No abstract

No abstract

Notes 252 nm (e 760), 257 (740); nmr r 8.46 (s, 6 H) and 9.82 (s, 9 ).Experimental Section 3-Phenylbut-l-yne (IV).-A solution of dilithio-l-phenylpropyne was prepared as reported1 from 1 g of 1-phenylpropyne and 14.5 ml of 1.2 F butyllithium in ether. This solution was cooled in an acetone-Dry Ice bath and gaseous methyl bromide was bubbled through it during 15 min. The reaction mixture was allowed to reach room temperature and poured on ice, and the ether layer separated. The reaction product, containing 80% of IV and 20% of 1-phenylpropyne, was separated into its components by glpc.Anal. Caled for Ci0Hi0: C, 92.31; H, 7.69. Found: C, 92.42; , 7.81.l-Trimethylsilyl-3-phenylbut-l-yne (V) was prepared as above but trimethylchlorosilane was added after the product of reaction with methyl bromide reached room temperature. The solution was left overnight and poured on water and the product in the ether layer purified by glpc on Apiezon L on Chromosorb, yield 80%.

This Account highlights William von Eggers Doering's important discoveries in many fields of chemistry. His synthetic and mechanistic studies have contributed to areas including non-benzenoid aromatics, carbenes, pericyclic reactions, and diradical intermediates. Doering's synthesis with L. H. Knox of the highly stable tropylium ion and their investigation of its reactivity were the starting point for the development of the field of non-benzenoid aromatics. Working with A. K. Hoffmann, Doering demonstrated the synthesis of dichloro- and dibromocarbene by base-induced alpha elimination of HCl or HBr from CHCl3 or CHBr3 under anhydrous conditions. These results allowed for the synthesis of a variety of cyclopropanes and derivatives including allenes. Using 14C labeling experiments, Doering and Prinzbach showed that the mechanism of insertion of singlet methylene into a C-H bond was a concerted process.In their work on the Cope rearrangement, Doering and Roth's outstanding stereochemical analysis showed that the rearrangement of acyclic 1,5-hexadienes proceeds concertedly, passing over a chairlike transition state. This work has had an enormous impact on the understanding of stereochemical control in synthetic organic chemistry, and many fruitful applications in synthesis have stemmed directly from this finding. Transition-state resonance structures analogous to those for ground-state aromatics can qualitatively explain the relatively large substituent effects on the rate of the Cope rearrangement. However, quantum chemical calculations have quantitatively described these effects. The rapid degenerate Cope rearrangements in the cis-divinylcyclopropane units of 3,4-homotropilidene, barbaralone, and bullvalene establish these molecules as having fluxional structures. The unique molecule bullvalene has more than 1.2 million possible structures interconnected by degenerate Cope rearrangements, which average all H and all C atoms. Doering has also examined stepwise thermal reorganizations that pass through intermediary 1,3- or 1,4-diradicals and do not show conformational equilibration as would be expected for classical intermediates. Doering calls these processes "not-obviously concerted". He discusses "continuous diradicals" as transition states and rationalizes the course of these reactions through the concept of a "caldera" (a flat surface with small energy wells as found on the top of volcanoes).The understanding of fundamental chemical reactions remains the focus of Doering's research. In his terms, "understanding" means not only gaining deep insight but also the intellectual control that allows researchers to predict a reaction's course. Because the interplay between theory and experiment has led to great progress in this predictive ability, Doering's experimental work has provided an important input for computational chemistry and to the essential understanding of chemical reactions.