98560-52-2

Upstream product

• 109-99-9 tetrahydrofuran 
• 107671-67-0 4-tert-Butylperoxy-but-1-ene 
• 123-91-1 1,4-dioxane 
• 15061-83-3 (E)-[2,2']bifurylidene-5,5'-dione 

Relevant academic research and scientific papers

DEPLACEMENTS HOMOLYTIQUES INTRAMOLECULAIRES . 12 - DECOMPOSITION INDUITE DE PEROXYDES ETHYLENIQUES : INFLUENCE DE LA LONGUEUR DE LA CHAINE

Products analyses of the thermolyses of the peroxides CH2=CH-(CH2)nOOtBu, 1, (n=1-5) showed that an induced decomposition of 1 occurred for n=1,2,3,4.Free radical additions of THF, carbon tetrachloride, bromotrichloromethane to 1 have been performed at lower temperature; they allowed, through the isolation of an adduct peroxide, at least in one case for each peroxide, to prove that a two-steps mechanism (addition of radical Z. to the double bond, intramolecular homolytic displacement) is involved in the induced decomposition of 1.The order of magnitude of the rate constants of these SHi reactions could be estimated.

The photolysis of tetrahydrofuran and of some of its methyl derivatives at 185 nm

The uv photolysis of tetrahydrofuran, 1, 2-methyltetrahydrofuran, 2, cis-2,5-dimethylterahydrofuran, 3, trans-2,5-dimethyltetrahydrofuran, 4, and 2,2,5,5-tetramethyltetrahydrofuran, 5, has been investigated by product analysis in the liquid phase, and quantum yields have been determined.The photolysis of tetrahydrofuran itself was also studied in the gas phase at pressures ranging from 1 to 120 atm (pressurizing gas N2); and very little difference was found between the photolytic behaviour of the vapour at 120 atm and that of the liquid.The major products are in all cases the cyclopropanes and the corresponding carbonyl compounds, as well as the olefinic alcohols and the carbonyl compounds that are isomeric with the starting material.These products are considered to be formed by the two primary processes and . The cyclopropanes formed in reaction retain some excess energy (apparently more then is needed to realize the trimethylene form), and in the photolysis of tetrahydrofuran vaapour the hot cyclopropane rearranges to a considerable extent into propene.The propene to cyclopropane yield ratio falls strongly with increasing pressure, to a value of 0.065 at 120 atm.A similar value is observed in the liquid phase photolysis.The five-membered oxyl alkyl diradical from reaction is the likely intermediate in the cis-trans photoisomerization that is observable with the 2,5-dimethyltetrahydrofurans (Φ(cis -> trans) ca. Φ(trans -> cis) ca. 0.2).The photolysis of these compounds also demonstrates that steric factors have a strong bearing on the course of the reaction, e. g. the quantum yield of methylcyclopropane from the cis compound is 0.22, vs. 0.08 from the trans compound.Molecular hydrogen is produced if the tetrahydrofurans carry hydrogen in α-position.Its production is enhanced if the α-position is shared with a methyl group (1 gives a hydrogen quantum yield of 0.07, 2 of 0.17, 3 of 0.27, 4 of 0.29, and 5 of zero).