- A new efficient method for the preparation of intermediate aromatic ketones by Friedel–Crafts acylation
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Abstract: As the most important method to prepare pharmaceutical and chemical intermediate aromatic ketones, Friedel–Crafts (F–C) acylation is used to seek a novel catalytic system which is imminently consistent with the concept of green chemistry. In this study, six deep eutectic solvents (DES) were synthesized for the Friedel–Crafts acylation reaction as a catalytic solvent. Among the six DES, choline chloride-zinc chloride ([ChCl][ZnCl2]2) proved to be the most competent candidate of electron-rich arenes with acylation reagent. It got the highest yield when 1.0 equivalent of [ChCl][ZnCl2]2 used with acyl halides at 70?°C. Recycled DES was reused directly without any extra process. After five cycles, the catalytic activity did not decrease significantly (80–85%). Finally, according to experimental validation, the possible mechanism of this reaction was considered. Graphical Abstract: [Figure not available: see fulltext.].
- Jin, Xiaojun,Wang, Ailing,Cao, Hongyu,Zhang, Shujia,Wang, Lihao,Zheng, Xueliang,Zheng, Xuefang
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p. 5521 - 5530
(2018/04/30)
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- Synthesis of diaryl ketones through oxidative cleavage of the C-C double bonds in N -Sulfonyl enamides
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An oxidative cleavage of a C-C double bond is developed from the photochemical [2+2]-cycloaddition of diaryl N-tosyl enamides, aryl heteroaryl N-tosyl enamides, and N-tosyl cyclic enamides with singlet molecular oxygen, followed by a ring-opening reaction mediated by Cs2CO3 under air and sunlight without the use of photosesitizer, producing symmetrical and unsymmetrical diaryl, heterodiaryl, and cyclic ketones in good to excellent yields. Moreover, the oxidative cleavage of C-C triple bonds from 1-alkynes is demonstrated for the synthesis of symmetrical and unsymmetrical ketones from the Cu-catalyzed [3+2]-cycloaddition, Rh-catalyzed alkoxyarylation, photooxygenation, and ring-opening reaction in one-pot. Because the synthesis of the symmetrical and unsymmetrical diaryl and/or heterodiaryl ketones bearing an electron-donating group is not easy, the present method is notable.
- Kim, Hyunseok,Park, Sangjune,Baek, Yonghyeon,Um, Kyusik,Han, Gi Uk,Jeon, Da-Hye,Han, Sang Hoon,Lee, Phil Ho
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p. 3486 - 3496
(2018/04/14)
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- COMPOUND AND COMPOSITION CONTAINING THE SAME, AND METHOD FOR MANUFACTURING DEVICE USING THE COMPOSITION
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PROBLEM TO BE SOLVED: To provide a compound which efficiently absorbs extreme ultraviolet radiation (EUV) such as KrF excimer laser and ArF excimer laser or an electron beam, has low sensitivity to OoB, and has high contrast. SOLUTION: A compound is represented by formula (1) and formula (2). In formulae (1) and (2), R1a and R1a are each independently a first monovalent organic group containing a divalent hydrocarbon group selected from an alkylene group; a group bonded directly to sulfur atom (S+) is the divalent hydrocarbon group; R2 is a hydrogen atom, an alkyl group and the like; R3 to R6 are a hydrogen atom, a hydroxy group or a second monovalent organic group; X- is a monovalent anion; and R1a and R1b in Formula (1) or R1a and R1b in Formula (2) may be bonded to each other to form a ring. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0152-0154
(2017/09/14)
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- P -Selective (sp2)-C-H functionalization for an acylation/alkylation reaction using organic photoredox catalysis
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p-Selective (sp2)-C-H functionalization of electron rich arenes has been achieved for acylation and alkylation reactions, respectively, with acyl/alkylselenides by organic photoredox catalysis involving an interesting mechanistic pathway.
- Pandey, Ganesh,Tiwari, Sandip Kumar,Singh, Bhawana,Vanka, Kumar,Jain, Shailja
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supporting information
p. 12337 - 12340
(2017/11/20)
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- Direct C-H Cyanation of Arenes via Organic Photoredox Catalysis
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Methods for the direct C-H functionalization of aromatic compounds are in demand for a variety of applications, including the synthesis of agrochemicals, pharmaceuticals, and materials. Herein, we disclose the construction of aromatic nitriles via direct C-H functionalization using an acridinium photoredox catalyst and trimethylsilyl cyanide under an aerobic atmosphere. The reaction proceeds at room temperature under mild conditions and has proven to be compatible with a variety of electron-donating and -withdrawing groups, halogens, and nitrogen- and oxygen-containing heterocycles, as well as aromatic-containing pharmaceutical agents.
- McManus, Joshua B.,Nicewicz, David A.
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p. 2880 - 2883
(2017/03/11)
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- An efficient combination of Zr-MOF and microwave irradiation in catalytic Lewis acid Friedel-Crafts benzoylation
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A zirconium-based metal-organic framework, an effective heterogeneous catalyst, has been developed for the Friedel-Crafts benzoylation of aromatic compounds under microwave irradiation. Constructed by a Zr(iv) cluster and a linker 1,4-bis(2-[4-carboxyphenyl]ethynyl)benzene (H2CPEB), the MOF, possessing large pores and high chemical stability, was appropriate for the enhancement of Lewis acid activity under microwave irradiation. The reaction studies demonstrated that the material could give high yields for a few minutes and maintain its reactivity and structure over several cycles.
- Doan, Tan L. H.,Dao, Thong Q.,Tran, Hai N.,Tran, Phuong H.,Le, Thach N.
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supporting information
p. 7875 - 7880
(2016/05/24)
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- Carbonylative coupling of aryl tosylates/triflates with arylboronic acids under CO atmosphere
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The carbonylative Suzuki-Miyaura reaction between aryl tosylates/triflates with arylboronic acid is herein reported, using base-free conditions and a balloon pressure of carbon monoxide. Under these conditions, unsymmetrical biaryl ketones were obtained in modest to excellent yields. This method was adapted to the synthesis of oxybenzone and ketoprofen in good yields under mild conditions.
- Hao, Cheng Yi,Wang, Dan,Li, Ya Wei,Dong, Lin Lin,Jin, Ying,Zhang, Xiu Rong,Zhu, He Yun,Chang, Sheng
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p. 86502 - 86509
(2016/09/23)
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- Efficient Synthesis of Diaryl Ketones by Nickel-Catalyzed Negishi Cross-Coupling of Amides by Carbon–Nitrogen Bond Cleavage at Room Temperature Accelerated by a Solvent Effect
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The first Negishi cross-coupling of amides for the synthesis of versatile diaryl ketones by selective C?N bond activation under exceedingly mild conditions is reported. The cross-coupling was accomplished with bench-stable, inexpensive precatalyst [Ni(PPh3)2Cl2] that shows high functional-group tolerance and enables the synthesis of highly functionalized diaryl ketone motifs. The coupling occurred with excellent chemoselectivity favoring the ketone (cf. biaryl) products. Notably, this process represents the mildest conditions for amide N?C bond activation accomplished to date (room temperature, 10 min). Considering the versatile role of polyfunctional biaryl ketone linchpins in modern organic synthesis, availability, and excellent functional-group tolerance of organozinc reagents, this strategy provides a new platform for amide N?C bond/organozinc cross-coupling under mild conditions.
- Shi, Shicheng,Szostak, Michal
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p. 10420 - 10424
(2016/07/21)
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- Nickel-catalyzed diaryl ketone synthesis by N-C cleavage: Direct negishi cross-coupling of primary amides by site-selective N,N-Di-boc activation
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A general Negishi acylation of primary amides enabled by a combination of site-selective N,N-di-Boc activation and nickel catalysis is reported for the first time. The reaction is promoted by a bench-stable, inexpensive Ni catalyst. The reaction shows excellent functional group compatibility, affording functionalized diaryl ketones by selective N-C cleavage. Most notably, this protocol represents the first amide cross-coupling by direct metal insertion of simple and readily available primary amides. The overall strategy by N,N-di-Boc activation/metal insertion is suitable for a broad range of coupling protocols via acylmetals. Mechanistic experiments suggest high reactivity of N,N-di-Boc activated 1° amides in direct amide C-N cross-couplings.
- Shi, Shicheng,Szostak, Michal
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p. 5872 - 5875
(2016/11/29)
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- An efficient and green method for regio- and chemo-selective Friedel-Crafts acylations using a deep eutectic solvent ([CholineCl][ZnCl2]3)
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[CholineCl][ZnCl2]3, a deep eutectic solvent between choline chloride and ZnCl2, has been used as a dual function catalyst and green solvent for the Friedel-Crafts acylation of aromatic compounds instead of using the moisture-sensitive Lewis acids and volatile organic solvents. The reactions are performed with high yields under microwave irradiation with short reaction times for the synthesis of ketones. Interestingly, indole derivatives are regioselectively acylated in the 3-position under mild conditions with high yields without NH protection. Three new ketone products are synthesized. [CholineCl][ZnCl2]3 is easily synthesized from choline chloride and zinc chloride at a low cost, with easy purification and environmentally benign compounds. [CholineCl][ZnCl2]3 can be reused up to five times without loss of catalytic activity, making it ideal in industrial processes.
- Tran, Phuong Hoang,Nguyen, Hai Truong,Hansen, Poul Erik,Le, Thach Ngoc
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p. 37031 - 37038
(2016/05/24)
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- Hexafluoro-2-propanol-Promoted Intermolecular Friedel-Crafts Acylation Reaction
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The intermolecular Friedel-Crafts acylation was carried out in hexafluoro-2-propanol to yield aryl and heteroaryl ketones at room temperature without any additional reagents.
- Vekariya, Rakesh H.,Aubé, Jeffrey
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supporting information
p. 3534 - 3537
(2016/08/16)
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- Catalysis of the acylation of aromatic derivatives by metallic tosylates
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A series of metallic tosylates were prepared by ultrasonic metal activation and were further used as efficient catalysts for the acylation of aromatic derivatives.
- Morizur, Vincent,Szafranek, Jessica,Bonhomme, Dominique,Olivero, Sandra,Desmurs, Jean Roger,Du?ach, Elisabet
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p. 6813 - 6817
(2015/08/24)
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- Erbium trifluoromethanesulfonate catalyzed Friedel-Crafts acylation using aromatic carboxylic acids as acylating agents under monomode-microwave irradiation
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Erbium trifluoromethanesulfonate is found to be a good catalyst for the Friedel-Crafts acylation of arenes containing electron-donating substituents using aromatic carboxylic acids as the acylating agents under microwave irradiation. An effective, rapid and waste-free method allows the preparation of a wide range of aryl ketones in good yields and in short reaction times with minimum amounts of waste.
- Tran, Phuong Hoang,Hansen, Poul Erik,Nguyen, Hai Truong,Le, Thach Ngoc
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p. 612 - 618
(2015/02/19)
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- Improvement of the Friedel-Crafts benzoylation by using bismuth trifluoromethanesulfonate in 1-butyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid under microwave irradiation
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Bismuth trifluoromethanesulfonate (bismuth triflate) catalyzed the Friedel-Crafts benzoylation of activated aromatic compounds when dissolved in 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIM]OTf) ionic liquid. Immobilization of bismuth triflate (5 mol %) in [BMIM]OTf allowed the synthesis of aryl ketones in good to excellent yields with short reaction times under microwave irradiation. This catalytic system was easily recovered and reused several times without any significant loss of the activity.
- Hoangtran, Phuong,Bichle Do, Ngoc,Ngocle, Thach
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p. 205 - 208
(2014/01/06)
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- Microwave-assisted facile and rapid friedel-crafts benzoylation of arenes catalyzed by bismuth trifluoromethanesulfonate
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The catalytic activity of metal triflates was investigated in Friedel-Crafts benzoylation under microwave irradiation. Friedel-Crafts benzoylation with benzoyl chloride of a variety of arenes containing electron-rich and electron-poor rings using bismuth triflate under microwave irradiation is described. This method allows the preparation of aryl ketones under solventless conditions in good to excellent yields and short reaction time. Bismuth triflate was easily recovered and reused five times without significant loss of the catalytic activity.
- Tran, Phuong Hoang,Hansen, Poul Erik,Pham, Thuy Thanh,Huynh, Vy Thanh,Huynh, Vy Hieu,Thi Tran, Thao Du,Huynh, Thanh Van,Le, Thach Ngoc
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p. 2921 - 2929
(2014/10/15)
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- Efficient and recyclable rare earth-based catalysts for Friedel-Crafts acylations under microwave heating: Dendrimers show the way
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The catalytic system involving Sc(OTf)3 and a dendritic terpyridine ligand is able to promote the Friedel-Crafts acylation of a wide range of aromatics under microwave irradiation. The expected products are obtained in high yields after short reaction times and the nano-sized catalyst can be recovered and successfully used in 12 consecutive runs.
- Perrier, Arnaud,Keller, Michel,Caminade, Anne-Marie,Majoral, Jean-Pierre,Ouali, Armelle
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supporting information
p. 2075 - 2080
(2013/09/24)
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- Friedel-Crafts acylation using bismuth triflate in [BMI][PF6]
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Bismuth trifluoromethanesulfonate was found to be a good catalyst for the Friedel-Crafts acylation. Bismuth triflate immobilized in an ionic liquid was the most efficient catalytic system. Bismuth triflate in [BMI][PF6] catalyzes this reaction under microwave irradiation allowing the rapid synthesis of aryl ketones in excellent yields. The catalyst system was easily recovered and reused several times.
- Tran, Phuong Hoang,Duus, Fritz,Le, Thach Ngoc
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experimental part
p. 222 - 224
(2012/01/30)
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- Modular synthesis of polyphenolic benzofurans, and application in the total synthesis of malibatol A and shoreaphenol
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A modular strategy for the synthesis of hexacyclic dimeric resveratrol polyphenolic benzofurans is reported. The developed synthetic technology was applied to the total synthesis of malibatol A, shoreaphenol, and other biologically relevant polyphenols.
- Chen, David Y.-K.,Kang, Qiang,Wu, T. Robert
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experimental part
p. 5909 - 5927
(2010/11/05)
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- Friedel-Crafts acylation of aromatic compounds with carboxylic acids in the presence of P2O5/SiO2 under heterogeneous conditions
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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
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scheme or table
p. 6715 - 6719
(2009/04/07)
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- Phenyltellanyl triflate (PhTeOTf) as a powerful tellurophilic activator in the friedel-crafts reaction
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A powerful electrophilic activator for organotellurium compounds was developed. Phenyltellanyl triflate (PhTeOTf) prepared in situ from dibromophenyl(phenyltellanyl)telluride and AgOTf selectively activated various organotellurium compounds in the presence of aromatic compounds yielding the corresponding Friedel-Crafts reaction products. Polymer-end organotellurium compounds were also activated by PhTeOTf providing the corresponding end-functionalized polymers. Copyright
- Yamada, Takeshi,Mishima, Eri,Ueki, Kazuya,Yamago, Shigeru
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p. 650 - 651
(2008/12/20)
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- Synthesis of sterically hindered ortho-substituted tetraphenylethenes. Electronic effects in the McMurry olefination reaction
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Contrary to literature consensus, the McMurry olefination reaction can be extended to the direct synthesis of sterically encumbered tetrakis(2- substituted) tetraphenylethenes from the corresponding 2,2′-disubstituted benzophenones. The reaction exploits
- Chung, Mee-Kyung,Qi, Guizhong,Stryker, Jeffrey M.
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p. 1491 - 1494
(2007/10/03)
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- Hf[N(SO2C8F17)2] 4-catalyzed Friedel-Crafts acylation in a fluorous biphase system
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In a fluorous biphase system, Hf[N(SO2C8F 17)2]4 complex (1 mol %) catalyzes Friedel-Crafts acylation of aromatic compounds such as anisole, toluene and chlorobenzene, and the corresponding aromatic ketones are obtained in satisfactory to high yields. The catalyst is selectively soluble in lower fluorous phase and can be easily recovered by simple phase separation. Furthermore, the catalyst can be reused without decrease of activity in most cases.
- Hao, Xiuhua,Yoshida, Akihiro,Nishikido, Joji
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p. 2697 - 2700
(2007/10/03)
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- Catalytic Friedel-Crafts acylation of aromatic ethers using Sml3
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10% mol Sml3 catalysed the Friedel-Crafts acylation of aromatic ethers by acyl chlorides in acetonitrile with the yields of 48-82%. Reactions of various substituted aromatic ethers with acyl chloride were studied. The structures of compounds were established by IR and 1H NMR. The main product obtained with anisole is the para-substituted compound with only a trace (3, a pattern repeated with the other aromatic ethers used.
- Chen, Xiaohang,Yu, Mingxin,Wang, Meijun
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- Aluminum dodecatungstophosphate (AlPW12O40) as a non-hygroscopic Lewis acid catalyst for the efficient Friedel-Crafts acylation of aromatic compounds under solvent-less conditions
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Stable and non-hygroscopic aluminum dodecatungstophosphate (AlPW 12O40), which is prepared easily from cheap and commercially available compounds was found to be an effective catalyst for Friedel-Crafts acylation reactions using carboxylic acids, acetic anhydride and benzoyl chloride in the absence of solvent under mild reaction conditions.
- Firouzabadi, Habib,Iranpoor, Nasser,Nowrouzi, Farhad
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p. 10843 - 10850
(2007/10/03)
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- An efficient route towards aromatic ketones without solvent and support under electromagnetic microwave activation
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Five aromatic ketones were synthetized by Friedel-Crafts reaction from aromatic compounds and acid chlorides using electromagnetic micro-waves, without solvent and absorbent inorganic support.
- Brǎtulescu, George
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p. 175 - 177
(2007/10/03)
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- Nickel-catalyzed coupling of aryl iodides with aromatic aldehydes: Chemoselective synthesis of ketones
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Aryl iodide (ArI) couple with aryl aldehydes (Ar'CHO) in the presence of Ni(dppe)Br2 and Zn to give the corresponding biaryl ketones (ArCOAr′). The use of a bidentate phosphine complex is critical to the success of this catalytic reaction. The
- Huang, Yi-Chun,Majumdar, Kanak Kanti,Cheng, Chien-Hong
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p. 1682 - 1684
(2007/10/03)
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- BeCl2 as a new highly selective reagent for dealkylation of aryl-methyl ethers
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An efficient and simple method is introduced for the selective removal of methyl group from poly aryl-methyl ethers, in some important derivatives of benzophenones, xanthones, anthraquinones, aryl esters, benzamides and nitroanisoles with BeCl2.
- Sharghi, Hashem,Tamaddon, Fatemeh
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p. 13623 - 13640
(2007/10/03)
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- Photochromic naphthopyran compounds
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Described are novel reversible photochromic naphthopyran compounds having at least one ortho substituted phenyl group at the 3-position of the pyran ring. Also described are organic host materials that contain or that are coated with such compounds. Articles such as ophthalmic lenses or other plastic transparencies that incorporate the novel naphthopyran compounds or combinations thereof with complementary photochromic compounds, e.g., spiro(indolino)-oxazine type compounds, are also described.
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- 2-(Trifluoromethylsulfonyloxy)pyridine as a Reagent for the Ketone Synthesis from Carboxylic Acids and Aromatic Hydrocarbons
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A new reagent 2-(trifluoromethylsulfonyloxy)pyridine (TFOP) was prepared by the reaction of sodium salt of 2-pyridinol with trifluoromethylsulfonyl chloride in dioxane.The conpound TFOP in trifluoroacetic acid has been found to intermolecularly dehydrate from benzoic acid and aromatic hydrocarbons to give the corresponding benzophenones in high yield.It was further elucidated, in the reaction of fluorene, that a variety of carboxylic acids can be used as the acyl precursor for the aromatic ketone synthesis in conjunction with the TFOP/TFA system.This acylation procedure has been applied to the synthesis of 2-acylthiophenes, which are hard to prepare in a satisfactory yield by the classical Friedel-Crafts reaction using aluminum chloride as the catalyst.
- Keumi, Takashi,Yoshimura, Kiichiro,Shimada, Masakazu,Kitajima, Hidehiko
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p. 455 - 460
(2007/10/02)
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- Triflic acid catalyzed aroylation of arenes with aromatic nitriles
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In the presence of triflic acid, the reaction of different aromatic nitriles with arenes under a variety of conditions was examined.In addition to the normal reaction products (the s-triazines), aroylation of the arene to produce diaryl ketones in 20 to 50 percent yield was observed.Possible mechanism for the reaction was proposed.
- El-Khagawa, Ahmed M.
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p. 372 - 374
(2007/10/02)
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- 2-Substituted 1,3-Benzoxathiolium Tetrafluoroborates as Useful Acylating Agents of Electron-Rich Aromatic and Heteroaromatic Compounds
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2-Substituted 1,3-benzoxathiolium tetrafluoroborates were used for the two-step acylation of electron-rich aromatic and heteroaromatic compounds: 1,3-dimethoxybenzene, 1,3,5-trimethoxybenzene, pyrrole and indoles.In most of the cases intermediate 2,2-disubstituted 1,3-benzoxathioles were obtained in good to high yields (55-100percent) and subsequent hydrolysis of these with mercury(II) oxide and aqueous tetrafluoroboric acid (35percent) in tetrahydrofuran afforded the corresponding ketones in almost quantitative yields.
- Cadamuro, Silvano,Degani, Iacopo,Fochi, Rita,Gatti, Antonella,Regondi, Valeria
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p. 311 - 314
(2007/10/02)
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- The Chemistry of Nitrilium Salts. Part 3. The Importance of Triazinium Salts in Houben-Hoesch Reactions Catalyzed by Trifluoromethanesulphonic Acid
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In the presence of trifluoromethanesulphonic (triflic) acid, isobutyronitrile reacts with anisole, 1,3-dimethoxybenzene, resorcinol, 1,3,5-trimethoxybenzene, and phloroglucinol at room temperature to give acylation products.A study of the reactions of acetonitrile and isobutyronitrile with triflic acid has shown that these modified Houben-Hoesch reactions occur by initial cyclotrimerization of the nitriles to 1,3,5-triazinium triflate salts followed by a slow reaction of the salts with the aromatic substrate.Support for this comes from the isolation of 2-(4-methoxyphenyl)-2,4,6-tri-isopropyl-1,2-dihydro-1,3,5-triazine from the reaction between anisole, triflic acid, and isobutyronitrile.Similar 1,2-dihydro-s-triazines and their salts have been prepared by reaction of trimethyl-s-triazinium triflate with 1,3-(MeO)2C6H4, and tri-isopropyl-s-triazinium triflate with 1,3-(RO)2C6H4 (R = H or Me) and 1,3,5-(MeO)3C6H3; these salts are easily hydrolyzed to the corresponding aromatic ketones.The salt +23SCF3 also reacts with o-phenylenediamine to give 2-methylbenzimidazolinium triflate in 83percent yield.Nitrilium salts NMe>+NMe>+3SCF3 at room temperature.
- Amer, Muhannad I.,Booth, Brian L.,Noori, Ghazi F. M.,Proenca, M. Fernanda J. R. P.
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p. 1075 - 1082
(2007/10/02)
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- The Synthesis and Some Reactions of N-Methylnitrilium Trifluoromethanesulphonate Salts
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N-Methylnitrilium trifluoromethanesulphonate (triflate) salts, prepared from nitriles and methyl triflate, have been shown to be useful reagents for the synthesis of aromatic ketimines and ketones, amidinium, imidate, and thioimidate salts, benzimidazoles, benzoxazoles, benzothiazoles, quinazolinones, and 1,2,4-triazolinium salts.
- Booth, Brian L.,Jibodu, Kehinde O.,Proenca, M. Fernanda
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p. 1151 - 1153
(2007/10/02)
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