169294-55-7

Upstream product

• 126781-85-9 1-(tert-butyl)-4-(methoxymethylene)cyclohexane 
• 67-56-1 methanol 
• 98-53-3 4-tercbutyl-cyclohexanone 
• 13294-73-0 1-tert-butyl-4-methylenecyclohexane 

Downstream Products

• 229323-96-0 1,1-dihydroperoxy-(4-tert-butyl)cyclohexane 
• 98-53-3 4-tercbutyl-cyclohexanone 

Relevant academic research and scientific papers

Hydroperoxide-mediated C-C bond formation: Synthesis of 1,2-dioxolanes from alkoxyhydroperoxides in the presence of Lewis acids

Lewis-acid activation of ozonolysis-derived hydroperoxyketals affords intermediate hydroperoxycarbenium ions (protonated carbonyl oxides) which undergo addition of allyltrimethylsilane to directly afford 1,2-dioxolanes.

Iodine as a catalyst for efficient conversion of ketones to gem-dihydroperoxides by aqueous hydrogen peroxide

Iodine has been shown to be an efficient catalyst for the selective dihydroperoxidation of ketones with aqueous hydrogen peroxide. Ketones were directly converted to their corresponding gem-dihydroperoxides using a "green" oxidant (30% aq H2O2) and a simple catalyst (iodine) under neutral conditions in acetonitrile. The yield of hydroperoxidation of various cyclic ketones was 60-98% including androstane-3,17-dione, and acyclic ketones were converted with a similar efficiency.

A mild one-pot conversion of alkenes into amines through tandem ozonolysis and reductive amination

The selective reduction of hydroperoxyacetals to aldehydes by sodium triacetoxyborohydride provides the basis for a mild one-pot synthesis of amines from alkenes. Georg Thieme Verlag Stuttgart.

Spiro- and dispiro-1,2-dioxolanes: Contribution of iron(II)-mediated one-electron vs two-electron reduction to the activity of antimalarial peroxides

Fourteen spiro- and dispiro-1,2-dioxolanes were synthesized by peroxycarbenium ion annulations with alkenes in yields ranging from 30% to 94%. Peroxycarbenium ion precursors included triethylsilyldiperoxyketals and -acetals derived from geminal dihydroperoxides and from a new method employing triethylsilylperoxyketals and -acetals derived from ozonolysis of alkenes. The 1,2-dioxolanes were either inactive or orders of magnitude less potent than the corresponding 1,2,4-trioxolanes or artemisinin against P. falciparum in vitro and P. berghei in vivo. In reactions with iron(II), the predominant reaction course for 1,2-dioxolane 3a was two-electron reduction. In contrast, the corresponding 1,2,4-trioxolane 1 and the 1,2,4-trioxane artemisinin undergo primarily one-electron iron(II)-mediated reductions. The key structural element in the latter peroxides appears to be an oxygen atom attached to one or both of the peroxide-bearing carbon atoms that permits rapid β-scission reactions (or H shifts) to form primary or secondary carbon-centered radicals rather than further reduction of the initially formed Fe(III) complexed oxy radicals.

The effect of iodine on the peroxidation of carbonyl compounds

(Chemical Equation Presented) Peroxidation of ketones and aldehydes with iodine as a catalyst was studied. Ketones reacted with 30% aq hydrogen peroxide in the presence of 10 mol % of iodine to yield gem-dihydroperoxides in acetonitrile and hydroperoxyketals in methanol. The yield of hydroperoxidation of various cyclic ketones was 60-98%, including androstane-3,17-dione, while acyclic ketones were converted with a similar efficiency. Aromatic aldehydes were also converted to gem-dihydroperoxides with hydrogen peroxide and iodine as catalyst in acetonitrile and to hydroperoxyacetal in methanol, while the reactivity of aliphatic ones remained the same as in noncatalyzed reactions. tert-Butylhydroperoxide reacted in a similar manner, giving the corresponding perether derivatives. A study was also made of the relative kinetics of dihydroperoxidation from which the Hammet equation gave a reaction constant (ρ) of -2.76, indicating the strong positive charge development in the transition state and the important role of rehybridization in the conversion of hydroperoxyhemiketal to gem-dihydroperoxide. In acetonitrile, the iodine catalyst is apparently able to discriminate between the elimination of a hydroxy, methoxy, and hydroperoxy group and addition of water, methanol, and H2O2 to a carbonyl group.

Peroxycarbenium-mediated C-C bond formation: Applications to the synthesis of hydroperoxides and peroxides

The Lewis acid-mediated reaction of alkene nucleophiles with peroxyacetals provides an effective route for the synthesis of homologated peroxides and hydroperoxides. In the presence of Lewis acids such as TiCl4, SnCl4, and trimethylsilyl triflate, peroxyacetals and peroxyketals undergo reaction with allyltrimethylsilane, silyl enol ethers, and silyl ketene acetals to afford homoallyl peroxides, 3-peroxyketones, and 3-peroxyalkanoates, respectively. Reactions of peroxyacetals are Lewis acid dependent; TiCl4 promotes formation of ethers while SnCl4 and trimethylsilyl triflate promote formation of peroxides. Lewis acid-promoted reactions of silylated hydroperoxyacetals furnish silylated hydroperoxides, which can be deprotected to homologated hydroperoxides. Hydroperoxyketals undergo Lewis acid-mediated allylation to furnish 1,2-dioxolanes via attack of hydroperoxide on the intermediate carbocation. Lewis acid-mediated cyclization of unsaturated peroxyacetals furnishes 1,2-dioxanes, 1,2-dioxepanes, and 1,2-dioxacanes through 6-endo/exo, 7-endo/endo, and 8-endo/endo pathways. The corresponding reactions involving 6-endo/endo and 5-endo/exo pathways were unsuccessful.