10027-71-1

Upstream product

• 67-56-1 methanol 
• 4747-15-3 1-(2-methoxyvinyl)benzene 
• 100-52-7 benzaldehyde 
• 1125-88-8 benzaldehyde dimethyl acetal 
• 100-42-5 styrene 

Downstream Products

• 93-58-3 benzoic acid methyl ester 
• 100-52-7 benzaldehyde 
• 22039-97-0 4-methoxy-4-phenyl-1-butene 
• 295357-38-9 (1,1-dimethylethyl)dimethylsilyl 1-methoxy-1-phenylmethyl peroxide 
• 61040-98-0 3,6-diphenyl-1,2,4-trioxane 
• 16204-37-8 3,6-diphenyl-1,2,4,5-tetraoxane 

Relevant academic research and scientific papers

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.

Synthesis of Primary gem-Dihydroperoxides and Their Peroxycarbenium [3 + 2] Cycloaddition Reactions with Alkenes

It is long known that dihydroperoxidation of aliphatic aldehydes is extremely difficult and normally stops halfway at the hydroxyhydroperoxide stage. This strange phenomenon now has been explored, and a highly effective protocol for conversion of aliphatic aldehydes into gem-dihydroperoxides has been developed. Silyl protection of primary gem-dihydroperoxides, which is also a challenge due to unexpected based-induced decomposition, was achieved using 2,6-lutidine as the base. The silyl-protected gem-dihydroperoxides were then examined in a peroxycarbenium [3 + 2] cycloaddition reaction with alkenes for the first time. Aromatic substrates normally reacted smoothly, affording the expected 1,2-dioxolanes smoothly. Aliphatic aldehydes generally failed to yield 1,2-dioxolane. In all cases, unexpected formation of either a chlorohydrin or a 1,2-dichloride (with Cl atoms derived from TiCl4) depending on the alkene employed was observed, which displays some so far unknown facets of the cycloaddition and helped to gain many mechanistic insights.

Intramolecular rearrangement of α-azidoperoxides: An efficient synthesis of tert-butyl esters

An unprecedented intramolecular rearrangement of α-azidoperoxides, promoted by simple organic base to provide tert-butyl esters, has been presented. Further, a one-pot methodology consisting of in situ generation of the α-azidoperoxides from corresponding aldehydes followed by base-promoted rearrangement to obtain the desired ester has also been executed. Relevant mechanistic studies, to provide the proof for intramolecular alkoxy transfer, are investigated.

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.

Ozonolysis of Vinyl Ethers in Solution and on Polyethylene

Ozonolyses of the vinyl ethers 1a-f in methanol afforded almost exclusively the corresponding α-methoxy hydroperoxides 4, suggesting the preferred formation of the carbonyl oxides 2.In aprotic solvents including methyl formate, the predominant modes of decay of the carbonyl oxides 2 were cyclodimerization, reduction, and rearrangement, yet no ozonide formation.By contrast, ozonolyses of 1a-f on polyethylene gave the α-methoxy-substituted ozonides 14 in fair yields.Ozonolyzes of 1a-f in the presence of added carbonyl compounds 6 in methylene chloride or ether yielded the corresponding cross ozonides.Judged from the ozonide yields, the reactivities of the carbonyl compounds follow the sequence: (ClCH2)2C=O > ClCH2COCH3 > (CH3)2C=O and 2-CF3C6H4CHO > PhCHO.

Synthesis of 1,2,4-Dioxazolidines by the Ozonolysis of Vinyl Ethers in the Presence of Imines. The First Cycloaddition of Carbonyl Oxide to the Carbon-Nitrogen

Carbonyl oxides, derived from the ozonolysis of vinyl ethers, readily undergo cycloaddition reactions with imines affording 1,2,4-dioxazolidines in good yield.