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Peracids epoxidation with, 449-451, 525 hydroxylation of benzene with, 494 oxidation of alkanes with, 434, 521 alkynes with, 490 process, for manufacture of propylene oxide, 508 Perborates, epoxidation with, 523 Percarbonates, epoxidation with, 523, 524 Perchloric acid in ionic hydrogenation, 652 in pseudocationic polymerization of styrene, 739 Perdeutero-2-butene, metathesis of, 700 Perdeuteroethylene, ozonation of, 478 Perfluorination, 589 Perfluoroalkanesulfonic acids in acylation, 409-411 in carboxylation of methane, 393 Perfluoroalkanesulfonic acid resins, see also Nafion-H in alkylation, 232, 240 in carbomethoxylation, 382 in polymerization of isobutylene, 725 Peri cyclic rearrangement, 189, 199 Permanganate ion, oxidation with, 482, 483, 499, 502 Peroxides in hydrosilylation, 322 as initiators, in free-radical polymerization, 744,774 in radical hydrobromination, 293 Peroxometallacycle intermediate, 457, 473 Peroxyacetic acid, ring cleavage of aromatics with, 499 Peroxy acids, see Peracids Peroxydiphosphate, oxydation with, 492 Peroxydisulfate, in oxidation of aromatics, 492, 504 Peroxytrifluoroacetic acid-BF 3, in vinylic oxidation, 475 Perrier method, for acylation, 410 Petroleum, 7, 10, 13,30. See also Crude oil Phase-transfer catalysis in epoxidation, 454, 455, 497 in hydrogenation, 638, 643 in hydrohalogenation, 294 in oxidation, 467, 483, 488, 502, 527 in polymerization of phenylacetylene, 769 Phenanthrene oxidative ring cleavage of, 499 partial hydrogenation of, 632, 643, 649

Known as the "endo rule," it was first formulated by Alder and Stein530,532 and explained as the maximum accumulation of double bonds. Now endo selectivity is considered to be the result of stabilizing secondary orbital interactions. 533 The endo rule, however, strictly applies only for cyclic dienophiles. The abovementioned rate acceleration and selectivity enhancement brought about by catalysts are particularly marked when unactivated dienes and dienophiles are involved. Two molecules of 1,3-butadiene can react in a Diels-Alder reaction, one acting as diene and the other as a dienophile to produce 4-vinylcyclohexene (in 0.1 % yield at 250 C in the absence of a catalyst). Cs+, Cu,+ and trivalent transitionmetal exchanged montmorillonites534 as well as large-pore sodium zeolites (Na ZSM-20, NaY) and carbon molecular sieves,535 result in 20-35% yields with 95% selectivity. Large rate enhancement was observed when 1,3-cyclohexadiene underwent a similar cycloaddition536 in the presence of Kl 0 montmorillonite doped with Fe3+:

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