How one might go about answering the question: do alkenes promote anomeric effects? A search of chemical abstracts does not appear to cite any examples (I may have missed them of course, since it depends very much on the terminology you use, and new effects may not yet have any agreed terminology) and a recent excellent review of hyperconjugation does not mention it. Here I show how one might provide an answer.
Posts Tagged ‘Andrew White’
In 1890, chemists had to work hard to find out what the structures of their molecules were, given they had no access to the plethora of modern techniques we are used to in 2010. For example, how could they be sure what the structure of naphthalene was? Well, two such chemists, William Henry Armstrong (1847-1937) and his student William Palmer Wynne (1861-1950; I might note that despite working with toxic chemicals for years, both made it to the ripe old age of ~90!) set out on an epic 11-year journey to synthesize all possible mono, di, tri and tetra-substituted naphthalenes. Tabulating how many isomers they could make (we will call them AW here) would establish beyond doubt the basic connectivity of the naphthalene ring system. This was in fact very important, since many industrial dyes were based on this ring system, and patents depended on getting it correct! Amazingly, their collection of naphthalenes survives to this day. With the passage of 120 years, we can go back and check their assignments. The catalogued collection (located at Imperial College) comprises 263 specimens. Here the focus is on just one, specimen number number 22, which bears an original label of trichloronaphthalene [2:3:1] and for which was claimed a melting point of 109.5°C. What caught our attention is that a search for this compound in modern databases (Reaxys if you are interested, what used to be called Beilstein) reveals the compound to have a melting point of ~84°C. So, are alarm bells ringing? Did AW make a big error? Were many of the patented dyes not what they seemed?