Phenanthrene photolysis

Photolysis at 254 nm, CH3OH, CH2CI2, phenanthrene, 51-84% yield. These conditions are selective for ally lie and benzylic alcohols. In the absence of the phenanthrene, TBDMS ethers are also cleaved. ... 

Dihydro-9,10-epoxyphenanthrene and related arene oxides are of considerable interest as carcinogens formed by polycyclic aromatic hydrocarbons in vivo.45 Phenanthrene oxide does not isomerize to the corresponding dibenzoxepin under thermal conditions. Photolysis of... 

Cyclopropanated phenanthrenes revert to phenanthrene and carbenes on photolysis CH2,49 CC12,50 CBr2,51 CBrCl,51 and f-BuCH15d have been generated this way. Platz et al.25 used 37 (R=PhCH2) to generate benzylchlorocarbene (10a) for comparison with 10a generated from diazirine 9a cf. Scheme 2. 

Clomiphene citrate is used as a mixture of E (58) and Z (60) isomers to treat infertility. Photolysis of a chloroform solution with a high-pressure mercury lamp gave the expected phenanthrenes (59) and (61), which were separated and identified by GC-MS. Study of the separate isomers (58) and (60) indicated that rapid cis-trans photoisomerization preceded ring closure so that each gave a mixture of phenanthrenes (60) and (61) (Scheme 2.2) [52],... 

Phosphorane, (dichloromethylene) TRIPHENYL-1, 46, 33 Phosphorus pentachloride, for conversion of D,L-10-camphorsulfonic acid to acid chloride, 46,14 reaction with styrene, 46, 99 Photolysis of substituted stilbenes to phenanthrenes, 46, 91... 

The photocyclization has been found not to occur with stilbenes substituted with acetyl, dimethylamino, or nitro groups, lodo substituents are replaced by hydrogen by photolysis in cyclohexane solution. w-Substituted stilbenes give mixtures of 2- and 4-substituted phenanthrenes which generally are difficult to separate. 

Photolysis ofbenzylchlorodiazirine (3) in the presence of tetramethylethylene (TME) is known to produce ( )- and (Z)-/l-chlorostyrene (4) and the cyclopropane (5). Plots of [5]/[4] vs [TME] are curved, consistent with the existence of two pathways for the formation of the alkenes (4). Benzylchlorocarbene (BnClC ) was generated by laser flash photolysis of the phenanthrene (6) in the presence of TME. In this case, plots of [5]/[4] vs [TME] are linear, mling out the possibility that the second pathway to the alkenes (4) involves reaction of a carbene-alkene complex. Time-resolved IR spectroscopy revealed that diazirine (3) rearranges to the corresponding diazo compound, but this process is too inefficient to account for the curvatures. It is proposed that the second pathway to alkene formation involves the excited state of the diazirine. 

This yellow coloration is undoubtedly due to DHP (i), whose oxidation product, phenanthrene, was observed by Smakula as an oxidation product in the photolysis of cis-stilbene ... 

The valence tautomerism 251 257 has been proposed to account for the formation of iV-methylthiobenzamide by irradiation (2537 A) in methyl cyanide solution. The valence tautomer 257, R = Me, = Ph, has been detected spectroscopically (p , 2060 cm —N=C=S) either during photolysis at 25° or by heating at 160°. Photochemical oxidative cyclization of 4,5-diaryl derivatives (251, R = R = Ar) analogous to the formation of phenanthrene from stilbene has been reported. Thus, irradiation of the 4,5-diphenyl derivative 251, R = R = Ph, yields the tetracyclic meso-ionic compound (258). ... 

P 15.6 Does Direct Photolysis Affect the Phenanthrene-to-Anthracene Ratio in Aerosol Droplets ... 

Gschwend and Hites (1981) observed that the two closely related polycyclic aromatic hydrocarbons, phenanthrene and anthracene, occur in a ratio of about 3-to-l in urban air. In contrast, sedimentary deposits obtained from remote locations (e.g., Adirondack mountain ponds) exhibited phenanthrene-to-anthracene ratios of 15-to-l. You hypothesize that these chemicals are co-carried in aerosol droplets from Midwestern U.S. urban environments via easterly winds to remote locations (like the Adirondacks) where the aerosol particles fall out of the atmosphere and rapidly accumulate in the ponds sediment beds without any further compositional change (i.e., the phenanthrene-to-anthracene ratio stops changing after the aerosols leave the air). If summertime direct photolysis was responsible for the change in phenanthrene-to-anthracene ratio, estimate how long the aerosols would have to have been in the air. Comment on the assumptions that you make. What are your conclusions ... 

Figure 21.2 The interplay of transport and reaction, exemplified by the hypothetical vertical concentration profile of phenanthrene in a lake, (a) The rate of photolysis decreases with depth due to the diminishing light intensity with water depth, (b) Two possible vertical profiles of phenanthrene concentration if vertical mixing in the water column is strong, the profile is constant (profile 1). If vertical mixing is slow, a distinct vertical concentration gradient develops with small values at the water surface where photolysis is strongest (profile 2).

In Section 21.1 we discussed the simultaneous influence of transport and transformation processes on the spatial distribution of a chemical in an environmental system. As an example we used the case of phenanthrene in the surface water of a lake. In Fig. 212b two situations were distinguished which differed by the relative importance of the rate of vertical mixing versus the rate of photolysis. Yet, neither was a quantitative method given to calculate the resulting vertical concentration profile (profiles 1 and 2 in Fig. 21.26), nor did we explain how the rates of such diverse mechanisms as diffusion, advection, and photolysis should be compared in order to calculate their relative importance. In this section we will develop the mathematical tools which are needed for dealing with such situations. 

First, recall that the nondimensional Damkohler number, Da (Eq. 22-11 b), allows us to decide whether advection is relevant relative to the influence of diffusion and reaction. As summarized in Fig. 22.3, if Da 1, advection can be neglected (in vertical models this is often the case). Second, if advection is not relevant, we can decide whether mixing by diffusion is fast enough to eliminate all spatial concentration differences that may result from various reaction processes in the system (see the case of photolysis of phenanthrene in a lake sketched in Fig. 21.2). To this end, the relevant expression is L (kr / Ez)1 2, where L is the vertical extension of the system, Ez the vertical turbulent diffusivity, and A, the first-order reaction rate constant (Eq. 22-13). If this number is much smaller than 1, that is, if... 

In the vapor phase phenanthrene and hydrogen were products of the photolysis of c/.v-stilbene in addition to the expected mww-stilbene.65 The photolysis of 1,4-diphenyl-1,3-butadiene to give a-phenylnaphtha-lene is an analogous process.65 It was proposed that the intermediate dihydrophenanthrene was a cis form.66... 

The photolysis of aryl iodides is of use in the preparation of biphenyls, and the application of this reaction to the synthesis of phenanthrenes has already been discussed. Seven- and 8-membered nitrogen-containing heterocycles can also be obtained by an intramolecular arylation of this type photolysis of the iodoamine (345) affords, for example, 6,7-dihydro-5/ -dibenz[c,e]azepine (346).381... 

Recently, several studies have been made of the photolysis of disilanes or polysilanes in the presence of an electron-deficient alkene using a photosensitizer (such as phenanthrene) and acetonitrile as solvent. These conditions result in the addition of silyl groups to one end of the alkene double bond and hydrogen to the other end (equation 18) and evidently involve the reaction of the radical anions of the electron-deficient silene with silyl radicals67 (see also Section VIII.A). 

For the preparation of larger amounts of the phenanthrene the reaction should be repeated photolysis of more concentrated solutions is to be avoided in order to minimise the possibility of photodimerisation to give a cyclobutane derivative. 

Frith RG, Phillipou J. Application of clomiphene photolysis to assay based on analysis of the derived phenanthrenes. J Chromatogr 1986 367 260-266. 

We note in conclusion that different PAHs exhibit differing levels of photoreactivity when adsorbed on coal ash, with the reactivity order in this case being anthracene, BaA > phenanthrene, pyrene, BaP. To the extent that this question has been addressed in other studies of PAH photolysis on coal ash substrates, our results are consistent with those previously reported (7-10) ... 

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