Phenanthrene-Sodium

Dechlorination.1 Treatment of a mixture of cis- and trans,exo,exo-3,4-dichloro-tetracyclo[4.4.2.02,5.07,1 ° dodeca-8,11-diene, (1) and (2), with phenanthrene sodium until the green color persists affords exo,exo-tetracyclo[4.4.2.02,501,l°]dodecatriene (3) in 69% yield. 

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). 

Hydrogen and sodium do not react at room temperature, but at 200—350°C sodium hydride is formed (24,25). The reaction with bulk sodium is slow because of the limited surface available for reaction, but dispersions in hydrocarbons and high surface sodium react more rapidly (7). For the latter, reaction is further accelerated by surface-active agents such as sodium anthracene-9-carboxylate and sodium phenanthrene-9-carboxylate (26—28). 

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. 

Increased removal of phenanthrene from soil columns spiked with the rhamnolipid mixture synthesized by Pseudomonas aeruginosa UG2 has been demonstrated, and shown to depend both on the increased desorption of the substrate and on partitioning into micelles (Noordman et al. 1998). However, the addition of the biosurfactant from the same strain of Pseudomonas aeruginosa UG2 or of sodium dodecyl sulfate had no effect on the rate of biodegradation of anthracene and phenanthrene from a chronically contaminated soil. 

A combined effect of natural organic matter and surfactants on the apparent solubility of polycyclic aromatic hydrocarbons (PAHs) is reported in the paper of Cho et al. (2002). Kinetic studies were conducted to compare solubilization of hydro-phobic contaminants such as naphthalene, phenanthrene, and pyrene into distilled water and aqueous solutions containing natural organic matter (NOM) and sodium dodecyl sulfate (SDS) surfactant. The results obtained after 72hr equilibration are reproduced in Fig. 8.19. The apparent solubility of the three contaminants was higher in SDS and NOM solutions than the solubility of these compounds in distilled water. When a combined SDS-NOM aqueous solution was used, the apparent solubility of naphthalene, phenanthrene, and pyrene was lower than in the NOM-aqueous solution. 

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. ... 

To obtain a true k in MEEKC, it is important to trace the migration of the pseudostationary phase accurately. Sudan III, timepidium bromide, and quine, which have generally been used as tracers for micelles in MEKC, could not be employed as tracers for microemulsions consisting of sodium dodecylsulfate salt (SDS) or cetyltrimethylammonium bromide (CTAB), n-butanol and heptane (12). An iteration method based on a linear relationship between log k and the carbon number for alkylbenzenes (13) seems to provide a reasonable value of the migration time of the microemulsions. Dodecylbenzene shows a migration time larger than the value calculated by the iteration method and those of other hydrophobic compounds, such as phenanthrene, fluoranthrene, and Sudan III (Table 1). Methanol and ethanol were used as tracers for the aqueous phase. 

The structural determination of aristolochic acid I (1) was first accomplished by Pailer et al. Aristolochic acid I(Ci7Hn07N) is easily soluble in alkali as well as sodium bicarbonate. It was esterified with diazomethane in dioxane to give a methyl ester (C,gHi307N), and the methyl ester was readily saponified to recover aristolochic acid I. Zinc distillation of 1 gave a phenanthrene (Scheme 6). Aristolochic acid I was decarboxylated with copper powder in quinoline to yield a nitro phenanthrene derivative (OjgHjjOjN.Sl). 

Sodium reacts with naphthalene in dimethyl ether to form a dark green reactive complex. This addition product, naphtalenesodium, CioHsNa, is stabilized by solvation with ether. Anthracene, phenanthrene, biphenyl, and many other aromatics form similar complexes with sodium in the presence of methylethyl ether, tetrahyrofuran, dioxane, and other ethers. 

A. Purification of phenanthrene. 1. By azeotropic distillation.2 A mixture of 300 g. of commercial phenanthrene (Note 1), 90 g. of maleic anhydride, and 600 ml. of xylene, contained in a 2-1. round-bottomed flask, is heated under reflux for 20 hours (Note 2). The initially yellow solution rapidly turns to a dark brown on heating. This solution is cooled to room temperature and filtered by suction to remove any insoluble adduct. The filtrate is then extracted with two 100-ml. portions of dilute sodium hydroxide, and the basic extracts are discarded. The organic phase is next washed with water and saturated sodium chloride solution, and finally is filtered through a layer of anhydrous magnesium sulfate. The excess xylene is removed by distillation, first at atmospheric pressure then the final portions are removed at reduced pressure. The residue, while still hot, is poured into a large mortar and, after solidification, is powdered to a convenient size. The yield of crude phenanthrene is 230-240 g. 

The submitter used a 65-cm. Podbielniak type column equipped with partial reflux head.6 For distillation of the sodium-treated phenanthrene the checkers employed a 6-in. Vigreux column. For the fractionation of the dihydrophenanthrene, the checkers employed a 15-cm. spinning-band column obtainable from Nester and Faust, Exton, Pennsylvania. 

Phenanthrene purified by the sodium treatment was found superior to that from the azeotropic distillation, but both products gave satisfactory results. A good grade of commercially available phenanthrene ( white label grade supplied by the Eastman Kodak Company), although recrystallized and treated with Raney nickel, resisted hydrogenation under the described conditions. 

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... 

Soil Addition of 10 ml water and deuterated standards to 50 g of soil followed by equilibration for 1 h. Sonication 3 times with acetone/ hexane. Phase separation followed by water removal using sodium sulfate, concentration using K-D, and nitrogen blow-down. Spiking with phenanthrene-... 

The present method is based on the earlier described ozonolysis of phenanthrene in methanol. The reduction of the peroxidic reaction mixture with trimethyl phosphite to give diphenaldehyde, isolated as the di- -nitrophenylhydrazone, in quantitative yield has been described recently.10 The disadvantage of this method is that the dialdehyde cannot be isolated in the free state in high yield. Diphenaldehyde has also been obtained by sodium... 

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