Organic Photochemistry
Examples of photochemical organic reactions are electrocyclic reactions, photoisomerization and Norrish reactions.
Alkenes undergo many important reactions that proceed via a photon-induced π to π* transition. The first electronic excited state of an alkene lack the π-bond, so that rotation about the C-C bond is rapid and the molecule engages in reactions not observed thermally. These reactions include cis-trans isomerization, cycloaddition to other (ground state) alkene to give cyclobutane derivatives. The cis-trans isomerization of a (poly)alkene is involved in retinal, a component of the machinery of vision. The dimerization of alkenes is relevant to the photodamage of DNA, where thymine dimers are observed upon illuminating DNA to UV radiation. Such dimers interfere with transcription. The beneficial effects of sunlight are associated with the photochemically induced retro-cyclization (decyclization) reaction of ergosterol to give vitamin D. In the DeMayo reaction, an alkene reacts with a 1,3-diketone reacts via its enol to yield a 1,5-diketone. Still another common photochemical reaction is Zimmerman's Di-pi-methane rearrangement.
In an industrial application, about 100,000 tonnes of benzyl chloride are prepared annually by the gas-phase photochemical reaction of toluene with chlorine. The light is absorbed by chlorine molecule, the low energy of this transition being indicted by the yellowish color of the gas. The photon induces homolysis of the Cl-Cl bond, and the resulting chlorine radical converts toluene to the benzyl radical:
- Cl2 + hν → 2 Cl·
- C6H5CH3 + Cl· → C6H5CH2· + HCl
- C6H5CH2· + Cl· → C6H5CH2Cl
Mercaptans can be produced by photochemical addition of hydrogen sulfide (H2S) to alpha olefins.
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