Pyrolysis anthracenes

Sources of Raw Materials. Coal tar results from the pyrolysis of coal (qv) and is obtained chiefly as a by-product in the manufacture of coke for the steel industry (see Coal, carbonization). Products recovered from the fractional distillation of coal tar have been the traditional organic raw material for the dye industry. Among the most important are ben2ene (qv), toluene (qv), xylene naphthalene (qv), anthracene, acenaphthene, pyrene, pyridine (qv), carba2ole, phenol (qv), and cresol (see also Alkylphenols Anthraquinone Xylenes and ethylbenzenes). 

Starting from 27, cyclo-Cig was prepared in the gas phase by laser flash heating and the neutral product, formed by stepwise elimination of three anthracene molecules in retro-Diels-Alder reactions, was detected by resonant two-photon-ionization time-of-flight mass spectrometry [23]. However, all attempts to prepare macroscopic quantities of the cyclocarbon by flash vacuum pyrolysis using solvent-assisted sublimation [50] only afforded anthracene and polymeric material. 

A few routes to new silenes, usually involving flash vacuum pyrolysis at high temperatures, have been reported. Silenes were proposed as the result of the thermal expulsion of trimethylmethoxysilane, or a similar volatile fragment, from the starting material but frequently, proof that the silenes proposed to account for the observed products were in fact formed was not provided.116 119 The other thermal route employed was the retro-Diels-Alder regeneration of a silene from an adduct with an aromatic compound—often a 9,10-anthracene or 1,4-naphthalene adduct or, in some cases, a 1,4-benzene adduct, as illustrated in Eq. (19).120... 

The finely divided hydride produced by pyrolysis is pyrophoric in air, while synthesis from the elements produces a substantially air-stable product [1]. That prepared by reduction of butylmagnesium bromide with lithium tetrahydroalumi-nate is pyrophoric and reacts violently with water and other protic compounds [2], The hydride produced from magnesium anthracene has a very large specific surface area and is pyrophoric [3], In the context of use of the hydride for energy storage purposes, ignition and combustion behaviour of 100-400 g portions were studied, as well as the reaction with water [4],... 

Several methods can be employed to convert coal mto liquids, with or without the addition of a solvent or vehicle. Those methods which rely on simple pyrolysis or carbonization produce some liquids, but the main product is coke or char Extraction yields can be dramatically increased by heating the coal over 350°C in heavy solvents such as anthracene or coal-tar oils, sometimes with applied hydrogen pressure, or the addition of a catalyst Solvent components which are especially beneficial to the dissolution and stability of the products contain saturated aromatic structures, for example, as found in 1,2,3,4 tetrahydronaphthalene Ilydroaromatic compounds are known to transfer hydrogen atoms to the coal molecules and, thus, prevent polymerization... 

The polyaromatic hydrocarbons in the soil sample were quantitated by using an external standard of anthracene. The results reportedly for a polluted soil and sediment sample indicate that this flash evaporation-pyrolysis technique combined with gas chromatography-mass spectrometry is a valuable tool for rapidly screening polluted samples for virtually all types of anthropogenic contaminants except for heavy metals. 

Pyrolysis of bis(2-ethylhexyl) phthalate in the presence of polyvinyl chloride at 600 °C produced the following compounds methylindene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, biphenyl, dimethylnaphthalene, acenaphthene, fluorene, methylacenaphthene, methylfluorene, phenanthrene, anthracene, methylphenanthrene, methylanthracene, methylpyrene or fluoranthene, and 17 unidentified compounds (Bove and Dalven, 1984). 

Primary Conversions and Influence of Mobile Phase Yields for the various H-donor and non-donor solvent extractions of Linby coal at 400% are summarised in Table III the conversions for the THF-extracted coal include the extracted material. Surprisingly, pre-extraction with THF significantly increases primary conversions in the polynuclear aromatic compounds (PACs) investigated. These findings appear to be contrary to those of other liquefaction (16) and pyrolysis (17) studies where prior removal of chloroform-extractable material significantly reduced conversions. However, Rincon and Cruz (18) have reported recently that pre-swelling coals in THF increases conversions for both anthracene oil and tetralin. The fact that Point of Ayr (87% dmmf C) coal yielded over 80% pyridine-solubles in pyrene (C.E. Snape, unpublished data) without pre-extraction is consistent with the earlier results of Qarke et al (19) for anthracene oil extraction where UK coals... 

Solvent-Refined Coal Process. In the 1920s the anthracene oil fraction recovered from pyrolysis, or coking, of coal was utilized to extract 35—40% of bituminous coals at low pressures for the purpose of manufacturing low cost newspaper inks (113). Tetralin was found to have higher solvent power for coals, and the I. G. Farben Pott-Broche process (114) was developed, wherein a mixture of cresol and tetralin was used to dissolve ca 75% of brown coals at 13.8 MPa (2000 psi) and 427°C. The extract was filtered, and the filtrate vacuum distilled. The overhead was distilled a second time at atmospheric pressure to separate solvent, which was recycled to extraction, and a heavier liquid, which was sent to hydrogenation. The bottoms product from vacuum distillation, or solvent-extracted coal, was carbonized to produce electrode carbon. Filter cake from the filters was coked in rotary kilns for tar and oil recovery. A variety of liquid products were obtained from the solvent extraction-hydrogenation system (113). A similar process was employed in Japan during Wodd War II to produce electrode coke, asphalt (qv), and carbonized fuel briquettes (115). 

Diels-Alder reactions are, of course, reversible, and the pathway followed for the reverse reaction (2,3 arrows) can sometimes be as telling as the pathway for the forward reaction. The direction in which any pericyclic reaction takes place is determined by thermodynamics, with cycloadditions, like the Diels-Alder reaction, usually taking place to form a ring because two n-bonds on the left are replaced by two Diels-Alder reaction can be made to take place in reverse when the products do not react with each other rapidly, as in the pyrolysis of cyclohexene 2.3 at 600°. It helps if either the diene or the dienophile has some special stabilization not present in the starting material, as in the formation of the aromatic ring in anthracene 2.15 in the synthesis of diimide 2.16 from the adduct 2,14, and in... 

A reversible vinylidene insertion was proposed to explain die formation of (55) on flash vacuum pyrolysis of the anthracene derivative (56) at 1100 °C.65 The expected loss of HC1 followed by 1,2-H shift and 1,5-CH insertion of the resulting vinylidene species would give rise to the strained paracyclophane (57). This is proposed to ring open to the alternative alkylidene (58) before proceeding to the observed product (55). 

Flash vacuum pyrolysis of [4+4] dimers of o-xylylenes gives anthracenes as the major products, and this "remarkable transformation" is highly regiospecific. Thus, the methyl-substituted derivative 1 gives 2 while 3 gives 4. 

As benzothiophene was a product of both the reaction of benzyne with thiophene and the pyrolysis of thiophene alone (Fields and Meyerson, 1966d), we investigated the reaction of benzyne with benzothiophene. Pyrolysis of a mixture of phthalic anhydride and benzothiophene gave the products shown in Table 11. Anthracene and dibenzothiophene probably arose via 1,2-, and phenanthrene via 1,4-addition to the thiophene ring ... 

Flash vacuum pyrolysis (FVP) of o-substituted benzylidene and benzyl chlorides154 was found to be a convenient method for the preparation of 1-chlorobenzocyclobutene, anthracene or benzofuran. In the case of o-methylbenzylidene chloride at 700 °C, 89% 1-chlorobenzocyclobutene were formed. Several benzylidene chlorides having different o-substituents were also pyrolyzed. Either o-benzylbenzylidene or o-benzylbenzyl chlorides gave anthracene in good yield. These processes were believed to proceed as shown in equation 70. 

Miyazawa et al. (92) related rates of decrease of aliphatic hydrogen protons during pyrolysis of ethylene tar pitch to formation of mesophase. Yokono et al, (93) used the model compound anthracene to monitor the availability of transferable hydrogen. Co-carboniza-tions of pitches with anthracene suggested that extents of formation of 9,10-dihydroanthracene could be correlated with size of optical texture. The method was then applied to the carbonization behaviour of hydrogenated ethylene tar pitch (94). This pitch, hydrogenated at 573 K, had a pronounced proton donor ability and produced, on carbonization, a coke of flow-type anisotropy compared with the coarse-grained mosaics (<10 ym dia) of coke from untreated pitch. 

In the flow pyrolysis of indole, only small amounts of nitrogen heterocycles, such as quinoline (4.4%), isoquinoline (1.0%), and carbazole (2.5%), were generated. Benzonitrile (13.1%) and 9-anthracenecarbonitrile (5.2%) as well as their isomers were found in larger amounts. The larger amount of phenanthrene (9.1%) and anthracene (3.5%) compared with that of naphthalene (2.2%) is remarkable (Scheme 6). In the pyrolysis of pyrrole it was much lower, and this indicates that different reaction paths are followed. 

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