No abstract

Rate constants for the overall rearrangement of the 2,2-dimethyl-3-buten-1-yl radical to the 1,1 -dimethyl-3-buten-1-yl radical, kC=C, have been measured from −145 °C to −101 °C by kinetic epr spectroscopy and at 40 °C by spin trapping with 1-methyl-4-nitroso-3,5-diphenylpyrazole. The temperature dependence can be represented by[Formula: see text]where θ = 2.3RT kcal mol−1. This rearrangement, which must proceed via a 2,2-dimethylcyclopropylcarbinyl radical as an intermediate, is one of the fastest rearrangements involving a primary alkyl radical. At 25 °C, kC=C = 4.3 × 107 s−1, which makes this rearrangement about 10 000 times faster than the rearrangement of the simplest homoallyl radical, 3-buten-1-yl. This rate enhancement is attributed to steric acceleration of ring closure by the gem dimethyl groups (Thorpe–Ingold effect).

SynopsisThin-film composite membranes containing photoreactive groups have been developed. The presence of these groups facilitates the subsequent photochemical conversion of the membrane to include a range of different chemical moieties. For example, a cationic or an anionic membrane can be made from the same initial composite membrane. In this paper the selection of an appropriate photolabile group is investigated.

Irradiation of the oxadiazolines (III), prepared by oxidative ring closure of the hydrazides (I), gives the unstable diazoalkanes (IV).