- MOF-5 as an efficient heterogeneous catalyst for Friedel-Crafts alkylation reactions
-
A highly porous metal-organic framework (MOF-5) was synthesized by a solvothermal method, and used as an efficient heterogeneous acid catalyst for Friedel-Crafts alkylation reactions. The solid acid catalyst was characterized using a variety of different techniques, including X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), atomic absorption spectrophotometry (AAS), and nitrogen physisorption measurements. Quantitative conversion was achieved under mild conditions without the need for an inert atmosphere. The MOF-5 catalyst could be facilely separated from the reaction mixture, and could be reused several times without significant degradation in catalytic activity. Furthermore, no contribution from homogeneous catalysis of active acid species leaching into reaction solution was detected.
- Phan, Nam T.S.,Le, Ky K.A.,Phan, Tuan D.
-
-
Read Online
- METHOD FOR PRODUCING ARENE COMPOUNDS AND ARENE COMPOUNDS PRODUCED BY THE SAME
-
Provided is a method for producing (alkyl)arene compounds represented by Formulae 3-1, 3-2, and 3-3 by the Friedel-Crafts alkylation reaction of alkyl halide compounds and arene compounds using organic phosphine compounds as a catalyst.
- -
-
Paragraph 0125
(2021/06/26)
-
- Efficient cross-coupling of aryl Grignard reagents with alkyl halides by recyclable ionic iron(iii) complexes bearing a bis(phenol)-functionalized benzimidazolium cation
-
A novel bis(phenol)-functionalized benzimidazolium salt, 1,3-bis(3,5-di-tert-butyl-2-hydroxybenzyl)benzimidazolium chloride (H 3LCl, 1), was designed and used to prepare ionic iron(iii) complexes of the type [H3L][FeX4] (X = Cl, 2; X = Br, 3). Both 2 and 3 were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The catalytic performances of 2 and 3 in cross-coupling reactions using aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens were studied. This analysis shows that complex 2 has good potential for alkyl chloride-mediated coupling. In comparison, complex 3 showed slightly lower catalytic activity. After decanting the product contained in the ethereal layer, complex 2 could be recycled at least eight times without significant loss of catalytic activity.
- Xia, Chong-Liang,Xie, Cun-Fei,Wu, Yu-Feng,Sun, Hong-Mei,Shen, Qi,Zhang, Yong
-
p. 8135 - 8144
(2013/12/04)
-
- IRON BISPHENOLATE COMPLEXES AND METHODS OF USE AND SYNTHESIS THEREOF
-
The present application, relates to iron bisphenolate complexes and methods of use and synthesis thereof. The iron complexes are prepared from tridentate or tetradentate ligands of Formula I: wherein R1 and R2 are as defined herein. Also provided are methods and processes of using the iron bisphenolate complexes as catalysts in cross-coupling reactions and in controlled radical polymerizations.
- -
-
Paragraph 00187-00191
(2013/04/25)
-
- Microwave-assisted silica-supported aluminum chloride-catalyzed Friedel-Crafts alkylation
-
Microwave irradiation is a popular method in organic synthesis to achieve high yields in shorter reaction times. This decreases total 'man-hours' in a synthetic setting. Another technique used in organic chemistry to decrease manual manipulations, is solid support reagents. The benefits of this approach is that upon completion of a reaction, a simple filtration can be performed which expedites the work-up and also produces less organic waste. Friedel-Crafts alkylation has been explored using microwave chemistry as well as with solid-supported reagents. In comparison with traditional heating, as well as with AlCl3, superior yields were observed with silica-gel bound aluminum chloride (Si-AlClx) when microwave irradiated for only 5 min.
- Zupp, Laurine R.,Campanella, Veronica L.,Rudzinski, Diandra M.,Beland, Franois,Priefer, Ronny
-
p. 5343 - 5346
(2012/10/30)
-
- Ionic iron(iii) complexes of bis(phenol)-functionalized imidazolium cations: Synthesis, structures and catalysis for aryl Grignard cross-coupling of alkyl halides
-
A series of bis(phenol)-functionalized imidazolium salts, 1,3-bis(4,6-di-R1-2-hydroxybenzyl)-2-R2-4,5-di-R 3-imidazolium chlorides H3LnCl (R1 = tBu, R2 = R3 = H, H3L 1Cl, 1; R1 = CH3, R2 = R3 = H, H3L2Cl, 2; R1 = tBu, R 2 = H, R3 = Cl, H3L3Cl, 3; R 1 = tBu, R2 = CH3, R3 = H, H3L4Cl, 4), were used to produce a novel series of ionic iron(iii) complexes [H3Ln][FeX4] (n = 1, X = Cl, 5; n = 2, X = Cl, 6; n = 3, X = Cl, 7; n = 4, X = Cl, 8; n = 1, X = Br, 9; n = 3, X = Br, 10). All of the complexes were characterized by Raman spectroscopy and electrospray ionization mass spectrometry. Elemental analysis and X-ray crystallography were also used. All of the complexes were non-hygroscopic and air-stable, with five of them existing as solids (5, 7-10) and one as an oil (6) at room temperature. A preliminary catalytic study on the cross-coupling reactions of aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens, revealed that all of the ionic iron(iii) complexes exhibited good to excellent catalytic activity. Complexes 5, 6 and 8 exhibited optimal activity, whereas 7, 9 and 10 showed only moderate activity. Furthermore, by simply decanting the cross-coupling product in the ether layer, complexes 5 and 6 could be reused in at least seven successive runs without significant loss in catalytic activity.
- Deng, Hai-Ning,Xing, Ya-Lin,Xia, Cong-Liang,Sun, Hong-Mei,Shen, Qi,Zhang, Yong
-
p. 11597 - 11607
(2013/02/23)
-
- Catalytic alkylation of aryl Grignard reagents by iron(iii) amine-bis(phenolate) complexes
-
Reaction of n-propylamino-N,N-bis(2-methylene-4-tert-butyl-6-methylphenol), H2L1, n-propylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol), H2L2, and benzylamino-N,N-bis(2-methylene-4-tert-butyl-6- methylphenol), H2L3, with anhydrous ferric chloride in the presence of base yields the products, [FeL1(μ-Cl)]2 (1), [FeL2(μ-Cl)]2 (2) and [FeL3(μ-Cl)]2 (3). In the solid state, these complexes exist as chloride-bridged dimers giving distorted trigonal bipyramidal iron(iii) ions. Reaction of H2L1 with FeBr 3, however, results in the formation of a tetrahedral iron(iii) complex possessing two bromide ligands. The amine-bis(phenolate) ligand is bidentate in this complex and bonds to the iron(iii) ion via the phenolate O-donors. The central amine donor is protonated, resulting in a quaternized ammonium fragment and the iron(iii) centre possesses a negative formal charge. As a result, this complex is zwitterionic and formulated as FeBr2L1H (4). Complex 1 is an air-stable, non-hygroscopic, single-component catalyst for C-C cross-coupling of aryl Grignard reagents with primary and secondary alkyl halides, including chlorides. Good to excellent yields of cross-coupled products are obtained in diethyl ether at room temperature. In some cases where low yields are obtained under these conditions, the use of microwave-assisted heating of the reaction mixture can improve yields. The Royal Society of Chemistry 2011.
- Qian, Xin,Dawe, Louise N.,Kozak, Christopher M.
-
experimental part
p. 933 - 943
(2011/04/23)
-
- Direct cobalt-catalyzed cross-coupling between aryl and alkyl halides
-
An operationally simple cross-coupling reaction between aryl halides and alkyl halides with high selectivity has been developed. The underlying domino process utilizes CoCl2/Me4-DACH as a catalyst system. The methodology exhibits hig
- Czaplik, Waldemar Maximilian,Mayer, Matthias,Jacobi Von Wangelin, Axel
-
experimental part
p. 2931 - 2934
(2010/01/21)
-
- Domino iron catalysis: Direct aryl-alkyl cross-coupling
-
(Chemical Equation Presented) Striking while the iron is hot: Cheap FeCl3 serves as the precatalyst for the direct cross-coupling of aryl and alkyl halides that is based on the sequence of Grignard formation and subsequent cross-coupling. This
- Czaplik, Waldemar Maximilian,Mayer, Matthias,Von Wangelin, Axel Jacobi
-
supporting information; experimental part
p. 607 - 610
(2009/04/14)
-
- Iron-catalyzed desulfinylative C-C cross-coupling reactions of sulfonyl chlorides with grignard reagents
-
(Chemical Equation Presented) A friendly couple: Conditions have been uncovered that allow the desulfinylative C-C cross-coupling reaction of inexpensive sulfonyl chlorides and Grignard reagents (see scheme, acac = acetylacetonate, NMP = N-methylpyrrolidone). The reactions rely on environmentally friendly iron catalysts and do not require expensive and/or toxic ligands.
- Rao Volla, Chandra M.,Vogel, Pierre
-
p. 1305 - 1307
(2008/12/22)
-
- Iron(III) amine-bis(phenolate) complexes as catalysts for the coupling of alkyl halides with aryl Grignard reagents
-
Catalytic cross-coupling of aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens is achieved using Fe(III) amine-bis(phenolate) halide complexes. The Royal Society of Chemistry.
- Chowdhury, Rajoshree Roy,Crane, Angela K.,Fowler, Candace,Kwong, Philip,Kozak, Christopher M.
-
-
- Iridium-catalyzed enantioselective hydrogenation of terminal alkenes
-
Iridium complexes derived from chiral P,N ligands are efficient catalysts for the enantioselective hydrogenation of 2-aryl-substituted terminal alkenes. Using 0.1-1 mol % of catalyst at room temperature and ambient hydrogen pressure, high enantioselectivi
- McIntyre, Steven,Hoermann, Esther,Menges, Frederik,Smidt, Sebastian P.,Pfaltz, Andreas
-
p. 282 - 288
(2007/10/03)
-
- Tetraorganoindates as Nucleophilic Coupling Partners in Pd-Catalyzed Cross-Coupling Reactions
-
(Equation presented) In situ generated ate complex In situ-generated tetraorganoindate complexes from the reaction of 1 equiv of indium trichloride with 4 equiv of appropriate organometallics are efficient nucleophiles in Pd-catalyzed cross-coupling reactions. In this novel reaction tetraorganoindates containing methyl, 1°- and 2°-alkyl, vinyl, alkynyl, and aryl groups transfer the four organic groups to a variety of electrophiles with high atom efficiency.
- Lee, Phil Ho,Lee, Sung Wook,Seomoon, Dong
-
p. 4963 - 4966
(2007/10/03)
-
- Pd-catalyzed carbonylative cross-coupling reactions by triorganoindiums: Highly efficient transfer of organic groups attached to indium under atmospheric pressure
-
(Matrix presented) A highly atom-efficient synthetic method of unsymmetrical ketones was developed by using trialkyl- and triarylindiums, which could be employed as effective cross-coupling partners in Pd-catalyzed carbonylative cross-coupling reactions with a variety of organic electrophiles. The present method produced unsymmetrical ketones and 1,4-diacylbenzenes in good yields with highly efficient transfer of almost all the organic groups attached to the indium under atmospheric pressure of CO gas in THF at 66°C.
- Lee, Phil Ho,Lee, Sung Wook,Lee, Kooyeon
-
p. 1103 - 1106
(2007/10/03)
-
- Synthesis and transformations of metallacycles 20.* Cp2ZrCl2-catalyzed cycloalumination of arylolefins with AlEt3
-
The Cp2ZrCl2-catalyzed reaction of arylolefins (styrene, o-and p-methylstyrenes, trans-stilbene, 1,4-diphenyl-1,3-butadiene) with AlEt3 resulting in mono-and disubstituted alumacyclopentanes and substituted alumacyclopropa
- Ibragimov,Khafizova,Satenov,Khalilov,Yakovleva,Rusakov,Dzhemilev
-
p. 1574 - 1580
(2007/10/03)
-
- Probing gaseous ion-molecule complexes with chiral agents: The reaction of arenium ions with (R)-(-)-s-butyl chloride
-
Enantiomerically pure, gaseous reagents can be used to probe the chemical identity and the spatial arrangement of reaction partners confined within ion molecule complexes. The addition of gaseous arenium ions to (R)-(-)s-C4H9Cl affords complexes within which aromatic alkylation proceeds with complete racemization. This suggests that the components of the complex undergo mutual rotation and that the s-butyl cation is the electrophile.
- Aschi,Cacace,Troiani
-
-
- 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)
-
- Use of Aluminium as a Friedel-Crafts Catalyst
-
Toluene has been alkylated with isopropyl bromide, n-butyl bromide, s-butyl bromide, t-butyl chloride and benzyl chloride using aluminium as a Friedel-Crafts catalyst to obtain p-isopropyl-, p-s-butyl-, p-s-butyl-, p-t-butyl- and p-benzyltoluenes respectively in good yields, except in the case of p-(s-butyl)toluene which is obtained in 30 percent yield.
- Akhter, F.,Bahar, M. H.
-
-
- REACTION OF PHOSPHORUS OXYACID ESTERS WITH p-TOLUENESULFONIC ACID
-
The reaction of primary alkyl esters of phosphorus oxyacids with p-toluenesulfonic acid (TsOH) in refluxing solvents gave the corresponding p-toluenesulfonates (TsOR).We found that the secondary alkyl esters reacted with TsOH at lower temperature (r.t.-40 deg C) to afford TsORs in good yields.It is suggested that sulfonic acids may be useful for the selective dealkylation of mixed esters.Keywords-p-toluenesulfonic acid; p-toluenesulfonate; trialkyl phosphate; trialkyl phosphite; dialkyl phenylphosphonate; transesterification; dealkylation; solvolysis.
- Nitta, Yoshihiro,Arakawa, Yasushi,Ueyama, Naoto
-
p. 2710 - 2718
(2007/10/02)
-
- Alkylation of Nitriles with Gaseous Carbenium Ions. The Ritter Reaction in the Dilute Gas State
-
Radiolytically formed carbenium ions, such as sec-C3H7+, sec-C4H9+, and t-C4H9+, react in the gas phase with model aliphatic and aromatic nitriles yielding the corresponding nitrilium ions.The latter undergo efficient condensation with water that eventually leads to the formation of the corresponding N-alkylamides.The mechanism is analogous to the Ritter reaction in solution.The reactivity and selectivity of the gas-phase electrophilic attack on nitriles has been deduced from competition experiments under conditions that largely exclude the effects of solvation, ion pairing, etc., which complicate the interpretation of solution-chemistry measurements.
- Cacace, Fulvio,Ciranni, Giovanna,Giacomello, Pierluigi
-
p. 2258 - 2261
(2007/10/02)
-
- Liquid Phase Alkylation of Toluene with n-Butene
-
Alkylation of toluene with n-butene to obtain s-butyltoluene (SBT) has been studied in the presence of AlCl3.The isomer distribution of the product is found to vary with catalyst concentration, reaction temperature and the contact period.Using 1.7 mol percent catalyst, butene conversion is > 95 percent at 32 deg C with a selectivity of 85 percent towards SBT formation.At low catalyst concentration and subzero temperatures, mainly o- and p-SBT are formed.Above 5 deg C, m- and p-isomers are predominant.The results indicate that initially formed o- and p-SBT isomerise mainly by an intermolecular mechanism to m-SBT, the isomerisation of former being faster, to finally attain an equilibrium composition of o-, 2-3 percent; m-, 71-72 percent and p-, 25-27 percent.H2SO4 and BF3-H3PO4 catalysts result mainly in o- and p-isomers.This variation in the isomer distribution is considered to be due to differences in the acidity of the catalysts.
- Kulsrestha, Girendra N.,Shanker, Uma,Pathania, Bikram S.,Negi, Janaki,Bhattacharyya, Kshitindra K.
-
p. 298 - 302
(2007/10/02)
-
- Aromatic Substitution in the Gas Phase. Alkylation of Arenes by Gaseous C4H9+ Cations
-
Butyl cations, obtained in the dilute gas state from the radiolysis of butane in the pressure range from 70 to 750 torr, have been allowed to react with benzene, toluene, and their mixtures or with trace amounts of o-xylene in the gaseous system.The gas-phase butylation yields invariably sec-butylarenes, remarkably free of isomeric byproducts, namely n- and tert-butylarenes.Other alkylation experiments, where gaseous butyl cations from the reaction of butane with radiolytically formed H3+ ions were used as reagent, confirmed the exclusive formation of sec-butylarenes.The butylation process displays the positional and substrate selectivity and the dependence of orientation on the pressure of the system, typical of other gas-phase ionic substitutions.At high pressures, ortho-para orientation predominates in the sec-butylation of toluene, with a ortho:meta:para ratio of 43:30:27 at 715 torr.As the pressure is reduced, a gradual shift in favor of the thermodynamically most stable meta-subsltituted arenium ion is observed, leading to a ortho:meta:para ratio of 31:48:21 at 70 torr.
- Cacace, Fulvio,Ciranni, Giovanna,Giacomello, Pierluigi
-
p. 1513 - 1516
(2007/10/02)
-