Naphthalenes—continued

The effect of pressure (measured at the pump) on this separation can be seen in Figure 3 and Table I. As the pressure is increased, the retention volume of benzene and naphthalene continually Increase, while the retention volume of anthracene, chrysene, and benz(a)pyrene first increase, go through a maximum, and then decrease. The maximum separation occurs at 38.5 bar while the minimum satisfactory separation volume (shortest analysis... 

A = 13945 CioHs CioHuN Naphthalene (continued) Diethylaniline 218.05 217.05 Nonazeotrope 31... 

Heat the water in the beaker sufficiently to cause all of the naphthalene to melt. Be sure that the bulb of the thermometer dips completely below the surface of the molten naphthalene and that all of the naphthalene is below the level of the water in the beaker. Stop heating the water, and allow the apparatus to cool slowly while you stir the naphthalene continuously with a slow up-and-down motion of the wire stirrer. The stirrer must not touch the thermometer. When the thermometer reading has dropped to 82°C, start reading and recording the temperature to the nearest 0.1° every half-minute. Continue to take readings until it becomes impossible to stir. Record your temperature-time data in TABLE 20.1. 

Many valuable chemicals can be recovered from the volatile fractions produced in coke ovens. Eor many years coal tar was the primary source for chemicals such as naphthalene [91-20-3] anthracene [120-12-7] and other aromatic and heterocycHc hydrocarbons. The routes to production of important coal-tar derivatives are shown in Eigure 1. Much of the production of these chemicals, especially tar bases such as the pyridines and picolines, is based on synthesis from petroleum feedstocks. Nevertheless, a number of important materials continue to be derived from coal tar. 

Because naphthalene vapors can cause eye irritation at concentrations of 15 ppm in air and because continued exposure may result in adverse effects to the eye, a threshold limit value of 10 ppm (50 mg/m ) has been set by the ACGIH (45). This amount is about 30% of the air-saturation value at 27°C. 

Isopropylnaphthalenes can be prepared readily by the catalytic alkylation of naphthalene with propjiene. 2-lsopropylnaphthalene [2027-17-0] is an important intermediate used in the manufacture of 2-naphthol (see Naphthalenederivatives). The alkylation of naphthalene with propjiene, preferably in an inert solvent at 40—100°C with an aluminum chloride, hydrogen fluoride, or boron trifluoride—phosphoric acid catalyst, gives 90—95% wt % 2-isopropylnaphthalene however, a considerable amount of polyalkylate also is produced. Preferably, the propylation of naphthalene is carried out in the vapor phase in a continuous manner, over a phosphoric acid on kieselguhr catalyst under pressure at ca 220—250°C. The alkylate, which is low in di- and polyisopropylnaphthalenes, then is isomerized by recycling over the same catalyst at 240°C or by using aluminum chloride catalyst at 80°C. After distillation, a product containing >90 wt % 2-isopropylnaphthalene is obtained (47). 

Sulfonation can be conducted with naphthalene—92 wt % H2SO4 in a 1 1.1 mole ratio with staged acid addition at 160°C over 2.5 h to give a 93% yield of the desired product (20). Continuous mono sulfonation of naphthalene with 96 wt % sulfuric acid in a cascade reactor at ca 160°C gives... 

A naphthalene sulfonation product that is rich in the 2,6-isomer and low in sulfuric acid is formed by the reaction of naphthalene with excess sulfuric acid at 125°C and by passing the resultant solution through a continuous wiped-film evaporator at 245°C at 400 Pa (3 mm Hg) (26). The separation in high yield of 99% pure 2,6-naphthalenedisulfonate, as its anilinium salt from a cmde sulfonation product, has been claimed (27). A process has been patented for the separation of 2,6-naphthalenedisulfonic acid from its isomers by treatment with phenylenediarnine (28). 

H-acid, l-hydroxy-3,6,8-ttisulfonic acid, which is one of the most important letter acids, is prepared as naphthalene is sulfonated with sulfuric acid to ttisulfonic acid. The product is then nitrated and neutralized with lime to produce the calcium salt of l-nitronaphthalene-3,6,8-ttisulfonic acid, which is then reduced to T-acid (Koch acid) with Fe and HCl modem processes use continuous catalytical hydrogenation with Ni catalyst. Hydrogenation has been performed in aqueous medium in the presence of Raney nickel or Raney Ni—Fe catalyst with a low catalyst consumption and better yield (51). Fusion of the T-acid with sodium hydroxide and neutralization with sulfuric acid yields H-acid. Azo dyes such as Direct Blue 15 [2429-74-5] (17) and Acid... 

Naphthalene (qv) from coal tar continued to be the feedstock of choice ia both the United States and Germany until the late 1950s, when a shortage of naphthalene coupled with the availabihty of xylenes from a burgeoning petrochemical industry forced many companies to use o-xylene [95-47-6] (8). Air oxidation of 90% pure o-xylene to phthaUc anhydride was commercialized ia 1946 (9,10). An advantage of o-xylene is the theoretical yield to phthaUc anhydride of 1.395 kg/kg. With naphthalene, two of the ten carbon atoms are lost to carbon oxide formation and at most a 1.157-kg/kg yield is possible. Although both are suitable feedstocks, o-xylene is overwhelmingly favored. Coal-tar naphthalene is used ia some cases, eg, where it is readily available from coke operations ia steel mills (see Steel). Naphthalene can be produced by hydrodealkylation of substituted naphthalenes from refinery operations (8), but no refinery-produced napthalene is used as feedstock. Alkyl naphthalenes can be converted directiy to phthaUc anhydride, but at low yields (11,12). 

Replacing one carbon atom of naphthalene with an a2omethene linkage creates the isomeric heterocycles 1- and 2-a2anaphthalene. Better known by their trivial names quinoline [91-22-5] (1) and isoquinoline [119-65-3] (2), these compounds have been the subject of extensive investigation since their extraction from coal tar in the nineteenth century. The variety of studies cover fields as diverse as molecular orbital theory and corrosion prevention. There is also a vast patent Hterature. The best assurance of continuing interest is the frequency with which quinoline and isoquinoline stmctures occur in alkaloids (qv) and pharmaceuticals (qv), for example, quinine [130-95-0] and morphine [57-27-2] (see Alkaloids). 

Several descriptions have been pubUshed of the continuous tar stills used in the CIS (9—11). These appear to be of the single-pass, atmospheric-pressure type, but are noteworthy in three respects the stills do not employ heat exchange and they incorporate a column having a bubble-cap fractionating section and a baffled enrichment section instead of the simple baffled-pitch flash chamber used in other designs. Both this column and the fractionation column, from which light oil and water overhead distillates, carboHc and naphthalene oil side streams, and a wash oil-base product are taken, are equipped with reboilers. 

Figure 22-8 shows the features of a horizontal center-fed column [Brodie, Au.st. Mech. Chem. Eng. Tran.s., 37 (May 1979)] which has been commercialized for continuous purification of naphthalene and p-dichlorobenzene. Liquid feed enters the column between the hot purifying section and the cold freezing or recovery zone. Ciystals are formed internally by indirect cooling of the melt through the walls of the refining and recovery zones. Residue liquid that has been depleted or product exits from the coldest section of the column. A spiral conveyor controls the transport of solids through the unit. 

Anhyd NH3(g) was bubbled through a stirring mixture of 6,7-di(phenylselanyl)naphthalene-2,3-dicarbo-nitrile (200 mg, 0.43 mmol), NaOMe (0.22 mmol) and 2-methoxyelhanol (5 mL) for 30 min. With continued NH3 introduction, the mixture was heated to 65 "C for 3 h. The solution was evaporated in vacuo. CuCl (21.8 mg, 0.22 mmol) and quinoline (5 mL) were added to the residue and refluxed for 2 h. MeOH was added and the precipitate was filtered, washed with acetone, CH2C12. and toluene yield 105 mg (51 %). 

The bacterial aerobic degradation of pyrene is initiated by the formation of cfi-pyrene-4,5-dihydrodiol. Analysis for this metabolite was used to demonstrate the biodegradability of pyrene in an environment in which there was continuous input of the substrate, when it was not possible to use any diminution in its concentration as evidence for biodegradation (Li et al. 1996). The corresponding metabolite from naphthalene—cfi-naphthalene-1,2-dihydrodiol—has been used to demonstrate biodegradation of naphthalene both in site-derived enrichment cultures and in leachate from the contaminated site (Wilson and Madsen 1996). 

Before the advent of the petrochemical industry carbocyclic aromatic compounds, such as naphthalene, phenol, and pyridine, provided the source of many important industrial chemicals including dyestuffs, while the monocyclic compounds continue to play an important role as fuels and starting materials. 

Dissolve 71 g. of P-methylnaphthalene in 460 g. (283 ml.) of A.B. carbon tetrachloride and place the solution in a 1 -litre three-necked flask equipped with a mechanical stirrer and reflux condenser. Introduce 89 g. of JV-bromosuccinimide through the third neck, close the latter with a stopper, and reflux the mixture with stirring for 16 hours. Filter ofiT the succinimide and remove the solvent under reduced pressure on a water bath. Dissolve the residual brown oil (largely 2-bromomethyl naphthalene) in 300 ml. of A.R. chloroform, and add it to a rapidly stirred solution of 84 g. of hexamine in 150 ml. of A.R. chloroform contained in a 2-litre three-necked flask, fitted with a reflux condenser, mechanical stirrer and dropping funnel maintain the rate of addition so that the mixture refluxes vigorously. A white solid separates almost immediately. Heat the mixture to reflux for 30 minutes, cool and filter. Wash the crystalline hexaminium bromide with two 100 ml. portions of light petroleum, b.p. 40-60°, and dry the yield of solid, m.p. 175-176°, is 147 g. Reflux the hexaminium salt for 2 hours with 760 ml. of 60 per cent, acetic acid, add 160 ml. of concentrated hydrochloric acid, continue the refluxing for 5 minutes more, and cool. Extract the aldehyde from the solution with ether, evaporate the ether, and recrystallise the residue from hot -hexane. The yield of p-naphthaldehyde, m.p. 69-60°, is 60 g. 

Remove the test tube from the boiling water bath by repositioning the test-tube clamp so that it is no longer over the beaker. CAUTION The test-tube clamp may be hot. Monitor the temperature of the naphthalene as it cools. Continue stirring the naphthalene as it cools to ensure that the temperature is constant throughout. 

In order to determine the freezing point accurately, the cooling curve must be observed both above and below the freezing point. Thus, continue recording the temperature even after the naphthalene has frozen. Stop making measurements once the temperature has dropped below 70°C. 

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