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Book your free demo and find out what else Mya 4 from Radleys can do. At the bench recently, I had cause to develop new conditions for a desulfurisation reaction — with some precedent to suggest that the process could be induced by light. It would turn out to be a very tricky problem indeed. The molecule contained not only the necessary structural components for the intended photoreaction, but also a host of ketones.

I feared these might be susceptible to unwanted photo-excitation and cleavage, following a mechanism elucidated by British physical chemist Ronald Norrish. How would I achieve selectivity for my intended reaction? Norrish rose to become the head of the department of physical chemistry in Cambridge, and won a Nobel prize in for his work on flash photolysis and chemical kinetics.

At the end of his career, Norrish 1 was asked how much his early work investigating the reaction kinetics of photochemical processes had influenced the emergence of applied photochemistry in the midth century. Yet serendipity also played its part in his accomplishments.

Born in Cambridge, Norrish excelled in the sciences and mathematics at school. Aged 17 he was awarded a scholarship to Emmanuel College, Cambridge, but deferred his entry to serve in the Royal Field Artillery during the first world war. Captured in early and held as a prisoner of war, Norrish would never forget his good fortune in later returning safely to Cambridge.

The odds of making it in academic life had been shortened. Achieving a double first in natural sciences, he embarked upon doctoral studies under Eric Rideal but quickly began to explore his own ideas in the emerging area of photochemical kinetics. Over the next decade, Norrish elucidated the details of initiation, propagation and termination steps in these reactions — cementing the new theory of radical chain reactions.

From here, he became interested in the photochemical processes of complex reactions involving bigger organic molecules. Norrish realised that the products formed in a light-induced reaction could be used to untangle the processes, and began by exploring photo-decomposition of simple ketones. When irradiated, acetone decomposes to form ethane and carbon monoxide. Norrish recognised that this might occur by a coupling of the two methyl groups within the same molecule, or by initial dissociation to form two radicals methyl and acyl.

Rapid loss of CO from the acyl radical would produce another methyl radical, and combination of these two methyl radicals leads to the ethane product. If the reaction were conducted with an unsymmetrical ketone, then the radical mechanism would generate two different alkyl radicals, and hence a mixture of products, whereas intramolecular coupling could only lead to one alkane.

Norrish conducted gas-phase reactions to test the hypothesis using two unsymmetrical ketones — butanone and 2-hexanone figure 2.

The vapour in the neck of the flask was irradiated with a mercury lamp E and the gaseous products collected in a large bulb C before their separation by fractional distillation under vacuum, each fraction being collected in a gas burette using a cooled trap H.

Norrish designed apparatus to collect and separate the complex product mixtures from photoreactions. Irradiation of butanone forms ethane, propane and butane in similar proportions, suggesting the presence of radicals.

If the mechanism was an intramolecular coupling, irradiating butanone would give only propane. Norrish showed it produces a mixture of etahne, propane and butane, indicating that radicals must be involved. But it was irradiation of 2-hexanone that gave an unexpected result. Once excited, the initial radical abstracts a hydrogen from the side chain a 1,5-hydrogen atom shift , and the resultant radical undergoes cleavage of the a,b bond to give an alkene and an enol, which tautomerises to a ketone.

When ketones with longer side chains are irradiated, there is an opportunity for the initial radical to abstract a hydrogen atom, leading to very different products. Well yes — I got a strong lamp and waited for something to happen.

Fellows R. Faraday Soc. Site powered by Webvision Cloud. Thanks for registering! Subscribe and support our work Subscribers get unlimited access to Chemistry World. Thanks for subscribing! Your subscription expires soon In a few days your subscription will expire. Your subscription expires tomorrow Your subscription expires tomorrow. Your subscription expires today If you do not renew today then from tomorrow you will only have limited access to premium content on our website and will no longer receive our print or digital magazine.

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Sitewide message. Subscribe to this podcast series. No comments. Illuminating the radical photoreactions of ketones. Norrish began by looking at how ketones fragment when irradiated. Related articles. Opinion Curtius rearrangement T An explosive tale of serendipitous discovery. Opinion Reformatskii reaction T The survivor of a once-great empire of zinc chemistry. No comments yet. You're not signed in. To link your comment to your profile, sign in now.

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An indolent artist in Portland, Oregon becomes addicted to marijuana, prompting his girlfriend to flee to New York City with a heroin addict. The definitive documentary about the zany, underground filmmaking twins, George and Mike Kuchar. An experimental film that features graphic sexual imagery, an earthquake, and a lipstick commercial.

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Company Credits. Technical Specs. Plot Summary. Plot Keywords. Parents Guide. External Sites. User Reviews. User Ratings. External Reviews. Metacritic Reviews. Photo Gallery. Trailers and Videos. Crazy Credits. Alternate Versions. Rate This. Involves a nurse trapped in an unhappy marriage who escapes the big city in search of greener pastures in Blessed Prairie, Oklahoma.

Swerving from earnest homage to dark satire. Director: George Kuchar. Added to Watchlist. Film General Recommends. Underrated movies from the 70's. Use the HTML below. You must be a registered user to use the IMDb rating plugin. Photos Add Image Add an image Do you have any images for this title? Peed Into the Wind. Pornogra Follies. Sparkle's Tavern Comedy Drama Fantasy. Sins of the Fleshapoids Short Comedy Sci-Fi. Hold Me While I'm Naked Short Comedy Drama. Bongwater Comedy Romance.

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