Benzo hydrogenation

Pascal and coworkers found unexpectedly that pyrolysis of phencyclones 424 forms diaryltetrabenz[ ,c,/r,7 ]anthracenes 425 (Scheme 6.112) [261]. The compounds 425 possess large twists of the polyacene units (66, 61, and 70, respectively), because benzannulated acenes with phenyl groups positioned to clash with the benzo hydrogens give molecules with the largest end-to-end twists. 

In addition to CuCfi, some other compounds such as Cu(OAc)2, Cu(N03)2-FeCl.i, dichromate, HNO3, potassium peroxodisulfate, and Mn02 are used as oxidants of Pd(0). Also heteropoly acid salts comtaining P, Mo, V, Si, and Ge are used with PdS04 as the redox system[2]. Organic oxidants such as benzo-quinone (BQ), hydrogen peroxide and some organic peroxides are used for oxidation. Alkyl nitrites are unique oxidants which are used in some industrial... 

This volume is intended to present a comprehensive description of the chemistry of thiazole and its monocyclic derivatives, based on the chemical literature up to December, 1976. It is not concerned with polycyclic thiazoles, such as benzo- or naphthothiazole, nor with hydrogenated derivatives, such as thiazolines or thiazolidines later volumes in this series are devoted to these derivatives. The chemistry of thiamine has also been excluded from the present volume because of the enormous amount of literature corresponding to the subject and is developed in another volume. On the other hand, a discussion of selenazole and its monocyclic derivatives has been included, and particular emphasis has been given to the cyanine dyes derived from thiazolium salts. 

Ben zotricbl oride is hydrolyzed to benzoic acid by hot water, concentrated sulfuric acid, or dilute aqueous alkaH. Benzoyl chloride [98-88-4] is produced by the reaction of benzotrichloride with an equimolar amount of water or an equivalent of benzoic acid. The reaction is catalyzed by Lewis acids such as ferric chloride and zinc chloride (25). Reaction of benzotrichloride with other organic acids or with anhydrides yields mixtures of benzoyl chloride and the acid chloride derived from the acid or anhydride (26). Benzo triflu oride [98-08-8] is formed by the reaction of benzotrichloride with anhydrous hydrogen fluoride under both Hquid- and vapor-phase reaction conditions. 

The mass spectrum of 2-pyrone shows an abundant molecular ion and a very prominent ion due to loss of CO and formation of the furan radical cation. Loss of CO from 4-pyrone, on the other hand, is almost negligible, and the retro-Diels-Alder fragmentation pathway dominates. In alkyl-substituted 2-pyrones loss of CO is followed by loss of a hydrogen atom from the alkyl substituent and ring expansion of the resultant cation to the very stable pyrylium cation. Similar trends are observed with the benzo analogues of the pyrones, although in some cases both modes of fragmentation are observed. Thus, coumarins. 

As might be anticipated from the behaviour of the parent heterocycles, C-2 of indole, benzo[i]furan and benzo[i]thiophene (Table 13) is shifted to lower field than C-3. However, the shifts for C-2 (O, 144.8 Se, 128.8 S, 126.1 NH, 124.7 Te, 120.8) and C-7a (O, 155.0 Se, 141.3 S, 139.6 NH, 135.7 Te, 133.0) in the benzo[i] heterocycles vary irregularly (80OMR(l3)3l9), and the sequence is different to that observed for C-2 in the parent heterocycles, namely 0>Se>Te>S>NH. Also noteworthy is the upheld position of C-7, especially in indole and benzofuran, relative to the other benzenoid carbons at positions 4, 5 and 6. A similar situation pertains in the dibenzo heterocycles (Table 14), where not only are C-1 and C-8 shifted upheld in carbazole and dibenzofuran relative to the corresponding carbons in dibenzothiophene and fluorene, but similar, though smaller, shifts can be discerned for C-3 and C-6 in the former compounds. These carbon atoms are of course ortho and para to the heteroatom and the shifts reflect its mesomeric properties. Little variation in the carbon-hydrogen coupling constants is observed for these dibenzo compounds with V(qh) = 158-165 and V(c,h) = 6-8 Hz. 

Benzo[/i]quinoIines hydrogenation, 2, 329 Skraup synthesis, 2, 467 structure, 2, 110 synthesis, 2, 468 from benzindoline, 2, 491 from propargyinaphthylamines, 2, 416 Benzoquinolinium cations metabolism, 1, 234 Benzoquinolinium salts Beyer synthesis, 2, 474 Benzoquinolinones synthesis, 2, 448... 

Benzo[a]quinoIizinium bromide, 7-methyl-electrochemical reductions, 2, 534 Benzo[c]quinolizinium bromide ring opening, 2, 533 Benzo[c]quinolizinium chloride hydrogenation, 2, 536 Benzo[c]quinoIizinium chloride, 6-amino-synthesis, 2, 554... 

Oxidations of pyridopyrimidines are rare, but the covalent hydrates of the parent compounds undergo oxidation with hydrogen peroxide to yield the corresponding pyridopyrimidin-4(3 T)-ones. Dehydrogenation of dihydropyrido[2,3-(i]pyrimidines by means of palladized charcoal, rhodium on alumina, or 2,3-diehloro-5,6-dicyano-p-benzo-quinone (DDQ) to yield the aromatic derivatives have been reported. Thus, 7-amino-5,6-dihydro-1,3-diethylpyrido[2,3-d]-pyri-midine-2,4(lif,3f/)-dione (177) is aromatized (178) when treated with palladized charcoal in refluxing toluene for 24 hours. 

Hydrogen usually adds to benzo-annulated oxepins in the presence of noble-metal catalysts such as platinum or palladium with saturation of the nonbenzenoid C-C double bonds to give 6152,154 and 7.17-89-93... 

Hydrogen iodide has also been used as a catalyst for hydrogen exchange581, rate coefficients (lO7 ) at 25 °C for reaction with [2H]C6H4R being (R =) 2,3-benzo(l position of naphthalene), 500 4-Me, 40 2-Me, 21 4-Ph, 42 2-Ph, 10. The reaction was catalysed by added iodine, the rate being directly proportional to the concentration of this, and for the latter compound rates were measured... 

Mandelate and lactate esters have been found to generate diastereoselectivity in reactions of hydroxy-substituted quinodimethanes generated by thermolysis of benzo-cyclobutenols.88 The reactions are thought to proceed by an exo TS with a crucial hydrogen bond between the hydroxy group and a dienophile carbonyl. The phenyl (or methyl in the case of lactate) group promotes facial selectivity. 

The inhibitory function of the sulfur compounds then would appear to be to prevent the subsequent reaction of the initially formed ketyl radicals by catalyzing hydrogen transfer reactions. With this in mind, one can write the following mechanism for the inhibition of the photoreduction of benzo-phenone by sulfur compounds ... 

The hydrogen-labeled benzobarrelene indicates that the formation of benzo-cyclooctatetraene from the direct photolysis takes place predominantly via benzovinyl bridging<44) j... 

Benzyne reacts with benzene to give a mixture of products in low yield. The original experiments 38> showed that the 1,4-cyclo-adduct (benzo-barrelene) (19), the valence-bond isomerised 1,2-cyclo-adduct (benzo-cyclo-octatetraene) (20), and the product of insertion into a carbon-hydrogen bond (biphenyl) (21), were obtained in 2,8, and 6% yields respectively. 

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