Dihydronaphthalenes, 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). 

Jerina, D.M., Daly, J.W., Jeffrey, A.M., and Gibson, D.T. cis-l,2-Dihydroxy-l,2-dihydronaphthalene abacterial metabolite from naphthalene, Arch. Biochem. Biophys., 142 394-396, 1971. 

Jerina, D. M., Daly, J. W., Jeffrey, A. M. Gibson, D. T. (1971). cis-1,2-Dihydroxy-l,2-dihydronaphthalene A bacterial metabolite from naphthalene. Archives of Biochemistry... 

For benzene, it has not been possible to measure directly the rate constant kv for deprotonation of the benzenonium ion in order to complete the determination of Ka (— kp/kg). However, this has been possible for 1-protonated naphthalene,106 9-protonated phenanthrene,25 9-protonated anthracene, and 2-protonated benzofuran.75 In the case of the naphthalene, Thibblin and Pirinccioglu showed that the naphthalene hydrate is sufficiently reactive to form the naphthalenonium ion in aqueous azide buffers (pH 4-5).106 Formation of this ion leads to competition between loss of a proton and trapping by azide ion to form the 2-azido-l,2-dihydronaphthalene. From the trapping ratio kp is determined as 1.6xlOlos 1 by the usual clock method. 

A one-pot tandem addition/oxidative decomplexation methodology has been developed, which yields substituted dihydronaphthalenes from [Os]-naphthalenes. The process involves... 

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. ... 

The preparation of annelated tetrakisdehydro[18]annulenes 349 and 350 and the reference dehydroannulene 351 afforded further insight into the 7t-electron delocalization in annelated annulenes . When a dihydronaphthalene nucleus in 351 was replaced by naphthalene to form the annelated dehydroannulene 350, an appreciable suppression of diatropicity in 350 was observed. Further replacement of the dihydronaphthalene by naphthalene to give the dinaphtho-annelated derivative 349 resulted in a further suppression of the diatropicity in contrast to the increase of diamagnetic ring current in the case of transition from 342 to 340 and from 343 to 341. 

Diphenylpicrylhydrazyl, which is prepared from MA -diphenyl-A -(2,4,6-trinitrophenyl)hydrazine by oxidation with lead dioxide [982], is used for the dehydrogenation of 1,4-dihydronaphthalene to naphthalene and of hydrazobenzene to azobenzene [983]. Simpler and cheaper compounds are, however, available for such purposes (equation 21). 

We also know the enthalpies of formation of the triene, l,6-(butane-l,4-diyl)-tropilidene (bicyclo[4.4.1]undeca-l,3,5-triene, 88) as well as of the related tetraene [ 1,6-(2-butene-1,4-diyl)-tropilidene, 89] and pentaene [l,6-( 1,3-butadiene-1,4-diyl)-tropilidene, 90], respectively. Choosing Roth s suggested value for the enthalpy of formation of the parent tropilidene so that all four species are taken from the same primary source, we find that attachment of these varying 4-carbon chains increase the enthalpy of formation by —40, 74 and 136 kJ mol respectively. Upon affixing these same 4-carbon chains to benzene to form tetralin, 1,4-dihydronaphthalene and naphthalene (91, 92 and 7, respectively) the corresponding enthalpy of formation changes by —57, 51 and 68 kJmoU. ... 

A one-pot tandem addition/oxidative decomplexation methodology has also been developed for naphthalene which yields 1,4-disubstituted dihydronaphthalenes from osmium(ll) naphthalene complexes. The process involves the re-gio- and stereo specific addition of an electrophile and a nucleophile to generate cfs-l,4-dihydronaphthalene complexes. Oxidative decomplexation produces 1,4-dihydronaphthalenes in good overall yield (Table 5) [27]. 

C9,10, the initial product from pyrolysis of BV in a flow system at 350°C, is converted to 1,4-dihydronaphthalene, 1,2-dihydronaphthalene, and naphthalene at 400°C in a ratio of 4 2 1. The origin of the 1,4-dihydronaphthalene is unclear but 1,2-dihydronaphthalene most reasonably results from two successive 1,5-hydrogen shifts (Scheme 11.16). 

Jerina, D.M., J.W. Daly, A.M. Jeffrey, and D.T. Gibson. 1971. C/s-l,2-dihydroxy-1,2-dihydronaphthalene a bacterial metabolite from naphthalene. Archives of Biochemistry and Biophysics 142 394-396. 

Perhydroxylation and Epoxidation. By metabolic perhydroiqrl-ation is meant formation of dihydrodiols from compounds containing double bonds. lodobenzene, chlorobenzene, naphthalene, anthrar cene, phenanthrene, benzpyrene, and 1-chloro- and 1-bromonaphtha-lene are known to undergo this transformation (Table XIII). 1,2-Dihydroxy-l,2-dihydronaphthalene, but not oc-naphthol, is formed from naphthalene in the presence of liver slices (95) conversion of diol to phenol under these conditions cannot be detected. The major product formed from naphthalene by rabbit liver microsomes is a dihydrodiol-like material which yields a-naphthol upon add hydrolysis (558). 

Another hydrogen atom lost from the a- or 0-Tetralinyl radicals forms either 1,2-dihydronaphthalene by reaction 1 or 1,2- and 1,4-dihydronaphthalene by reactions 2A and 2B. Loss of two more alkyl hydrogens forms naphthalene. The dihydronaphthalenes, which have been detected in low concentrations (6), were not observed under our experimental conditions. 

Now the interesting question arose of whether the intermediate analogous to 215 but devoid of the methyl groups, that is, 3d2-l H-naphthalene (221), would also be interceptable, because 221 should show a high thermodynamic acidity owing to its conversion into the 2-naphthyl anion (224) on deprotonation and because of the use of the strong base KOtBu for the liberation of 221 from 3-bromo-l, 2-dihydro-naphthalene (220) (Scheme 6.52). In the event, the major product was indeed naphthalene. However, there were further products, namely the enol ether 223 and small quantities of 2,2 -binaphthyl (228) as well as 1,2-dihydronaphthalene (226). The overall yield amounted to 92% [137]. 

Scheme 6.52 Generation of 3<52-l H-naphthalene (221) by /j-elimination from 3-bromo-l, 2-dihydronaphthalene (220) and reaction sequences started by attacks of KOtBu at 221.

Wilson and Madsen [152] used the metabolic pathway for bacterial naphthalene oxidation as a guide for selecting l,2-dihydroxy-l,2-dihydronaphthalene as a unique transient intermediary metabolite whose presence in samples from a contaminated field site would indicate active in situ naphthalene biodegradation (Fig. 26). Naphthalene is a component of a variety of pollutant mixtures. It is the major constituent of coal tar [345], the pure compound was commonly used as a moth repellant and insecticide [345], and it is a predominant constituent of the fraction of crude oil used to produce diesel and jet fuels [346]. Prior studies at a coal tar-contaminated field site have focused upon contaminant transport [10,347], the presence of naphthalene catabolic genes [348, 349], and non-metabolite-based in situ contaminant biodegradation [343]. 

Boyd, D.R., McMordie, R.A S., Sharma, N.D., Dalton, H., Williams, P. and Jenkins, R.O., Stereospecific benzylic hydroxylation of bicyclic alkenes by Pseudomonas putida isolation of (+)-/ -l-hydroxy-l,2-dihydronaphthalene, an arene hydrate of naphthalene from metabolism of... 

Exposure of naphthalene dissolved in liquid ammonia to europium metal immediately results in the characteristic green color of naphthalene anion-radical. ESR analysis reveals a signal that comes from an unpaired electron interacting with Eu and Eu nuclei. No hyperfine coupling with naphthalene protons is observed, although treatment with water leads to 1,4-dihydronaphthalene (Stevenson et al. 1999). This means that naphthalene has indeed been reduced to its anion-radical and undergone a normal Birch reaction. These results are consistent with the initial donation of two... 

Dihydronaphthalen-1,4-iwmes from Isoindoles The naphthalen-l,4-imine derivatives 91-99 have been obtained by addition of acetylenedicarboxylic esters to the appropriate isoindoles. 3- ss Some such adducts react further with acetylenic esters (see Sections III, G and H), so that A -ethyl- and A-n-butylisoindole give 1 2 adducts with dimethyl aoetylenedicarboxylate instead. iV-Methylisoindole appears to be exceptional in giving an oily 2 1 adduct, for which structure (100) was suggested on analogy with the 2 1 adduct obtained from l,3-diphenylbenz[c]furan and acetylenedicarboxylic acid. ... 

When l,4-dihydronaphthalen-l,4-imine (2) was first obtained via the hydrobromide (113), it was shown to react with phenyl azide to give an adduct (127). The analogous phenyl azide adduct (128) from compound 103 has been better characterized. Naphthalen-l,4-imines also add diazomethane across the 2,3-double bond, forming pyrazolines, e.g., 104 -> 129, two of which have been photolyzed to give the corresponding cyclopropane derivatives (130) with extrusion of nitrogen. ... 

Since different reactivity is observed for both the stoichiometric and the catalytic version of the arene-promoted lithiation, different species should be involved in the electron-transfer process from the metal to the organic substrate. It has been well-established that in the case of the stoichiometric version an arene-radical anion [lithium naph-thalenide (LiCioHg) or lithium di-ferf-butylbiphenylide (LiDTBB) for using naphthalene or 4,4 -di-ferf-butylbiphenyl (DTBB) as arenes, respectively] is responsible for the reduction of the substrate, for instance for the transformation of an alkyl halide into an alkyllithium . For the catalytic process, using naphthalene as the arene, an arene-dianion 2 has been proposed which is formed by overreduction of the corresponding radical-anion 1 (Scheme 1). Actually, the dianionic species 2 has been prepared by a completely different approach, namely by double deprotonation of 1,4-dihydronaphthalene, and its X-ray structure determined as its complex with two molecules of N,N,N N tetramethylethylenediamine (TMEDA). ... 

An alternative mode of reactivity is observed for [Os]-naphthalene when the nucleophile for the tandem addition is built into the electrophile. The normal mode of reactivity results in the formation of cis-l,4-dihydronaphthalenes (vide supra), but when a solution of the methyl vinyl ketone Michael addition product 24 in methanol (Table 6, entry 1) and a catalytic amount of triflic acid are allowed to react, the complexed hydrophenanthrenone 25 is isolated in 89 % yield [18]. This reactivity results from the pendant ketone undergoing a tauto-merization to form an enol, which can then attack the allyl cation at C2. The stereochemistry of the nucleophilic addition is still anti to the face involved in the metal coordination, but the... 

Naphthalene oxides. The Diels-Alder reaction of 1,4-diacetoxybutadiene (1) with benzyne (generated from o-benzenediazonium carboxylate, 1, 46) gives the diacetate of l,4-dihydronaphthalene-cis-l,4-diol (2) in 53% yield. The product is converted into 3 by reaction with hydrogen peroxide and catalytic amounts of osmium tetroxide. The monotosylate of 3 is converted into 4 by treatment with base. This epoxy diol has the stereochemistry found in the carcinogenic epoxy diols formed as metabolites of aromatic hydrocarbons. The dimesylate of 3 is converted into the syft-diepoxide 5. 

---