61414-49-1Relevant academic research and scientific papers
Towards ortho-selective electrophilic substitution/addition to phenolates in anhydrous solvents
Lopu?anskaja, Eleana,Kooli, Anni,Paju, Anne,J?rving, Ivar,Lopp, Margus
, (2021/02/16)
Alkyl-substituted Li-phenolates with BnBr in water solution lead to a mixture of o- and p-Bn-substituted phenols together with a substantial amount of phenol Bn ether. In CPME, and especially in toluene with 1–2 equivalents of ether or alcohol additives, ortho-selective alkylation is achieved. In the case of o,o,p-tri- and o,o-di-substituted phenols dearomatization occurs affording o-Bn-substituted alkyl cyclohexadienones with yields up to 92% with an o/p ratio up to 90/1.
Reactions of 6-Benzyl-2-t-butyl-4,6-dimethyl-cyclohexa-2,4-dienone and 6-Benzyl-4-t-butyl-2,6-dimethylcyclohexa-2,4-dienone with Nitrogen Dioxide
Hartshorn, Michael P.,Robinson, Ward T.,Waller, Grant A.,Wright, Graeme J.
, p. 1547 - 1568 (2007/10/02)
Reaction of the 2-t-butyl-4-methylcyclohexa-2,4-dienone (7) with nitrogen dioxide in benzene gives the four 4,5-dinitrocyclohex-2-enones (9)-(12), the three 2,5-dinitrocyclohex-3-enones (13)-(15), and the 2-hydroxy-5-nitrocyclohex-3-enone (17).Under the same reaction conditions the 4-t-butyl-2-methylcyclohexa-2,4-dienone (8) gives the four 2,5-dinitrocyclohex-3-enones (19)-(22), and the three 2-hydroxy-5-nitrocyclohex-3-enones (23)-(25).X-Ray structure determinations are reported for compounds (9), (10), (13), (14), (19) and (25).In solution at 40 deg the dinitro ketone (20) rearranges to give dinitro ketone (19) and 2-hydroxy-5-nitro ketones (23) and (24).The reaction mechanisms for the various reactions are discussed.
