18220-90-1Relevant academic research and scientific papers
Friedel-Crafts Alkylation of Benzenes Substituted with Meta-Directing Groups
Shen, Yu-Sheng,Liu, Hong-Xia,Wu, Ming,Du, Wu-Qin,Chen, Yi-Qiu et al
, p. 7160 - 7162 (1991)
In protonic acids, benzaldehyde, acetophenone, benzophenone, and ethyl benzoate were ring-alkylated by alcohols.Benzonitrile was N-alkylated rather than ring-alkylated.Ethyl n-propyl, isopropyl, and n-butyl alcohol were effective alkylating agents, wherea
Perfluoroalkanesulfonic acid catalyzed acylations of alkylbenzenes: Synthesis of alkylanthraquinones
Effenberger,Buckel,Maier,Schmider
, p. 1427 - 1430 (2000)
The acylation of alkylbenzenes 1 with benzoyl chloride 2 and catalytic amounts of perfluorobutanesulfonic acid affords the corresponding 2-, 3-, and 4-alkylbenzophenones 3 with unusually high amounts of ortho products. Surprisingly, even tert-butylbenzene reacts under these reaction conditions without any acid catalyzed dealkylation. The yield of benzoylation of p-xylene 4 with benzoic acid in the presence of 5 mol% C4F9SO3H to give 2,5-dimethylbenzophenone 5 could significantly be improved from 14% to 90% by continuous removal of water formed during the acylation. Also in the preparation of alkylanthraquinones 7 by reaction of alkylbenzenes with phthalic anhydride, water removal is the decisive factor to obtain satisfactory yields for the second acylation, allowing to cyclize 6 with catalytic amounts (10 mol%) of CF3SO3H in organic solvents to the corresponding alkylanthraquinones 7.
Mechanochemical Solvent-Free Suzuki–Miyaura Cross-Coupling of Amides via Highly Chemoselective N?C Cleavage
Ma, Yangmin,Shao, Lei,Szostak, Michal,Wang, Ruihong,Zhang, Jin,Zhang, Pei
supporting information, (2022/01/04)
Although cross-coupling reactions of amides by selective N?C cleavage are one of the most powerful and burgeoning areas in organic synthesis due to the ubiquity of amide bonds, the development of mechanochemical, solid-state methods remains a major challe
Selective electrochemical oxidation of aromatic hydrocarbons and preparation of mono/multi-carbonyl compounds
Li, Zhibin,Zhang, Yan,Li, Kuiliang,Zhou, Zhenghong,Zha, Zhenggen,Wang, Zhiyong
, p. 2134 - 2141 (2021/09/29)
A selective electrochemical oxidation was developed under mild condition. Various mono-carbonyl and multi-carbonyl compounds can be prepared from different aromatic hydrocarbons with moderate to excellent yield and selectivity by virtue of this electrochemical oxidation. The produced carbonyl compounds can be further transformed into α-ketoamides, homoallylic alcohols and oximes in a one-pot reaction. In particular, a series of α-ketoamides were prepared in a one-pot continuous electrolysis. Mechanistic studies showed that 2,2,2-trifluoroethan-1-ol (TFE) can interact with catalyst species and generate the corresponding hydrogen-bonding complex to enhance the electrochemical oxidation performance. [Figure not available: see fulltext.]
Pd-Catalysed carbonylative Suzuki-Miyaura cross-couplings using Fe(CO)5under mild conditions: generation of a highly active, recyclable and scalable ‘Pd-Fe’ nanocatalyst
Zhu, Zhuangli,Wang, Zhenhua,Jian, Yajun,Sun, Huaming,Zhang, Guofang,Lynam, Jason M.,McElroy, C. Robert,Burden, Thomas J.,Inight, Rebecca L.,Fairlamb, Ian J. S.,Zhang, Weiqiang,Gao, Ziwei
supporting information, p. 920 - 926 (2021/02/09)
The dual function and role of iron(0) pentacarbonyl [Fe(CO)5] has been identified in gaseous CO-free carbonylative Suzuki-Miyaura cross-couplings, in which Fe(CO)5supplied COin situ, leading to the propagation of catalytically active Pd-Fe nanoparticles. Compared with typical carbonylative reaction conditions, CO gas (at high pressures), specialised exogenous ligands and inert reaction conditions were avoided. Our developed reaction conditions are mild, do not require specialised CO high pressure equipment, and exhibit wide functional group tolerance, giving a library of biaryl ketones in good yields.
Method for selectively synthesizing benzyl trifluoromethyl sulfide
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Paragraph 0026-0030, (2020/05/29)
The invention discloses a method for selectively synthesizing benzyl trifluoromethyl sulfide. The method comprises the following steps: taking alkyl aromatic hydrocarbon ArCHR1R2 as a raw material; and under irradiation by a blue light lamp, in a solution, under the argon atmosphere and under presence of a small amount of potassium carbonate, taking 4CzIPN as a photocatalyst to react with 2-((trifluoromethyl) sulfenyl)isoindoline-1, 2, 3, 4-thiadiazole to obtain photocatalyst 4CzIPN shown in the benzyl trifluoromethyl sulfide ArCR1R2SCF3 (3), wherein the photocatalyst 4CzIPN has the followingstructure shown in the specification. According to the method, the reaction conditions are mild, no oxidizing agent or high-temperature condition is needed, residues of transition metal are avoided, and benzyl trifluoromethyl sulfide is directly obtained from alkyl arene and trifluoromethyl sulfide reagents which are stable and easy to obtain.
Synthesis, structure, and characterization of picolyl- and benzyl-linked biphenyl palladium N-heterocyclic carbene complexes and their catalytic activity in acylative cross-coupling reactions
Muniyappan, Nalluchamy,Sabiah, Shahulhameed
, (2020/01/28)
N-heterocyclic carbene ligands with picolyl (L1H2Br2, L3H2Br2) and benzyl (L2H2Br2, L4H2Br2) linked biphenyl backbone were synthesized and characterized. Their palladium(II) complexes [PdL1]Br2 (1), [PdL2Br2] (2), [PdL3]Br2 (3), and [PdL4Br2] (4) were synthesized by direct method using Pd(OAc)2. All complexes (1–4) were characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and single-crystal X-ray diffraction. Molecular structures confirm the distorted square planar geometry around the Pd(II) center. All of them showed good catalytic activity in acylative Suzuki cross coupling of phenyl boronic acid with benzoyl chloride to afford benzophenone in good yields.
Nickel/Photoredox-Catalyzed Methylation of (Hetero)aryl Chlorides Using Trimethyl Orthoformate as a Methyl Radical Source
Kariofillis, Stavros K.,Shields, Benjamin J.,Tekle-Smith, Makeda A.,Zacuto, Michael J.,Doyle, Abigail G.
supporting information, p. 7683 - 7689 (2020/04/22)
Methylation of organohalides represents a valuable transformation, but typically requires harsh reaction conditions or reagents. We report a radical approach for the methylation of (hetero)aryl chlorides using nickel/photoredox catalysis wherein trimethyl orthoformate, a common laboratory solvent, serves as a methyl source. This method permits methylation of (hetero)aryl chlorides and acyl chlorides at an early and late stage with broad functional group compatibility. Mechanistic investigations indicate that trimethyl orthoformate serves as a source of methyl radical via β-scission from a tertiary radical generated upon chlorine-mediated hydrogen atom transfer.
Binuclear Palladium Complex Immobilized on Mesoporous SBA-16: Efficient Heterogeneous Catalyst for the Carbonylative Suzuki Coupling Reaction of Aryl Iodides and Arylboronic Acids Using Cr(CO)6 as Carbonyl Source
Niakan, Mahsa,Asadi, Zahra,Emami, Mohammad
, p. 404 - 418 (2020/01/03)
Abstract: In this study, a binuclear palladium complex immobilized on the organo-functionalized SBA-16 was prepared and structurally characterized by routine techniques. Characterizations indicated that the mesostructure of SBA-16 was maintained after the immobilization of palladium complex. Then, the prepared nanomaterial was applied as a heterogeneous catalyst in the carbonylative Suzuki coupling reaction of aryl iodides with arylboronic acids using Cr(CO)6 as carbonyl source. The catalyst was efficiently promoted the coupling reactions of various aryl iodides and arylboronic acids to give the corresponding diaryl ketones in excellent yields. Moreover, the catalyst was readily recovered by filtration and could be reused for seven cycles without losing its structural integrity and catalytic activity. Graphic Abstract: [Figure not available: see fulltext.].
Carbonylative Suzuki coupling reactions catalyzed by ONO pincer–type Pd(II) complexes using chloroform as a carbon monoxide surrogate
Layek, Samaresh,Agrahari, Bhumika,Ganguly, Rakesh,Das, Parthasarathi,Pathak, Devendra D.
, (2020/01/25)
Benzoylhydrazone Schiff base–ligated three new ONO pincer–type palladium(II) complexes, [(PdL1(PPh3)] (1), [(PdL2(PPh3)] (2), and [(PdL3(PPh3)] (3), were synthesized by the reaction of the respective ligand, N-(2-hydroxybenzylidene)benzohydrazide (HL1), N-(2-hydroxy-3-methoxybenzylidene)benzohydrazide (HL2), or N-(5-bromo-2-hydroxybenzylidene) benzohydrazide (HL3), with Pd(OAc)2 and PPh3 in methanol and isolated as air-stable reddish-orange crystalline solids in high yields (78%–83%). All three complexes were fully characterized by elemental analysis, Fourier-transform infrared spectroscopy, UV–Visible, 1H nuclear magnetic resonance (NMR), 13C{1H} NMR, and 31P{1H} NMR spectroscopic studies. The molecular structure of all three complexes was established unambiguously by single-crystal X-ray diffraction studies which revealed a distorted square planar geometry of all three complexes. The ONO pincer–type ligands occupied three coordination sites at the palladium, while the fourth site is occupied by the monodentate triphenylphosphine ligand. The catalytic potential of all three complexes was explored in the carbonylative Suzuki coupling of aryl bromides and iodides with arylboronic acids to yield biaryl ketones, using CHCl3 as the source of carbonyl. The reported protocol is convenient and safe as it obviates the use of carbon monoxide (CO) balloons or pressured CO reactors which are otherwise needed for the carbonylation reactions. The methodology has been successfully applied to the synthesis of two antineoplastic drugs, namely, phenstatin and naphthylphenstatin, in good yields (81% and 85%, respectively). Under the optimized reaction conditions, complex 2 exhibited the best catalytic activity in the carbonylative Suzuki couplings. The reported catalysts have wide reaction scope with good functional group tolerance. All catalysts could be retrieved from the reaction after completion and recycled up to three times with insignificant loss in the catalytic activity.
