Phenanthrene methylated

Naphtho[2,l,8-(jira] naphthacene Naphtho[l,2-f>] triphenylene Ovalene Pentacene Pentaphene Perylene Phenanthrene Phenanthrene, dimethyl-Phenanthrene, methyl-Phenanthrene, tetramethyl-Picene Pyrene... 

Fig. 14. Choleic acid inclusion chemistry (a) crystal stmcture of DCA inclusion compound with phenanthrene (b) view along a DCA inclusion helix accommodating DMSO and water guest molecules (oxygen and sulfur atoms and methyl groups are represented by open circles and large and small black...

The addition product, C QHgNa, called naphthalenesodium or sodium naphthalene complex, may be regarded as a resonance hybrid. The ether is more than just a solvent that promotes the reaction. StabiUty of the complex depends on the presence of the ether, and sodium can be Hberated by evaporating the ether or by dilution using an indifferent solvent, such as ethyl ether. A number of ether-type solvents are effective in complex preparation, such as methyl ethyl ether, ethylene glycol dimethyl ether, dioxane, and THF. Trimethyl amine also promotes complex formation. This reaction proceeds with all alkah metals. Other aromatic compounds, eg, diphenyl, anthracene, and phenanthrene, also form sodium complexes (16,20). 

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. 

B. HCl, m.p. 242-3°). The methiodide, m.p. 104-7°, of this, on treatment with potassium hydroxide in methyl aleohol, yielded 5 6-pimethoxy-8-vinylphenanthrene, m.p. 86-7°, along with dimethyl-de-iV-methylnorroemerine, oil, [aju + 13-55° (EtOH) the methiodide, m.p. 278°, of this, on like treatment also yielded 5 6-dimethoxy-8-vinyl-phenanthrene, whose identity was established by its oxidation by permanganate to 5 6-dimethoxyphenanthrene-8-earboxylie aeid. Rcemerine is, therefore, 5 6-methylenedioxy-iV-methylaporphine, and this eon-stitution has been confirmed by Marion and Grassie s synthesis of the alkaloid. 

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. 

Elimination of sulfur from methyl dibenzo[/),/]thiepin-10-carboxylatcs 15 (R2 = Me) can be achieved in moderate yields (39-55%) upon refluxing in diethyl phthalate in the presence of copper bronze.60 For the dibenzo[A,/]thiepin-10-carboxylic acids 15 (R2 = H), the loss of sulfur is accompanied by decarboxylation. Thus, treatment of these acids with copper bronze in refluxing quinoline for four hours gives the corresponding phenanthrenes 16 (R3 = H) in moderate yield (50%). However, the exposure time to high temperatures influences the product formation. Thus, the decarboxyiated dibenzothiepins are obtained after refluxing for only five minutes.60... 

An interesting reaction of dimsyl anion 88 is the methylation of polyaromatic compounds. Thus naphthalene, anthracene, phenanthrene, acridine, quinoline, isoquinoline and phenanthridine were regiospecifically methylated upon treatment with potassium t-butoxide and DMSO in digyme or with sodium hydride in DMSO123-125. Since ca. 50% of D was found to remain in the monomethyl derivative 93 derived from 9-deuteriophenanthrene 92, the mechanistic route shown in Scheme 2 was suggested125. 

Brom-9-methyl-phenanthren liefert 9-Methyl-phenanthren [Hg( —1,8 V vs Ag/AgJ/DMF), DMF/NaC104]5. 

The latter reagent also methylates certain heterocyclic compounds (e.g., quinoline) and certain fused aromatic compounds (e.g., anthracene, phenanthrene). The reactions with the sulfur carbanions are especially useful, since none of these substrates can be methylated by the Friedel-Crafts procedure (11-12). It has been reported that aromatic nitro compounds can also be alkylated, not only with methyl but with other alkyl and substituted alkyl groups as well, in ortho and para positions, by treatment with an alkyllithium compound (or, with lower yields, a Grignard reagent), followed by an oxidizing agent such as Bra or DDQ (P- 1511). 

---