Studies On The Reaction Of Allyltrimethylsilane And 4-trifluoromethyl-p-quinols

Allylation is an important synthetic method in organic synthesis chemistry.The compounds with structural units of carbonyl,imide or epoxy groups,as well as acetal and acyl chloride,can undergo allylation under certain reaction conditions,and obtain important organic synthesis intermediates such as allyl substituted aldehydes,ketones and amines.However,for compounds containing?,?-unsaturated carbonyls,such as quinones or quinols,the allylation on its?-position is rarely reported.p-Quinol compounds are important aromatic precursors with multiple reaction sites.Due to the special role of trifluoromethyl in organic synthesis chemistry,such as,can be used for dye,modification of polymer materials,adjusting the metabolic activity of drugs,improving the lipid solubility,targeting selectivity,biological permeability of molecule,increasing medicative and proceeding pharmacokinetics research,so introducing trifluoromethyl into p-quinols can expand a novel and efficient approach to the application of p-quinols in organic synthesis.Therefore in recent years,our research group has been engaged in the synthesis of p-quinols based on trifluoromethyl,and obtained a series research results.Based on the previous work,this paper focusing on the allylation of 4-trifluoromethyl-p-quinols with allyltrimethylsilane,further expand the application of trifluoromethyl-p-quinols in the synthesis.The experimental results show the competition between[2+2]cycloaddition and allylation in the reaction of 4-trifluoromethyl-p-quinol compounds with allyltrimethylsilane.By controlling the reaction conditions,the selectivity of this reaction can be controlled.A series of cyclohexanone compounds were synthesized by selective[2+2]cycloaddition reaction.3-allyl-cyclohexenone compounds were synthesized by selective allylation reaction.The structures of the new compounds synthesized in this paper were confirmed by the data of ¹H-NMR,¹³C-NMR and Mass Spectrometry.The possible mechanism of this reaction is also discussed.