Tetralin reaction with

Dihydioxytetiahydionapthacenedione derivatives, used as intermediates for the anthracycline antibiotics have been prepared by Friedel-Crafts reaction of tetralin derivatives with orthophthaloyl chlotide [88-95-9J in high yields (93). 

A remarkable feature of the Birch reduction of estradiol 3-methyl ether derivatives, as well as of other metal-ammonia reductions, is the extreme rapidity of reaction. Sodium and -butyl alcohol, a metal-alcohol combination having a comparatively slow rate of reduction, effects the reduction of estradiol 3-methyl ether to the extent of 96% in 5 minutes at —33° lithium also effects complete reduction under the same conditions as is to be expected. Shorter reaction times were not studied. At —70°, reduction with sodium occurs to the extent of 56 % in 5 minutes, although reduction with lithium is virtually complete (96%) in the same time. (The slow rates of reduction of compounds of the 5-methoxytetralin type is exemplified by 5-methoxy-tetralin itself with sodium and f-butyl alcohol reduction occurs to the extent of only 50% in 6 hours vs. 99+% with lithium.) The iron catalyzed reaction of sodium with alcohols must be very fast since it competes so well with the rapid Birch reduction. One cannot compensate for the presence of iron in a Birch reduction mixture containing sodium by adding additional metal to extend the reaction time. The iron catalyzed sodium-alcohol reaction is sufficiently rapid that the aromatic steroid still remains largely unreduced. 

That the reaction with a lower rate constant is taking place preferentially and that the rate increases during the reaction are phenomena that can also occur with parallel reactions. As an example, Wauquier and Jungers (48), when studying competitive hydrogenation of a series of couples of aromatic hydrocarbons on Raney-nickel, have observed these phenomena for the couple tetraline-p-xylene (Table I). The experimental result was... 

These results suggest that the transition states leading to the formation of the cyclo-adducts (33) and (34) are product-like and that the greater than statistical formation of adducts (34) is due to the increased thermodynamic stability of a trisubstituted double bond. In agreement with this explanation is the fact that in reactions with for example p-xylene and durene (1,2,4,5-tetramethylbenzene) only the adducts (35) and (36) were obtained 54-59). Also as expected, two adducts were obtained with tetralin but only the compound (37) was obtained using 5,8-dimethyltetralin, which we may regard as a 1,2,3,4-tetra-alkylben-zene 54>. 

In the work now reported coal fractions derived from a solubilised coal were reacted individually with Tetralin, without any additions of catalyst or gaseous hydrogen, and the reaction products studied to determine the effect that chemical type had on the reaction. The untreated whole coal was also reacted to test whether phenol, present in the coal fractions as a result of the fractionation procedure, was having any significant effect on the reaction with the fractions. 

Recovery of Coal Material from the Reaction with Tetra in. The yields of the different products from the reactions of the various fractions with tetralin are summarised in Table II. 

Yields of Original Coal Fractions and their Products of Reaction with Tetralin, g/lOOg Original Dry Coal. 

The nmr analyses of the bottoms products given in Table IV show the material to have a large aliphatic content. The aromatic/aliphatic ratios of the fractions are higher than for the whole coal because of the presence of combined phenol reaction with Tetralin reduces these ratios considerably, presumably by transfer of much of this material to the solvent-range product, but some of it must remain in the bottoms as the aromatic/aliphatic ratio of the composite bottoms product from the fractions is higher than that from the whole coal. It was not possible to calculate the contribution that the diluents, excess solvent and combined phenol, made to the aromatic H, but the large monoaromatic content of the bottoms product must be due, in part, to these. 

The main part of this research deals with the reaction of deuterium gas and Tetralin-d12 with a bituminous coal. In a separate experiment, naphthalene-d8 was used for investigating the chemistry of hydrogen transfer between coal and a nondonor solvent. In each experiment, the coal products and spent solvent were analyzed for toal deuterium content and for deuterium incorporation in each structural position. 

Sym-octahydrophenanthrene (HgPh) would be expected to follow the same rearrangement-dehydrogenation reactions as Tetralin, except with more isomer and product possibilities. The reactions shown in Figure 1 illustrate the many structures expected from sym-HgPh in the presence of free radical acceptors. Unlike Tetralin, hydrophenanthrenes have multiple structures which each, in turn, form various isomers. The amounts of these isomers are dependent upon the type of hydrogen-transfer reactions and the environment of the system. 

When reactions with oxygen-containing acceptors were performed [3] in the 300-400°C region, the formation of adducts occurred with both Tetralin and mesitylene. This reaction was observed when benzyl radicals were generated from dibenzyl ether, dibenzyl sulfide, benzyl alcohol, and benzaldehyde. 

Aryl phosphites inhibit the initiated oxidation of hydrocarbons and polymers by breaking chains on the reaction with peroxyl radicals (see Table 17.3). The low values of the inhibition coefficient / for aryl phosphites are explained by their capacity for chain autoxidation [14]. Quantitative investigations of the inhibited oxidation of tetralin and cumene at 338 K showed that with increasing concentration of phosphite /rises tending to 1 [27]. 

The effectiveness of complexes metal-acetylacetonate with tris(l,l-dimethylethyl-4-methylphenyl) phosphite in their reaction with peroxyl radicals of styrene and tetralin (323 K) decreases in the row Co2+ > V02+ > Cr3+ > Fe2+ [88]. 

Materials. Chemically pure solvents and reagent grade ceric ammonium nitrate were used as received. Cumene hydroperoxide was purified via the sodium salt. Lucidol tert-butyl hydroperoxide was purified by low temperature crystallization. Tetralin hydroperoxide, cyclohexenyl hydroperoxide, and 2-phenylbutyl-2-hydroperoxide were prepared by hydrocarbon oxidation and purified by the usual means. 1,1-Diphenyl-ethyl hydroperoxide and triphenylmethyl hydroperoxide were prepared from the alcohols by the acid-catalyzed reaction with hydrogen peroxide (10). 

When a slow steady-state autoxidation of a suitable hydrocarbon is disturbed by adding either a small amount of inhibitor or initiatory a new stationary state is established in a short time. The change in velocity during the non-steady state can be followed with sensitive manometric apparatus. With the aid of integrated equations describing the nonsteady state the individual rate constants of the autoxidation reaction can be derived from the results. Scope and limitations of this method are discussed. Results obtained for cumene, cyclohexene, and Tetralin agree with literature data. 

Thioketals are readily prepared by treating the corresponding ketone with ethanedithiol and propane-1,3-dithiol. The 12-ketone fails to react with monothiols such as ethanethiol or thiophenol92 or with the bulkier 1-phenylethane-1,2-dithiol or tetralin-2,3-dithiol.93 The A9(11)-12-ketone readily forms a thioketal on reaction with ethanedithiol.28 The selective protection of 11,12-diones (83) as the 12-monothioketals (84) is possible due to the poor reactivity of the 11-ketone.46,10... 

Less activity than that observed in the HDS reaction is seen for the hydrogenation of naphthalene (Figure 27.6(b)). All three catalysts exhibit comparable hydrogenation activity as evidence by the rates in Table 27.3. Tetralin is found to be the main product of the reaction with little decalin produced. Even though the sulfated hematite shows the highest percentage of hydrogenation, the oxynitride and the oxycarbide are more active per unit area of catalyst (Table 27.3). 

More important, they are less selective in reactions with tetralin. The presence of sulfur containing compounds in the macerals has a notable influence on their reactivity in hydrogen transfer reactions. 

Figure 2. Order of reaction with respect to Tetralin hydroperoxide at 80° C.

For model compound studies in excess tetralin, reaction 13 will occur with a pseudo-first-order rate constant k/s l ... 

Materials. Tetralin, purchased commercially, was passed over activated alumina and stored under argon before use. In order to correctly identify the isomer of methylindan found in the product mixtures, authentic 1- and 2-methylindans were prepared from the corresponding indanones by reaction with methyl-magnesium iodide, dehydration, and subsequent hydrogenation over Pd on asbestos. 

Figure 4. Yields of 1-methylindan and naphthalene and the ratio of trans/cis Decalin as a function of pyrite concentration after reaction with Tetralin at 450°C for 15 min...

Azido-5-formyl-l,3-dimethyluracil is cyclized with hydrazines to afford pyrazolo[3,4-reaction with triphenylphosphine in benzene result in the formation of isoxazolo[3,4-c/]pyrimidine and pyrimido[4,5-[Pg.182]

Cocker et al found the tetralin derivative (1) to be dehydrogenated normally by sulfur at 230-240° but to lose the n-buty1 group to give (3) on reaction with selenium at 330-350°. Dehydrogenation with palladium charcoal at 260-280° gave a mixture of (2) and (3). 

---