Phenanthrene, sulfonation

Carbonaceous materials are obtained via heat treatment from various sources, including coal, liquefied coal, coke, petroleum, resins, carbon blacks, paraffins, olefins, pitch, tar, polycyclic aromatic compounds (naphthalene, biphenyl, naphthalene sulfonic acid, anthracene sulfonic acid, phenanthrene sulfonic acid, etc.), polymers (polyethylene, polymethylacrylale, polyvinyl chloride, phenol resin, polyacrylonitrile, etc.) [99-101J. This kind of fluids is claimed to. show a strong ER effect, low electric power consumption and excellent durability [101]. Several publications addressed the ER effect and physical properties of carbonaceous ER fluids [102-104]. 

Poly(arylene ether ketone)s can also be modified by introducing the functional groups using similar approaches to polysulfones. For example, poly(arylene ether ketone)s were sulfonated.189 In addition, o-dibenzoylbenzene moieties in the poly(arylene ether)s can be transformed to heterocycles by cyclization with small molecules. These polymers can react with hydrazine monohydrate in the presence of a mild acid in chlorobenzene or with benzylamine in a basic medium.190 Another example of the use of the o-benzyl cyclization strategy is the intramolecular ring closure of poly(arylene ketone)s containing 2,2/-dibenzoylbiphenyl units to form poly(arylene ether phenanthrenes).191... 

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. 

Isocyanates 345 react with phenanthrenequinone 346 and triphenylarsine oxide to give photochromic oxazines 347 (Equation 48) <1993PS(81)37>. The isocyanate can be replaced by a phosphinimine and the phenanthrene structure can also be replaced by the corresponding phenanthroline (Equation 49) <2003WO42195>. The /ra r-fused tetrahydrooxazine 349 was prepared from epoxide 348 and 2-aminoethyl sulfate (ethanolamine 0-sulfonic acid) (Equation 50) <1987AP625>. 

The condition for stabilization of the semiquinone by resonance is that the two structures IV be equivalent. This condition is satisfied for the semiquinone anion, but not for the semiquinone III itself, in which the presence of the hydrogen atom destroys the equivalence of the two structures. We thus expect the semiquinone to be stable only in the form of the anion. This is verified by experiment. Michaelis and his collaborators67 have shown that the semiquinone of phenanthrene-3-sulfonate is stable in alkaline solution as the semiquinone ion,... 

The reactions of the higher hydrocarbons with electrophilic reagents are more complex than of naphthalene. For example, phenanthrene can be nitrated and sulfonated, and the products are mixtures of 1-, 2-, 3-, 4-, and 9-substituted phenanthrenes ... 

The details of protonation of several alkyl-substituted phenanthrenes by superacids have been reported.73 The observed mono- and di-cations are usually in agreement with those predicted by AMI MO calculations. Molecular modelling studies have suggested a multi-step pathway for the sulfonation of toluene widi sulfur trioxide.74 Intermediate 71-complcx. Wheland intermediate and pyrosulfonate species (34) are suggested, the product (p-toluenesulfonic acid) arising from an exothermic reaction between toluene and the acid (35) fonned by a facile prototropic rearrangement of (34). The sulfur trioxide monosulfonation of isopyrene and some derivatives leads usually to sulfonated... 

Fig. 6.3. Effect of sodium dodecylsulfate in the mobile phase upon electrochromatography of polycyclic aromatic hydrocarbons on a C18-derivatized continuous bed containing sulfonic acid groups (Reprinted with permission from [30]. Copyright 1996 American Chemical Society). Capillary 14 cm (10 cm effective length) x 100 pm i.d. Applied voltage 3.0 kV Eluent 60% (v/v) acetonitrile in 4 mmol/1 sodium phosphate (pH 7.4). (a) 1.0 mmol/1 SDS added to the eluent (b) without addition of SDS (control). Peaks naphthalene (1), 2-methylnaphthalene (2), fluorene (3), phenanthrene (4), anthracene (5).

Preparation of toluene-4-sulfonic acid 7,8-dihydro-6H-5-oxa-l-aza-phenanthren-6-yl-methyl ester... 

Partial condensers, 24, 341 Partial reduction, 79, 113 Patent blues, 301 Permanent red 2G, 267 Phenanthrene, 1 Phenol, 51, 86 from chlorobenzene, 76, 88 technical observations, Phenolphthalein paper, 395 Phenols, separation, 30 Phend-o-svdfonic acid, 51 Phenol-m-sulfonic acid, 144,145... 

The /i-toluidine salt of phenanthrene-2-sulfonic acid forms flat needles or plates melting at 282° (291° corr.) that of the 3-acid forms thick needles melting at 217° (222° corr.). 

For some reactions, such as alkali fusion, the barimn salt is a suitable form in which to use the phenanthrene-2-sulfonic acid. For conversion into the potassium salt, it is highly advisable to use the barium salt in the moist and finely divided condi-... 

The sulfonation is carried but in a 2-I. round-bottomed, three-necked flask fitted with a thermometer, a dropping funnel, and a stirrer (Note i). Five hundred grams (2.8 moles) of pure phenanthrene (Note 2) is melted in the flask, which is clamped in an oil bath heated to 110°. Mechanical stirring is started, and 327 cc. (600 g., 5.8 moles) of concentrated sulfiaric acid is run in at such a rate that the internal temperature does not rise above rao (ten to fifteen minutes). The reaction mixture is stirred and maintained at a temperature of 120-125° for three and one-half hours, when a test portion should give a nearly clear solution in water. The reaction is exothermic, and the bath must be kept at a temperature 5-10° bdow that of the mixtmre. Some sulfur dioxide is given off, and the mixture becomes green. 

The yields are barium phenanthrene-2-sulfonate, 150-200 g. (17-21 per cent) potassium phenanthrene-3-sulfonate, 200-220 g. (24-26 per cent) (Notes 7,-8). 

The sulfonation of phenanthrene has been studied by Werner and his students, by Sandqvist, by Fieser,i and by Ioffe. ... 

Upon sulfonation, phenanthrene-3-sulfonic acid gives mainly (but not exclusively) the 3,6-disulfonic acid (Fieser, L. F. J. Am. Chem. Soe. 1929, 51, 2471), but the starting phenanthrene-3-sulfonic acid can be obtained from phenanthrene in only ca. 25% yield, and then isolated only from a mixture including a comparable amount of the 2-sulfonic acid (Fieser, L. F. Org. Synth., Coll. Vol. II1943, 482). 

Sulfonation of phenantkrene. Solomon and Hennessy added 88 g. (1.1 moles) of Sulfan B dropwise with stirring and ice cooling to 100 ml. of dioxane in 350 ml. of ethylene dichloride. They then added 1 mole of phenanthrene and heated the mixture for 5 hrs. at 60°. The formulas show a comparison of the yields of monosulfonates obtained with the complex and with coned, sulfuric acid."... 

Reactions of another type involve cleavage of a carbon-carbon bond. Phenanthrene-quinone is oxidized smoothly to diphenic acid by hydrogen peroxide in warm acetic acid. Use of the reaction in structure elucidation is illustrated as follows. One of five disulfonic acids formed on sulfonation of phenanthrene was converted into the dimethoxyphenanthrene, which on oxidation afforded a dimethoxy-9,10-phenan-threnequinone. Oxidation of this quinone with HjOa-AcOH gave an acidic product... 

Derivation (1) From crude anthracene cake by selective solution of the phenanthrene with crude solvent naphtha, removal of the anthracene by conversion into a sulfonic derivative, and extraction by means of water. (2) Synthetically from o-aminobi-phenyl. 

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