58219-46-8

Upstream product

• 6135-54-2 2-tert-Butyl-2-methyl-1,3-dioxolane 
• 624-48-6 dimethyl cis-but-2-ene-1,4-dioate 
• 712-74-3 1,2,4,5-tetracyanobenzene 
• 624-49-7 dimethylfumarate 
• 3531-47-3 (t-butyl)trimethylstannane 
• 75-98-9 Trimethylacetic acid 
• 92976-53-9 tert-Butyl-dimethyl-octyloxy-silane 
• 2568-29-8 2-(1,1-dimethylethyl)-1,3-dioxolane 
• 6135-60-0 2-tert-butyl-2-phenyl-[1,3]dioxolane 

Relevant academic research and scientific papers

Radical addition to alkenes via electron transfer photosensitization

A method for radical addition to alkenes is reported which is based on the photosensitized oxidation of a tetraalkylstannane by an excited acceptor (A*), fragmentation of the radical cation, and addition of the thus formed radical to an electron-withdrawing substituted alkene (acrylonitrile and dimethyl maleate). Aromatic nitriles and esters can be used as the electron acceptors, and they are chosen in such a way that their radical anion (A?-) reduces the adduct (and not the educt) radical. In this way the adduct radical is reduced and protonated to yield the end product, and the acceptor functions as a nonconsumed electron transfer sensitizer. In several cases the alkylation occurs more efficiently in the presence of a secondary donor (phenanthrene or biphenyl). However, when the acceptor is too easily reduced in the ground state (as with 1,2,4,5-benzenetetracarbonitrile), coupling of the adduct radical with A?- competes with its reduction.

Alkylation of alkenes by radicals generated through photoinduced single electron transfer

Irradiation of 1,2,4,5-benzenetetracarbonitrile (TCB) in the presence of several donors (some 2-t-butyl-1,3-dioxolanes, pivalic acid, t-butyltrimethylstannane, t-butyldimethylsilyl n-octyl ether) leads to fragmentation of the donor radical cation to give

Radicals through Photoinduced Electron Transfer. Addition to Olefin and Addition to Olefin-Aromatic Substitution Reactions

The radical cations of 2,2-dialkyl- and 2-alkyl-2-aryl-1,3-dioxolanes, when generated in solution by photoinduced electron transfer to 1,2,4,5-benzenetetracarbonitrile (TCB), fragment to yield alkyl radicals.These are trapped by electron-withdrawing substituted alkenes (acrylonitrile, methyl acrylate, methyl vinyl ketone, as well as dimethyl maleate and fumarate).The radicals thus formed are either reduced by the TCB radical anion or add to it.In the first process (observed only with the diesters) the end result is reductive alkylation of the olefin, while the latter process results in an addition to the olefin-aromatic substitution reaction.The selectivity of the process is explained on the basis of steric hindrance, since the radicals react when still in the cage with the aromatic radical anion.