Accident, Suicide, or Murder? A Question of Stereochemistry Because of PBS (Public Broadcasting Service) television, there has been a recent upsurge in popularity of the mystery navels of Dorothy L. Sayers. "Clouds of Witness" and "The Unpleasantness a t the Bellona Club" are two of her Peter Wimsey novels which readers may he familiar with, because they were recently produced on the Masterpiece Theatre program. While attending the National ACS meeting in Atlantic City (September, 1974), where the Van't Hoff-LeBel Centenary was celebrated, I was exposed for two days to a barrage of both nostalgic and modern stereachemistry. I was reminded, when my mind occasionally wandered during some of the papers, of s somewhat less well-known murder mystery of Miss Sayers, in which the resolution of the crime depends entirely on stereachemistry. The novel is called "The Documents in the Case." and i t was written eollaborativelv hv Miss Savers and Robert Eustace (the Den name of Eustace Robert Barton.. a ohvsician who often orovided scientific informa&m in novels written bv others. and who was a rontempcmry of Conan Duy1t.l. I t is available in paperback from Avon Rooks for about 95c and I strongly recommend it as supplementary reading fur undergrad~~ate organir rrudrntu. It would be a mistake, of course, to give away the whole mystery. In the hook, the story is revealed through letters. newspaper articles, and other documents (depositions, etc.). The main point is that a plant expert, with a taste for gourmet dishes of mushrooms, is found dead of muscarine poisoning. Did be err and eat a toxic variety of mushrooms? Did he eat them purposely (suicide)? or was it murder? At a dinner party, a Dr. Waters, (stout, red-faced, with a boisterous manner and "the coming man in chemistry" a t Oxford) in a brief cocktail party type of philosophical discussion of the oriein of life on earth. describes what we would now call chiral molecules. and the distinction between raeemie and ootically active furmi. I t is on this clue that the resolution of the mystery depends, and it i5 d l told in a satisfying way that the layman ran understand, and that the student in urganir chemistry, with his extra knowledge. will especially appreclate and enjoy. There are some interesting technical points for the historian. The novel was written in 1930. At that time an incorrect structure was attributed t o muscarine. The correct constitution was not deduced until a n X-ray structure of musearine iodide was published as recently as 1957 [An interesting account of the history and chemistry of muscarine was published by S. Wilkinson in Quart. Reu., 15.153 (1961)j. Sayers and Eustace describe a preparation of synthetic muscarine by "heating etbene oxide with triethylamine. That gives you your cholin. Then you oxidize it with dilute nitric acid-the stuff you etch with, you know. Result, musearine. Pretty, isn't it?" Despite the error (trimethylamine, not trietbylamine; this could he a misprint) i t was+claimed, and believed for a long time (roughly 1881-1914), that the material one gets this way (which is actually ( C H ~ ) ~ N C H ~ C H Z O N was O )synthetic muscarine. But with that structure, it was of course incapable of optical activity. There are also problems with the empirical formula. Formulas C5Hz402Nt and CsHtaOzNt held sway for many years before the present structure, C9HmOsNC was deduced. The Sayers-Eustaee formula ( C ~ H I J N Oon ~ , page195 of the A w n version) presumably was the first of these, as the hydroxide, though this formula had been fairly well discredited by 1922. But the novelists were fairly up on some of the recent literature of the time. because ontical activitv of the natural material was not reallv firmlv established until iust about the time their novel was publihed l ~ a p f h & m t e and r Bischdf. Z Ph)siol. ~ h e m . 191.'182 . 11930,I. In far;, the molecule has three chiral renters, being the quaternary trimethylammonium salt of (2s; 37;GS1-5-aminomethyltetr~hydro-R-hydrox~-2methylfuran
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muscarine One wanders about the chemist Waters. Dorothy Sayers was one of the first women to obtain a,degree from Oxford (in 1915). The name of W. A. Waters has of course for many years been associated with organic chemistry a t Oxford. Are they one and the same? Does the real Waters fit her description? I think not. I found by checking the literature that a t the time of the novel, and for several years afterwards, the Waters was a t the University of Durham, and only went t o Oxford later. Perhaps the authoress anticipated this move (i.e., was a seer-Sayer). Finally, a technical error (called to my attention by colleague W. H. Reuscb, another Sayers fan). In the closing moments of the novel, three of the characters are in a laboratory about to place a sample in the polarimeter. One of them, later deseribina the scene.. savs . "He snaooed off the liehts. .. . and we were left with onlv the sodium flame. In that >ereen 11rulir.
