Phenanthrene-9-sulfonic acid

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). 

Phenanthrene (Table XII, p. 189). Phenanthrene is as readily sul-fonated as anthracene when the reaction is carried out for three hours at 120-125° with concentrated sulfuric acid, more than 40% of the phenanthrene is converted into disulfonic acids. Two monosulfonic acids are isolated under these experimental conditions phenanthrene-2-sulfonic acid (25% yield) and phenanthrene-3-sulfonic acid (27% yield). The same acids are obtained by sulfonating at 100.° for eight hours (2-acid, 7% 3deld 3-acid, 9% yield), and in addition a third acid, phenanthrene-9-sulfonic acid (6% 3deld) is formed. The 9-acid is formed in larger amounts at lower temperatures (14.5% at 20°, twenty days). A fourth monosulfonic acid, the 1-acid, is isolated from the sulfonation reaction conducted at 60° for several days. The 3uelds of the four monosulfonic acids isolated under these conditions are 4% of the 1-acid, 18% of the 2-acid, 19% of the 3-acid, and 13% of the 9-acid. There is no indication that the only other possible monosulfonic acid, the 4-isomer, is ever formed, probably because the 4-position of phenanthrene is particularly hindered. 

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]. 

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>. 

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-... 

Practically any aromatic hydrocarbon or aryl halide can be sulfonated if the proper conditions are chosen. As the compound becomes more complex, however, the tendency toward the production of by-products and mixtures of isomers is increased. It is usually difficult to prevent polysubstitution of a reactive hydrocarbon. For example, even when phenanthrene is sulfonated incompletely at room temperature, some disulfonic acids are formed. The sulfonation of anthracene follows such a complex course that the 1- and 2-sulfonic acid derivatives are made from the readily available derivatives of anthraquinone. The foUowii sections include comments.on the accessibility of the reaction products of the commonly available hydrocarbons and aryl halides. The examples cited and still others are listed in Tables I-XIII. 

Phenanthrene. Studies in the sulfonation of phenanthrene 52 indicated a positional order of reactivity of 3 > 2 > 9 > 1 This is different from the theoretical order of 9 > 1 > 4 > 3 > 2, because of steric hindrance which accounts for the complete absence of the 4-isomer. Reaction of phenanthrene 52 with chlorosulfonic acid (one equivalent) in boiling chloroform affords the 2- and 3-sulfonic acids 53 and 54 (Equation 16) (85% yield of the mixture of isomers was isolated as the lead sulfonates). ... 

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... 

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... 

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. 

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... 

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