Photolytic decomposition

Decomposition. Acetaldehyde decomposes at temperatures above 400°C, forming principally methane and carbon monoxide [630-08-0]. The activation energy of the pyrolysis reaction is 97.7 kj/mol (408.8 kcal/mol) (27). There have been many investigations of the photolytic and radical-induced decomposition of acetaldehyde and deuterated acetaldehyde (28—30). 

Most chlorofluorocarbons are hydrolytically stable, CCI2F2 being considerably more stable than either CCl F or CHCI2F. Chlorofluoromethanes and ethanes disproportionate in the presence of aluminum chloride. For example, CCl F and CCI2F2 give CCIF and CCl CHCIF2 disproportionates to CHF and CHCl. The carbon—chlorine bond in most chlorofluorocarbons can be homolyticaHy cleaved under photolytic conditions (185—225 nm) to give chlorine radicals. This photochemical decomposition is the basis of the prediction that chlorofluorocarbons that reach the upper atmosphere deplete the earth s ozone shield. 

Chemical Properties. Diacyl peroxides (20) decompose when heated or photoly2ed (<300 mm). Although photolytic decompositions generally produce free radicals (198), thermal decompositions can produce nonradical and radical iatermediates, depending on diacyl peroxide stmcture. Symmetrical aUphatic diacyl peroxides of certain stmctures, ie, diacyl peroxides (20, = alkyl) without a-branches or with a mono-cx-methyl... 

Nitroimidazoles and 2-azidoimidazoles are available via the diazonium fluoroborates, and photolytic decomposition of the fluoroborates gives 2-fluoroimidazoles (80AHC(27)24i). 

The thermal and photolytic processes have been extensively studied in connection with the mechanism (concerted or diradical) and the stereochemistry of the decomposition. For a classical paper see (66JA3963) and for more recent studies, Table 33. 

Photolysis of 3-phenyl-2,l-benzisoxazole in 48% HBr produced reduction and substitution products via a proposed triplet state nitrenium ion intermediate (71HCA2111). Photolytic decomposition of 5-bromo-3-phenyl-2,l-benzisoxazole in 48% HBr gave 2-amino-5-bromoacetophenone and 2-amino-3,5-dibromoacetophenone (Scheme 18). A nitrenium ion intermediate was also proposed for the photolytic decomposition of 3-phenyl-2,l-benzisoxazole in concentrated HCl (Scheme 19) (7IHCA2111). 

Because of the possibility of focusing laser beams, tlrin films can be produced at precisely defined locations. Using a microscope train of lenses to focus a laser beam makes possible tire production of microregions suitable for application in computer chip production. The photolytic process produces islands of product nuclei, which act as preferential nucleation sites for further deposition, and tlrus to some unevenness in tire product film. This is because the subsuate is relatively cool, and therefore tire surface mobility of the deposited atoms is low. In pyrolytic decomposition, the region over which deposition occurs depends on the drermal conductivity of the substrate, being wider the lower the thermal conductivity. For example, the surface area of a deposit of silicon on silicon is nanower dran the deposition of silicon on silica, or on a surface-oxidized silicon sample, using the same beam geomeU y. 

The radical is generated by photolytic decomposition of di-/-butyl peroxide in methylcy-clopropane, a process that leads to selective abstraction of a methyl hydrogen from methylcyclopropane ... 

There are several reaction sequences which involve such intramolecular hydrogen abstraction steps. One example is the photolytically intitiated decomposition of N-haloamines in acidic solution, which is known as the Hofinann-Loffier reactionThe reaction leads initially to y-haloamines, but these are usually converted to pyrrolidines by intramolecular nucleophilic substitution ... 

The photolytic and thermolytic decomposition of azides in the presence of olefins has been applied to aziridine synthesis. However, only a limited number of steroid aziridines have been prepared in this manner. The patent literature reports the use of cyanogen azide at ca. 50° for 24 hours in ethyl acetate for the preparation of an A-nor- and a B-norsteroidal aziridine. The addition is believed to proceed via a triazoline. The reaction of cholest-2-ene with ethyl azidoformate takes place in a nonselective manner to produce a mixture of substances, including C—H insertion products. 

The photolytic decomposition of a-diazoketones, accompanied by rearrangement to ketene (photolytic Wolff rearrangement), has been used successfully in the preparation of A-nor- and C-norsteroids. The method is reviewed in chapter 15 by R. M. Scribner. ... 

In this review an attempt is made to discuss all the important interactions of highly reactive divalent carbon derivatives (carbenes, methylenes) and heterocyclic compounds and the accompanying molecular rearrangements. The most widely studied reactions have been those of dihalocarbenes, particularly dichlorocarbene, and the a-ketocarbenes obtained by photolytic or copper-catalyzed decomposition of diazo compounds such as diazoacetic ester or diazoacetone. The reactions of diazomethane with heterocyclic compounds have already been reviewed in this series. ... 

Properties attributed to the intermediate complex from reaction of 4-nitrofluorobenzene with azide ion were found later to be due to an artifact resulting from photolytic decomposition of the... 

Tlie isolable stable 1,2-dithietaiie, dithiatopazine (73), was prepared in 1988 and fully characterized (the name dithiatopazine was coined for its beautifully yellow-orange topazlike crystalline form) (87JA3801 88JA4856 90JA3029). Tlius, controlled photoirradiation of a dithiono-lactone (117) produced 73 in 65% yield along with an alkene 118 in 12% yield. Photolytic or thermal decomposition of 73 led to the alkene 118, a conversion that could be also carried out by a variety of reagents [m-BusShH-AIBN, Raney Ni, MCPBA, Fe2(CO)9, Mo(CO)6] in excellent yields. 

The nitrene can be generated by a variety of methods, the most popular being the thermal or photolytic decomposition of azidoformates. Other methods, particularly the base-catalyzed a-elimination of arylsulfonate ion from 7V-[(arylsulfonyl)oxy]urethanes, are useful as they avoid the use of the potentially explosive azido esters. 

The thermal, and more importantly, the photolytic decomposition of aryl azides in the presence of nucleophiles, generally amines or alcohols, is the commonest method for preparing 3H-azepines. In fact, jV-phenyl-3//-azepin-2-amine (32, R = Ph), the first example of a 3//-azepine, was prepared by thermal decomposition of phenyl azide in aniline.32... 

Photolytic reactions such as the decomposition of ozone by light are also unimolecular processes ... 

Breakdown of Certain Double-Bond Compounds. The most common method of forming nitrenes is photolytic or thermal decomposition of azides," " ... 

Mechanisms for the thermal and photolytic decomposition of N -nitrosamides are briefly reviewed, and recent results for their decomposition by acidic and basic catalysts are summarised and discussed ... 

N-Nitrosamides are much less stable than the parent N-nitros-amines and they can decompose by either thermal, photolytic or acid and base (nucleophilic) catalysed pathways Thermal decomposition has attracted much attention as a clean method of deamin-... 

---