886-58-8Relevant articles and documents
Green, Mild, and Efficient Friedel–Crafts Benzylation of Scarcely Reactive Arenes and Heteroarenes under On-Water Conditions
La Manna, Pellegrino,Soriente, Annunziata,De Rosa, Margherita,Buonerba, Antonio,Talotta, Carmen,Gaeta, Carmine,Neri, Placido
, p. 1673 - 1683 (2019/03/26)
Metal-free Friedel–Crafts benzylation (FCB) of scarcely reactive arenes and heteroarenes was performed under on-water conditions by an environmentally sustainable procedure. The catalytic strategy exploits the hydrophobicity of the resorcinarene macrocycle 1 a. The proposed mechanism is based on the activation of benzyl chloride by H-bonding interactions with catalyst 1 a. In fact, under on-water conditions the hydrophobic amplification of the strength of the H-bonding interactions between the OH groups of the resorcinarene catalyst and the chlorine atom of benzyl chloride leads to polarization of the C?Cl bond, which consequently promotes electrophilic attack of the π nucleophile. Thus, many arenes and heteroarenes were efficiently benzylated under mild on-water conditions by using resorcinarene 1 a as catalyst. The FCB of benzene is industrially relevant for the synthesis of diphenylmethane, and hence the on-water procedure was extended to the gram-scale synthesis of diphenylmethane, starting from benzene and benzyl chloride in the presence of resorcinarene catalyst 1 a.
Bisulfate Salt-Catalyzed Friedel-Crafts Benzylation of Arenes with Benzylic Alcohols
Tang, Ren-Jin,Milcent, Thierry,Crousse, Benoit
, p. 14001 - 14009 (2018/11/23)
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.
Cross-Coupling of Phenol Derivatives with Umpolung Aldehydes Catalyzed by Nickel
Lv, Leiyang,Zhu, Dianhu,Tang, Jianting,Qiu, Zihang,Li, Chen-Chen,Gao, Jian,Li, Chao-Jun
, p. 4622 - 4627 (2018/05/22)
A nickel-catalyzed cross-coupling to construct the C(sp2)-C(sp3) bond was developed from two sustainable biomass-based feedstocks: phenol derivatives with umpolung aldehydes. This strategy features the in situ generation of moisture/air-stable hydrazones from naturally abundant aldehydes, which act as alkyl nucleophiles under catalysis to couple with readily available phenol derivatives. The avoidance of using both halides as the electrophiles and organometallic or organoboron reagents (also derived from halides) as the nucleophiles makes this method more sustainable. Water tolerance, great functional group (ketone, ester, free amine, amide, etc.) compatibility, and late-stage elaboration of complex biological molecules exemplified its practicability and unique chemoselectivity over organometallic reagents.
A highly efficient catalyst for Suzuki-Miyaura coupling reaction of benzyl chloride under mild conditions
Guan, Zhenhong,Li, Buyi,Hai, Guoliang,Yang, Xinjia,Li, Tao,Tan, Bien
, p. 36437 - 36443 (2014/11/08)
Diarylmethane derivatives, essential building blocks in organic synthesis, are usually synthesized through the traditional electrophilic substitution reaction i.e., Friedel-Crafts reaction, which suffers from the rearrangement and weak reactivity of aromatic compounds with deactivating/electron-withdrawing groups. The Suzuki-Miyaura coupling reaction of low-cost benzyl chloride as an alternative method overcomes these defects. Pd(ii) organometallic catalysts immobilized on the triphenylphosphine-functionalized microporous knitting aryl polymer (KAPs(Ph-PPh3)-Pd) as a novel heterogeneous catalyst was employed in Suzuki-Miyaura coupling reaction of benzyl chloride and exhibited excellent catalytic activity under mild conditions with a turnover frequency (TOF) up to 76 min-1 (4569 h-1). This work reveals that the microporous structure of the catalyst can rapidly adsorb substrates, consequently facilitating their interaction, and eventually promoting the catalytic efficiency. the Partner Organisations 2014.
Synthesis of diarylmethanes via a Friedel-Crafts benzylation using arenes and benzyl alcohols in the presence of triphenylphosphine ditriflate
Khodaei, Mohammad Mehdi,Nazari, Ehsan
experimental part, p. 5131 - 5135 (2012/09/22)
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.
The efficacy of unsupported and supported tungstophosphoric acid and its Fe - And Al - Salts in the benzylation of arenes using benzyl alcohol and benzyl chloride
Tipnis, Amol S.,Deodhar, Deepak K.,Samant, Shriniwas D.
experimental part, p. 340 - 345 (2010/10/18)
The efficacy of unsupported and supported tungstophosphoric acid and its Fe(III) and Al(III) salts for catalyzing the benzylation reaction using benzyl alcohol and benzyl chloride has been studied. The supports used are silica, zeolite HZSM-5 and an acidic clay montmorillonite KlO. The significant observation of this investigation is the contrast in the activities of the unsupported and supported catalysts in the benzylation using benzyl chloride and benzyl alcohol, which may be a result of the 'pseudo liquid phase' behavior of heteropoly compounds.
An efficient synthesis of unsymmetrical diarylmethanes from the dehydration of arenes with benzyl alcohols using InCl3·4H2O/acetylacetone catalyst system
Sun, Hong-Bin,Li, Biao,Chen, Songjie,Li, Jie,Hua, Ruimao
, p. 10185 - 10188 (2008/02/13)
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.
Rare earth(III) perfluorooctanesulfonates catalyzed Friedel-Crafts alkylation in fluorous biphase system
Yi, Wen-Bin,Cai, Chun
, p. 831 - 833 (2007/10/03)
The catalyst of rare earth(III) perfluorooctanesulfonates (RE(OSO 2C8F17)3, RE = Sc, Y, La-Lu) were prepared from either rare earth chlorides(III) or oxides and perfluorooctanesulfonic acid. The perflates thus obtained act as novel catalysts for Friedel-Crafts alkylation in fluorous biphasic system. Perfluorohexane (C6F14), perfluoromethylcyclohexane (C7F 14), perfluorotoluene (C7F8), perfluorooctane (C8F18), perfluorooctyl bromide (C8F 17Br) and perfluorodecalin (C10F18, cis- and trans-mixture) can be used as fluorous solvents for this reaction. By simple separation of the fluorous phase containing only catalyst, alkylation can be repeated many times.
Friedel-crafts benzylation of arenes over mixed oxides
Jadhav, Sujit R.,Sawant, Manohar R.
, p. 135 - 138 (2007/10/03)
The replacement of liquid acid catalyst by solid acids for the Friedel-Crafts reaction of aromatic alkylation is a challenging task. Mixed oxide possessing spinel structures were found to catalyze the Friedel-Craft benzylation of arenes. It was found that the reaction was very fast at 80 °C, hence the reaction was studied with respect to more substrate. The significant point was even at this temperature monobenzylation, with the para isomer predominating, was achieved. Mixed oxides were prepared by co-precipitation method and were characterized by XRD technique.
Friedel-Crafts benzylation of arenes using FeCI3 impregnated montmorillonite K10
Pai,Bajpai,Deshpande,Samant
, p. 2267 - 2273 (2007/10/03)
FeCI3 impregnated Montmorillonite K10 was found to catalyze the Friedel-Crafts benzylation of arenes. Monobenzylation, with the para isomer predominating, was achieved with trace amounts of dibenzylated product.
