Phenanthrene, reduction

A new synthesis of 9,10-iminophenanthrene takes advantage of the easy addition of bromine azide, in the presence of nitromethane, to the nucleophilic 9,10-bond of phenanthrene/° Reduction of the bromo-azide gives a moderate yield of the required product (Scheme 68). 

The synthetic procedure described is based on that reported earlier for the synthesis on a smaller scale of anthracene, benz[a]anthracene, chrysene, dibenz[a,c]anthracene, and phenanthrene in excellent yields from the corresponding quinones. Although reduction of quinones with HI and phosphorus was described in the older literature, relatively drastic conditions were employed and mixtures of polyhydrogenated derivatives were the principal products. The relatively milder experimental procedure employed herein appears generally applicable to the reduction of both ortho- and para-quinones directly to the fully aromatic polycyclic arenes. The method is apparently inapplicable to quinones having an olefinic bond, such as o-naphthoquinone, since an analogous reaction of the latter provides a product of undetermined structure (unpublished result). As shown previously, phenols and hydro-quinones, implicated as intermediates in the reduction of quinones by HI, can also be smoothly deoxygenated to fully aromatic polycyclic arenes under conditions similar to those described herein. 

Reduction of phenanthrene-9,10-dione with HI in acetic acid afforded 9-hydroxyphenanthrene as sole product, while an analogous reaction without acetic acid furnished phenanthrene essentially quantitatively. 

It has become clear that benzoate occupies a central position in the anaerobic degradation of both phenols and alkylated arenes such as toluene and xylenes, and that carboxylation, hydroxylation, and reductive dehydroxylation are important reactions for phenols that are discussed in Part 4 of this chapter. The simplest examples include alkylated benzenes, products from the carboxylation of napthalene and phenanthrene (Zhang and Young 1997), the decarboxylation of o-, m-, and p-phthalate under denitrifying conditions (Nozawa and Maruyama 1988), and the metabolism of phenols and anilines by carboxylation. Further illustrative examples include the following ... 

The redox system consists of pyrene or 9,10-phenanthrene quinone as oxidant and an alkyl ester of 3,3, 3"-nitrilopropionic acid as reductant.121 This system deactivates oxidation by bisimidazole when irradiated at 380-550nm, since the quinone is reduced to hydroquinone and thus stabilizing the previously generated dye image.122,123... 

Although phenanthrene is noncarcinogenic, some of its methylated derivatives exhibit significant activity as mutagens (52,53). The 1,2- and 3,4-dihydrodiols of phenanthrene were first synthesized by Jerina et al. (54) by a method involving reduction of the corresponding quinones with LiAlH. However, the yields in the rein Polycyclic Hydrocarbons and Carcinogenesis Harvey, R. ... 

The phenanthrene 1,2- and 3,4-diones are synthetically accessible from the related 8 phenols. Oxidation of 2-phenanthrol with either Fremy s salt ((KS0 )2N0) or phenylseleninic anhydride gave phenanthrene 1,2-dione directly (55). Unexpectedly, oxidation of 3-phenanthrol with (KSOg NO yielded 2,2-dihydroxybenz(e)indan-l,3-d-ione (Figure 10). However, phenanthrene 3,4-dione was readily obtained from 3-phenanthrol by Fieser s method entailing diazonium coupling, reduction, and oxidation of the resulting 4-amino-3-phen-anthrol with chromic acid (56). 

Partial reduction of polyarenes has been reported. Use of boron trifluoride hydrate (BF3 OH2) as the acid in conjunction with triethylsilane causes the reduction of certain activated aromatic systems 217,262 Thus, treatment of anthracene with a 4-6 molar excess of BE3 OH2 and a 30% molar excess of triethylsilane gives 9,10-dihydroanthracene in 89% yield after 1 hour at room temperature (Eq. 120). Naphthacene gives the analogously reduced product in 88% yield under the same conditions. These conditions also result in the formation of tetralin from 1-hydroxynaphthalene (52%, 4 hours), 2-hydroxy naphthalene (37%, 7 hours), 1-methoxynaphthalene (37%, 10 hours), 2-methoxynaphthalene (26%, 10 hours), and 1-naphthalenethiol (13%, 6 hours). Naphthalene, phenanthrene, 1-methylnaphthalene, 2-naphthalenethiol, phenol, anisole, toluene, and benzene all resist reduction under these conditions.217 Use of deuterated triethylsilane to reduce 1-methoxynaphthalene gives tetralin-l,l,3-yielding information on the mechanism of these reductions.262 2-Mercaptonaphthalenes are reduced to 2,3,4,5-tetrahydronaphthalenes in poor to modest yields.217 263... 

Sediment reduction t,/2(est.) = 1196 h, t,/2(exptl) = 825 h for chemical available phenanthrene and tA = 151 h for bioavailable phenanthrene for amphipod, P. hoyi in Lake Michigan sediments at 4°C. The average uptake clearance from sediment was (0.041 + 0.023)g of dry sediment-g-1 of organism-h-1, and the rate constants to become biologically unavailable was (0.0055 0.003) h-1 resulting a bioavailable t,/2 = 126 h (Landrum 1989) desorption t,/2 = 8.6 d from sediment under conditions mimicking marine disposal (Zhang et al. 2000). 

Poly(methyl methacrylate) [PMMA] is an excellent polymer for studying photoresist dissolution because of its minimal swelling characteristic. For this work, PMMA molecules were labelled with phenanthrene (Phe) dye since its fluorescence is quenched by MEK. In addition, this dye has the advantage of forming few excimers (23-241 which results in self-quenching. Thus, the reduction in fluorescence intensity of PMMA-Phe is virtually solely due to MEK quenching. Consequently, the permeation of MEK into a PMMA film can be monitored from fluorescence intensity decay. 

Reduction of stilbene [18] or dipheny-lacetylene [214] in DME yields 1,2,3,4-tetraphenylbutane, whereas phenanthrene [214] provides 9,9, 10,10 -tetra-hydro-9.9 -biphenanthrene. Hydrodimerization was also observed with benzalfluo-rene [225]. If DME is replaced by acetonitrile, protonation completely dominates hydrodimerization [18]. In carefully dried ethers, using alkali or alkaline earth metals salts as supporting electrolyte, 1,1-diphenylethylene can be reduced ca-thodicaUy to give stable solutions of 1,1,4,4-tetraphenylbutane dianions [226]. These dianions can be cleaved by flash... 

Lund and coworkers [131] pioneered the use of aromatic anion radicals as mediators in a study of the catalytic reduction of bromobenzene by the electrogenerated anion radical of chrysene. Other early investigations involved the catalytic reduction of 1-bromo- and 1-chlorobutane by the anion radicals of trans-stilhene and anthracene [132], of 1-chlorohexane and 6-chloro-l-hexene by the naphthalene anion radical [133], and of 1-chlorooctane by the phenanthrene anion radical [134]. Simonet and coworkers [135] pointed out that a catalytically formed alkyl radical can react with an aromatic anion radical to form an alkylated aromatic hydrocarbon. Additional, comparatively recent work has centered on electron transfer between aromatic anion radicals and l,2-dichloro-l,2-diphenylethane [136], on reductive coupling of tert-butyl bromide with azobenzene, quinoxaline, and anthracene [137], and on the reactions of aromatic anion radicals with substituted benzyl chlorides [138], with... 

Palladium-on-charcoal in reduction of (-butyl azidoacetate to glycine (-butyl ester, 46, 47 Pelargonyl fluoride, 46, 6 3,3-Pentamethylenediazirine, 46, 83 oxidation to 3,3-dimethyIazarine by silver oxide, 46, 83 Peroxyvanadic acid, 46, 27 Phenanthrene, 9-phenyi, 46, 91 Phenol, 46, 90... 

Oxidative cyclization, substituted stil-benes to phenanthrenes, 46, 91 Oximes, reduction with lithium aluminum hydride, 48, 23 Oximinomalononitrile, from nitrosation of malononitrile, 48,1 reduction with aluminum amalgam, 48,2 ... 

Phenanthrene is converted to partially and totally reduced phenanthrene by catalytic hydrogenation [415, 416, 417], Partial reduction to 1,2,3,4-tetra-hydrophenanthrene can also be achieved by sodium [418. ... 

A peculiar reduction occurred on treatment of a dialdehyde, diphenyl-2,2 -dicarboxaldehyde, with tris(dimethylamino)phosphine at room temperature phenanthrene-9,10-oxide was formed in 81-89% yield [302],... 

Lithium aluminum hydride reduced p-benzoquinone to hydroquinone (yield 70%) [576] and anthraquinone to anthrahydroquinone in 95% yield [576]. Tin reduced p-benzoquinone to hydroquinone in 88% yield [174] Procedure 35, p. 214). Stannous chloride converted tetrahydroxy-p-benzoquinone to hexa-hydroxybenzene in 70-77% yield [929], and 1,4-naphthoquinone to 1,4-di-hydroxynaphthalene in 96% yield [180]. Other reagents suitable for reduction of quinones are titanium trichloride [930], chromous chloride [187], hydrogen sulfide [248], sulfur dioxide [250] and others. Yields are usually good to excellent. Some of the reagents reduce the quinones selectively in the presence of other reducible functions. Thus hydrogen sulfide converted 2,7-dinitro-phenanthrene quinone to 9,10-dihydroxy-2,7-dinitrophenanthrene in 90% yield [248]. 

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