SRN1 mechanism in heteroaromatic nucleophilic substitution. Generality of photostimulated reactions of ketone enolates with 2-chloroquinoline

Electrochemically induced aromatic nucleophilic substitution in liquid ammonia. Competition with electron transfer

“…Assuming that competition is under ECE control for 2bromoquinoline as in the preceding case, application of eq 13 to the data obtained for the reaction of this compound with benzenethiolate (Figure 5b) leads to k\/k2 = 9 X 10-3 M L-1 and therefore to A: j = 1.3 X 105 s-1. Examination of conditions 12 and 14 shows that the system is at limit between the ECE and DISP controls under the concentration and sweep rate conditions corresponding to Figure 5b.…”

“…In the ECE case, i.e., for fast decomposition of the ArX-* anion radical k\ (s-1) > 3.5 X 107C°2/3 (M L-1) u1/3 (V s-1) (at -40 °C) (12) The current function of ;p/0'p)d Up is the observed peak current; (ip)d is the peak current that would correspond to a oneelectron reversible electron transfer Increasing the value of this parameter results in a decrease of the peak height from 2 to 0 electrons for E\0 > E2°a nd from 2 to 1 electrons for E] °< £2°. As anticipated from the firstorder character of all reactions in this case (Nuis assumed to be in sufficient excess over ArNu for reaction 2 to be pseudo first order), the current (13) for the catalytic case. Correspondingly, the substitution yield upon electrolysis beyond peak (H) does not depend upon C°and upon the stirring rate.…”

“…These systems have been investigated previ- ously from a preparative point of view under photostimulation. 13 The substitution product gives rise to one reversible wave in the first case and to two reversible waves in the second. They are all located at potentials markedly negative to the wave of quinoline.…”

Synthesis of ε-oxo acids by photostimulated reactions of 2-(2-iodophenyl)acetate ion with carbanions by the SRN1 mechanism. Synthesis of novel 3-benzazepin-2-ones

“…21 Similar results have been described in the reaction of 2-chloroquinoline and i-propylmethyl ketone enolate ion. 22 2-Butanone can form isomeric enolate ions 2d and 2d′. However, 7 reacts exclusively with 2d to yield the ε-oxo acid 3d in a 24% yield; no traces of product 10 being found (Scheme 2; Table 1, entry 8).…”

TheSRN1 reaction of organic halides

“…step (59) is more efficient than step (60). In the reactions of both p-nitrobenzylidene dichloride (X = Y = C1) and the corresponding bromide chloride (X = CI, Y = Br)139, the SRNl cycle predominates, i.e.…”