Hydroxy-phenanthrene

Synthese von 2,4-Dimethoxy-6-hydroxy-phenanthren und Konstitution des Or-chinols, by E. Hardegger, H. R. Biland, and H. Corrodi (28. Mitteilung, Welkstoffe und Antobiotika), Helv. Chim. Acta, 46 (1963) 1354-1360. 

Figure 6.9 Synthesis of star-shaped 2D COFs by co-condensation of 9,10-hydroxy-phenanthrene cyclotrimer (HPCT) with BDBA, PDBA, and BPDA. (Printed with permission from Feng et...

We started the study by testing the reactivity of 1-nitronaphthalene with Danishefsky s diene since it is one of the strongest dienes and is appropriate to test these aromatic substrates. Thus, when 68 and 7 were heated in sealed ampoule (150 °C, 72 h) using benzene as solvent, 62% of 2-hydroxy-phenanthrene 75 was regioselectively produced. (Figure 18)... 

When 68 and 7 were heated in a sealed ampoule (60°C, 24 h) using EAN or [HMIM][BF4] as solvent, 65% of 2-hydroxy-phenanthrene 75 was regioselectively produced. In a similar way 2-nitronaphthalene 69 reacted in the same conditions to give 43% of 3-hydroxyphenanthrene. The regioselectivity of both reactions was controlled by both the nitro group of the dienophile and the methoxyl group of Danishefsl s diene. 

Considerable progress has also been made with the alternative line of work, the search for a synthetic analgesic as effective as morphine and without its disadvantages. The work of the American Committee has shown that it is possible to produce analgesics with a dibenzofuran or carbazole nucleus in place of the phenanthrene or phcnanthrylene oxide nucleus of morphine and it is stated that synthetic products with analgesic potency equal to that of codeine have been prepared. In the 1938 report moderate analgesic potency was recorded for preparation No. 421, 9-methyl-2-(l-hydroxy-3-diethylamino)-propylcarbazole at 10 mgm. by injection. 

Common Name 13-methyl-17-ethynyl-l7-hydroxy-1,2,3,4,6,7,8,9,11,12,13,14,16,17-tetra-decahydro-15H-cyclopenta(a)phenanthren-3-one... 

Convenient starting materials are the ethers of 3-hydroxy-13-methyl-1,4,6,7,8,9,11,12,13,-14,16,17-dodecahydro-15H-cyclopenta(a)phenanthren-17-one described in U.S. Patent 2,655,518, according to U.S. Patent 2,691,028 mhere the folloming preparation is also de-scribad. The methyl ether is also designated as 3-methoxy-17-oxo-2,5-estradlene. 

As discussed in Section 10.3, the system consisting of a diazonium ion and cuprous ions can be used for hydroxy-de-diazoniation at room temperature in the presence of large concentrations of hydrated cupric ions (Cohen et al., 1977 see Schemes 10-7 to 10-9). With (Z)-stilbene-2-diazonium tetrafluoroborate under these conditions, however, the major product of ring closure of the initially formed radical was phenanthrene (64%). When the cupric nitrate was supplemented by silver nitrate the yield increased to 86% phenanthrene. Apparently, the radical undergoes such rapid ring closure that no electron transfer to the cupric ion takes place. 

Adachi K, T Iwabuchi, H Sano, S Harayama (1999) Structure of the ring cleavage product of l-hydroxy-2-naphthoate, an intermediate of the phenanthrene-degradative pathway of Nocardioides sp. strain KP7. J Bacterial 181 757-763. 

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... 

Biological. Catechol is the central metabolite in the bacterial degradation of phenanthrene. Intermediate by-products include l-hydroxy-2-naphthoic acid, 1,2-dihydroxynaphthalene, and salicylic acid (Chapman, 1972 Hou, 1982). It was reported that Beijerinckia, under aerobic conditions, degraded phenanthrene to as-3,4-dihydroxy-3,4-dihydrophenanthracene (Kobayashi and Rittman, 1982). 

In a different study, anthracene, phenanthrene, perylene 93 (Fig. 31), and 2,7-di-tert-butylpyrene underwent regioselective oxidative-substitution reactions with iodine(III) sulfonate reagents in dichloromethane to give the corresponding aryl sulfonate esters. The use of [hydroxy(tosyloxy)iodo]benzene, in conjunction with trimethylsilyl isothiocyanate, led to thiocyanation of the PAH nucleus. 

Hydroxy-4b/ -methyI-7-ethylenedioxy-l,2,3,4,4aa, 4b/ , 5,6,7,8,10,10a/ -dodecahydrophenanthren-l-one.184 To a solution of 2 g (6.9 mmoles) of 4b/ -methyl-7-ethylenedioxy-1,2,3,4,4aa, 4b) ,5,6,7,8,10,1 Oaa-dodecahydro-phenanthrene-1 / ,4/ -diol in 50 ml (0.48 mole) of cyclohexanone and 45 ml of anhydrous benzene is added a solution of 2 g (9.7 mmoles) of freshly distilled aluminum isopropoxide in 5 ml of benzene. The mixture is heated at reflux for 16 hr. After cooling the reaction mixture is treated dropwise with 4 ml of water. The precipitated aluminum salts are collected by filtration and thoroughly washed with benzene. The filtrate is concentrated initially at aspirator pressure, then finally at 0.1 mm at 135-140° to leave a crystalline residue. The residue is triturated with petroleum ether-ether (1 1) and filtered. After washing with the same solvent, the residue is recrystallized from acetone to give 1.35 g of 4/ -hydroxy-4b/ -methyl-7-ethylenedioxy-l,2,3,4,4aa,4b/ ,5, 6,7,8,10,10aa-dodecahydrophenanthren-l-one mp 218-219.5° (68%). 

Thermochemical data are available (Ref 2) on the heats of combustion and formation for all five isomers, on the heats of nitration from various Dinitrotoluenes for the 23,4-, 2,4,5-, and 2,3,6-isomers, and on the heats of crystn for the 2,3,4- and 2,4,5-isomers. Data are also available (Ref 1) on the shock sensitivities of all of the isomers except 2,3,6-, and on the rates of decompn at 140° of the 23,4-, 2,4,5-, and 23,5-isomers. The detonation pressure and the temp coefficient of decompn between 140 and 180° have been measured for the 2,4,5-isomer 2,3,4- and 2,4,5-TNT form addition compds ( 7r-complexes ) at 1 1 molar ratio with several polycyclic aromatic hydrocarbons (naphthalene, acenaphthene, fluorene, phenanthrene and anthracene) (Ref 2). 2,4,5-TNT forms complexes with 4-aminozaobenzene, 4-aminoacetophenone, bis (2 hydroxy ethyl) amine, and tris (2-hydroxy-ethyl) amine (Ref 1). The first two have a 1 1 molar ratio, the third 1 2, and the fourth 2 1. Upon heating, the two 4-amino compds react with replacement of the 5-nitro group, as discussed below... 

With K-region oxides, sodium salts of phenol or cresols also produce addition products. Thus heating a mixture of 1 and sodium phenoxide in dimethylformamide at 100°C under a nitrogen atmosphere produced 9,10-dihydro-frans-9-hydroxy-10-phenoxyphenanthrene (248, 19%), 9-phenoxy-phenanthrene (249, 68%), and traces of 9-phenanthrol and phenanthrene-9,10-quinone. When the reaction was carried in the presence of air, a significant amount of 9-hydroxy-10-phenoxyphenanthrene (250) was formed instead of 248 and 249.150... 

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