Photochemical reactions: bromination

Benzo[b]furan, 2-nitro-reduction, 4, 74, 647 Benzo[b]furan, 5-nitro-mass spectrometry, 4, 583 Benzo[b]furan, 2-(4-nitrophenyl)-properties, 4, 708 Benzo[b]furan, 2-phenyl-bromination, 4, 605 chloromethylation, 4, 607 nitration, 4, 604 photochemical reactions, 4, 636 properties, 4, 697 Benzo[b]furan, 3-phenyl-synthesis, 4, 697... 

Allylic bromination of pregnenolone acetate with dibromodi-methylhydantoin affords the 7-bromo compound (155) of undefined stereochemistry. Dehydrobromination by means of collidine followed by saponification affords the 5,7 endocyclic cis,cis-diene, 156. This compound contains the same chromophore as ergosterol, a steroid used as a vitamin D precursor. The latter displays a complex series of photochemical reactions among the known products is lumisterol, in which the stereochemistry at both C9 and Cio is inverted. Indeed, irradiation of 156 proceeds to give just such a product (158). This reaction can be rationalized by... 

If equations 4.2.25 and 4.2.26 are substituted for equations 4.2.11 and 4.2.15, respectively, in the mechanism described above, the effect is to replace kx by k [M] and k5 by /c 5[M] everywhere that they appear. Since these quantities appear as a ratio in the final rate expression, the third body concentration will drop out and kjks) becomes identical with k /k 5 The necessity for the use of the third body concentration thus is not obvious in kinetic studies of the thermal reaction. However, from studies of photochemical reaction between hydrogen and bromine, there is strong evidence that the termination reaction is termolecular. This fact and... 

Aranda et al. (1997) have shown in laboratory studies that CH302 also reacts with BrO in a manner analogous to the H02 reaction (123), with a rate constant at 298 K of 5.7 X 10"12 cm3 molecule 1 s 1. About 80% of the reaction generates HOBr + CH202, with the remainder forming Br + CH30 + 02. In either case, photochemically active bromine species are regenerated. 

Arctic at polar sunrise. The mechanism likely involves regeneration of photochemically active bromine via heterogeneous reactions on aerosol particles, the snow-pack, and/or frozen seawater. The source of the bromine is likely sea salt, but the nature of the reactions initiating this ozone loss remains to be identified. For a review, see the volume edited by Niki and Becker (1993) and an issue of Tellus (Barrie and Platt, 1997). 

Hexa- and other higher brominated biphenyls are expected to be present in the particle-adsorbed state in the atmosphere. These PBBs photolyze in solution and in soil (Hill et al. 1982 Ruzo and Zabik 1975 Trotter 1977). Since PBBs present in surface soil are known to photolyze, particle-sorbed PBBs present in the atmosphere may also undergo photolysis. The importance of the photochemical reaction under sunlight illumination conditions for the degradation/transformation of PBBs in air cannot be evaluated due the lack of information. 

Miller and Walling1 6 have shown that both bromine and sulfonyl chloride groups can be displaced during the photochemical reaction of chlorine with p-bromobenzenesulfonyl chloride and that a similar displacement of the sulfonyl group of benzenesulfonyl chloride occurs to give chlorobenzene. 

This means that in the photochemical reaction the concentration of the bromine atoms which prevails is about 300 times greater than in the dark reaction, since all other parts of the reaction mechanism are identical. The rate of combination is simply an indicator of the concentration of atomic bromine. Thus this concentration is found by the relation... 

The concentration of bromine atoms in the dark reaction is known from the concentration of molecular bromine and the thermal dissociation constant of bromine, hence that prevailing at any stage of the photochemical reaction is found. 

The reactions initiated by atoms do not belong in the realm of photochemistry since under a given set of experimental conditions these reactions will be the same no matter how the atoms are formed. The classical work on reactions initiated by chlorine after absorption of light has shown that chain reactions may be started38. The thermal and photochemical hydrogen-bromine reactions lead to the same products with the same mechanism, the one distinction being that bromine atoms... 

The bromination of cinnamic acid dissolved in carbon tetrachloride or other inert solvent.offers a convenient system for study. The dibromocinnamic acid produced remains in the carbon tetrachloride solution. The thermal reaction is so slow that it can barely be measured at room temperature and it is entirely negligible in comparison with the photochemical reaction at ordinary intensities. The quantum yield is so large that considerable reaction occurs even if the intensity of light is much reduced by the monochromator or other device for confining the light to a narrow range of frequencies. Furthermore, the reaction is easily and accurately followed by titration with sodium thiosulfate. Potassium iodide is added and the iodine liberated is a measure of the remaining bromine. 

Bromination of 2-methylquinoxaline using l,3-dibromo-5,5-dimethylhydantoin in the presence of dibenzoyl peroxide (DBPO) under photochemical reaction conditions gives 2-bro-momethylquinoxaline which is a useful synthon for the synthesis of L-quinoxal-2-yiaianine. - ... 

Reactions involving the formation of carbon heteroatom bonds include the industrially best known photochemical reactions. In fact, chlorination, bromination and sulfochlorination are major processes in industrial chemistry, and oxygenation has likewise an important role. Due to the focus on fine chemistry of this chapter, the discussion below is limited to laboratory-scale preparations and in particular to some bromination and oxygenation reactions illustrating the advantage of the photochemical approach, as well as to some alkoxylation, hydroxylation and amination reactions. 

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