Tetralin, from naphthalene

A number of basic studies in the area of donor solvent liquefaction have been reported (2 -9). Franz (10J reported on the interaction of a subbituminous coal with deuterium-labelled tetra-lin, Cronauer, et al. (11) examined the interaction of deuterium-labelled Tetralin with coal model compounds and Benjamin, et al. (12) examined the pyrolysis of Tetralin-l-13C and the formation of tetralin from naphthalene with and without vitrinite and hydrogen. Other related studies have been conducted on the thermal stability of Tetralin, 1,2-dihydronaphthalene, cis-oecalin and 2-methylin-dene (13,14). 

The NMR spectrum of the spent solvent from E10 is shown in Figure 3. Tetralin and naphthalene absorption peaks are evident in this spectrum, and the peaks at positions 1, 2 and 3 are due to decal ins and in part to methylindan and n-butylbenzene. Methyl in-dan and n-butylbenzene were detected and analyzed by GC-MS. In Figure 3, the large difference in amplitude between the Har Hx and Hj absorptions of Tetralin show that protium was incorporated to a greater degree into the position than into the other positions. The spectrum also shows that the H absorption of the naphthalene in the spent solvent is much more intense than the absorption. 

Partial reduction of polyarenes has been reported. Use of boron trifluoride hydrate (BF3 OH2) as the acid in conjunction with triethylsilane causes the reduction of certain activated aromatic systems 217,262 Thus, treatment of anthracene with a 4-6 molar excess of BE3 OH2 and a 30% molar excess of triethylsilane gives 9,10-dihydroanthracene in 89% yield after 1 hour at room temperature (Eq. 120). Naphthacene gives the analogously reduced product in 88% yield under the same conditions. These conditions also result in the formation of tetralin from 1-hydroxynaphthalene (52%, 4 hours), 2-hydroxy naphthalene (37%, 7 hours), 1-methoxynaphthalene (37%, 10 hours), 2-methoxynaphthalene (26%, 10 hours), and 1-naphthalenethiol (13%, 6 hours). Naphthalene, phenanthrene, 1-methylnaphthalene, 2-naphthalenethiol, phenol, anisole, toluene, and benzene all resist reduction under these conditions.217 Use of deuterated triethylsilane to reduce 1-methoxynaphthalene gives tetralin-l,l,3-yielding information on the mechanism of these reductions.262 2-Mercaptonaphthalenes are reduced to 2,3,4,5-tetrahydronaphthalenes in poor to modest yields.217 263... 

Cyclization to five-membered rings forms the alkylindans and indenes cyclization to six-membered rings gives tetralins and naphthalenes. Tetralins and decalins, however, were not observed in any of the experiments, because of unfavorable equilibrium. For example, less than 0.02-0.1% tetralin and less than 0.001% decalins would be expected if they were in equilibrium with the naphthalene formed in the n-butylbenzene experiments. [Equilibrium conversions calculated from the data of Egan (15), Allam and Vlugter (16), and Frye and Weitkamp (17)]... 

C5- and C6- cyclizations are parallel reactions. Csicsery has shown that isomerization of tetralin to methylindan over platinum-alumina at 371°C is extremely slow (22). Davis and Venuto provided further evidence by showing that methylindan is also not converted to tetralin or naphthalene over platinum on silica-alumina (23). This behavior is similar to that observed in the cyclization of aliphatic hydrocarbons. Davis and Venuto also reported that the major aromatic products obtained from ten C8-C9 paraffins and olefins at 482°C are only formed by direct six-membered ring... 

Methylindan and smaller amounts of tetralin and naphthalene are formed from all three butylbenzene isomers over the acidic chromia-alumina catalyst. These reactions proceed by a cationic mechanism. 

Dehydrogenation (the conversion of alicyclic or hydroaromatic compounds into their aromatic counterparts by removal of hydrogen - and also, in some cases, of other atoms or groups) has found wide application in the determination of structure of natural products containing complex hydroaromatic systems. Dehydrogenation is employed also for the synthesis of polycyclic hydrocarbons and their derivatives from readily accessible synthetic hydroaromatic compounds. The general process is illustrated by the conversion of tetralin into naphthalene. 

Usually o.v-dccalin is formed more selectively from tetralin than from naphthalene. Baker and Schuetz obtained a mixture of 77% cis- and 23% frans-decalin in the hydrogenation of naphthalene over Adams platinum oxide in acetic acid-ether at 25°C and 12.8 MPa H2, while cA-decalin was obtained exclusively in the hydrogenation of tetralin in acetic acid under similar conditions.23... 

The products from these hydrogenations were separated into gases (analyzed by G.C.), water (analysed by azeotropic distillation), insolubles (CH2CI2 insolubles), asphaltene (CH2CI2 soluble/X4 insoluble) (Shell X4 40-60 C b.p. light petroleum), oils (CH2CI2 soluble/X4 soluble). Hydrogen transferred from the donor solvent was determined by G.L.C. analysis of the ratio of tetralin to naphthalene in the total hydrocarbon liquid product. 

Naphthalene is reduced to 1,4-dihydronaphthalene by sodium and alcohol. Isomerization of this product to 3,4-dihydronaphthalene occurs with sodamide in liquid ammonia. Tetrahydronaphthalene (tetralin) is formed from naphthalene by sodium in amyl alcohol or by reduction with nickel-aluminum alloy and aqueous alkali. Catalytic hydrogenation of naphthalene can be stopped at the tetralin stage over copper chromite, Raney nickel, or alkali metal catalysts. cis-Decahydronaphthalene is produced by high-pressure hydrogenation of tetralin over Adams catalyst, whereas a mixture of cis- and trans-decalins is obtained from naphthalene under the same conditions. ... 

Commercial tetralin contains naphthalene as the principal impurity and this interferes with the preparation of tetralin-1-hydroperoxide or with use of the hydrocarbon as hydrogen donor in hydrogen-transfer reactions. An early purification procedure is uninviting fractionation extraction in turn with mercury (to remove sulfur impurities), with mercuric acetate solution (to remove olefins), and with sulfuric acid fractionation. More recently Bass sulfonated the crude hydrocarbon with coned, sulfuric acid and added ammonium chloride to precipitate ammonium tetralin-6-sulfonate. The salt was crystallized until pure and hydrolyzed by steam distillation from sulfuric acid solution. Distillation from sodium gave material showing no ultraviolet bands characteristic of naphthalene. 

Hydrogen donors labelled with deuterium, such as tetralin-and naphthalene-4 have also been used to study the reaction mechanism of the hydrogen transfer. Tetralin-(ii2 is rapidly substituted in the 1-position by hydrogen from coal. At a reaction temperature of 400 °C the deuterium content of the 1-position remains, after a reaction time of 15 min, relatively constant at 66%. The 2-position, however, participates much less in the exchange reaction. On the other hand, the deu-... 

Figure 6. Chemical transformations used to interrelate tetralins from E, orbiculatum and Emmotin-A. Conversion of tetralones into naphthalene lactones.

Tetrahydronaphthalene [119-64-2] (Tetralin) is a water-white Hquid that is insoluble in water, slightly soluble in methyl alcohol, and completely soluble in other monohydric alcohols, ethyl ether, and most other organic solvents. It is a powerhil solvent for oils, resins, waxes, mbber, asphalt, and aromatic hydrocarbons, eg, naphthalene and anthracene. Its high flash point and low vapor pressure make it usehil in the manufacture of paints, lacquers, and varnishes for cleaning printing ink from rollers and type in the manufacture of shoe creams and floor waxes as a solvent in the textile industry and for the removal of naphthalene deposits in gas-distribution systems (25). The commercial product typically has a tetrahydronaphthalene content of >97 wt%, with some decahydronaphthalene and naphthalene as the principal impurities. 

---