Vapor-phase irradiation

Irradiation of hexafluorobiacetyl in the vapor phase produces a 2 1 mole ratio of carbon monoxide and hexafluoroethane, products consistent with an initial carbon-carbon bond cleavage.62 However, vapor phase irradiation of hexafluorobiacetyl in the presence of a large excess of 2,3-dimethylbutane vapor or in 2,3-dimethylbutane solution gave less than 1% carbon monoxide and trifluoromethane. No trifluoroacetaldehyde or hexafluoroacetone was produced in the latter reaction. Instead a complex mixture of products, which was not separated and identified but whose infrared showed the presence of a hydroxyl band and a diminished carbonyl band, was obtained. This observation is consistent with product formation via hydrogen abstraction. 

Several further experimental results lend support to the mechanisms postulated to explain the formation of the photoproducts. Thus irradiation of thiophene and substituted thiophenes in the presence of -propylamine leads to pyrroles, presumably via cyclopro-penylthiocarbonyl, or Dewar thiophene, intermediates (75T785). An extremely interesting development is the isolation of l,2,3,4-tetrakis(trifluoromethyl)-5-thiabicyclo[2.1.0]pent-2-ene, or perfluoro(tetramethyl Dewar thiophene) (2) by vapor-phase irradiation of perfluorotetramethylthiophene (81ACR76) the yield is about 58%. The half-life of thermal rearomatization of (2) at 160 °C is 5.1 h. The fluxional behaviour of the Dewar thiophene... 

The formation of 1,2-dimethylcyclobutene (Formula 385) in the vapor phase irradiation of 2,3-dimethyl-l,3-butadiene (Formula 384) is not quenched by oxygen or nitric oxide (169). Addition of inert vapor (diethyl ether) increased the quantum efficiency in this reaction (169). The inert vapor presumably removes excess vibrational energy from the product cyclobutene thus stabilizing the product (169). Rate studies on the cis- and Jrans-isomers of 1,3-pentadiene in solution indicate that the iraras-isomer is the only source of 3-methylcyclobutene (169). The photoisomerization to 3-methylcyclobutene is faster than photoisomerization of trans- to m-l,3-pentadiene (169). 

Cycloheptatrienes. Cycloheptatriene (Formula 391) gives the bicyclic photoisomer (Formula 392) on irradiation in ether solution (160, 173). Vapor-phase irradiation of cycloheptatriene gives toluene and... 

Some synthetically useful examples involve fluorinated pyridazines. Thus, the preparative-scale irradiation of perfluoroalkylpyridazines 124 at 254 nm in the vapor phase produces perfluoroalkylpyrazines 127. This permutation process is suggested to occur through the bicydic species 125 and 126, which have been isolated and characterized (Scheme 12.34) [75, 76]. Another example involves the vapor-phase irradiation of 4,5-difluoro-3,6-bis(trifluoromethyl)pyridazine to produce the corresponding perfluoro-2,5-dimethylpyrazine in 58% isolated yield, with 40% of the starting material being recovered [77]. 

Typical experimental procedures for a vapor-phase irradiation and for a solution-phase photolysis are given. Applications of the method that led to synthetically interesting yields or to products difficult to obtain by other methodology are summarized in Table 10. 

Synthesis of Semibnllvalene (S) by Vapor-Phase Irradiation of Cyclooctatetraene (4) Typical Procedure ... 

However, benzene sensitized vapor-phase irradiation of cyclonona-1,2-diene (1) yielded predominantly the tricyclo[4.3.0.0 ]nonane (3, 89%) together with three minor products bi-cyclo[4.3.0]non-2-ene (10,2%), bicyclo[4.3.0]non-l-ene (11,5%) and bicyclo[4.3.0]non-l(9)-ene... 

The choice of the solvent also has a profound influence on the observed sonochemistry. The effect of vapor pressure has already been mentioned. Other Hquid properties, such as surface tension and viscosity, wiU alter the threshold of cavitation, but this is generaUy a minor concern. The chemical reactivity of the solvent is often much more important. No solvent is inert under the high temperature conditions of cavitation (50). One may minimize this problem, however, by using robust solvents that have low vapor pressures so as to minimize their concentration in the vapor phase of the cavitation event. Alternatively, one may wish to take advantage of such secondary reactions, for example, by using halocarbons for sonochemical halogenations. With ultrasonic irradiations in water, the observed aqueous sonochemistry is dominated by secondary reactions of OH- and H- formed from the sonolysis of water vapor in the cavitation zone (51—53). 

However, if the azepine is C-monosubstituted, e.g. 14, or unsymmetrically substituted, then two isomeric 2-azabicycloheptadienes, e. g. 15 and 16, may result corresponding to electrocyclic ring closure involving C2-C5 or C4-C7 of the azepine ring. In practice, the ratio of the two isomers formed (which may be separated by vapor phase chromatography) varies with the position of the substituent.236 In contrast, irradiation of methyl 2,5-di-tm-butyl-l//-azepine-l-carboxylatein methanol yields only methyl 3,5-di-tert-bulyl-2-azabicycIo[3.2.0]hepta-3,6-diene-2-carboxylate (81 %).70... 

During the last few years, new developments in polymer photochemistry have made it possible to graft various functional monomers onto surfaces of inert polymers like polyethylene, polypropylene and polyethyleneterephthalate. In the first attempts, initiator and monomer were transferred in vapor phase into a "UV Cure" irradiator containing the polymer sheet to be surface grafted. 

In the vapor phase experiments, the photograftings are carried out in specially designed photoreactor constructed and built in our laboratory (Figure 1). The reactor is equipped with a 1 kW high pressure mercury UV lamp (HPM-15 from Philips) which can be moved to vary the distance to the substrate. The grafting takes place in an atmosphere of nitrogen in a thermostated chamber closed with a clear quartz window. Sensitizer and monomer evaporates from a solution of a volatile solvent in an open bucket which is shielded from the UV-irradiation with aluminium foil. 

The two-step process of epitaxial polymerization has been applied to symmetrically substituted diacetylenes First, the monomers have been crystallized epitaxially on alkali halides substrates from solution and the vapor phase. The oriented monomer crystals are then polymerized under the substrate s influence by gamma-irradiation. The diacetylenes in this study are 2,4-hexadiyn-l,6-diol (HD) and the bis-phenylurethane of 5,7-dodecadiyn-l,12-diol (TCDU). The polydiacetylene crystal structures and morphologies have been examined with the electron microscope. Reactivity and polymorphism are found to be controlled by the substrate. 

Photolytic. Based on data for structurally similar compounds, acenaphthylene may undergo photolysis to yield quinones (U.S. EPA, 1985). In a toluene solution, irradiation of acenaphthylene at various temperatures and concentrations all resulted in the formation of dimers. In water, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, 1,2-epoxyacenaphthylene, and 1-naphthoic acid. In methanol, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, methyl 8-formyl-1-naphthoate, and dimethoxyacetal 1,8-naphthalene dialdehyde (Chen et al., 1979). Acenaphthylene reacts with photochemically produced OH radicals and ozone in the atmosphere. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with OH radicals (500,000/cm ) at 25 °C are 8.44 x lO " cmVmolecule-sec and 5 h, respectively. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with ozone at 25 °C are... 

Photolytic. A carbon dioxide yield of 46.5% was achieved when aniline adsorbed on silica gel was irradiated with light (X >290 nm) for 17 h (Freitag et al., 1985). Products identified from the gas-phase reaction of ozone with aniline in synthetic air at 23 °C were nitrobenzene, formic acid, hydrogen peroxide, and a nitrated salt having the formula [CeHsNHsl NOs" (Atnagel and Himmelreich, 1976). A second-order rate constant of 6.0 x 10 " cmVmolecule-sec at 26 °C was reported for the vapor-phase reaction of aniline and OH radicals in air at room temperature (Atkinson, 1985). 

Photolytlc. The sunlight irradiation of 1,3,5-trichlorobenzene (20 g) in a 100-mL borosilicate glass-stoppered Erlenmeyer flask for 56 d yielded 160 ppm pentachlorobiphenyl (Uyeta et al, 1976), A photooxidation half-life of 6.17 months was reported for the vapor-phase reaction of 1,3,5-trichlorobenzene with OH radicals (Atkinson, 1985). 

Irradiation of ///-xylene isomerizes to p-xylene (Calvert and Pitts, 1966). Glyoxal, methylglyoxal, and biacetyl were produced from the photooxidation of ///-xylene by OH radicals in air at 25 °C (Tuazon et al, 1986a). The photooxidation of ///-xylene in the presence of nitrogen oxides (NO and NO2) yielded small amounts of formaldehyde and a trace of acetaldehyde (Altshuller et al, 1970). ///-Tolualdehyde and nitric acid also were identified as photooxidation products of ///-xylene with nitrogen oxides (Altshuller, 1983). The rate constant for the reaction of ///-xylene and OH radicals at room temperature was 2.36 x 10 " cmVmolecule-sec (Hansen et al., 1975). A rate constant of 1.41 x 10" L/molecule-sec was reported for the reaction of ///-xylene with OH radicals in the gas phase (Darnall et ah, 1976). Similarly, a room temperature rate constant of 2.35 x 10"" cmVmolecule-sec was reported for the vapor-phase reaction of ///-xylene with OH radicals (Atkinson, 1985). At 25 °C, a rate constant of 2.22 x 10"" cm /molecule-sec was reported for the same reaction (Ohta and Ohyama, 1985). Phousongphouang and Arey (2002)... 

If the photo-Fries reaction would occur via a concerted mechanism, the absence of solvent should be of minor importance for the formation of rearranged products. However, conclusive evidence supporting the radical pair mechanism arises from the experiments carried out with phenyl acetate (10) in the vapor phase. The major product in the irradiations of 10 is phenol (13), which accounts for 65% of the photoproducts. Under these conditions, less than 1% of ortho -hydroxyace-tophenone (11) appears to be formed [19,20]. Conversely, when a high cage effect is expected, as in rigid matrixes (i.e., polyethylene), the result is completely different, and phenol is practically absent from the reaction mixtures [29]. In the intermediate situation (liquid solution), both rearranged products and phenol are formed in variable amounts depending on solvent properties. These observations... 

In cases where the reaction must be carried out in the vapor phase, the reactants can be contained in a quartz bulb or tube and irradiated... 

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