Syntheses from Naphthalene Derivatives

On condensation of peri-hydroxynaphthaldehydes with the Fischer base (82KGS1501) or with 1,3,3-trimethylisobenzofurylium perchlorate (86DOK639), 2-substituted heterocyclic 2//-naphtho[6c]furan derivatives 

37 and 39 have been obtained. Heterocyclization of the condensed product 

38 proceeds by the action of bases and results in ring-closed five- and seven-membered heterocycles. Compounds 39 and 40 thus formed have been separated by chromatography. 

Naphtho[bc]furan derivatives are formed from peri-hydroxy-naphthylbenzyl ketone 49 by acidic or basic catalysis (83ZOR41I  

86ZOR2398). Thus, on heating this compound in glacial acetic acid or in formyl acetate in the presence of sodium formate, 2-benzyIidene-5-methoxynaphtho[frc]furan 50 has been obtained, whereas extended boiling of 49 in a mixture of acetic anhydride and triethylamine has led to C-acetyl derivative 51. 

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Many valuable chemicals can be recovered from the volatile fractions produced in coke ovens. Eor many years coal tar was the primary source for chemicals such as naphthalene [91-20-3] anthracene [120-12-7] and other aromatic and heterocycHc hydrocarbons. The routes to production of important coal-tar derivatives are shown in Eigure 1. Much of the production of these chemicals, especially tar bases such as the pyridines and picolines, is based on synthesis from petroleum feedstocks. Nevertheless, a number of important materials continue to be derived from coal tar. 

Anthraquinone dyes are derived from several key compounds called dye intermediates, and the methods for preparing these key intermediates can be divided into two types (/) introduction of substituent(s) onto the anthraquinone nucleus, and (2) synthesis of an anthraquinone nucleus having the desired substituents, starting from benzene or naphthalene derivatives (nucleus synthesis). The principal reactions ate nitration and sulfonation, which are very important ia preparing a-substituted anthraquiaones by electrophilic substitution. Nucleus synthesis is important for the production of P-substituted anthraquiaones such as 2-methylanthraquiQone and 2-chloroanthraquiaone. Friedel-Crafts acylation usiag aluminum chloride is appHed for this purpose. Synthesis of quinizatia (1,4-dihydroxyanthraquiQone) is also important. 

Besides the technical method starting from naphthalene, phthalic acid and its substituted derivatives can be prepared by oxidation of o-xylene to phthalic acid with potassium permanganate. This compound can be subsequently transformed via an anhydride, imide, and amide to a derivative of phthalonitrile, which is the more convenient starting material for several coordination compounds. The synthesis of the ferf-butyl-substituted dicarbonitrile, which is a very common starting material for highly soluble phthalocyanines, is shown below.97,105... 

Kwakman et al. [65] described the synthesis of a new dansyl derivative for carboxylic acids. The label, N- (bromoacetyl)-A -[5-(dimethylamino)naphthalene-l-sulfonyl]-piperazine, reacted with both aliphatic and aromatic carboxylic acids in less than 30 min. Excess reagent was converted to a relatively polar compound and subsequently separated from the derivatives on a silica cartridge. A separation of carboxylic acid enantiomers was performed after labeling with either of three chiral labels and the applicability of the method was demonstrated by determinations of racemic ibuprofen in rat plasma and human urine [66], Other examples of labels used to derivatize carboxylic acids are 3-aminoperylene [67], various coumarin compounds [68], 9-anthracenemethanol [69], 6,7-dimethoxy-l-methyl-2(lH)-quinoxalinone-3-propionylcarboxylic acid hydrazide (quinoxalinone) [70], and a quinolizinocoumarin derivative termed Lumarin 4 [71],... 

Another possibility to increase the diastereoselectivity in an asymmetric synthesis can arise from different thermodynamic stabilities of the diasteieoisomeric products. If the thermodynamic stabilities of these are different enough, then, under conditions of equilibrium, a complete conversion of the less stable into the more stable can be achieved. For example, the diastereoselective hydrogenation of naphthalene derivates over Pd/C catalyst leads to a mixture of dihydronaphtalenes in which the cA-isomer predominates. The conversion of this isomer into the tram occurs by changing the properties of the reaction medium, namely by equilibration with a base. For such a purpose, NaOMe in IHF can be used [263], Generally, such an increase in stability in the six-membered rings can result from a rearrangement of the substituents from an axial to an equatorial position. 

While the condensation of amines with nitroso compounds appears to have wide applicability in the benzene series, it seems to lead to complex dye molecules in the naphthalene series. A method has been developed using a somewhat complex reaction between thionylamines and substituted hydroxylamines which does produce azo compounds derived from naphthalenes. This synthesis is of particular interest because it helped to settle the question whether true naphthylazo compounds with hydroxyl groups could exist [36]. 

The structure of the substrates is not necessarily restricted to monocyclic aromatic compounds such as those shown in Scheme 16.1-2. The dioxygenase activity of Pseudomonas putida and Beijerinckia species has been used exclusively for the synthesis of cis dihydrodiols from polycyclic 202 and heterocyclic 203 derivatives. Such products have been obtained from naphthalene, anthracene, phenanthrene, benz[a]pyrene, benz[a]anthracene, and methylsubstituted benz[a]anthracenes, and... 

Naproxen derived from naphthalene acetic acid analogue proved to be the leading compoimd of an extensive series of promising elinieal agents. Deseribe its synthesis from 6-methoxy naphthalene. 

Hantzsch s first important research was the synthesis of pyridine from acetoacetic ester and aldehyde ammonia, a general method of synthesis of pyridine derivatives. Coumarone, discovered by Fittig and Ebert (see p. 768), was (with some derivatives) synthesised by Hantzsch, who called it the fur-furane of the naphthalene series . He synthesised thiazole, and benzene, pyridine, and thiophen derivatives from derivatives of pentamethylene, and pyrrole, investigated tetrazoles, and perthiocyanic acid C2N2S3H2 (discovered by Wohler), giving it a cyclic structure." ... 

Chen, X., Yin, Y., Tanaka, K., Kita, H., Okamoto, K.I. (2006) Synthesis and characterization of novel sulfonated polyimides derived from naphthalenic dianhydride. High... 

Wolff—Kizhner methods led to the corresponding isomer of dehydro-doiS5molic acid (178) [284, 285], An attempt at the direct synthesis of (178) by the condensation of the diene (169) with oj-methyl-/ -acrylic acid was unsuccessful because of the undesirable structural directivity [286]. A repetition of the Arndt—Eistert reaction with (175) and Dieckmann cy-clization of the diester obtained (176) yielded the cis-C/D isomer of 8(9)-dehydroestrone (179) [287]. Dehydrogenation of the adduct (173) led to a naphthalene derivative (174), opening of the anhydride ring in which gave the semiester (177). The methyl ether of cis-equilenin (37) was obtained from the latter by two extensions of the side chain by the Arndt—Eistert reaction and by cyclization [283]. 

The corannulenes are the simplest examples of compounds with a curved surface. They include fluoranthenes that are important synthetic intermediates in the construction of corannulenes and their derivatives. Indenofluoranthenes have a curvature of a higher order due to the inclusion of two 5-membered rings. Methods for the synthesis of fluoranthenes from naphthalene and indenocorannulenes from corannulenes offer approaches to the formation of high-order spherical and tubular structures. 

The synthesis of fluoranthene derivatives from l,8-his(arylethynyl)-naphthalenes 2.337 and alkynes 2.338 includes formal [(2- -2)- -2] cycloaddition [164, 165]. This method has been successfully applied... 

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