119015-52-0

Upstream product

• 637-69-4 4-Methoxystyrene 
• 7647-01-0 hydrogenchloride 
• 7732-18-5 water 
• 100-66-3 methoxybenzene 
• 621-62-5 chloroacetaldehyde diethyl acetal 
• 59457-26-0 1-chloro-1λ³-benzo[d][1,2]iodaoxol-3(1H)-one 
• 3319-15-1 rac-1-(4-methoxyphenyl)-ethanol 

Downstream Products

• 477727-71-2 1-[2-chloroethenyl]-4-methoxybenzene 
• 40811-01-6 1-(1-chloroethenyl)-4-methoxybenzene 
• 857590-90-0 1-(1-ethoxy-2-chloro-ethyl)-4-methoxy-benzene 
• 2196-99-8 2-chloro-1-(4-methoxyphenyl)ethanone 

Relevant academic research and scientific papers

Difunctionalization of Alkenes Using 1-Chloro-1,2-benziodoxol-3-(1H)-one

Difunctionalization of alkenes with 1-chloro-1,2-benziodoxol-3-(1H)-one (1) was investigated. Various additional nucleophiles were tested, and oxychlorination, dichlorination, azidochlorination, chlorothiocyanation, and iodoesterfication were demonstrated. The oxychlorination product was obtained efficiently when the reaction was operated in water. Dichlorination occurred in the presence of a Lewis basic promoter, such as 4-phenylpyridine N-oxide, as an additive. The reaction with in situ-generated azido anion afforded azidochlorinated compounds with a chlorine atom at the terminal position, while the reaction with trimethylsilyl isothiocyanate produced chlorothiocyanation adducts with a chlorine atom at the benzylic position. On the other hand, when 1 was treated with tetra-n-butylammonium iodide prior to the addition of alkenes, only iodoesterification occurred selectively. These mild reactions enable convenient site-selective difunctionalizations of substrates having two alkene moieties. NMR experiments suggested that the electrophilic reactive species in each reaction varied depending on the nature of the added nucleophile.

Green and Efficient: Iron-Catalyzed Selective Oxidation of Olefins to Carbonyls with O2

A mild and operationally simple iron-catalyzed protocol for the selective aerobic oxidation of aromatic olefins to carbonyl compounds is described. Catalyzed by a Fe(III) species bearing a pyridine bisimidazoline ligand at 1 atm of O2, α- and β-substituted styrenes were cleaved to afford benzaldehydes and aromatic ketones generally in high yields with excellent chemoselectivity and very good functional group tolerance, including those containing radical-sensitive groups. With α-halo-substituted styrenes, the oxidation took place with concomitant halide migration to afford α-halo acetophenones. Various observations have been made, pointing to a mechanism in which both molecular oxygen and the olefinic substrate coordinate to the iron center, leading to the formation of a dioxetane intermediate, which collapses to give the carbonyl product. (Chemical Equation).

THE REACTION OF BENZYLIC ALCOHOLS WITH CHLOROTRIMETHYLSILANE/DIMETHYL SULPHOXIDE

With catalytic amounts of chlorotrimethylsilane/dimethyl sulphoxide (CTMSO/DMSO) in acetonitrile benzylic alcohols have been found to give high yields of styrenes.By using stoicheiometric amounts of reagents, different reaction pathways are observed: an elimination-addition sequence occurs with secondary and tertiary alcohols affording vicinal dichloro derivatives, β-chloro thioethers and allyl chlorides, whereas a nucleophilic substitution to the corresponding monochlorides occurs starting from primary and sterically hindered substrates.

THE REACTION OF STYRENES WITH CHLOROTRIMETHYLSILANE/DIMETHYL SULPHOXIDE

The chlorotrimethylsilane-dimethylsulphoxide reagent system gives rise to smooth and high yield transformations of: i) β-alkyl- and β,β-dialkyl-styrenes into vicinal dichlorides, ii) α,β-dialkyl- and α,β.β-trialkyl-styrenes into allyl chlorides.