81824-03-5

Upstream product

• 123-91-1 1,4-dioxane 
• 908094-04-2 phenyldiazomethane 
• 23125-71-5 2-chloro-1,4-dioxacyclohexene 
• 6921-34-2 benzylmagnesium chloride 
• 17876-99-2 (4-chlorobenzyl)trimethylsilane 
• 1833-42-7 (3-chlorobenzyl)trimethylsilane 
• 68307-67-5 2-chloro[(trimethylsilyl)methyl]benzene 
• 81824-02-4 endo-7-phenyl-2,5-dioxabicyclo<4.1.0>heptane 
• 81824-02-4 endo-7-phenyl-2,5-dioxabicyclo<4.1.0>heptane 

Relevant academic research and scientific papers

Singlet vs Triplet Reactivity of Photogenerated α,n-Didehydrotoluenes

The reactivity of α,n-didehydrotoluenes (DHTs) in protic media (organic/aqueous mixtures) was explored by means of a combined computational and experimental approach. These intermediates were generated via a photoinduced double elimination process occurring in (chlorobenzyl)trimethylsilanes and led to the formation of a varied products distribution, depending on the isomer tested. Irradiation of ortho- and para-derivatives resulted, respectively, in the formation of triplet α,2- and α,4-DHTs, whose diradical reactivity led to both radical and polar products. On the other hand, irradiation of the meta-precursor led to the singlet α,3-DHT isomer. The latter showed a marked preference for the formation of polar products and this was rationalized, as supported by computational evidence, via the involvement of a zwitterionic species arising through interaction of the nucleophilic solvent with the benzylic position of the DHT.

MODIFICATION OF SINGLET CARBENE REACTIVITIES BY SOLVENT

The solvent effect on the reactivity of singlet carbenes has been investigated.Competition reactions between pairs of alcohols for arylcarbenes in various solvents indicates that the O-H insertion selectivity is influenced only by 1,4-dioxane.Thus, phenylcarbene is some 33 times more reactive toward methanol relative to t-butyl alcohol in 90 molpercent dioxane than without solvent.Similar competition reactions between alcohol and olefin indicate that the O-H insertion-addition selectivities of arylcarbenes are considerably altered by dioxane.These results are interpreted as indicating that dioxane stabilizes singlet carbenes by complexing with its ione pairs of electrons.

Synthesis and Stereochemical Assignment of endo-7-Phenyl-2,5-dioxabicycloheptane

The synthesis and stereochemical assignment of endo-7-phenyl-2,5-dioxabicycloheptane is reported.The stereochemical assignment was made based on both spectral and chemical data.

The Synthesis and Stereochemical Assignment of exo-7-Phenyl-2,5-dioxabicycloheptane

The synthesis and stereochemical assignment of exo-7-phenyl-2,5-dioxabicycloheptane is reported.The stereochemical assignment was made based on data obtained from variable temperature nmr spectra.