oxide (GO) and sodium nitrite (NaNO2) as highly efficient catalysts and air as the green oxidant under mild conditions. The mechanism of deprotection and recycling use of catalyst were revealed in deep experiment. The carboxylic acid groups on the GO were essential for high catalytic activity. (Figure presented.).
- Tong, Qiaolin,Liu, Yang,Gao, Xuezhi,Fan, Zhanfang,Liu, Tianfu,Li, Bo,Su, Dangsheng,Wang, Qinghe,Cheng, Maosheng
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supporting information
p. 3137 - 3145
(2019/05/01)
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- Heterocyclic phosphodiesterase inhibitor and uses thereof
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The present invention belongs to the technical field of medicine, and particularly relates to a heterocyclic phosphodiesterase inhibitor compound represented by a formula (I), or a pharmaceutically acceptable salt and a stereoisomer thereof, and a pharmaceutical preparation, a pharmaceutical composition and applications of the compound, wherein R1, R2, R3, R4, ring A, m and n are defined in the specification. According to the present invention, the compound can be used for preparing drugs for treatment or prevention of diseases associated with PDE9 kinase.
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Paragraph 0149-0153
(2019/11/04)
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- Preparation method of 4-methylsulfonyl benzaldehyde
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The invention discloses a preparation method of 4-methylsulfonyl benzaldehyde. The preparation method of the 4-methylsulfonyl benzaldehyde comprises the following steps: firstly, performing a reactionrepresented by a formula shown in the description on a compound 2 and sodium thiomethoxide in a solvent under the protection of an inert gas and action of a catalyst, mixing the obtained product andwater, performing an oxidation reaction under action of a catalyst, performing crystallization on the product in water, and performing filtration to obtain the target product 4-methylsulfonyl benzaldehyde. The method provided by the invention has simple and short steps, and the raw materials have a low price; the high efficiency heat mass transfer characteristic of a fixed bed reactor is utilized,so that the method is significantly distinguished from a current kettle-type synthetic process; and the high catalytic activity of the catalyst makes 4-(methylmercapto)toluene completely converted, the catalyst can be recycled and reused, the production process is green and environmentally friendly, emission of three waste (waste water, waste gas and solid waste) can be reduce, and the method ismore suitable for industrial production.
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Paragraph 0018; 0021-0023; 0026-0027
(2019/07/29)
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- Highly efficient and practical aerobic oxidation of alcohols by inorganic-ligand supported copper catalysis
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The oxidation of alcohols to aldehydes or ketones is a highly relevant conversion for the pharmaceutical and fine-chemical industries, and for biomass conversion, and is commonly performed using stoichiometric amounts of highly hazardous oxidants. The aerobic oxidation of alcohols with transition metal complex catalysts previously required complicated organic ligands and/or nitroxyl radicals as co-catalysts. Herein, we report an efficient and eco-friendly method to promote the aerobic oxidation of alcohols using an inorganic-ligand supported copper catalyst 1, (NH4)4[CuMo6O18(OH)6], with O2 (1 atm) as the sole oxidant. Catalyst 1 is synthesized directly from cheap and commonly available (NH4)6Mo7O24·4H2O and CuSO4, which consists of a pure inorganic framework built from a central CuII core supported by six MoVIO6 inorganic scaffolds. The copper catalyst 1 exhibits excellent selectivity and activity towards a wide range of substrates in the catalytic oxidation of alcohols, and can avoid the use of toxic oxidants, nitroxyl radicals, and potentially air/moisture sensitive and complicated organic ligands that are not commercially available. Owing to its robust inorganic framework, catalyst 1 shows good stability and reusability, and the catalytic oxidation of alcohols with catalyst 1 could be readily scaled up to gram scale with little loss of catalytic activity, demonstrating great potential of the inorganic-ligand supported Cu catalysts in catalytic chemical transformations.
- Wei, Zheyu,Ru, Shi,Zhao, Qixin,Yu, Han,Zhang, Gang,Wei, Yongge
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supporting information
p. 4069 - 4075
(2019/08/07)
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- A Simple, Mild and General Oxidation of Alcohols to Aldehydes or Ketones by SO2F2/K2CO3 Using DMSO as Solvent and Oxidant
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A practical, general and mild oxidation of primary and secondary alcohols to carbonyl compounds proceeds in yields of up to 99% using SO2F2 as electrophile in DMSO as both the oxidant and the solvent at ambient temperature. No moisture- and oxygen-free conditions are required. Stoichiometric amount of inexpensive K2CO3, which generates easy to separate by-products, is used as the base. Thus, 5-gram scale runs proceeded in nearly quantitative yields by a simple filtration as the work-up. The use of a polar solvent such as DMSO, which usually promotes competing Pummerer rearrangement, is also noteworthy. This protocol is compatible with a variety of common N-, O-, and S-functional groups on (hetero)arene, alkene and alkyne substrates (68 examples). The protocol was applied (99% yield) to a formal synthesis of the important cholesterol-lowering drug Rosuvastatin. (Figure presented.).
- Zha, Gao-Feng,Fang, Wan-Yin,Leng, Jing,Qin, Hua-Li
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supporting information
p. 2262 - 2267
(2019/04/17)
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- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
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supporting information
p. 3190 - 3194
(2019/05/21)
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- Efficient molybdenum catalyzed chemoselective, solvent-free oxidation of sulfides to sulfones at room temperature
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An effcient and reusable molybdenum-based catalyst has been prepared by tethering dioxomolybdenumacetylacetonate complex, MoO2(acac)2, via postsynthesis modifcation of zeolite beta. The catalyst has been characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) and inductively coupled plasma (ICP). The catalyst exhibited very high activity for the selective oxidation of sulfdes to sulfones at room temperature. The catalyst can be recycled and reused four times without signifcant loss of activity.
- Hadigavabar, Ali Dadashi,Tabatabaeian, Khalil,Zanjanchi, Mohammad Ali,Mamaghani, Manouchehr
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p. 3829 - 3833
(2018/05/24)
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- Method for preparing methylsulfonyl benzaldehyde
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The invention discloses a method for preparing methylsulfonyl benzaldehyde. The method comprises the following steps: putting distilled water into sodium methanesulfinate, further adding p-fluorobenzaldehyde, performing a heat-preservation pressure-keeping reaction, and performing vacuum distillation on a product, so as to obtain a product. The method is simple in production process, gentle in reaction condition, high in security, free of other reagent, small in wastewater amount, thereby being small in environment influence, high in product yield and good in quality; in addition, as reactionbyproducts can be recycled or prepared into commodities sold in the market, the production cost is reduced.
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Paragraph 0021-0038
(2018/03/26)
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- Highly practical and efficient preparation of aldehydes and ketones from aerobic oxidation of alcohols with an inorganic-ligand supported iodine catalyst
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Herein, we divulge an efficient protocol for aerobic oxidation of alcohols with an inorganic-ligand supported iodine catalyst, (NH4)5[IMo6O24]. The catalyst system is compatible with a wide range of groups and exhibits high selectivity, and shows excellent stability and reusability, thus serving as a potentially greener alternative to the classical transformations.
- Zhang, Mengqi,Zhai, Yongyan,Ru, Shi,Zang, Dejin,Han, Sheng,Yu, Han,Wei, Yongge
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supporting information
p. 10164 - 10167
(2018/09/13)
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- Catalyst-free oxidation of sulfides to sulfoxides and diethylamine catalyzed oxidation of sulfides to sulfones using Oxone as an oxidant
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Abstract: We describe here our journey from the failure of our attempts in controlled oxidation of sulfides to sulfoxides using an Oxone–KBr combination to our success in the development of a catalyst-free protocol for the oxidation of sulfides to sulfoxides using Oxone as an oxidant. We also describe the failure of our attempts at the oxidation of sulfides to sulfones using an excess of Oxone–KBr as well as Oxone, and our success towards the development of a rapid, scalable and chromatography-free protocol for the oxidation of sulfides to sulfones using diethylamine–Oxone as an unprecedented catalyst–oxidant combination.
- Kupwade,Khot,Lad,Desai,Wadgaonkar
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p. 6875 - 6888
(2017/10/06)
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- 1,1,2,2-Tetrahydroperoxy-1,2-diphenylethane as new oxidant for chemoselective and catalyst free oxidation of sulfides to sulfoxides and sulfones
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A catalyst free and chemoselective oxidation of sulfides to sulfoxides or sulfones was developed using 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane as a new oxidant. This scope has shown the achievement of various sulfoxides and sulfones which were obtained selectively in high yields at room temperature.
- Khosravi, Kaveh,Naserifar, Shirin,Mahmoudi, Boshra,Khalaji, Kobra
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p. 316 - 321
(2017/02/18)
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- Preparation method of p-methylsulfonyl benzaldehyde
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The invention relates to a preparation method of p-methylsulfonyl benzaldehyde. The preparation method includes: dissolving p-methylsulfonyl methylbenzene and a catalyst in water; mixing for reaction to obtain p-methylsulfonyl benzaldehyde, wherein the catalyst is 1, 4-dichloro-1, 4-diazacyclo [2, 2, 2] octane. The preparation method has the advantages of simplicity, easiness in operation, suitability for large-scale industrial production and high economic benefit.
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Paragraph 0043; 0050; 0051; 0059; 0068-0076
(2017/08/29)
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- Synthetic method of methylsulfonyl benzaldehyde
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The invention provides a synthetic method of methylsulfonyl benzaldehyde. The synthetic method specifically comprises the following steps: 1) adding p-toluene sulfonic acid, azodiisobutyronitrile and orthodichlorobenzene into a reactor, firstly, introducing nitrogen to replace, stirring the mixture and raising the temperature to 30-60 DEG C, and introducing chlorine, wherein methyl p-tolyl sulfone bichloride is mainly generated by equipment monitoring; and 2) in the reactor, adding water or a diluted acid and heating the mixture to 30-80 DEG C, then adding the methyl p-tolyl sulfone bichloride solution obtained in the step 1) and having temperature of 30-80 DEG C into the reactor, stirring and heating the mixture to 90-105 DEG C, keeping the temperature till hydrolysis is finished, after performing suction filtration to obtain a methylsulfonylbenzaldehyde coarse product, pulping the product with water, adjusting the pH to about weakly alkaline, and performing suction filtration to obtain the methylsulfonyl benzaldehyde. According to the synthetic method provided by the invention, the reaction yield is increased, the total yield reaches 85%, the product purity reaches 99.0%, and the cost of raw materials is greatly lowered; in addition, energy consumption and three waste emission are reduced, and the synthetic method is more suitable for industrial production.
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Paragraph 0015; 0018; 0020; 0022
(2017/08/29)
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- Synthesis of Aldehydes by Organocatalytic Formylation Reactions of Boronic Acids with Glyoxylic Acid
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Reported herein is a conceptually novel organocatalytic strategy for the formylation of boronic acids. New reactivity is engineered into the α-amino-acid-forming Petasis reaction occurring between aryl boronic acids, amines, and glyoxylic acids to prepare aldehydes. The operational simplicity of the process and its ability to generate structurally diverse and valued aryl, heteroaryl, and α,β-unsaturated aldehydes containing a wide array of functional groups, demonstrates the practical utility of the new synthetic strategy.
- Huang, He,Yu, Chenguang,Li, Xiangmin,Zhang, Yongqiang,Zhang, Yueteng,Chen, Xiaobei,Mariano, Patrick S.,Xie, Hexin,Wang, Wei
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supporting information
p. 8201 - 8205
(2017/06/30)
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- Visible-Light-Promoted Nickel- and Organic-Dye-Cocatalyzed Formylation Reaction of Aryl Halides and Triflates and Vinyl Bromides with Diethoxyacetic Acid as a Formyl Equivalent
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A simple formylation reaction of aryl halides, aryl triflates, and vinyl bromides under synergistic nickel- and organic-dye-mediated photoredox catalysis is reported. Distinct from widely used palladium-catalyzed formylation processes, this reaction proceeds by a two-step mechanistic sequence involving initial in situ generation of the diethoxymethyl radical from diethoxyacetic acid by a 4CzIPN-mediated photoredox reaction. The formyl-radical equivalent then undergoes nickel-catalyzed substitution reactions with aryl halides and triflates and vinyl bromides to form the corresponding aldehyde products. Significantly, besides aryl bromides, less reactive aryl chlorides and triflates and vinyl halides serve as effective substrates for this process. Since the mild conditions involved in this reaction tolerate a plethora of functional groups, the process can be applied to the efficient preparation of diverse aromatic aldehydes.
- Huang, He,Li, Xiangmin,Yu, Chenguang,Zhang, Yueteng,Mariano, Patrick S.,Wang, Wei
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supporting information
p. 1500 - 1505
(2017/02/05)
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- A chemoselective oxidation of sulfides to sulfoxides and sulfones using urea-2,2-dihydroperoxypropane as a novel oxidant
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Background: Sulfoxides and sulfones have been in the center of attention due to their wide range of promises in various approaches. The functional groups presented in these compounds serve as important building blocks in numerous natural, pharmeceutical and agricultural compounds. These deriatives have been prepared through a multitude of routes which were accompanied by several drawbacks. Therefore, there has been an ever-increasing interest to find a new methodology that leads to the production of these compounds via an environmentally benign path bringing about high yields. Recently, gem-dihydroperoxides have attracted much attention due to their oxidizing power and they have been utilized in several oxidation processes. Methods: We carried out a chemoselective oxidation of sulfides to sulfoxides and sulfones on treatment with urea-2,2-dihydroperoxypropane, a solid oxidant composed of equal amounts of 2,2-dihydroperoxypropane and urea, using THF as the solvent under catalyst-free conditions at room temprature. Results: Sulfides possessing a variety of substitutions namely dialkyl, diaryl, ally l and alkyl-aryl were subjected to the optimized reaction conditions and they could successfully afford different amounts of sulfoxides and sulfones depending on the amount of the oxidant utilized. Based on the results, electron-donating groups accelerated the reaction while electron-withdrawing substituents lowered the reactivity. Conclusion: Urea-2,2-dihydroperoxypropane as a solid oxidant which can be stored for several months without any loss in its activity has proved its capability to oxidize sulfides to sulfoxides and sulfones under catalyst-free and mild conditions. This approach is a cost-effective and environmentally benign methodology via which the products have been synthesized in high yields and short reaction times.
- Khosravi, Kaveh,Naserifar, Shirin,Asgari, Atefeh
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p. 749 - 756
(2017/02/05)
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- Visible light photocatalysis with CBr4: A highly selective aerobic photooxidation of methylarenes to aldehydes
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A metal-free, operationally simple and efficient means of aerobic photooxidation of methylarenes to aromatic aldehydes at room temperature employing visible light photocatalysis with CBr4 is reported. The reaction is highly selective as it proceeds without any over oxidation to carboxylic acids. The utilisation of visible light and molecular oxygen is inexpensive, readily available, non-toxic and the sustainable reagents make the protocol compatible with green chemistry demands. A plausible mechanism for the formation of aldehydes from methylarenes is also provided.
- Tripathi, Shubhangi,Singh, Sachchida N.,Yadav, Lal Dhar S.
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p. 14547 - 14551
(2016/02/19)
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- Preparation method of p-methylsulfonylphenylserine copper
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The invention provides a preparation method of p-methylsulfonylphenylserine copper. The method comprises the following steps: melting 1 part by weight of p-methylsttlfonyltoluene at 90-120DEG C, and decolorizing by using active carbon; adding 0.001-0.05 parts by weight of a catalyst, heating and stirring the obtained mixture, adding 1.8-3 parts by weight of bromine multiple times at 158-180DEG C under gradual heating, and carrying out heat insulation; slowly adding a complexing agent while stirring, adjusting the pH value of the obtained mixture to 8-10, and reacting at 80-100DEG C; and cooling the obtained material to 40-80DEG C, adjusting the pH value of the cooled material to 8-10, adding 0.1-2.0 parts by weight of glycine and 0.25-2.5 parts by weight of copper sulfate to obtain a light blue product, carrying out pressing filtration at 40-80DEG C, washing the obtained material, and drying the washed material at 80-150DEG C to obtain a finished product. P-methylsulfonylphenylserine copper is prepared through a continuous reaction of p-methylsttlfonyltoluene as a raw material in a same reaction system, so the method has the advantages of high conversion rate, low cost, high product quality and environmental protection.
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- Chlorination of florfenicol (FF): reaction kinetics, influencing factors and by-products formation
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Florfenicol (FF) is a widely used antibiotic, which is commonly found in natural waters. In this study, we investigated the removal fate of FF in two different drinking water treatment plants (DWTPs), which suggest that FF was easily transformed by free available chlorine (FAC) and the potential reactions of FF with FAC was the focus of this study. The oxidation kinetics of FF by FAC (7 × 10?4 mol) are very rapid with large pseudo-first-order rate constants kobs = 0.31 min?1, while FF (5 mg L?1) can be completely transformed in 30 min. The results showed that high Cl? (the dominant seawater constituent), Br?, and lower humic acid (HA, main constituents in freshwater) favor the FF oxidation. 21 degradation products were identified by liquid chromatography-tandems mass spectrometry (LC-MS/MS) and the possible routes for FF chlorination were proposed. These results are of importance toward the goal of assessing the persistence of FF in water chlorination.
- Zhang, Yansen,Shao, Yisheng,Gao, Naiyun,Chu, Wenhai,Chen, Juxiang,Li, Shuo,Wang, Yue,Xu, Shuaixian
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p. 107256 - 107262
(2016/11/25)
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- Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid
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The invention discloses a combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid. The method comprises the following steps: (1) oxidation: a step of continuously introducing substituted toluene, a catalyst and oxygen-contained gas into an oxidation reactor and carrying out reaction so as to obtain oxidation reaction liquid; (2) hydrolyzation: a step of allowing the oxidation reaction liquid to continuously enter a hydrolysis reactor, and continuously adding water into the hydrolysis reactor and carrying out reaction so as to obtain a hydrolysis reaction mixture; (3) liquid-liquid layering: a step of layering the hydrolysis reaction mixture so as to obtain an oil phase and an aqueous phase; and (4) separation of products: a step of subjecting the oil phase to distillation so as to respectively obtain incompletely-reacted substituted toluene, substituted benzyl alcohol and substituted benzaldehyde, and subjecting the aqueous phase to cooling, crystallizing and filtering so as to obtain filtrate and substituted benzoic acid. The combined production method provided by the invention has the advantages of high raw material conversion rate, few by-products, good selectivity of target products, greenness and environmental protection.
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Paragraph 0071; 0072
(2017/01/31)
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- Polyoxomolybdate-Calix[4]arene Hybrid: A Catalyst for Sulfoxidation Reactions with Hydrogen Peroxide
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An easily accessible polyoxomolybdate-calix[4]arene hybrid 1 has been synthesized and applied as a heterogeneous catalyst in the sulfoxidation of thioethers to sulfoxides and to sulfones under strictly stoichiometric amounts of 30% H2O2 in CH3CN as the solvent. This study represents the first promising example of successful employment of calixarenes-polyoxometalate (POM) hybrid materials in the area of catalytic oxidations.
- Meninno, Sara,Parrella, Alessandro,Brancatelli, Giovanna,Geremia, Silvano,Gaeta, Carmine,Talotta, Carmen,Neri, Placido,Lattanzi, Alessandra
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supporting information
p. 5100 - 5103
(2015/11/03)
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- HIV INTEGRASE INHIBITORS
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The present invention features compounds that are HIV integrase inhibitors and therefore are useful in the inhibition of HIV replication, the prevention and/or treatment of infection by HIV, and in the treatment of AIDS and/or ARC.
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- Carbon-supported metal-modified lacunary tungstosilicic polyoxometallates used as catalysts in the selective oxidation of sulfides
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Lacunary tungstosilicic polyoxometallates modified with transition metal ions [SiW11O39M(H2O)]6-, where M = Mn2+, Fe2+, Co2+or Cu2+, were synthesized and supported on activated carbon to obtain the SiW11MC catalysts. The samples were characterized by FT-IR, XRD, N2 adsorption-desorption measurements, and the acidic properties were determined using the isopropanol dehydration test reaction. The activity and selectivity of the catalysts were evaluated in the selective oxidation of a series of sulfides to sulfoxides or sulfone. The reaction was carried out in acetonitrile as solvent using H2O2 35% p/V as a clean oxidant. The conversion values decreased in the following order: SiW11MnC > SiW11FeC > SiW11CuC > SiW11CoC. The catalysts were reused without appreciable loss of their catalytic activity. It was found that the activity of the catalysts decreases in parallel with the increment in the reduction temperature values. The most easily reducible catalyst displayed the highest conversion values. We found a convenient and selective procedure for oxidizing sulfides to sulfoxides or sulfones using aqueous hydrogen peroxide and a catalytic amount of lacunary tungstosilicic polyoxometallates supported on carbon at low temperatures (20-50 °C) in a reasonably short reaction time
- Frenzel, Romina,Sathicq, ángel G.,Blanco, Mirta N.,Romanelli, Gustavo P.,Pizzio, Luis R.
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- A molybdenum based metallomicellar catalyst for controlled and selective sulfoxidation reactions in aqueous medium
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A surfactant based molybdenum system that exhibits catalytic activity for sulfoxidation reactions of various organic sulfides in aqueous medium has been developed and comprehensively characterized using IR, XRD, NMR, ESI-MS, DLS and TEM. The catalyst showcases remarkable selectivity for the preparation of both sulfoxides and sulfones in the range of good to excellent yields. Furthermore, the catalyst showed a high degree of tolerance towards various sensitive functional groups such as hydroxyl, acetal, aldehyde, amine, imine, oxime, cyano and alkene. the Partner Organisations 2014.
- Chakravarthy, Rajan Deepan,Ramkumar, Venkatachalam,Chand, Dillip Kumar
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p. 2190 - 2196
(2014/04/17)
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- Selective synthesis of sulfoxides and sulfones from sulfides using silica bromide as the heterogeneous promoter and hydrogen peroxide as the terminal oxidant
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Silica bromide as a heterogeneous promoter and reagent is prepared from the reaction of silica gel with PBr3as a non-hydroscopic, filterable, cheap, and stable yellowish powder that can be stored for months. The results show that silica bromide is a suitable and efficient promoter for the chemoselective oxidation of sulfides to the corresponding sulfoxides or sulfones in the presence of 30% H2O2in acetonitrile. The excellent yields, heterogeneous conditions, simplicity, compatibility with a variety of functionalities, and ease of isolation of the products make our procedure a practical alternative.
- Maleki, Behrooz,Hemmati, Saba,Sedrpoushan, Alireza,Ashrafi, Samaneh Sedigh,Veisi, Hojat
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p. 40505 - 40510
(2015/02/03)
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- One-pot transformation of methylarenes into aromatic aldehydes under metal-free conditions
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On the basis of studies of the transformation of benzylic bromides into the corresponding aromatic aldehydes by treatment with N-methylmorpholine N-oxide, various methylarenes were treated either with DBDMH in the presence of AIBN in acetonitrile at reflux (Method A) or with NBS in CCl4 under irradiation with a tungsten lamp at 30 °C (Method B), followed by treatment with N-methylmorpholine N-oxide to provide aromatic aldehydes in good yields. These methods could be adopted in one-pot transformations of methylarenes into aromatic aldehydes under conditions free of less toxic reagents and transition metals. Copyright
- Tabata, Masayuki,Moriyama, Katsuhiko,Togo, Hideo
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p. 3402 - 3410
(2014/06/09)
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- TEMPO-mediated oxidation of primary alcohols to aldehydes under visible light and air
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A homogeneous visible light photoredox TEMPO-mediated selective oxidation of primary alcohols to the corresponding carbonyl compounds was developed using molecular oxygen from air as the terminal oxidant. Ru(bpy)3(PF 6)2 (bpy: bipyridyl) and Ir(dtb-bpy)(ppy) 2(PF6) (dtb-bpy: 4,4′-di-tert-butyl-2,2′- bipyridyl; ppy: 2-phenylpyridine) were used as the sensitizers. A homogeneous visible light photoredox TEMPO-mediated selective oxidation of primary alcohols to the corresponding carbonyl compounds was developed. Molecular oxygen from air was the terminal oxidant. Copyright
- Liu, Dongwang,Zhou, Hongxia,Gu, Xiangyong,Shen, Xiaoqin,Li, Pixu
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supporting information
p. 117 - 122
(2014/03/21)
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- Practical organic solvent-free Cu(OAc)2/DMAP/TEMPO-catalyzed aldehyde and imine formation from alcohols under air atmosphere
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A highly efficient and practical organic solvent-free Cu(OAc)2/DMAP/TEMPO catalyst system for the selective aerobic oxidation of benzylic and allylic alcohols to aldehydes and phenones under an ambient air atmosphere was reported. A wide range of functional groups such as phenolic hydroxyl, amino, and methylthio are compatible with the catalyst system. The organic solvent-free aerobic oxidative imine synthesis from benzyl alcohol and amines was also achieved via the newly developed Cu(OAc)2/DMAP/TEMPO catalyst. 100 g-scale reactions for aldehyde and imine formation were achieved with over 90% yield using 0.5 mol% catalyst loading in 36 hours, presenting a potential valuable protocol for both economical and environmental considerations. This journal is
- Guan, Mingyu,Wang, Chao,Zhang, Jingyu,Zhao, Yingsheng
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p. 48777 - 48782
(2014/12/10)
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- Chiral resolution of racemic p-methylsulfonylphenyl serine ethyl ester with lipases: The mechanism of side reaction and its suppression
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The d-threo form of p-methylsulfonylphenyl serine ethyl ester (MPSE) is a key intermediate for the synthesis of florfenicol. In this study, chiral resolution of dl-threo-p-MPSE with lipases was investigated. Among a series of lipases, Novzyme 435 was the best to resolve dl-threo-p-MPSE with the conversion rate of 36.83% and ee value of 35.13%. To improve the conversion rate and ee value, a number of byproducts were identified and characterized using reverse-phase HPLC, normal-phase HPLC, 1H NMR, and LC-MS when threo-p-MPSE was hydrolyzed by lipases in organic medium. Mechanisms of generating main byproducts are proposed, and a suppressing method is provided. The results showed that byproduct p-methylsulfonyl benzaldehyde serves as the key intermediate during the whole side reaction process. It was also observed that threo-p-MPSE with a proper hydrolytic velocity served as a driving force to generate p-methylsulfonyl benzaldehyde and accelerated the side reactions. Finally, a feasible approach to suppress side reactions in enzymatic catalysis is offered. The conversion rate and ee value were greatly improved by 69.29 and 46.26%, respectively, using Zn2+ compared to those without Zn 2+.
- Guo, Rui,Fan, Yong-Xian,Chen, Xiao-Long,Shen, Yin-Chu
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p. 157 - 166
(2013/03/29)
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- Solvent-free chemoselective oxidation of thioethers and thiophenes by mechanical milling
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Organosulphur compounds can be easily and selectively oxidized to sulfones using a small excess of Oxone (1.6 eq.) under solventless mechanical milling conditions. This green procedure has been efficiently applied to a series of model compounds and to the desulphurization of medium/high sulphur content paraffins (up to 3000 mg kg-1).
- Cravotto, Giancarlo,Garella, Davide,Carnaroglio, Diego,Gaudino, Emanuela Calcio,Rosati, Ornelio
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p. 11632 - 11634,3
(2012/12/12)
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- Development of isoform selective PI3-kinase inhibitors as pharmacological tools for elucidating the PI3K pathway
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Using a parallel synthesis approach to target a non-conserved region of the PI3K catalytic domain a pan-PI3K inhibitor 1 was elaborated to provide alpha, delta and gamma isoform selective Class I PI3K inhibitors 21, 24, 26 and 27. The compounds had good cellular activity and were selective against protein kinases and other members of the PI3K superfamily including mTOR and DNA-PK.
- Bruce, Ian,Akhlaq, Mohammed,Bloomfield, Graham C.,Budd, Emma,Cox, Brian,Cuenoud, Bernard,Finan, Peter,Gedeck, Peter,Hatto, Julia,Hayler, Judy F.,Head, Denise,Keller, Thomas,Kirman, Louise,Leblanc, Catherine,Grand, Darren Le,McCarthy, Clive,O'Connor, Desmond,Owen, Charles,Oza, Mrinalini S.,Pilgrim, Gaynor,Press, Nicola E.,Sviridenko, Lilya,Whitehead, Lewis
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scheme or table
p. 5445 - 5450
(2012/09/22)
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- Keggin heteropolycompounds as catalysts for liquid-phase oxidation of sulfides to sulfoxides/sulfones by hydrogen peroxide
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H4PMo11VO40, H5PMo 10V2O40 and H9PMo6V 6O40 acids and an acidic pyridinium salt of H 4PMo11VO40 were synthesized. They were characterized by FT-IR and the variations of their acid properties were determined by titration with n-butylamine. They proved to be highly active and selective catalysts for the hydrogen peroxide oxidation of methyl phenyl sulfide to the corresponding sulfoxide or sulfone. The conversion and selectivity results may be explained in terms of the co-existence of acidic and oxidative properties in the catalysts. On the other hand, a convenient catalytic homogeneous procedure has been found to oxidize different sulfides to sulfoxides or sulfones, with 35% aqueous H2O2, using (PyH)H 3PMo11VO40 as catalyst. The oxidation reaction is carried out at room temperature for sulfoxides or 40 °C for sulfones and requires a short time. The sulfoxides or sulfones were obtained with excellent yields by controlling the amount of H2O2.
- Romanelli, Gustavo P.,Villabrille, Paula I.,Cáceres, Cármen V.,Vázquez, Patricia G.,Tundo, Pietro
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p. 726 - 730
(2013/01/09)
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- Preparation and reactivity of polystyrene-supported iodosylbenzene sulfate: An efficient recyclable oxidizing system
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A new polymer-supported hypervalent iodine reagent, polystyrene-supported iodosylbenzene sulfate (PS-IBS), can be conveniently prepared by the reaction of polystyrene-supported (diacetoxyiodo)benzene (PS-DIB) with sodium bisulfate monohydrate under solvent-free conditions. This new recyclable reagent effects clean and efficient oxidation of a wide range of alcohols and sulfides to the corresponding carbonyl compounds or sulfoxides in high conversions under mild conditions. The final products are conveniently separated from the polymeric byproduct by simple filtration and isolated in good purity after evaporation of solvent. Recycling of the resin is possible with minimal loss of activity after several reoxidations.
- Chen, Jiang-Min,Zeng, Xiao-Mei,Zhdankin, Viktor V.
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experimental part
p. 2771 - 2774
(2010/12/25)
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- Simple and Friendly Sulfones Synthesis Using Aqueous Hydrogen Peroxide with a Reusable Keggin Molybdenum Heteropolyacid, Immobilized on Aminopropyl-Functionalized Silica
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Keggin molybdenum heteropolyacid (H3PMo12O 40), immobilized on aminopropyl-functionalized silica catalysts, were made using two immobilization methods: incipient wetness and equilibrium adsorption. The material prepared for the equilibrium adsorption technique was found to be a highly efficient, ecofriendly, and recyclable heterogeneous catalyst for the selective oxidation of sulfides to sulfones in excellent yields, under mild reaction condition using 35% w/v aqueous hydrogen peroxide as the oxidant.
- Palermo, Valeria,Romanelli, Gustavo P.,Vazquez, Patricia G.
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scheme or table
p. 3258 - 3268
(2010/04/26)
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