Dialkylbenzenes, synthesis

Synthesis ofp-Ethyltoluene. j )i7n7-Ethyltoluene, the feedstock for j )-methylstyrene, is difficult to separate from the products of toluene alkylation with ethane using conventional acidic catalysts. The unique configurational diffusion effect of ZSM-5 permits -dialkylbenzenes to be produced in one step. In the alkylation of toluene with ethene over a chemically modified ZSM-5, -ethyltoluene is obtained at 97% purity (58). 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

Octaalkyl-substituted phthalocyanine [152] can be synthesized by bromin-ation of dialkylbenzene accessible via a Grignard reaction. The synthesis of the alkoxy-substituted phthalocyanines [153] starts from catechol. The reaction with alkylhalide is followed by a bromination in positions 4 and 5. Alkoxy-methyl-substituted phthalocyanines [154] are obtained by substitution of o-xylene with bromine and subsequent radical bromination of the two methyl groups of l,2-dibromo-4,5-dimethylbenzene. The alkoxy groups are introduced by reacting the tetrabromo compound with the corresponding alcoholate. 

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