Phenanthrene 9,10-dihydro

CAS 84-11-7 EINECS/ELINCS 201-515-5 Synonyms 9,10-Phenanthraqulnone Phenanthrene, 9,10-dihydro-9,10-dioxo- 9,10-Phenanthrenedione Phenanthrenequinone Empirical C14H8O2... 

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... 

Dihydrovinylphenanthrenes are more reactive than the corresponding vinyl phenanthrenes and undergo Diels-Alder reactions easily. They have been used in the synthesis of polycyclic aromatic compounds and helicenes. Examples of cycloaddition reactions of the 3,4-dihydro-1-vinylphenanthrene (70), [61] 3,4-dihydro-2-vinylphenanthrene (71) [68] and l,2-dihydro-4-vinylphenanthrene (72) [69] are reported in Equation 2.22 and Schemes 2.27 and 2.28. 

To illustrate how this applies in the present circumstances we consider a passible group transfer reaction between A2 dihydro-naphthalene, (gQ) > a hydrogen donor, and phenanthrene,(g gr > a substrate (hydrogen acceptor) which models a polynuclear aromatic moiety commonly found in coal. In the overall group transfer reaction ... 

At typical coal liquefaction conditions, namely temperatures from 300 to 400 C and reaction times on the order of 1 hr, hydrogen transfer from model CIO donors, the A1- and A2-dialins, to model C14 acceptors, anthracene and phenanthrene, occurs in the sense allowed by the Woodward-Hoffman rules for supra-supra group transfer reactions. Thus, in the conversion of the C14 substrates to their 9, 10 dihydro derivatives the dialins exhibited a striking reversal of donor activity, the A dialin causing about twice as much conversion of phenanthrene but only one-tenth as much conversion of anthracene as did A2-dialin. 

Scheme 6/1.86. Synthesis of substituted 5,6-dihydro-8/-/-[5,7-a]diazacyclohepta[/7c] phenanthrene-4,7-diones.

Refluxing of benzo[l,2,4]triazine-3-thione 86 with epichlorohydrin in the presence of triethylamine in methanol for 14 h resulted in the formation of 3,4-dihydro-2H,97/-l-thia-4a,9,10-triaza-phenanthren-3-ol 87 <2003PS797> (Equation 7). 

In agreement with this, the analysis of the products forming during the alkylation over MCM-22 samples at different reaction time showed that about 80-90 wt. % of the recovered material is adsorbed on the external surface (phenol, o-TBP and p-TBP), whereas only about 10-20 wt.% is formed inside the zeolite ( coke constituted by p-TBP, naphthalenes, 9,10-dihydro-phenanthrene and acenaphthylene). Coke molecules could be formed in both supercages and sinusoidal channels. However, in the large supercages they would be converted into bulkier compounds, which is not the case. Therefore they are most likely located in the sinusoidal channels. 

Detailed kinetic studies comparing the chemical reactivity ofK-region vs. non-K-region arene oxides have yielded important information. In aqueous solution, the non-K-region epoxides of phenanthrene (the 1,2-oxide and 3,4-oxides) yielded exclusively phenols (the 1-phenol and 4-phenol, respectively, as major products) in an acid-catalyzed reaction, as do epoxides of lower arenes (Fig. 10.1). In contrast, the K-region epoxide (i.e., phenanthrene 9,10-oxide 10.29) gave at pH < 7 the 9-phenol and the 9,10-dihydro-9,10-diol (predominantly trans) in a ratio of ca. 3 1. Under these conditions, the formation of this dihydrodiol was found to result from trapping of the carbonium ion by H20 (Fig. 10.11, Pathway a). At pH > 9, the product formed was nearly ex-... 

Turning to enzymatic hydration, we see from the data in Table 10.1 that phenanthrene 9,10-oxide Fig. 10.10, 10.29) is an excellent substrate for epoxide hydrolase. Comparison of enzymatic hydration of the three isomeric phenanthrene oxides shows that the Vmax with the 9,10-oxide is greater than with the 1,2- or the 3,4-oxide the affinity was higher as well, as assessed by the tenfold lower Km value [90]. Furthermore, phenanthrene 9,10-oxide has a plane of symmetry and is, thus, an achiral molecule, but hydration gives rise to a chiral metabolite with high product enantioselectivity. Indeed, nucleophilic attack by epoxide hydrolase occurs at C(9) with inversion of configuration i.e., from below the oxirane ring as shown in Fig. 10.10) to yield the C-H9.S, 10.S )-9,10-dihydro-9,10-diol (10.30) [91],... 

Uses Explosives dyestuffs biochemical research synthesis of drugs preparation of 9,10-phen-anthrenequinone, 9,10-dihydrophenanthrene, 9-bromophenanthrene, 9,10-dibromo-9,10-dihydro-phenanthrene, and many other organic compounds. 

The major phytotoxic principles (Fig. 3) from M. densa, were shown to be the phenanthrene derivatives erianthridin (17 9,10-dihydro-2,7-dihydroxy-3,4-dimethoxyphenanthrene) and gymnopusin (18 2,7-dihydroxy-3,4,9 -trimethoxyphenan threne). ... 

Other cyclopropaphenanthrenes are, however, isolable. Recently, Billups et al. described the synthesis of dicycIopropa[b,/i]phenanthrene (165) and of its dihydro derivative 166 starting from tetramethylidenecyclohexane 164 by the cycloaddition... 

In this context one should also consider the formation of cis-4a,4b-dihydro-phenanthrenes (e.g., 4a and 4b hydrogens in cis conformation). While forbidden as an excited state concerted conrotatory process (see Sect. VI D) it could possibly take place by another route. Such cis-conformers would be less stable than the normal trans-conformers. ... 

D The MO Analysis of Reactivity in 1,2-DiarylethyIene — 4a,4b-Dihydro-phenanthrene Systems... 

Interrupted oxidations of 9,10-dihydroanthracene or 9,10-dihydro-phenanthrene in DMSO (80% )-terf-butyl alcohol (20%) containing potassium ferf-butoxide produced the 9,10-semiquinone radical anions, apparently as a product of oxidation of the monoanion. 

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