𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Isomerization of unsaturated radicals. V. Unimolecular isomerization of hot α,α- and α,β-dimethallyl radicals

✍ Scribed by Hélêne Deslauriers; Guy J. Collin

Publisher
John Wiley and Sons
Year
1988
Tongue
English
Weight
434 KB
Volume
20
Category
Article
ISSN
0538-8066

No coin nor oath required. For personal study only.

✦ Synopsis

The 147 nm photolysis of 3,3 dimethylbut-l-ene leads mainly to the formation of very hot ( ~3 7 5 kJ/mol) a,a-dimethallyl radicals. On the other hand, that of 3-methyl-cisand trans-pentene-2, as well as that of 2,3-dimethylbut-l-ene is a source of very hot a$-dimethallyl radicals. These allylic radicals are coolled down using pressure and are allowed to combine with available methyl radicals. From the formation of various CsHlz products, it is concluded that the very hot a,a-radical isomerizes towards the a,@-structure at low pressures and vice uersa. The equilibrium constant of the following process has been evaluated to be 1.72 t 0.30. CH3C(CH,)CHCH2* CH2C(CH3)CHCH3*

📜 SIMILAR VOLUMES

Photochemical isomerization of simple α,
Photochemical isomerization of simple α,β-unsaturated ketones
✍ N.C. Yang; Margaret J. Jorgenson 📂 Article 📅 1964 🏛 Elsevier Science 🌐 French ⚖ 230 KB

IN our detailed study of photochsmical behavior of simple acyclic a.rpdnsaturated ketones (I), us have observad three differsnt kinds of behavior of these ketones upon irradiation. One, tbs formation of cyclopropane derivatives when the carbon rtom y to the carbonyl group is a quarternary one (Ia, R

Radical-mediated hydroxytrifluoromethyla
Radical-mediated hydroxytrifluoromethylation of α,β-unsaturated esters
✍ Tomoko Yajima; Hajime Nagano; Chiaki Saito 📂 Article 📅 2003 🏛 Elsevier Science 🌐 French ⚖ 119 KB

Treatment of a,b-unsaturated esters with trifluoromethyl iodide and triethylborane in the presence of KF and H 2 O gave the corresponding hydroxytrifluoromethylated esters.