70588-24-8

Upstream product

• 63548-79-8 methyl 1-methyl-6-oxocyclohex-2-ene-1-carboxylate 
• 86990-75-2 6-carbomethoxy-6-methyl-2,4-cyclohexadien-1-one, dimethyl ketal 
• 124182-96-3 methyl 3,3-dibromo-1-methyl-2-oxocyclohexanecarboxylate 
• 21173-69-3 (+/-)-methyl 2-methoxy-1-methyl-2,5-cyclohexadiene-1-carboxylate 
• 86990-72-9 6-bromo-2-carbomethoxy-2-methyl-3-cyclohexen-1-one, dimethyl ketal 
• 41302-34-5 2-(methoxycarbonyl)cyclohexanone 

Downstream Products

• 14920-81-1 methyl 2,6-dimethylbenzoate 
• 15012-36-9 methyl 2,3-dimethylbenzoate 
• 15018-12-9 2-methoxymethyltoluene 

Relevant academic research and scientific papers

Some 6,6-disubstituted 2,4-cyclohexadien-1-ones and the facial selectivity in their Diels-Alder reactions with dimethyl acetylenedicarboxylate

6,6-Disubstituted 2,4-cyclohexadien-1-ones can be prepared by dibromination-bisdehydrobromination of the corresponding 6,6-disubstituted 2,2-dibromocyclohexanones.Such dienes undergo Diels-Alder reactions with dimethyl acetylenedicarboxylate to give 3,3-disubstituted 5,6-di(methoxycarbonyl)bicycloocta-5,7-dien-2-ones; when the substituents at C-6 in the dienones are different, two diastereomers of the adducts are formed in a ratio dependent on the "facial selectivity" in the Diels-Alder reactions.For the cases where one of the 6-substituents is methyl and the other is methoxycarbonyl, acetoxymethyl, dibromomethyl, or dichloromethyl it has been established via X-ray crystallograpfy and chemical correlation that the endo-3-methyl/exo-3-methyl product ratio is 3.0, 0.9, 8, and 6, respectively.The origin of these differences is discussed briefly and a spectroscopic method for the assignment of structures to the individual diastereomers is proposed.Key words: Diels-Alder reactions, substituted 2,4-cyclohexadien-1-ones, facial selectivity, dimethyl acetylenedicarboxylate.

The Synthesis and Selected Chemistry of 6-Alkyl-6-carbalkoxy- and 6-Alkyl-6-(aminocarbonyl)-2,4-cyclohexadien-1-ones and Cyclohexadienone Ketals

The preparation of several 6-alkyl-6-carbalkoxy-2,4-cyclohexadien-1-ones and corresponding C(1) ketals is described.Birch reduction-alkylation of methyl 2-methoxybenzoates gives 6-alkyl-6-carbomethoxy-1-methoxy-1,4-cyclohexadienes 4a-e and 5a-d, and these

SYNTHESIS OF 6-ALKYL-6-METHOXYCARBONYL-2,4-CYCLOHEXADIEN-1-ONES AND CYCLOHEXADIENONE KETALS

The title compouds are readily available by reductive-alkylation of o-methoxybenzoic acid esters followed by a bromination-dehydrobromination sequence.