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A new exploration towards aminothiazolquinolone oximes as potentially multi-targeting antibacterial agents: Design, synthesis and evaluation acting on microbes, DNA, HSA and topoisomerase IV
This work did a new exploration towards aminothiazolquinolone oximes as potentially multi-targeting antimicrobial agents. A class of novel hybrids of quinolone, aminothiazole, piperazine and oxime fragments were designed for the first time, conveniently synthesized as well as characterized by 1H NMR, 13C NMR and HRMS spectra. Biological activity showed that some of the synthesized compounds exhibited good antimicrobial activities in comparison with the reference drugs. Especially, O-methyl oxime derivative 10b displayed excellent inhibitory efficacy against MRSA and S. aureus 25923 with MIC values of 0.009 and 0.017 mM, respectively. Further studies indicated that the highly active compound 10b showed low toxicity toward BEAS-2B and A549 cell lines and no obvious propensity to trigger the development of bacterial resistance. Quantum chemical studies have also been conducted and rationally explained the structural features essential for activity. The preliminarily mechanism exploration revealed that compound 10b could not only exert efficient membrane permeability by interfering with the integrity of cells, bind with topoisomerase IV–DNA complex through hydrogen bonds and π-π stacking, but also form a steady biosupramolecular complex by intercalating into DNA to exert the efficient antibacterial activity. The supramolecular interaction between compound 10b and human serum albumin (HSA) was a static quenching, and the binding process was spontaneous, where hydrogen bonds and van der Waals force played vital roles in the supramolecular transportation of the active compound 10b by HSA.
Wang, Liang-Liang,Battini, Narsaiah,Bheemanaboina, Rammohan R. Yadav,Ansari, Mohammad Fawad,Chen, Jin-Ping,Xie, Yun-Peng,Cai, Gui-Xin,Zhang, Shao-Lin,Zhou, Cheng-He
p. 166 - 181
(2019)
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A Novel Method for Preparation of 2-Chloro Enesulfonamides
A novel method for the synthesis of 2-chloro enesulfonamides via the one-pot addition-elimination of N-chloro-N-fluorobenzenesulfonamides (CFBSA) to styrenes in the presence of Et3N is described. A total of 20 examples are presented to illustrate this concept including various of styrenes.
Zhao, Haiyong,Pu, Xiaoqiu,Yang, Xianjin
p. 1417 - 142
(2017)
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Straightforward Synthesis of α-Chloromethylketimines Catalyzed by Gold(I). A Clean Way to Building Blocks
α-Chloromethylketimines have been obtained through a gold-catalyzed hydroamination of aromatic and aliphatic 1-chloroalkynes with aromatic amines by using equimolar amounts of both reagents. This procedure has allowed the preparation and spectroscopic characterization of α-chloromethylketimines for the first time with a high degree of purity, complete conversion, and atom economy. The synthetic usefulness of the methodology has been demonstrated with the preparation of β-chloroamines and indoles.
Asensio, Gregorio,Cárcel, María,Olmos, Andrea,Ramírez De Arellano, Carmen,Sarmiento, Jeymy T.,Varea, Teresa
p. 3114 - 3122
(2022/03/14)

Tris-(2-pyridylmethyl)amine-ligated Cu(II) 1,3-diketonate complexes: Anaerobic retro-Claisen and dehalogenation reactivity of 2-chloro-1,3-diketonate derivatives
We report synthetic, structural and reactivity investigations of tris-(2-pyridylmethyl)amine (TPA)-ligated Cu(ii) 1,3-diketonate complexes. These complexes exhibit anaerobic retro-Claisen type C-C bond cleavage reactivity which exceeds that found in analo
Elsberg, Josiah G. D.,Anderson, Stephen N.,Tierney, David L.,Reinheimer, Eric W.,Berreau, Lisa M.
p. 1712 - 1720
(2021/02/22)

Facile Synthesis of α-Haloketones by Aerobic Oxidation of Olefins Using KX as Nonhazardous Halogen Source
An operationally simple and safe synthesis of α-haloketones using KBr and KCl as nonhazardous halogen sources is reported. It involves an iron-catalysed reaction of alkenes with KBr/KCl using O2 as terminal oxidant under the irradiation of visible-light. This strategy avoids the risks associated with handling halo-contained electrophiles (Cl2, Br2, NCS, NBS). The process is tolerant to several functional groups, and extended to a range of substituted styrenes in up to 89% yield. A radical reaction pathway is proposed based on control experiments and spectroscopy studies.
Luo, Zhibin,Meng, Yunge,Gong, Xinchi,Wu, Jie,Zhang, Yulan,Ye, Long-Wu,Zhu, Chunyin
supporting information
p. 173 - 177
(2020/01/02)

A N - [2 - hydroxy -2 - (4 - methoxyphenyl) ethyl] cinnamic amide synthesis method (by machine translation)
The present invention provides a N - [2 - hydroxy - 2 - (4 - methoxyphenyl) ethyl] cinnamic amide synthesis method, the method is to methoxy acetophenone as the starting material, through chlorination reaction, azide reaction, condensation reaction by the reaction of reduction. The invention available reaction raw materials, the reaction process is simple in operation, reaction low equipment requirements, relatively mild reaction conditions, yield, the content is high, the final resulting N - [2 - hydroxy - 2 - (4 - methoxyphenyl) ethyl] cinnamide of liquid phase HPLC purity is greater than 99%. (by machine translation)
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Paragraph 0044-0046; 0052-0054; 0060-0062

(2019/01/21)

Iodine-DMSO-promoted divergent reactivities of arylacetylenes
An unprecedented set of efficient, economical, atom-economic and exceedingly selective I2-DMSO-promoted methods is described for the generation of different structures. The reaction represents the first of its kind, involving the use of different iodine concentrations, temperatures, acids and salt to adjust the selectivity for the synthesis of different alkenes, α-functionalized ketones and α-ketomethylthioesters.
Rather, Suhail A.,Kumar, Atul,Ahmed, Qazi Naveed
supporting information
p. 4511 - 4514
(2019/04/26)

The Mn-catalyzed paired electrochemical facile oxychlorination of styrenes: Via the oxygen reduction reaction
Reported herein is the electrochemical engendering of chlorine radicals by a manganese catalyst with a controllable pattern, and inexpensive MgCl2 as the chlorine source. In combination with the oxygen reduction reaction, chloroacetophenones were synthesized with abundant styrene as the feedstock in good to excellent yields.
Tian, Siyu,Jia, Xiaofei,Wang, Ling,Li, Baoying,Liu, Siyuan,Ma, Li,Gao, Wei,Wei, Yingqin,Chen, Jianbin
supporting information
p. 12104 - 12107
(2019/10/14)

CV-driven Optimization: Cobalt-Catalyzed Electrochemical Expedient Oxychlorination of Alkenes via ORR
Instead of screening reaction conditions by yield-based chemical trial-and-error, potential-based cyclic voltammetry was alternatively employed for optimization of electrochemical oxychlorination of alkenes. With this unconventional screening method, the catalyst system including catalysts, molar ratio of chloride sources and solvents were identified in a rational, time- and energy-efficient manner. The optimal catalytic system in combination with oxygen reduction reaction enabled broad substrate scopes for the desired transformation by taking advantages of persistent radical effect. UV-vis and CV titration experiments confirmed the in-situ formed catalytic species [CoCl5]. Moreover, cyclic voltammetry was applied to obtain mechanistic insights in our reaction system. (Figure presented.).
Tian, Siyu,Lv, Shide,Jia, Xiaofei,Ma, Li,Li, Baoying,Zhang, Guofeng,Gao, Wei,Wei, Yingqin,Chen, Jianbin
supporting information
p. 5626 - 5633
(2019/11/22)

Iridium-Catalyzed Asymmetric Hydrogenation of Halogenated Ketones for the Efficient Construction of Chiral Halohydrins
Iridium-catalyzed asymmetric hydrogenation of prochiral halogenated ketones was successfully developed to prepare various chiral halohydrins with high reactivities and excellent enantioselectivities under basic reaction condition (up to >99% conversion, 99% yield, >99% ee). Moreover, gram-scale experiment was performed well in the presence of just 0.005 mol% (S/C=20 000) Ir/f-amphox catalyst with 99% yield and >99% ee. (Figure presented.).
Yin, Congcong,Wu, Weilong,Hu, Yang,Tan, Xuefeng,You, Cai,Liu, Yuanhua,Chen, Ziyi,Dong, Xiu-Qin,Zhang, Xumu
supporting information
p. 2119 - 2124
(2018/04/30)

Cascade Trisulfur Radical Anion (S3?-) Addition/Electron Detosylation Process for the Synthesis of 1,2,3-Thiadiazoles and Isothiazoles
Trisulfur radical anion (S3?-) mediated reactions with in situ formed azoalkenes and α,β-usaturated N-sulfonylimines for the construction of 1,2,3-thiadiazoles and isothiazoles has been developed. S3?- is in situ generated from potassium sulfide in DMF. These two approaches provide a new, safe, and simple way to construct 4-subsituted 1,2,3-thiadiazoles, 5-subsituted 1,2,3-thiadiazoles, and isothiazole in good yields. The reactions include the formation of the new C-S and N-S bonds via S3?- addition and electron detosylation under mild conditions.
Liu, Bei-Bei,Bai, Hui-Wen,Liu, Huan,Wang, Shun-Yi,Ji, Shun-Jun
p. 10281 - 10288
(2018/07/25)

Facile and efficient preparation of α-halomethyl ketones from α-diazo ketones catalyzed by iron(III) halides and silica gel
An efficient and mild method for the synthesis of α-halomethyl ketones from α-diazo ketones was developed using ferric chloride or bromide as the halogen source and silica gel as the hydrogen source, with good to excellent yields.
Shi, Xinxia,Zhang, Lingqiong,Yang, Pengfei,Sun, Han,Zhang, Yilan,Xie, Chunsong,Ou-yang, Zhen,Wang, Min
supporting information
p. 1200 - 1203
(2018/03/08)

Systematic Synthesis of Diphenyl-Substituted Carotenoids as Molecular Wires
A general method for the construction of diphenyl-substituted carotenoids has been developed through the stereoselective synthesis of dienyl sulfones with a phenyl substituent. Systematic synthetic pathways to the dienyl sulfones were delineated starting from readily available acetophenones with para-substituent X of various electronic natures, which provided the carotenoids with diverse physicochemical characteristics. The sulfone olefination method together with the Ramberg–B?cklund reaction produced a 9,9′-cis-10,10′-diphenylcarotene and all-trans-9,9′-diphenylcarotenes. Conductance measurements of the all-trans carotenoids by the scanning tunnelling microscopy break-junction method revealed a positional effect of the phenyl groups as well as a polar effect of the phenyl substituent X according to the electronic nature.
Lim, Boram,Oh, Eun-Taek,Im, JongOne,Lee, Kyu Sang,Jung, Hyunuk,Kim, Minsoo,Kim, Dahye,Oh, Jung Taek,Bae, Sung-Hee,Chung, Wook-Jin,Ahn, Kwang-Hyun,Koo, Sangho
p. 6390 - 6400
(2017/12/01)

A Simple and Efficient Method for the Preparation of α-Halogenated Ketones Using Iron(III) Chloride and Iron(III) Bromide as Halogen Sources with Phenyliodonium Diacetate as Oxidant
α-Halogenated ketones are both unique structure moieties existing in biologically natural products and valuable synthetic intermediates for the preparation of functional molecules. An efficient and scalable method for the preparation of α-halogenated ketone using iron (III) chloride and iron (III) bromide as halogen sources with phenyliodonium diacetate as oxidant has been developed, featuring mild reaction conditions, environmentally friendly reagents, and wide substrate scope. Notably, the three-step synthesis of drug prasugrel was achieved using this developed method as a key step with 30% yield on gram-scale. Additionally, the reaction mechanism involving chloride cation was proposed based on some preliminary control experiments. (Figure presented.).
Tang, Shi-Zhong,Zhao, Wenshuang,Chen, Tao,Liu, Yang,Zhang, Xiao-Ming,Zhang, Fu-Min
supporting information
p. 4177 - 4183
(2017/12/18)

Simple synthesis of 3-hydroxyquinolines via Na2S2O4-mediated reductive cyclization of (2-(2-nitrophenyl)oxiran-1-yl)(aryl)methanones (o-nitrobenzalacetophenone oxides)
An efficient sodium dithionite (Na2S2O4)-mediated method for construction of 3-hydroxyquinolines via in situ Meinwald rearrangement/intramolecular reductive cyclization of o-nitrobenzalacetophenone oxides has been developed. The practical approach is of excellent functional group compatibility with as high as 98% yield under mild reaction conditions. Moreover, further manipulation successfully furnished 4-bromo substituted derivatives which may provide a promising potential application in exploring biologically active analogs of 3-hydroxyquinolines.
Mamedov, Vakhid A.,Mamedova, Vera L.,Syakaev, Victor V.,Korshin, Dmitry E.,Khikmatova, Gul'naz Z.,Mironova, Ekaterina V.,Bazanova, Olga B.,Rizvanov, Il'dar Kh.,Latypov, Shamil K.
p. 5082 - 5090
(2017/07/28)

Metal-free hydration of aromatic haloalkynes to α-halomethyl ketones
A highly regioselective and efficient metal-free hydration of aromatic haloalkynes to α-halomethyl ketones using cheap tetrafluoroboric acid as catalyst is described. The protocol is conducted under convenient conditions and affords products in good to excellent yields, with broad substrate scope, including a variety of aromatic alkynyl chlorides, alkynyl bromides, and alkynyl iodides.
Ye, Min,Wen, Yuelu,Li, Huifang,Fu, Yejuan,Wang, Qinghao
supporting information
p. 4983 - 4986
(2016/10/21)

A novel acid-catalyzed rearrangement of 2-substituted-3-(2-nitrophenyl)oxiranes for the synthesis of di- and mono-oxalamides
A novel one-pot synthetic approach to N1-(2-carboxyaryl)-N2-(aryl or H)oxalamides from 3-(2-nitroaryl)oxirane-2-carboxamides via the classical Meinwald rearrangement and a new rearrangement sequence has been developed. The methodology is applicable to the synthesis of N-(2-carboxyphenyl)aryloxalmonoamides from (3-(2-nitrophenyl)oxiran-2-yl)(aryl)methanones. The method is operationally simple and high yielding, thus providing a new useful formula for both anthranilic acid derivatives and oxalamides.
Mamedov, Vakhid A.,Mamedova, Vera L.,Khikmatova, Gul'Nas Z.,Mironova, Ekaterina V.,Krivolapov, Dmitry B.,Bazanova, Olga B.,Chachkov, Denis V.,Katsyuba, Sergey A.,Rizvanov, Il'Dar Kh,Latypov, Shamil K.
p. 27885 - 27895
(2016/03/30)

Laboratory-Scale Membrane Reactor for the Generation of Anhydrous Diazomethane
A configurationally simple and robust semibatch apparatus for the in situ on-demand generation of anhydrous solutions of diazomethane (CH2N2) avoiding distillation methods is presented. Diazomethane is produced by base-mediated decomposition of commercially available Diazald within a semipermeable Teflon AF-2400 tubing and subsequently selectively separated from the tubing into a solvent- and substrate-filled flask (tube-in-flask reactor). Reactions with CH2N2 can therefore be performed directly in the flask without dangerous and labor-intensive purification operations or exposure of the operator to CH2N2. The reactor has been employed for the methylation of carboxylic acids, the synthesis of α-chloro ketones and pyrazoles, and palladium-catalyzed cyclopropanation reactions on laboratory scale. The implementation of in-line FTIR technology allowed monitoring of the CH2N2 generation and its consumption. In addition, larger scales (1.8 g diazomethane per hour) could be obtained via parallelization (numbering up) by simply wrapping several membrane tubings into the flask.
Dallinger, Doris,Pinho, Vagner D.,Gutmann, Bernhard,Kappe, C. Oliver
p. 5814 - 5823
(2016/07/26)

A novel β-(oxy)alkyl radical during copper(I)-mediated stereoselective synthesis of (Z)-ene-1,4-diones in a reaction of 2,2,2-trichloro-1-phenylethanone
A novel β-(oxy)alkyl radical derived from trichloro methyl compound containing neither a suitably located C-C multiple bond nor a leaving group or a H-atom at the β-position of the radical in a reaction of 2,2,2-trichloro-1-phenyl-ethanone with 2 mol equiv each of CuCl and bpy in refluxing DCE under a N2 atm underwent intramolecular heterolysis (just like formation of intact radical cation-anion pair) during stereoselective radical dimerization to Z-ene-1,4-dione along with small amount of reductive dechlorination product. The stereochemistry was established by X-ray diffraction spectroscopy of various solid crystalline products.
Ram, Ram N.,Tittal, Ram K.
supporting information
p. 2437 - 2440
(2016/05/19)

High-yielding aqueous synthesis of chloroacetophenones and aroyl chlorohydrins
The use of large amounts of volatile organic solvents in industrial chemical processes contributes to widespread environmental pollution. To help solve this problem, water and a phase transfer catalyst were used to replace organic solvents in the transformations of bromoacetophenones into chloroacetophenones and aroyl epoxides into aroyl chlorohydrins. The reactions were promoted by sulfonyl chlorides and gave quantitative or close to quantitative yields. Notably, chromatographic purification, which is laborious and consumes large amounts of organic solvents, was not needed. These two processes have opened a green and cost-effective channel to prepare the chemical intermediates chloroacetophenones and aroyl chlorohydrins. The reaction mechanisms are discussed based on control experiments.
Zhang, Xixi,Liu, Lei,Li, Chunbao
p. 25339 - 25345
(2016/03/22)

Fabrication of covalently functionalized mesoporous silica core-shell magnetite nanoparticles with palladium(II) acetylacetonate: Application as a magnetically separable nanocatalyst for Suzuki cross-coupling reaction of acyl halides with boronic acids
We report the preparation of supported palladium(II) acetylacetonate, Pd(acac)2, coordinated by pendant acac groups, by reacting palladium acetate with acac-functionalized doubly silica-coated magnetic nanoparticles. The solid support consists of an amorphous silica-coated (as magnetite protecting layer) magnetite core and a mesoporous silica shell. The magnetically separable palladium nanocatalyst is active for Suzuki cross-coupling reaction of acyl halides with boronic acids. The catalyst is simply isolated from the reaction mixture that allows fast and efficient isolation of product and catalyst compared to traditional methods that generally make use of time- and solvent-consuming procedures.
Hajipour, Abdolreza,Azizi, Ghobad
p. 247 - 253
(2015/03/30)

Vanadium-catalyzed chlorination under molecular oxygen
A catalytic chlorination of ketones was performed by using a vanadium catalyst in the presence of Bu4NI and AlCl3 under atmospheric molecular oxygen. This catalytic chlorination could be applied to the chlorination of alkenes to give the corresponding vic-dichlorides. AlCl3 was found to serve as both a Lewis acid and a chloride source to induce the facile chlorination. A combination of Bu4NI and AlI3 in the presence of a vanadium catalyst under atmospheric molecular oxygen induced the iodination of ketones.
Moriuchi, Toshiyuki,Fukui, Yasuhiro,Kato, Satoshi,Kajikawa, Tomomi,Hirao, Toshikazu
p. 177 - 180
(2015/03/04)

Photochemical reactions of halogenated aromatic 1,3-diketones in solution studied by steady state, one- and two-color laser flash photolyses
Photochemical processes of 4-tert-butyl-4′-methoxydibenzoylmethane (Avobenzone, AB), 4-phenylbenzoylbenzoyl-, 4-phenylbenzoyl-2′-furanyl- and 4-phenylbenzoyl-2′-thenoylmethanes (PB@Ph, PB@F and PB@T, respectively) substituted with Br and Cl at the C2 position were studied by stationary and laser flash photolyses in solution. The absorption spectral features showed that the molecular structures of the halogenated diketones are in the keto forms while those of halogen-free diketones are in the enol forms. The excited singlet and triplet state energies were determined from the absorption and emission spectra. From the absorption spectral changes upon steady state photolysis of brominated diketones in ethanol, the corresponding halogen-free diketones were formed due to Br elimination being the major photochemical process. The determined quantum yields for the formation of the halogen-free diketones were independent of the amount of dissolved oxygen, indicating that the elimination process is an event in the excited singlet (S1) states. In contrast, from the observed absorption spectra obtained upon photolysis of chlorinated AB and PB@Ph, it was inferred that Norrish type I is the major photochemical reaction in the S1 states in acetonitrile. Chlorinated PB@F and PB@T were found to undergo Cl elimination in the S1 states in cyclohexane to form the corresponding halogen-free diketones. Laser photolysis studies of brominated AB in acetonitrile and ethanol provided a transient absorption spectrum ascribable to the Avobenzone radical (ABR) produced by debromination as the initial intermediate, followed by the AB formation in ethanol. The quenching rate constant of ABR by ethanol and the quantum yield of the AB formation via ABR were determined. These observations provided evidence that H-atom abstraction of ABR from ethanol is responsible for the AB formation. Conversely, laser flash photolysis of brominated and chlorinated PB@Ph, PB@F and PB@T demonstrated the formation of the triplet-triplet absorption spectra. No chemical reactions were found to occur in the triplet (T1) states. Two-color two-laser photolysis studies were carried out on the T1 state of chlorinated PB@Ph, PB@F and PB@T, resulting in the formation of the corresponding halogen-free diketones. These observations confirmed the occurrence of Cl elimination in the highly excited triplet (Tn, n ≥ 2) states. Based on the computed bond dissociation energies for the C-halogen and C-C bonds, switching mechanisms of dehalogenation and α-cleavage were discussed.
Yamaji, Minoru,Suwa, Yurie,Shimokawa, Rieko,Paris, Cecilia,Miranda, Miguel ángel
p. 1673 - 1684
(2015/09/07)

Green and Efficient: Iron-Catalyzed Selective Oxidation of Olefins to Carbonyls with O2
A mild and operationally simple iron-catalyzed protocol for the selective aerobic oxidation of aromatic olefins to carbonyl compounds is described. Catalyzed by a Fe(III) species bearing a pyridine bisimidazoline ligand at 1 atm of O2, α- and β-substituted styrenes were cleaved to afford benzaldehydes and aromatic ketones generally in high yields with excellent chemoselectivity and very good functional group tolerance, including those containing radical-sensitive groups. With α-halo-substituted styrenes, the oxidation took place with concomitant halide migration to afford α-halo acetophenones. Various observations have been made, pointing to a mechanism in which both molecular oxygen and the olefinic substrate coordinate to the iron center, leading to the formation of a dioxetane intermediate, which collapses to give the carbonyl product. (Chemical Equation).
Gonzalez-De-Castro, Angela,Xiao, Jianliang
supporting information
p. 8206 - 8218
(2015/07/15)

Efficient and fast method for the preparation of Diaryl Ketones at room temperature
Palladium-catalyzed cross-coupling reaction of arylboronic acids with acid chlorides at room temperature under phosphine-free conditions affords the corresponding aromatic ketones in excellent yields within short times. This synthetic method overcomes common disadvantages of Friedel-Crafts acylation procedures and is compatible with both electron-donating and electron-withdrawing substituents on the aryl ring of the acyl chlorides. Georg Thieme Verlag Stuttgart New York.
Hajipour, Abdol Reza,Pourkaveh, Raheleh
p. 1101 - 1105
(2014/05/20)

The α-chlorination of aryl methyl ketones under aerobic oxidative conditions
The novel reaction system air/ammonium nitrate/iodine/hydrochloric acid [air/NH4NO3(cat.)/I2(cat.)/HCl] is introduced as a simple, safe, cheap, efficient and regioselective mediator for the α-chlorination of aryl, heteroaryl and alkyl methyl ketones under aerobic oxidative conditions. The inventive use of a catalytic amount of iodine enabled the moderate to quantitative, regioselective chlorination of a comprehensive scope of different methyl ketone derivatives including those bearing oxidizable heteroatom (S, N) substituents, some of which possess declared potential biological and pharmaceutical activity. Air oxygen under a slight overpressure plays the role of the terminal oxidant catalytically activated by redox cycles of nitrogen oxides released from the catalytic amount of ammonium nitrate (NH4NO3) under acidic conditions of hydrochloric acid (HCl) and co-catalyzed by elemental iodine (I2), which was found to be essential for the high efficiency of the reaction system.
Prebil, Rok,Stavber, Stojan
supporting information
p. 1266 - 1274
(2014/05/06)

Aerobic oxidative α-iodination of carbonyl compounds using molecular iodine activated by a nitrate-based catalytic system
The novel reaction system comprising air/NH4NO3(cat.)/I2/H2SO4(cat.)is introduced as a simple, safe, cheap, efficient, and regioselective mediator for direct aerobic oxidative α-iodination of aryl, heteroaryl, alkyl, and cycloalkyl methyl ketones. The reaction system enabled the moderate to quantitative regioselective iodination of a large range of different methyl ketone derivatives including those bearing oxidizable heteroatom (S, N) substituents. Several activated aromatic compounds were also efficiently and selectively iodinated. The practical applicability of the presented reaction system was shown on 20 mmol scale under ambient pressure and 100% conversion of substrate was achieved.
Prebil, Rok,Stavber, Stojan
supporting information
p. 5643 - 5647
(2014/12/11)

Experimental study on the reaction pathway of α-haloacetophenones with NaOMe: Examination of bifurcation mechanism
The reaction of PhCOCH2Br and NaOMe in MeOH gave PhCOCH 2OH as the major product and PhCOCH2OMe as the minor product. Substituent effects on the reactivity and product selectivity revealed that an electron-withdrawing substituent on the phenyl ring enhanced the overall reactivity and gave more alcohol than ether. It was indicated that the alcohol was formed via carbonyl addition-epoxidation, whereas the ether was formed by direct substitution. Substituent effects on the reaction rates, as well as the effects of NaOMe concentration on the rate and product ratio for both reactions of PhCOCH2Br and PhCOCH2CI are in line with the mechanism that the alcohol and ether products were formed via two independent and concurrent routes, carbonyl addition and a-carbon attack, respectively, and thus the reaction mechanism could be different from the bifurcation mechanism previously predicted for the reaction of PhCOCH2Br by a simulation study in the gas phase.
Tagawa, Kohei,Sasagawa, Keita,Wakisaka, Ken,Monjiyama, Shunsuke,Katayama, Mika,Yamataka, Hiroshi
p. 119 - 126
(2014/02/14)

LABILE ESTERS OF AGROCHEMICALS FOR CONTROLLED RELEASE AND REDUCTION OF OFF-SITE MOVEMENT
The present invention relates to esters of carboxylic acid agrochemicals comprising a labile protecting group and having formula (I). Certain of the esters of carboxylic acid agrochemicals do not undergo hydrolysis to a significant degree in the dark, but are cleaved to regenerate the parent carboxylic acid agrochemical when exposed to light. Others of the esters of carboxylic acid agrochemicals undergo hydrolysis under both light and dark conditions. The present invention further relates to methods for the controlled release of a carboxylic acid agrochemicals, and to methods of controlling unwanted plants comprising applying to the unwanted plants an ester of a carboxylic acid agrochemical.
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Paragraph 0185; 0186

(2013/04/25)

[Cu(dap)2Cl] as an efficient visible-light-driven photoredox catalyst in carbon-carbon bond-forming reactions
Copper sees the light of day: [Cu(dap)2Cl] proved to be an excellent photoredox catalyst for atom-transfer radical addition reactions, as well as for allylation reactions (see scheme), providing an attractive alternative to commonly used iridium- and ruthenium-based catalysts. Copyright
Pirtsch, Michael,Paria, Suva,Matsuno, Taisuke,Isobe, Hiroyuki,Reiser, Oliver
supporting information; experimental part
p. 7336 - 7340
(2012/09/08)

A simple and convenient method for direct α-chlorination of ketones with ammonium chloride and Oxone
When ketones were treated with ammonium chloride and Oxone in MeOH at room temperature, a direct α-chlorination of ketones was occurred and a series of the corresponding α-chloroketones were obtained in moderate to good yields after 24 h. In this reaction, ammonium chloride was used as the source of chlorine and Oxone was used as an oxidant. This method was simple, convenient and providing a novel procedure for preparation of α-chloroketones.
Zhou, Zhong Shi,Li, Li,He, Xue Han
p. 1213 - 1216,4
(2020/09/16)

New, efficient synthesis of α-chloroketones using SiCl 4/urea-hydrogen peroxide or SiCl4/iodosylbenzene reagent systems
Alkyl aryl ketones on treatment with SiCl4/urea-hydrogen peroxide (UHP) or SiCl4/iodosylbenzne reagent systems afforded -chloroketones in excllent yields, while ketones with higher enol content provide exclusively,-dichloroketones under exceedingly mild conditions. The reaction proceeds via the initial formation of silyl enol ethers. A polarized chlorine intermediate that resulted from the coordination of SiCl4 with the in situ formed trichlorosilyl hypochlorite Cl3SiOCl is thought to be the active chlorinating agent.
El-Ahl, Abdel Aziz S.,Elbeheery, Akram H.,Amer, Fathy A.
experimental part
p. 1508 - 1513
(2011/06/17)

Visible-light photoredox catalysis: Dehalogenation of vicinal dibromo-, α-halo-, and α,α-dibromocarbonyl compounds
vic-Dibromo-, α-halo-, or α,α-dibromocarbonyl compounds can be efficiently dehalogenated using catalytic tris(2,2′-bipyridyl) ruthenium dichloride (Ru(bpy)3Cl2) in combination with 1,5-dimethoxynaphthalene (DMN) and ascorbate as sacrificial electron donor. For this process, a visible light promoted photocatalytic cycle is proposed that involves the reduction of carbon halogen bonds via free radical intermediates.
Maji, Tapan,Karmakar, Ananta,Reiser, Oliver
supporting information; experimental part
p. 736 - 739
(2011/03/20)

Catalytic Friedel-Crafts acylation and benzoylation of aromatic compounds using activated hematite as a novel heterogeneous catalyst
Catalytic Friedel-Crafts acylation of benzene and unactivated benzenes such as chlorobenzene and nitrobenzene have been successfully carried out using activated hematite (α-Fe2O3) as a new, heterogeneous and green catalyst. Sonication of neat α-Fe2O3 in a water bath under air atmosphere at room temperature followed by heating at 200°C, dramatically increase the activity of α-Fe2O 3. With the catalyst loading as low as 5.0mol%, a wide variety of benzene derivatives were easily converted into the corresponding acylated products in a clean and high-yielding acylation reaction. It was found that the activated α-Fe2O3 could be efficiently recycled and reused several times by simple washing with ethyl acetate, this cannot be attained with most of the traditional catalysts. Copyright
Sharghi, Hashem,Jokar, Mahboubeh,Doroodmand, Mohammad Mahdi,Khalifeh, Reza
experimental part
p. 3031 - 3044
(2011/02/21)

Friedel-Crafts acylation of aromatic compounds with carboxylic acids in the presence of P2O5/SiO2 under heterogeneous conditions
A convenient and efficient procedure for the Friedel-Crafts acylation of aromatic compounds with carboxylic acids in the presence of P2O5/SiO2 is described. Both aromatic and aliphatic carboxylic acids reacted easily to afford the corresponding aromatic ketones. The use of non-toxic and inexpensive materials, simple and clean work-up, short reaction times and good yields of the products are the advantages of this method.
Zarei, Amin,Hajipour, Abdol R.,Khazdooz, Leila
scheme or table
p. 6715 - 6719
(2009/04/07)

Chloroacetylation of arenes using chloroacetyl chloride in the presence of FeCl3 modified montmorillonite K10
Chloroacetylation reaction of arenes using chloroacetyl chloride has been studied in the presence of Fe-modified montmorillonite K10 catalysts in a liquid phase. The catalysts have been prepared by treating montmorillonite K10 with aqueous solution of FeCl3. Good yields and selectivity are observed for the acylated product.
Paranjape, Tejashri B.,Gokhale, Geetanjali D.,Samant, Shriniwas D.
p. 310 - 314
(2008/09/20)

1,2,3-Thiadiazole thioacetanilides as a novel class of potent HIV-1 non-nucleoside reverse transcriptase inhibitors
A novel series of 1,2,3-thiadiazole thioacetanilide (TTA) derivatives have been designed, synthesized and evaluated for its anti-HIV activities in MT-4 cells. Some derivatives proved to be highly effective in inhibiting HIV-1 replication at nanomolar concentrations. Among them, 2-[4-(2,4-dichlorophenyl)-1,2,3-thiadiazol-5-ylthio]-N-(2-nitrophenyl)acetamide 7d2 was identified as the most promising compound (EC50 = 0.059 ± 0.02 μM, CC50 > 283.25 μM, SI > 4883). The structure-activity relationship (SAR) of these novel structural congeners is discussed. Crown Copyright
Zhan, Peng,Liu, Xinyong,Cao, Yuan,Wang, Yan,Pannecouque, Christophe,De Clercq, Erik
scheme or table
p. 5368 - 5371
(2009/06/18)

Copper(I)-promoted synthesis of chloromethyl ketones from trichloromethyl carbinols
(Chemical Equation Presented) Reaction of several trichloromethyl carbinols with 2 equiv of CuCl/bpy in refluxing DCE for 3 h afforded chloromethyl ketones in excellent yield by 1,2-H shift in the copper-chlorocarbenoid intermediate.
Ram, Ram N.,Manoj
p. 5633 - 5635
(2008/12/21)

Halogenation of carbonyl compounds by an ionic liquid, [AcMIm]X, and Ceric Ammonium Nitrate (CAN)
An ionic liquid, acetylmethylimidazolium halide ([AcMIm]X), in combination with ceric ammonium nitrate promotes halogenations of a wide variety of ketones and 1,3-keto esters at the ?-position. The ionic liquid acts here as reagent as well as reaction medium, and thus the reaction does not require any organic solvent or conventional halogenating agent. The reaction is completely arrested when the radical quencher TEMPO is used. A plausible radical mechanism is also suggested. CSIRO 2007.
Ranu, Brindaban C.,Adak, Laksmikanta,Banerjee, Subhash
p. 358 - 362
(2008/02/13)

Novel building blocks: 1-Aryl-2-chloro-1-ethoxyethenes - Preparations and transformations
We described here a simple method for the preparation of 1-aryl-2-chloro-1-ethoxyethenes 2a-u, which are prodrugs for Alzheimer's disease, by the reaction of dichloroacetaldehyde diethyl acetal with various aryl and alkenyllithium compounds in high yields. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Yoshimatsu, Mitsuhiro,Sakai, Miho,Moriura, Eri
p. 498 - 507
(2008/02/06)

α-chlorination of acetophenones using 1,3-dichloro-5,5- dimethylhydantoin
A novel method for the synthesis of α-chloroacetophenones using 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) and p-toluenesulfonic acid in methanol at 30-35°C is described. Substituted acetophenones at the para position or meta position of aromatic ring give α-chloroacetophenones in high yield. However, reaction of o-nitroacetophenone does not take place under the same condition. Copyright Taylor & Francis LLC.
Xu, Zijin,Zhang, Deyan,Zou, Xinzhuo
p. 255 - 258
(2007/10/03)

Synthesis of [4-14C]-pelargonidin chloride and [4- 14C]-delphinidin chloride
The synthesis of [4-14C]-pelargonidin chloride and [4- 14C]-delphinidin chloride via [formyl-14C]-2-(benzoyloxy)- 4,6-dihydroxybenzaldehyde, ω,4-diacetoxyacetophenone and ω,3,4,5-tetraacetoxyacetophenone is described. The first step comprised labelling of the carbonyl group of 2-(benzoyloxy)-4,6-dihydroxybenzaldehyde, verifying that the coupling with ω,4-diacetoxyacetophenone or ω,3,4,5-tetraacetoxyacetophenone under hydrogen chloride atmosphere resulted in the formation of [4-14C] labelled anthocyanidins. Copyright
Kraus, Michael,Biskup, Ellen,Richling, Elke,Schreier, Peter
p. 1151 - 1162
(2007/10/03)

Microwave-assisted synthesis of α-hydroxy ketone and α-diketone and pyrazine derivatives from α-halo and α,α′-dibromo ketone
A novel reaction of α-halo ketone (α-bromo and α-chloro ketone) with irradiation under microwave gave the corresponding α-hydroxyketone and pyrazine derivative in good yields. In the case of α,α′-dibromo ketone, α-diketone was obtained. This reaction affords a new, clean and convenient synthetic method for α-hydroxyketone, α-diketone, α-chloro ketone and pyrazine derivative.
Utsukihara, Takamitsu,Nakamura, Hiroaki,Watanabe, Masashige,Akira Horiuchi
p. 9359 - 9364
(2008/01/27)

Efficient microwave induced direct α-halogenation of carbonyl compounds
A novel and direct method for the synthesis of α-halocarbonyl compounds using sequential treatment of carbonyl compounds with [hydroxy(tosyloxy)iodo]benzene followed by magnesium halides under solvent-free microwave irradiation conditions is described.
Lee, Jong Chan,Park, Jin Young,Yoon, So Young,Bae, Yong Hun,Lee, Seung Jun
p. 191 - 193
(2007/10/03)

Method for preparing chiral diphosphines
The invention concerns a method for preparing a compound of formula (1) wherein: A represents naphthyl or phenyl optionally substituted; and Ar1, Ar2independently represent a saturated or aromatic carbocyclic group, optionally substituted.
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(2008/06/13)

Calcium receptor-active molecules
The present invention relates to the different roles inorganic ion receptors have in cellular and body processes. The present invention features: (1) molecules which can modulate one or more inorganic ion receptor activities, preferably the molecule can mimic or block an effect of an extracellular ion on a cell having an inorganic ion receptor, more preferably the extracellular ion is Ca2+and the effect is on a cell having a calcium receptor; (2) inorganic ion receptor proteins and fragments thereof, preferably calcium receptor proteins and fragments thereof; (3) nucleic acids encoding inorganic ion receptor proteins and fragments thereof, preferably calcium receptor proteins and fragments thereof; (4) antibodies and fragments thereof, targeted to inorganic ion receptor proteins, preferably calcium receptor protein; and (5) uses of such molecules, proteins, nucleic acids and antibodies.
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(2008/06/13)

α-(4-Nitro Phenoxy) chalcones as synthons for cis-(±)-1,5- benzothiazepines
α-(4-Nitro Phenoxy) chalcones, V have been utilized as intermediate for the synthesis of some new cis- (±)-2-aryl-3-(4-nitro phenoxy)-4-phenyl-1,5- benzothiazepine VI by cycloconden-sation of 2-amino thiophenol in the presence of mild base.
Rao,Arun Kumar Gupta,Gupta
p. 2763 - 2768
(2007/10/03)

Reactions of trichloromethanesulfonyl chloride and carbon tetrachloride with silyl enol ethers catalyzed by a ruthenium(II) phosphine complex
The reactions of trichloromethanesulfonyl chloride with trimethylsilyl enol ethers of acetophenones in the presence of a ruthenium(II) phosphine complex gave 1-aryl-3,3-dichloropropen-1-one together with α-chloroacetophenones. The product ratio depended on the substituent on the aromatic ring of the silyl enol ether. The reactions of carbon tetrachloride with the silyl enol ethers under similar conditions afforded 1-aryl-3,3-dichloropropen-1-one in good yield.
Kamigata, Nobumasa,Udodaira, Kumiko,Yoshikawa, Manabu,Shimizu, Toshio
p. 39 - 43
(2007/10/03)

α-chlorination of ketones with sodium chlorite, Mn(acac)3, and alumina in dichloromethane
Chlorination of a variety of aliphatic, alicyclic, and aromatic ketones with a reagent combination of NaC1O2 and Mn(acac)3 catalyst can be readily performed in dichloromethane to afford α-chloroketones in good yield under mild and neutral conditions with the aid of chromatographic neutral alumina.
Yakabe, Shigetaka,Hirano, Masao,Morimoto, Takashi
p. 131 - 138
(2007/10/03)

Reactions of perfluoroalkanesulfonyl chlorides with silyl enol ethers catalyzed by a ruthenium(II) phosphine complex
Reactions of trifluoromethane- and tridecafluorohexanesulfonyl chlorides with silyl enol ethers have been investigated in the presence of a ruthenium(II) phosphine complex. Perfluoroalkylation and chlorination occurred depending on the substituent of silyl enol ether; i.e. perfluoroalkylated compound was selectively obtained in the reactions with silyl enol ether possessing an electron-withdrawing group, on the other hand, chlorinated compounds selectively formed in the reaction with a silyl enol ether possessing electron-donating group.
Kamigata, Nobumasa,Udodaira, Kumiko,Shimizu, Toshio
p. 155 - 168
(2007/10/03)