- NITRATION
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The present invention relates to a process for preparing a nitrated compound, comprising the step of reacting a compound (A) comprising at least one substituted or unsubstituted aromatic or heteroaromatic ring, wherein said heteroaromatic ring comprises at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphor, selenium and nitrogen, with a compound of formula (I) wherein Y is selected from the group consisting of hydrogen and nitro.
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Page/Page column 36; 38; 43; 52-53; 68; 69
(2020/05/28)
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- Synthesis of Functionalized Ketones from Acid Chlorides and Organolithiums by Extremely Fast Micromixing
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Synthesis of ketones containing various functional groups from acid chlorides bearing electrophilic functional groups and functionalized organolithiums was achieved using a flow microreactor system. Extremely fast mixing is important for high chemoselectivity.
- Nagaki, Aiichiro,Sasatsuki, Kengo,Ishiuchi, Satoshi,Miuchi, Nobuyuki,Takumi, Masahiro,Yoshida, Jun-ichi
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supporting information
p. 4946 - 4950
(2019/03/21)
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- Fukuyama Cross-Coupling Approach to Isoprekinamycin: Discovery of the Highly Active and Bench-Stable Palladium Precatalyst POxAP
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An efficient and user-friendly palladium(II) precatalyst, POxAP (post-oxidative-addition precatalyst), was identified for use in Fukuyama cross-coupling reactions. Suitable for storage under air, the POxAP precatalyst allowed reaction between thioesters and organozinc reagents with turnover numbers of ～90000. A series of 23 ketones were obtained with yields ranging from 53 to 99%. As proof of efficacy, an alternative approach was developed for the synthesis of a key precursor of the natural product isoprekinamycin.
- Tang, Shuang-Qi,Bricard, Jacques,Schmitt, Martine,Bihel, Frédéric
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p. 844 - 848
(2019/01/30)
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- Method for preparing aromatic ketone in aqueous phase
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The invention discloses a method for preparing aromatic ketone in an aqueous phase, comprising the following steps: enabling aryl formyl potassium formate and aryl potassium fluoborate to generate decarboxylation acylation reaction in water under the actions of a silver catalyst and an oxidizing agent, and performing treatment after reaction is ended to obtain the disclosed aromatic ketone. According to the preparation method, the silver catalyst replaces a noble metal catalyst, water is taken as a solvent, an aromatic ketone product is obtained with relatively high yield, the adopted catalystis low in cost and easy to obtain, reaction conditions are mild, and meanwhile, the product is good in university, and therefore, the method has good application potential.
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Paragraph 0046-0049
(2018/04/26)
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- Palladium-Catalyzed Ligand-Free Decarboxylative Coupling of α- Oxocarboxylic Acid with Aryl Diazonium Tetrafluoroborate: An Access to Unsymmetrical Diaryl Ketones
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Diaryl ketones are of much importance in organic synthesis as versatile intermediates and in industry for their useful properties. A mild and efficient palladium-catalyzed traditional ligand-free decarboxylative coupling of aryl α-keto carboxylic acid with aryl diazonium fluoroborate has been developed. A series of unsymmetrical diaryl ketones has been synthesized in moderate to good yields using this procedure. A radical pathway involving the acyl radical has been suggested.
- Panja, Subir,Maity, Pintu,Ranu, Brindaban C.
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p. 12609 - 12618
(2018/10/20)
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- α-Chlorobenzylation of Nitroarenes via Vicarious Nucleophilic Substitution with Benzylidene Dichloride: Umpolung of the Friedel-Crafts Reaction
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Readily available α,α-dichlorotoluenes enter a vicarious nucleophilic substitution (VNS) reaction with electron-deficient arenes to give α-chlorobenzylated nitrobenzenes, as well as six- and five-membered heterocycles. Oxidation of the initially formed α-chlorobenzylic carbanions instead of protonation results in formation of diaryl ketones, providing a means for overall nucleophilic C-H benzoylation of electron-deficient aromatic rings. Alternatively, benzoylated nitroarenes can be obtained via the reaction of isolated α-chlorodiarylmethanes with sodium azide.
- Brze?kiewicz, Jakub,Loska, Rafa?,Makosza, Mieczys?aw
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p. 8499 - 8508
(2018/06/25)
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- Ag(i)/persulfate-catalyzed decarboxylative coupling of α-oxocarboxylates with organotrifluoroborates in water under room temperature
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The decarboxylative coupling reaction of α-oxocarboxylates and organotrifluoroborates was carried out smoothly in the presence of catalytic AgNO3 using K2S2O8 as oxidant to generate diarylketone products in high
- Chang, Sheng,Wang, Jian Feng,Dong, Lin Lin,Wang, Dan,Feng, Bo,Shi, Yuan Tai
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p. 51928 - 51934
(2017/11/22)
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- Synthesis of 3-Substituted 2,1-Benzisoxazoles by the Oxidative Cyclization of 2-Aminoacylbenzenes with Oxone
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An efficient approach to the synthesis of 2,1-benzisoxazoles through direct construction of the N-O bond by the chemoselective oxidation of 2-aminoacylbenzenes with Oxone is described. This alternative methodology is characterized by its simple and transition-metal-free conditions and good functional group compatibility utilizing Oxone as a green oxidant instead of hypervalent iodine compounds. Moreover, this new procedure simplifies the number of steps compared to the previously reported procedure by circumventing the use of 2-azido-substituted aryl ketones.
- Chiarini, Marco,Del Vecchio, Luana,Marinelli, Fabio,Rossi, Leucio,Arcadi, Antonio
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p. 3017 - 3030
(2016/10/12)
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- Preparation method of 2'-nitrobenzophenone
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The invention discloses a preparation method of 2'-nitrobenzophenone. According to the method, benzene is taken as a raw material and has condensation with 2-nitrobenzoyl chloride under the action of an aluminum trichloride or iron(III) chloride catalyst,
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Paragraph 0007; 0021; 0022
(2016/10/08)
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- Agglomeration of Pd0 nanoparticles causing different catalytic activities of Suzuki carbonylative cross-coupling reactions catalyzed by PdII and Pd0 immobilized on dopamine-functionalized magnetite nanoparticles
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Solvent-dispersible magnetite nanoparticles (Fe3O4) end-functionalized with amino groups were successfully prepared by a facile one-pot template-free method to immobilize PdII and Pd0 using a metal adsorption and reduction procedure. They were characterized by TEM, XRD, XPS, FT-IR and VSM. Interestingly, the PdII catalyst exhibited better catalytic activity for carbonylative cross-coupling reactions than the Pd0 catalyst. According to the catalytic activities of a variety of arylboronic acids and aryl iodides catalyzed by two kinds of Pd catalysts, the proposed reaction mechanism of Suzuki carbonylative cross-coupling reactions using the Pd catalyst was also inferred. More importantly, agglomeration of Pd0 nanoparticles was obviously observed in the TEM images of the catalysts after reactions. Therefore, agglomeration of Pd0 nanoparticles should be considered as a significant reason for different catalytic activities of the reactions catalyzed by immobilized PdII and Pd0 catalysts. Furthermore, the PdII catalyst revealed high efficiency and stability during recycling stages.
- Long, Yu,Liang, Kun,Niu, Jianrui,Tong, Xin,Yuan, Bing,Ma, Jiantai
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p. 2988 - 2996
(2015/04/14)
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- Pd-NHC-catalyzed synthesis of diaryl ketones
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With N-hetereocyclic carbene and palladium catalysis, diaryl ketones with a variety of functional groups that span from electron withdrawing to electron donating substitutions can be conveniently synthesized using the corresponding aryl boronic acid and N-acyloxyphthalimide.
- Gao, Feng,Feng, Huangdi,Sun, Zhihua
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p. 6451 - 6454
(2014/12/10)
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- Stabilizing PdII on hollow magnetic mesoporous spheres: A highly active and recyclable catalyst for carbonylative cross-coupling and Suzuki coupling reactions
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A hollow magnetic mesoporous silica sphere (HMMS) catalyst has been synthesized using polystyrene microspheres as a chemical template. The catalyst was characterized by TEM, XRD, XPS and vibrating sample magnetometry (VSM). The catalyst shows high activity for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids and Suzuki coupling reactions. The newly developed catalyst is easy to recover by magnetic separation from the liquid phase of the reaction and can be recycled. Importantly, the catalyst revealed high efficiency and high stability under the reaction conditions and during recycling stages.
- Niu, Jianrui,Liu, Mengmeng,Wang, Peng,Long, Yu,Xie, Miao,Li, Rong,Ma, Jiantai
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p. 1471 - 1476
(2014/05/06)
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- Preparation of recoverable Fe3O4/PPy-PdII catalysts for carbonylative cross-coupling reactions
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The hierarchical porous Fe3O4/PPy-PdII catalyst has been synthesized using Fe3O4 microspheres both as chemical template and oxidant source under sonication. The catalyst characterized by TEM, XRD, FT-IR, XPS and vibrating sample magnetometry (VSM). The catalyst showed high reactivity for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids. This newly developed catalyst could be easily recovered and revealed high efficiency and high stability under the reaction conditions and during recycling stages.
- Niu, Jianrui,Xie, Miao,Zhu, Xiaohang,Long, Yu,Wang, Peng,Li, Rong,Ma, Jiantai
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p. 247 - 252
(2014/07/07)
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- Preparation of recoverable Fe3O4@PANI-PdII core/shell catalysts for Suzuki carbonylative cross-coupling reactions
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We report on the synthesis, characterization and catalytic performance of a palladium-based superparamagnetic catalyst of Fe3O 4@polyaniline core/shell microspheres (Fe3O 4@PANI-PdII). The material was characterized by TEM, FT-IR, vibrating sample magnetometry (VSM), XRD, and XPS. The catalyst showed high activity for the carbonylative cross-coupling reaction of aryl iodide with arylboronic acid. Moreover it could selectively reduce the formation of a direct-coupling product. The newly developed catalyst could be recovered from the liquid phase easily by magnetic separation and recycled 5 times without any significant loss of activity. the Partner Organisations 2014.
- Zhu, Xiaohang,Niu, Jianrui,Zhang, Fengwei,Zhou, Jinghui,Li, Xinzhe,Ma, Jiantai
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p. 4622 - 4627
(2014/10/15)
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- Preparation of Recoverable Pd Catalysts for Carbonylative Cross-Coupling and Hydrogenation Reactions
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We report on the synthesis, characterization and catalytic performance of new, supported PdII and Pd0 catalysts. The catalysts are characterized by TEM, XRD, FTIR, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. The catalysts are found to be active in both forms, PdII and Pd0, for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids, and for the hydrogenation of aromatic nitro- and unsaturated compounds. The newly developed catalysts are prepared by a synthetic strategy that is similar to the one used for other supported catalysts but are easier to recover-they can be recycled by magnetic separation from liquid phase reactions-and can be used for at least 5 consecutive trials without any decrease in activity.
- Niu, Jian-Rui,Huo, Xing,Zhang, Feng-Wei,Wang, Hai-Bo,Zhao, Ping,Hu, Wu-Quan,Ma, Jiantai,Li, Rong
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p. 349 - 354
(2013/03/13)
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- Validation of PqsD as an anti-biofilm target in pseudomonas aeruginosa by development of small-molecule inhibitors
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2-Heptyl-4-hydroxyquinoline (HHQ) and Pseudomonas quinolone signal (PQS) are involved in the regulation of virulence factor production and biofilm formation in Pseudomonas aeruginosa. PqsD is a key enzyme in the biosynthesis of these signal molecules. Using a ligand-based approach, we have identified the first class of PqsD inhibitors. Simplification and rigidization led to fragments with high ligand efficiencies. These small molecules repress HHQ and PQS production and biofilm formation in P. aeruginosa. This validates PqsD as a target for the development of anti-infectives.
- Storz, Michael P.,Maurer, Christine K.,Zimmer, Christina,Wagner, Nathalie,Brengel, Christian,De Jong, Johannes C.,Lucas, Simon,Muesken, Mathias,Haeussler, Susanne,Steinbach, Anke,Hartmann, Rolf W.
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supporting information
p. 16143 - 16146
(2012/11/07)
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- Solvent-free rapid deprotection of ketone and aldehyde oximes using periodic acid
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Ketone and aldehyde oximes can be readily converted to the corresponding carbonyl compounds in high yields under solvent-free conditions when treated with periodic acid. Oximes bearing aliphatic C=C bonds can be selectively deoximated. The advantages of this protocol include a rapid reaction rate and a simple workup procedure. No volatile organic solvents are required in the reaction processes. Copyright Taylor & Francis, Inc.
- Li, Zheng,Ding, Run-Bo,Xing, Yu-Lin,Shi, Sheng-Yi
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p. 2515 - 2520
(2007/10/03)
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- Synthesis of 1H-indazoles by reductive cyclization of o-nitro-ketoximes
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ortho-Nitro-ketoximes are converted to 1H-indazoles upon reaction with carbon monoxide with [Cp*Fe(CO)2]2 as catalyst.
- O'Dell, David K.,Nicholas, Kenneth M.
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p. 373 - 382
(2007/10/03)
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- Highly diastereoselective arylation of (S)-mandelic acid enolate: Enantioselective synthesis of substituted (R)-3-hydroxy-3-phenyloxindoles and (R)-benzylic acids and synthesis of nitrobenzophenones
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An easy access to substituted (R)-3-hydroxy-3-phenyloxindoles, (R)-benzylic acids, and benzophenones is described. The reaction of the lithium enolate of the (2S,5S)-cis-1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde with several o- and p-halonitrobenzenes proceeds readily to give the corresponding arylation products in good yields and diastereoselectivities. The reduction of the nitro group with Zn/HCl/EtOH in the o-nitro arylation products with concomitant intramolecular aminolysis of the dioxolanone moiety leads directly to enantiomerically pure (R)-3-hydroxy-3- phenyloxindoles. On the other hand the basic hydrolysis of the dioxolanone moiety in all the arylation products (ortho and para) leads to enantiomerically pure substituted (R)-benzylic acids. The oxidative decarboxylation of these latter with oxygen as terminal oxidant in the presence of pivalaldehyde and the Co(III)-Me2opba complex as catalyst gives substituted nitrobenzophenones.
- Barroso, Santiago,Blay, Gonzalo,Cardona, Luz,Fernandez, Isabel,Garcia, Begona,Pedro, Jose R.
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p. 6821 - 6829
(2007/10/03)
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- Mandelic Acid as Synthetic Equivalent of Benzoyl Carbanion. Synthesis of Nitrobenzophenones
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Nitrobenzophenones are prepared from a mandelic acid dioxolanone. The sequence starts with the aromatic nucleophilic substitution of the enolate of the dioxolanone onto p-fluoronitrobenzenes, followed by hydrolysis of the acetal moiety and oxidative decarboxylation of the resulting α-hydroxyacids. The whole sequence involves the use of mandelic acid as synthetic equivalent of the benzoyl carbanion.
- Blay, Gonzalo,Cardona, Luz,Fernández, Isabel,Michelena, Raquel,Pedro, José R.,Ramírez, Teresa,Ruiz-García, Rafael
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p. 2325 - 2328
(2007/10/03)
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- Preparation of polyfunctional aryl and alkenyl zinc halides from functionalized unsaturated organolithiums and their reactivity in cross-coupling and conjugated addition reactions
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Functionalized aryl and alkenyl iodides undergo an iodine-lithium exchange at -90 to -80°C providing polyfunctional organolithiums which are stable for a short time at these low temperatures and can be transmetalated to organozinc derivatives by the addition of zinc bromide. The resulting unsaturated organozinc halides can then be warmed up and are perfectly stable at 25°C. They react directly with tosyl cyanide. In the presence of CuCN·2LiCl, they add in a Michael-fashion to alkylidenemalonates. In the presence of catalytic amounts of Pd(dba)2 and TPP or TFP, they undergo readily a cross-coupling at 25°C with aryl and alkenyl iodides. The Pd-catalyzed coupling of arylzinc bromides with aryl triflates could also be achieved by using dppf as a ligand and 60°C as reaction temperature.
- Klement, Ingo,Rottlaender, Mario,Tucker, Charles E.,Majid, Tahir N.,Knochel, Paul,Venegas, Patricia,Cahiez, Gerard
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p. 7201 - 7220
(2007/10/03)
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- Ozone-mediated Nitration of Aromatic Ketones and Related Compounds with Nitrogen Dioxide
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Alkyl aryl ketones react smoothly with nitrogen dioxide at low temperatures in the presence of ozone to give ortho- and meta-nitro derivatives as the principal products, the former usually being predominant (ortho:meta = 1.1-3.8:1.0).No attack was observed on the alkyl side chains.
- Suzuki, Hitomi,Murashima, Takashi
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p. 903 - 908
(2007/10/02)
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- Mechanism of Base-Catalyzed Desilylations of Aryl- and Heteroaryltrimethylsilanes
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The influence of different bases on the cleavage of silicium-carbon bonds in aryl- and heteroaryltrimethylsilanes is investigated in the presence of benzaldehyde as electrophilic scavenger for the aryl and heteroaryl anions formed in this process.A reactivity gradation of the various basic catalysts employed is determined from the reactions with 2-(trimethylsilyl)benzothiazole (1).The increase of catalytic activity of the anions parallels that of their ion potential.Attack of the base at the Si atom is postulated as the first step in this reaction sequence, with subsequent dissociation of the pentacoordinated intermediate in the rate-determining step.The carbanion thus liberated rapidly reacts with benzaldehyde.In the differently substituted aryltrimethylsilanes 13, 13', and 13'' the dependency of aryl anion stability in the base-catalyzed carbodesilylation was investigated.The relative rates of reaction correlate with Hammett's ?-constants rather than with the corresponding aryl anion stabilities.
- Effenberger, Franz,Spiegler, Wolfgang
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p. 3872 - 3899
(2007/10/02)
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- Hydroxyalkylation, Acylation, Formylation, and Carboxylation of 2-Nitro- and 2-Chloro-1-(trimethylsilyl)benzene
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The synthetic application of base-catalyzed carbodesilylation of aryltrimethylsilanes is demonstrated in the reactions of 2-nitro- (1a) and 2-chloro-1-(trimethylsilyl)benzene (1b) with aldehydes, ketones, acyl fluorides and carboxylic anhydrides, respectively, dimethylformamide, and carbon dioxide.The corresponding benzenes 3 and 8, (hydroxyalkyl)benzenes 4, 6, and 9, the benzophenones 12, the benzaldehydes 14, and the benzoic acids 17 are obtained in good yields.The new method is a useful alternative to the normal electrophilic substitution or the application of organometallic compounds, respectively, for the synthesis of polysubstituted benzenes.
- Effenberger, Franz,Spiegler, Wolfgang
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p. 3900 - 3914
(2007/10/02)
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- Regioselective Addition of Grignard Reagents to 3-Methoxy- and 3-Nitrophthalic Anhydride
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The regioselectivity in the addition of the grignard reagents 5a and 6a to the anhydrides 1 and 2 is determined by the solvent system: in a highly selective manner (3:97), the meta carbonyl group is attacked in tetrahydrofuran/tetramethylethylenediamine, while predominant, but relatively unselective (maximum 78:22) addition to the ortho carbonyl group is observed in diethyl ether.The influence of the solvent system on the regioselectivity is discussed.The LUMO-coefficients of the carbonyl carbon atoms in 1 and 2 were calculated.
- Braun, Manfred,Veith, Reiner,Moll, Gerard
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p. 1058 - 1070
(2007/10/02)
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- Benzophenones and benzhydrols
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Compounds having the formula STR1 WHERE X is --CO-- or --CHOH--, Y and Z are halogen, alkyl, trifluoromethyl, alkoxy, hydroxy, nitro, cyano, carboxy, carbalkoxy, carbamoyl, or alkylthio, and m and n are 0, 1, or 2 Are useful in controlling undesirable secondary growth in plants, particularly sucker growth in tobacco.
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