62706-94-9

Upstream product

• 104-83-6 1-Chloro-4-(chloromethyl)benzene 
• 100-66-3 methoxybenzene 
• 873-76-7 para-Chlorobenzyl alcohol 
• 107776-76-1 (4-Chloro-phenyl)-(2-methoxy-phenyl)-methanol 
• 3395-81-1 4-chlorobenzaldehyde dimethyl acetal 
• 104-88-1 4-chlorobenzaldehyde 

Downstream Products

• 78589-10-3 (4-chlorophenyl)(2-methoxyphenyl)methanone 

Relevant academic research and scientific papers

Highly efficient method for solvent-free synthesis of diarylmethane and triarylmethane from benzylic alcohols using P2O5/Al 2O3 or P2O5/SiO2 at room temperature

A highly efficient procedure for the synthesis of triarylmethane and diarylmethane via benzylation of aromatic hydrocarbons from benzyl alcohols using supported P2O5 on SiO2 and/or Al 2O3 under solvent-free conditions is described. Excellent yields of triarylmethane and diarylmethane were obtained using P 2O5-SiO2 (50%W/W) and/or P2O 5-Al2O3 (50%W/W) at room temperature. The reusability of both supported P2O5 on SiO2 and Al2O3 were examined. Both supported reagents show favorable activities in first and second runs, however, a decline in reactivity was observed in following attempts. The reaction is scalable to > 0.03 mole amounts.

Lithium tetrakis(pentafluorophenyl)borate-catalyzed Friedel-Crafts benzylation reactions

Lithium tetrakis(pentafluorophenyl)borate [LiB(C6F5)4], a neutral salt, effectively catalyzed Friedel-Crafts benzylation reactions of aromatic compounds with benzyl chloride or mesylate and their substituted derivatives. The LiB(C6F5)4-catalyzed reactions proceeded more efficiently in the coexistence of magnesium oxide.

Environmentally friendly arylmethylation of aromatics with benzyl halides using envirocat EPZ10 as the catalyst

The Friedel-Crafts arylmethylation of aromatics with benzyl halides or bis-(bromomethyl)-benzene in the presence of Envirocat EPZ10 affords selectively para-arylmethylated products in good yields. Isolation of pure products involving an eco-friendly procedure and recyclability of the catalyst are important features of this method.

Gallium Dichloride-Mediated Reductive Friedel-Crafts Reaction

In the presence of gallium dichloride, the reaction of carbonyl compounds or their dimethylacetals with aromatic compounds afforded Friedel-Crafts alkylated adducts in good yields.It was suggested that the adducts were obtained by way of a reduction of the carbonyl compounds or their dimethylacetals, followed by the Friedel-Crafts reaction in one-pot.This is the first organic synthetic method with gallium dichloride, low valent gallium.

Gallium dichloro-mediated reductive Friedel-Crafts reaction

In the presence of gallium dichloride, carbonyl compounds reacted with anisole to give alkylated anisoles in good yields. It was suggested that the adducts were obtained by way of the reduction of the carbonyl compounds followed by the Friedel-Crafts reaction in a one-pot. This is the first organic synthetic method with gallium dichloride, low valent gallium.

FRIEDEL-CRAFTS ALKYLATION OF ANISOLE AND ITS COMPARISON WITH TOLUENE. PREDOMINANT ORTHO-PARA SUBSTITUTION UNDER KINETIC CONDITIONS AND THE EFFECT OF THERMODYNAMIC ISOMERIZATIONS

The AlCl3 and BF3, as well as 65percent HPF6, catalyzed Friedel-Crafts alkylation of anisole with alkyl halides and alkohols was investigated.The alkylation of anisole with lower catalyst concentrations under mild conditions shows predominant ortho/para directing effect generally with a ratio of c.a. 2:1, with the amount of meta isomer uniformly less than 3percent.With "swamping" catalyst conditions the amount of meta substitution in methylation and ethylation can substantially increase.The isomer distribution in tert-butylation changes with time due to rapid ortho-para interconversion.Consequently, the AlCl3-catalyzed isomerization of isomeric alkylanisoles was also studied.In case of tert-butylanisoles, the ortho isomer shows relatively rapid conversion into para followed by much slower isomerization to meta.The para and meta isomers show isomerization to meta-para mixtures.Isomerization of ethyl-, isopropyl-, and benzylanisoles is generally slow whereas methylanisoles do not isomerize.Comparing results of the alkylation of anisole with toluene leads to the conclusion that the latter are readily affected by concurrent (and in some cases consecutive) isomerization.As the barrier for isomerization in the benzenium ion intermediates of the alkylations is higher in the case of CH3O- than CH3-substituted systems, anisole tends to give the kinetically controlled ortho-para alkylation products and the amount of meta isomer is low.Study of alkylation of 3,5-di- and 2,4,6-trideuterated toluene and anisole and comparing retained deuterium contents with isomer distributions shows that alkylated product formation in case of toluene, but not of anisole, is proceeded by intramolecular, 1,2-alkyl, and hydrogen-deuterium shifting resulting also in increased meta substitution.This effect is most predominant in methylation and ethylation where the alkyl shifts are intramolecular but not in tert-butylation and benzylation, where alkyl transfer is intermolecular.Isopropylation is intermediate in nature.No simple selectivity-reactivity relationship is indicated in the studied alkylation reactions.As shown in benzylations with increasingly electron-donating and -withdrawing substituted benzyl chlorides overall rate (i.e., substrate selectivity) and isomer distributions (i.e., regioselectivity) are not determined in the same step as significantly decreased substrate selectivity is not accompanied by loss of positional selectivity.Previously reported alkylations showing high degree of meta substitution therefore, must have been affected by thermodynamically controlled rearrangement processes, including intramolecular alkyl and hydrogen shifts in the arenium ion intermediates of the alkylation reactions.These are to be differentiated from possible subsequent product isomerizations.Under predominantly kinetic conditions anisole as well as toluene are substantially ortho-para directing in alkylations, as in other electrophilic aromatic substitutions.