- Functional mesoporous poly (ionic liquid) derived from P123: From synthesis to catalysis and alkylation of styrene and o-xylene
-
A novel strategy was proposed for the fabrication of high-performance acidic mesoporous poly ionic liquids catalyst. In this work, mesoporous poly ionic liquids (MPILs) were synthesized with P123 (PEO20PPO70PEO20) served a
- Wang, Beibei,Sheng, Xiaoli,Zhou, Yuming,Zhu, Zhiying,Liu, Yonghui,Sha, Xiao,Zhang, Chao,Gao, Huaying
-
-
Read Online
- Transition-Metal-Free Suzuki-Type Cross-Coupling Reaction of Benzyl Halides and Boronic Acids via 1,2-Metalate Shift
-
Cross-coupling of organoboron compounds with electrophiles (Suzuki-Miyaura reaction) has greatly advanced C-C bond formation and has been well received in medicinal chemistry. During the past 50 years, transition metals have played a central role throughout the catalytic cycle of this important transformation. In this process, chemoselectivity among multiple carbon-halogen bonds is a common challenge. In particular, selective oxidative addition of transition metals to alkyl halides rather than aryl halides is difficult due to unfavorable transition states and bond strengths. We describe a new approach that uses a single organic sulfide catalyst to activate both C(sp3) halides and arylboronic acids via a zwitterionic boron "ate" intermediate. This "ate" species undergoes a 1,2-metalate shift to afford Suzuki coupling products using benzyl chlorides and arylboronic acids. Various diaryl methane analogues can be prepared, including those with complex and biologically active motifs. The reactions proceed under transition-metal-free conditions, and C(sp2) halides, including aryl bromides and iodides, are unaffected. The orthogonal chemoselectivity is demonstrated in the streamlined synthesis of highly functionalized diaryl methane scaffolds using multi-halogenated substrates. Preliminary mechanistic experiments suggest both the sulfonium salt and the sulfur ylide are involved in the reaction, with the formation of sulfonium salt being the slowest step in the overall catalytic cycle.
- He, Zhiqi,Song, Feifei,Sun, Huan,Huang, Yong
-
supporting information
p. 2693 - 2699
(2018/02/28)
-
- MoO3 supported on ordered mesoporous zirconium oxophosphate: An efficient and reusability solid acid catalyst for alkylation and esterification
-
A series of molybdenum oxide supported on ordered mesoporous zirconium oxophosphate (MoO3/M-ZrPO) materials with different MoO3 loadings (0–20 wt%) and calcination temperatures (500–900 °C) have been designed, synthesized and employed as solid acid catalysts in alkylation and esterification. The XRD, TG-DSC, H2-TPR, N2-physisorption and TEM characterizations were taken to investigate the structural properties and states of introduced MoO3 species. The influence of MoO3 loadings and calcination temperatures in catalytic performance was detailedly investigated and optimal catalytic activity was reached at 10 wt% MoO3 loadings and treated at 700 °C. Moreover, MoO3/M-ZrPO catalysts exhibited outstanding catalytic performance in Friedel-Crafts alkylation of different aromatic compounds and esterification of levulinic acid with 1-butanol. Furthermore, it was noteworthy that the catalyst had superior reusability and no noticeable declines were observed in catalytic performance even after seven runs.
- Miao, Zhichao,Li, Zhenbin,Zhao, Jinping,Si, Weijiang,Zhou, Jin,Zhuo, Shuping
-
-
- Benzylation with Benzyl Alcohol Catalyzed By [ChCl][TfOH]2, a Br?nsted Acidic DES with Reaction Control Self-Separation Performance
-
Abstract: A deep eutectic solvent with strong Br?nsted acidity was prepared easily by choline chloride and trifluoromethanesulfonic acid. The obtained [ChCl][TfOH]2 catalyst which was characterized by FT-IR, 1H NMR and TG, possessed greatly enhanced stability than trifluoromethanesulfonic acid, and exhibited excellent catalytic performance in benzylation with benzyl alcohol. Especially, the prepared [ChCl][TfOH]2 catalyst could dissolve into the reactants to realize homogeneous catalysis, and then self-separate from the organic phase after reaction due to the entire consumption of benzyl alcohol. As a result, the catalyst could be recovered and reused simply for six-runs without noticeable loss of catalytic performance. Graphical Abstract: [Figure not available: see fulltext.].
- Yuan, Bing,Li, Yinglian,Yu, Fengli,Li, Xiaoqiang,Xie, Congxia,Yu, Shitao
-
p. 2133 - 2138
(2018/05/29)
-
- Bisulfate Salt-Catalyzed Friedel-Crafts Benzylation of Arenes with Benzylic Alcohols
-
We report here a method of direct Friedel-Crafts benzylation of arenes with benzylic alcohols using cheap and readily available bisulfate salt as the catalyst in hexafluoroisopropanol. The catalytic system is powerful with a quite diverse group of functionalized arenes and benzylic alcohols. These mild conditions provide a straightforward synthesis of a variety of unsymmetrical diarylmethanes in high yield with good to high regioselectivity. An SN1 mechanism involving activation of the hydroxy group through a hydrogen bond is proposed.
- Tang, Ren-Jin,Milcent, Thierry,Crousse, Benoit
-
p. 14001 - 14009
(2018/11/23)
-
- T-BuONa-Mediated Transition-Metal-Free Autoxidation of Diarylmethanes to Ketones
-
Autoxidative sp3 C-H transformation of diarylmethanes has been demonstrated using O2-mediation by t-BuONa. This protocol enables an alternative route for the access to diaryl ketones from benzyl derivatives in good to excellent yields under mild reaction conditions, without transition metal catalysts or additional chemical oxidants.
- Li, Jiang-Sheng,Yang, Fan,Yang, Qian,Li, Zhi-Wei,Chen, Guo-Qin,Da, Yu-Dong,Huang, Peng-Mian,Chen, Chao,Zhang, Yuefei,Huang, Ling-Zhi
-
supporting information
p. 994 - 998
(2017/05/10)
-
- Synthesis of Di- and Triarylmethanes through Palladium-Catalyzed Reductive Coupling of N -Tosylhydrazones and Aryl Bromides
-
A palladium-catalyzed reductive coupling between N-tosylhydrazones and aryl bromides has been developed. The reaction provides an efficient method for the synthesis of diarylmethanes and triarylmethanes via the formation of C(sp2)-C(sp3) single bonds. This new methodology for the synthesis of diarylmethanes and triarylmethanes is featured by the ready availability of the starting materials, mild reaction conditions, and the tolerance of wide range of functional groups. The reaction follows a pathway including palladium carbene formation, migratory insertion, and reduction of the alkylpalladium(II) intermediate.
- Xia, Yamu,Hu, Fangdong,Xia, Ying,Liu, Zhenxing,Ye, Fei,Zhang, Yan,Wang, Jianbo
-
p. 1073 - 1086
(2017/02/24)
-
- Alternative approach toward the generation of benzylic zinc reagent: Direct oxidative addition of active zinc into the carbon-oxygen bond of benzyl mesylates
-
The use of highly active zinc, prepared by the Rieke method, for the direct preparation of benzylic zinc mesylate was investigated. The oxidative addition of highly active zinc to benzyl mesylate was easily completed under mild conditions. The resulting benzylic zinc mesylates were employed in subsequent cross-coupling reactions with a broad range of electrophiles, and the formation of the corresponding products was successful.
- Jung, Hye-Soo,Kim, Seung-Hoi
-
p. 666 - 670
(2015/03/14)
-
- Benzylation of arenes with benzyl ethers promoted by the in situ prepared superacid BF3-H2O
-
An efficient and environmentally friendly benzylation of arenes with benzyl ethers as benzyl donors using BF3-Et2O to generate in situ the superacid BF3-H2O as an efficient promotor has been described. A wide variety of functional groups have been investigated and found to be compatible to give the desired diarylmethanes in yields of up to 99%. The crucial role of the moisture content in this transformation has been demonstrated by detailed investigations. This journal is the Partner Organisations 2014.
- Li, Yu,Xiong, Yan,Li, Xueming,Ling, Xuege,Huang, Ruofeng,Zhang, Xiaohui,Yang, Jianchun
-
p. 2976 - 2981
(2014/06/10)
-
- Iron-containing defect-rich mixed metal oxides for Friedel-Crafts alkylation
-
Several stable iron-containing spinel oxides with the composition CuFe 2O4 or FeCr2O4 were prepared by different methods including thermal nitrate decomposition, combustion synthesis, and mechano-chemical synthesis. Materials were compared to commercially available spinels produced by conventional ceramic route with respect to their structural properties and catalytic activity. Phase compositions and microstructures of the catalysts were studied in detail. The catalysts were tested in the Friedel-Crafts alkylation of various aromatic compounds with different alkyl halides as alkylating agents. Microstructural properties (microstrains) of the synthesized binary oxides have been identified as a reason for the increased reactivity. Even at low reaction temperatures of 50-70 °C catalysts maintained their high activity resulting in TOFs of up to 3000 h -1 and excellent selectivity with total heterogeneous behavior in catalysis.
- J?ger, Benjamin,Wermann, Antje,Scholz, Peter,Müller, Matthias,Reisl?hner, Udo,Stolle, Achim,Ondruschka, Bernd
-
-
- Synthesis of diarylmethanes via a Friedel-Crafts benzylation using arenes and benzyl alcohols in the presence of triphenylphosphine ditriflate
-
Triphenylphosphine ditriflate (TPPD) was found to be an efficient promoter for the Friedel-Crafts benzylation of arenes with benzyl alcohols in CH 2Cl2 at room temperature. The good yields, the 1:1 molar ratio of arene and benzyl alcohol, the benzylation of chlorobenzene as a nonactivated aromatic compound at room temperature, and no by-product formation are the main advantages of this procedure.
- Khodaei, Mohammad Mehdi,Nazari, Ehsan
-
experimental part
p. 5131 - 5135
(2012/09/22)
-
- Iron(iii)-based ionic liquid-catalyzed regioselective benzylation of arenes and heteroarenes
-
An easily prepared Fe(iii)-derived Lewis acid ionic liquid ([C 4mim][FeCl4]), being comprised of 1-butyl-3-methyl imidazolium cation and tetrachloroferrate anion, was found to be an efficient, recyclable catalyst for benzylation of various arenes/heteroarenes into the diarylmethanes derivatives under mild reaction conditions without utilization of additional organic solvent. Interestingly, the acidity of [C 4mim][FeCl4] could account for its catalytic activity in promoting the Lewis acid-catalyzed alkylation. Notably, this type of Fe(iii)-based ionic liquid (IL) shows excellent stability, and could be easily recovered, and reused for five times without significant loss of its catalytic activity.
- Gao, Jian,Wang, Jin-Quan,Song, Qing-Wen,He, Liang-Nian
-
supporting information; experimental part
p. 1182 - 1186
(2011/06/25)
-
- Mesoporous zirconium phosphate catalyzed reactions: Synthesis of industrially important chemicals in solvent-free conditions
-
Mesoporous zirconium phosphate (m-ZrP) having high specific surface area and narrow pore size distributions is synthesized in basic medium using zirconium carbonate as source of zirconium. The concentration of phosphate in precursor solutions, as well as the calcination temperature, is found to influence the textural properties and acidity of synthesized m-ZrP significantly. Microscopic analysis indicates the presence of worm like pores with spherical morphology. The porous structure has remarkable thermal stability (up to 800 °C). DRIFT and NH3-TPD analysis suggest the presence of reasonable amount of Lewis and Bro?nsted acid sites. High catalytic activity of synthesized m-ZrP is observed towards Friedel-Craft (F.C.) benzylation reaction. The effect of acid strength of catalyst, reaction time, temperature and amount of catalyst towards Friedel-Craft benzylation reaction are also studied. The m-ZrP is highly active towards other acid catalyzed reactions in solvent-free conditions. The catalytic activity of m-ZrP is much higher than that of conventional layered ZrP. The catalysts were separated easily from reaction mixture, regenerated after a simple activation step and reused at least six times without significant loss in catalytic activity.
- Sinhamahapatra, Apurba,Sutradhar, Narottam,Roy, Biplab,Tarafdar, Abhijit,Bajaj, Hari C.,Panda, Asit Baran
-
scheme or table
p. 22 - 30
(2011/02/23)
-
- Iron oxide nanoparticles grown on carboxy-functionalized graphite: An efficient reusable catalyst for alkylation of arenes
-
Here we report a simple procedure for the synthesis of a novel hybrid catalyst by growing iron oxide nanoparticles on carboxy-functionalized graphite. This hybrid catalyst demonstrated superior catalytic activity towards the alkylation of arenes with alkyl halides in contrast to commercial graphite or unsupported iron oxide nanoparticles in terms of yields and general applicability. The catalyst can be reused up to five times with a minimal loss of catalytic activity. Georg Thieme Verlag Stuttgart.
- Rajpara, Vikul,Banerjee, Subhash,Sereda, Grigoriy
-
experimental part
p. 2835 - 2840
(2010/10/04)
-
- A simple catalyst for the efficient benzylation of arenes by using alcohols, ethers, styrenes, aldehydes, or ketones
-
The compound [IrCp* (OTf)2(InBu)] (I nBu = 1,3-di-n-butyl-imidazolylidene) is an effective catalyst in the benzylation of arenes with different benzylating agents, such as alcohols, ethers and styrenes, representing an unprecedented highly versatile catalyst for this type of process. The same compound also catalyses a remarkable tandem process that allows the use of aldehydes and ketones as benzylating agents, through the base-free hydrogenation of C=O bonds with iPrOH and further use of the resulting primary or secondary alcohols as benzylating agents.
- Prades, Amparo,Corberan, Rosa,Poyatos, Macarena,Peris, Eduardo
-
experimental part
p. 4610 - 4613
(2009/12/26)
-
- Benzylation of arenes through FeCl3-catalyzed Friedel-Crafts reaction via C-O activation of benzyl ether
-
Various benzyl ethers were converted to benzyl arenes via a FeCl3-catalyzed Friedel-Crafts alkylation reaction under mild condition in good yields. This method also offered a simple and practical approach to synthesize di- or tri-aryl methanes and aryl heteroaryl methanes through the activation of C-O bonds.
- Wang, Bi-Qin,Xiang, Shi-Kai,Sun, Zuo-Peng,Guan, Bing-Tao,Hu, Ping,Zhao, Ke-Qing,Shi, Zhang-Jie
-
p. 4310 - 4312
(2008/09/21)
-
- Molecular iodine-catalyzed benzylation of arenes with benzyl alcohols
-
A novel molecular iodine-catalyzed benzylation of arenes with benzyl alcohols has been developed. The reaction can be carried out under mild conditions to afford a series of diarymethane derivatives in high yields and good regioselectivities.
- Sun, Gaojun,Wang, Zhiyong
-
p. 4929 - 4932
(2008/09/21)
-
- An efficient synthesis of unsymmetrical diarylmethanes from the dehydration of arenes with benzyl alcohols using InCl3·4H2O/acetylacetone catalyst system
-
An efficient and practical synthesis of unsymmetrical diarylmethanes has been achieved from the dehydration of arenes with benzyl alcohols in the presence of catalytic amount of InCl3·4H2O/acetylacetone.
- Sun, Hong-Bin,Li, Biao,Chen, Songjie,Li, Jie,Hua, Ruimao
-
p. 10185 - 10188
(2008/02/13)
-
- Gold-catalyzed benzylation of arenes and heteroarenes
-
Friedel-Crafts type benzylation of arenes and heteroarenes with benzylic acetates, alcohols, and carbonates is effectively promoted under mild reaction conditions using catalytic amounts of gold salts. The resulting 1,1-diarylalkanes and 1-aryl-1-heteroarylalkanes are obtained in high yields and with high selectivity. The utility of the method is demonstrated by a short synthesis of beclobrate {ethyl 2-[4-(4-chlorobenzyl)-phenoxy]-2-methylbutyrate (3)}, a fibric acid derivative.
- Mertins, Kristin,Iovel, Irina,Kischel, Jette,Zapf, Alexander,Beller, Matthias
-
p. 691 - 695
(2007/10/03)
-
- An effective bismuth-catalyzed benzylation of arenes and heteroarenes
-
A highly efficient Bi(OTf)3-catalyzed benzylation of arenes and heteroarenes has been developed. The mild reaction conditions, high yields, operational simplicity and practicability, broad scope, and remarkably low catalyst loading render this environment friendly process an attractive approach to diarylmethane derivatives. The extension to an intramolecular variant of this procedure provides a valuable route to substituted fluorenes.
- Rueping, Magnus,Nachtsheim, Boris J.,Ieawsuwan, Winai
-
p. 1033 - 1037
(2007/10/03)
-
- Transition-metal-catalyzed benzylation of arenes and heteroarenes
-
Friedel-Crafts-type benzylation of various aromatic and heteroaromatic compounds with benzylic acetates, alcohols, and carbonates was promoted under mild reaction conditions by a series of Rh, Ir, Pd, and Pt catalysts (see scheme; R1 = H, Me; R2 = H, Cl, MeO; R3 = H, Ac, CO2Me). The desired products were obtained in high yields and with high selectivities.
- Mertins, Kristin,Iovel, Irina,Kischel, Jette,Zapf, Alexander,Beller, Matthias
-
p. 238 - 242
(2007/10/03)
-
- An efficient and general iron-catalyzed arylation of benzyl alcohols and benzyl carboxylates
-
(Chemical Equation Presented) Green grow the diarylmethanes: Substituted arenes and heteroarenes can be easily benzylated in the presence of inexpensive and relatively nontoxic metal salts such as FeCl3 (see scheme). This arylation method with benzyl alcohols is a state-of-the-art green route to diarylmethanes as water is the only by-product.
- Iovel, Irina,Mertins, Kristin,Kischel, Jette,Zapf, Alexander,Beller, Matthias
-
p. 3913 - 3917
(2007/10/03)
-
- A convenient and improved montmorillonite K-10 catalysed Friedel-Crafts benzylation and allylation with activated esters
-
Benzyl benzoate and cinnamyl acetate has been effectively used respectively as alkylating and allylating substrates in Friedel-Crafts reaction catalysed by montmorillonite K-10 clay.
- Karade,Shirodkar,Potrekar
-
p. 652 - 654
(2007/10/03)
-
- Liquid phase benzylation of o-xylene over pillared clays
-
Iron, aluminium and mixed iron aluminium pillared clays have been prepared by partial hydrolysis method and doped with 10% Mo, V and Cr. The samples have been characterised by XRD, FTIR and surface area and pore volume measurements. The surface acid site
- Kurian, Manju,Sugunan
-
p. 2480 - 2486
(2007/10/03)
-
- The catalytic Friedel-Crafts alkylation reaction of aromatic compounds with benzyl or allyl silyl ethers using Cl2Si(OTf)2 or Hf(OTf)4
-
The Friedel-Crafts alkylation reaction of various aromatic compounds with benzyl or allyl silyl ethers is effectively promoted under mild reaction conditions using Lewis acid catalysts. A mixture of the desired phenyltolylmethanes is obtained in 80% yield from toluene with benzyl dimethylsilyl or trimethylsilyl ether at 50°C in the presence of a catalytic amount of Cl2Si(OTf)2 or Hf(OTf)4.
- Shiina, Isamu,Suzuki, Masahiko
-
p. 6391 - 6394
(2007/10/03)
-
- Hypophosphorous acid-iodine: A novel reducing system. Part 2: Reduction of benzhydrols to diarylmethylene derivatives
-
A mixture of hypophosphorous acid (H3PO2) and iodine in acetic acid reduces a variety of substituted benzhydrols to the corresponding methylene derivatives in very high yields. The active reducing agent is hydrogen iodide generated by reaction between iodine and hypophosphorous acid.
- Gordon, Paul E.,Fry, Albert J.
-
p. 831 - 833
(2007/10/03)
-
- Hypophosphorous acid-iodine: A novel reducing system. Part 1: Reduction of diaryl ketones to diaryl methylene derivatives
-
A mixture of hypophosphorous acid (H3PO2) and iodine in hot acetic acid reduces diaryl ketones quickly and aryl alkyl ketones slowly to the corresponding methylene derivatives. The active reducing agent is hydrogen iodide, generated by reaction between iodine and hypophosphorous acid. (C) 2000 Elsevier Science Ltd.
- Hicks,Han,Fry
-
p. 7817 - 7820
(2007/10/03)
-
- Acidity and catalytic activity studies on the benzylation of o-xylene using some rare-earth exchanged zeolite-Y
-
The acidity of the various rare-earth exchanged zeolite-Y catalysts has been examined by titration method using Hammett indicators and is correlated with the catalytic activity of the samples in the benzylation of o-xylene.
- Sugunan,Jacob, Bindhu
-
p. 1054 - 1056
(2007/10/03)
-
- Ruthenium complex-catalyzed novel transformation of alkyl formates
-
The following ruthenium-catalyzed novel transformations of alkyl formates have been developed: (1) selective decarbonylation of alkyl formates to the corresponding alcohols; (2) alkylation of arenes and alkenes using alkyl formates as an alkylating reagent via decarboxylation.Also the ruthenium-catalyzed addition of alcohols to alkenes has been developed as an appendant reaction, providing an effective method for the protection of alcohols.Keywords: Ruthenium; Catalysis; Alkyl; Arene; Alkene; Alcohol
- Kondo, Teruyuki,Kajiya, Satoshi,Tantayanon, Supawan,Watanabe, Yoshihisa
-
-
- Perfluorooctanesulfonic acid catalyzed Friedel-Crafts alkylation with alkyl halides
-
A new procedure to prepare superacid perfluorooctanesulfonic acid (POSA) is reported. POSA catalyzed Friedel-Crafts alkylation of aromatic compounds with alkyl halides in liquid-phase reactions. Alkylation gave higher total yields than the corresponding reactions with Nafion-H, without the need of any complex decomposition or work-up. The reactions do not need to be carried out under absolutely anhydrous condition. The catalyst POSA can be easily separated from the reaction mixture and reused or recovered. The reactivity of the alkylation reagents and the mechanism of the reaction are discussed.
- Fu,He,Lei,Luo
-
p. 1273 - 1279
(2007/10/02)
-
- RUTHENIUM COMPLEX CATALYZED BENZYLATION OF ARENES WITH BENZYL FORMATES; DECARBONYLATION AND DECARBOXYLATION OF ALKYL FORMATES
-
Ru3(CO)12-(CH3)3NO*2H2O showed high catalytic activity for the decarbonylation of alkyl formates to the corresponding alcohols at 150 -200 deg C under an argon atmosphere.Decarbonylation of β-phenetyl formate afforded β-phenetyl alcohol in 82 percent yield.On the other hand, when decarbonylation of benzyl formate was performed in the absence of (CH3)3NO*2H2O, benzylation of arenes, which were employed as a solvent, proceeded via catalytic decarboxylation of benzyl formate.For the reaction of toluene with benzyl formate, phenyltolylmethane (o-, m-, and p-mixture) was obtained in total 77 percent yield.
- Kondo, Teruyuki,Tantayanon, Supawan,Tsuji, Yasushi,Watanabe, Yoshihisa
-
p. 4137 - 4140
(2007/10/02)
-
- PREPARATION OF SOME TRIMETHYL- AND METHYLETHYLBIPHENYLS AND REACTIVITY OF AROMATIC HYDROCARBONS IN THE GOMBERG REACTION
-
Trimethyl- and methylethylbiphenyls with the alkyl groups in the both phenyl rings have been prepared by the Gomberg reaction and identified by the capillary gas-liquid chromatography.Depending on choice of the aromatic hydrocarbon either individual isomers or their mixtures (three at the most) have been obtained which were contaminated with compounds of diarylmethane type in many cases.The methylethylbiphenyls have only been prepared as mixtures contaminated with diarylmethanes.These side products have been prepared by independent syntheses.A method has been developed for isolation and separation of mixtures of trimethyl- and methylethylbiphenyls from the reaction products containing tarry products.The method is suitable for preparation of small amounts of some analytical standards.The HMO method has been used for calculation of values of the radical superdelocalizabilities at individual centres in the molecules of o-, m- and p-xylene, toluene and ethylbenzene, and these values have been compared with composition of the Gomberg reaction products from these hydrocarbons.The competitive technique has been used for comparison of the reactivities of the mentioned aromatic substrates in the Gomberg reactions.
- Novrocik, Jan,Novrocikova, Marta,Titz, Milos
-
p. 3140 - 3149
(2007/10/02)
-
- -
-
Grignard reagents react with thiobenzophenone to give mainly the compound resulting from addition of the' organic radical to the sulfur atom. Addition to carbon, double addition both to sulfur and to carbon, and formation of tetraphenylthiiranne are also observed. The stable alkylthiodiphenylmethyl radical has been detected in the reaction medium. A mechanism is proposed to account for the various reactions.
- Dagonneau,Vialle
-
p. 3119 - 3126
(2007/10/06)
-