Coupling phenanthrene

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). 

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... 

Fujimoto et al. [77] synthesized a novel phase by coupling a dodecylamino-substituted P-cyclodextrin (P-CD) to 3-glycidoxypropyl-derivatized silica gel. The surface coverage of this phase was reported as 0.37 xmol/m, which amounts to a surface coverage of 2.6 xmol/m for C12 chains (seven chains per fi-CD). An increase in shape selectivity was observed when compared with a conventional Cis monomeric phase as determined by selectivity differences between j9/m-terphenyl, j9/o-terphenyl, and coronene/phenanthro[3,4-c]phenanthrene solute pairs and was attributed to the localized high ligand density as constrained by the fi-CD platform structure. 

As is seen in Figure 15 the two isomers, 3 and 4, have opposite helicities, M and P, respectively, as they produce nearly mirror-image exciton couplets due to the coupling of the 1 / b transitions of the naphthalene and phenanthrene chromophores120. 

ET induced allylation of dicyanoalkenes (e.g., 137) is regioselective the allyl radical couples to the carbon p to the cyano groups (—> 138). ° The efficiency of these reactions can be improved by using a cosensitizer, such as phenanthrene. °... 

Fig.6 The distance dependence of electron-transfer rates in DNA hairpins [51]. The acceptor is a photoexcited derivatized stilbene (SA) or phenanthrene (PA) the electron donor is guanine (G), deazaguanine (Z), or inosine (I). The decay is much more rapid in the Z-PA couple compared to the G-SA couple because the tunneling energy is further from the bridge states in the case of Z-PA...

Dihydrophenanthrene has been prepared from 2,2 -bis(bromomethyl)biphenyl and sodium 8 from the reduction of 2,2 -diiodobibenzy 1 in the presence of 1% palladium on barium carbonate catalyst 8 by the hydrogenation of phenanthrene in the presence of nickel8 or copper-chromium oxide catalyst 10 and by the coupling of 2,2 -bis(bromomethyl)biphenyl with lithium phenyl.11... 

Previously, diphenaldehyde has been made by the Ullman coupling of o-iodobenzaldehyde,6 6 by bromination of o/Z-bitolyl and hydrolysis of the resulting tetrabromo compound,7 and by lithium aluminum hydride reduction of the N-methylanilide of diphenic add.8 These methods involve more steps and give poorer yields than ozonolysis of phenanthrene. 

The magnitudes of two-bond carbon-fluorine couplings 2JCF in trifluoroacetic acid and hexafluoroacetone hydrate are 44 and 34 Hz, respectively (Table 3.14). Five-bond couplings of more than 20 Hz are reported for l,4,8-trimethyl-5-fluorophenanthrene derivatives their magnitudes decrease on saturation of the 9,10 bond in the phenanthrene... 

Diphenic acid has been prepared by the reduction of diazotized anthranilic acid with cuprous ion,6 Ullman coupling of potassium o-bromobenzoate,6 and oxidation of phenanthrene or phen-anthrenequinone with various oxidizing agents.7 The latter methods have been reviewed recently.7 The ozonolysis method has also been carried out in solvents 8 that do not react with the zwitterion intermediate. ... 

Photoaddition of. V-melhylaniline to phenantherene ring via C—O cleavage also occurs to give N-, <>-, and p-(phenanthrylmethyl)-substituted /V-mcthylani-lines, as shown in Scheme 115 [390], It is explained in terms of one-electron transfer from iV-methylanilinc to the phenanthrene derivatives, followed by proton transfer and the radical cross-coupling. 

Previously, Ohashi and his co-workers reported the photosubstitution of 1,2,4,5-tetracyanobenzene (TCNB) with toluene via the excitation of the charge-transfer complex between TCNB and toluene [409], The formation of substitution product is explained by the proton transfer from the radical cation of toluene to the radical anion of TCNB followed by the radical coupling and the dehydrocyanation. This type of photosubstitution has been well investigated and a variety of examples are reported. Arnold reported the photoreaction of p-dicyanobenzene (p-DCB) with 2,3-dimethyl-2-butene in the presence of phenanthrene in acetonitrile to give l-(4-cyanophenyl)-2,3-dimethyl-2-butene and 3-(4-cyanophenyl)-2,3-dimethyl-l-butene [410,411], The addition of methanol into this reaction system affords a methanol-incorporated product. This photoreaction was named the photo-NO-CAS reaction (photochemical nucleophile-olefin combination, aromatic substitution) by Arnold. However, a large number of nucleophile-incorporated photoreactions have been reported as three-component addition reactions via photoinduced electron transfer [19,40,113,114,201,410-425], Some examples are shown in Scheme 120. 

Fig. 4. Electron-phonon coupling constants for the monoanions of phenanthrene-edge-type hydrocarbons.

The domino Suzuki coupling-Heck reaction sequence involving dihydroaromatic alkenyl-substituted boronic esters (186) with diiodobenzene, bromoiodobenzene, or iodoaniline derivatives yields substituted phenanthrene (187) and phenanthridene derivatives regiospecifically (Scheme 52).218... 

Tetraphenylethylene cyclizes anodically to 9,10-diphenylphenanthrene analogously to its photooxidative cyclization. The attempted anodic cyclization of cis- or frans-stilbene to phenanthrene however failed due to electrophilic reaction of the intermediate radical cation with the solvent 37S Primary aromatic amines are oxidized to radical cations which, depending on the pH of the electrolyte couple to aminodiphenylamines (C-N coupling (84) in Eq. (172) ), yield benzidines (85) at low pH (C-C coupling) or dimerize to hydrazobenzene (86) (N-N coupling) which is subsequently oxidized to azobenzene (Eq. (172) ) 2 5,376,377)... 

Our inability to distinguish between anthracene and phenanthrene, coupled with uncertainties arising from competition between addition... 

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