Synthesis of Substituted Naphthalenes

SCHEME 17.7 Synthesis of substituted naphthalenes from l-(2-allyl-3-isopropoxy-4-methoxyphenyl) prop-2-en-l-ol. (Reprinted with permission from Ref. [10]. Copyright (2009) American Chemical Society). 

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Fig. 5.34. Steps 1-3 of the five-step Haworth synthesis of substituted naphthalenes.

Huang, Q., Larock, R. C. Synthesis of Substituted Naphthalenes and Carbazoles by the Palladium-Catalyzed Annulation of Internal Alkynes. J. Org. Chem. 2003, 68, 7342-7349. 

An overview of the effect of catalyst in the reaction of arenes with chromium hexacarbrmyl has been published. The reactivity of 17-, 18-, and 19-etectron catkMis generated electrochemically from mesitylene-tungsten tricarbonyl has been examined. The gas phase ion chemistry of a range of arene tricarbonylchromium complexes has been investigated by F.T. mass spectrometry. An improved synthesis of substituted naphthalene chromium carbonyls has appeared. ... 

A further example is given below illustrating the use of a dibasic anhydride (succinic anhydride) the succinoylation reaction is a valuable one since it leads to aroyl carboxylic acids and ultimately to polynuclear hydrocarbons. This general scheme of synthesis of substituted hydrocarbons through the use of succinic anhydride is sometimes called the Haworth reaction. Thus a-tetralone (see below) may be reduced by the Clemmensen method to tetralin (tetrahydronaphthalene) and the latter converted into naphthalene either catal3d.ically or by means of sulphur or selenium (compare Section, VI,33). 

The naphthalene-catalyzed (2.5%) lithiation of phthalan 330 (or its substituted derivatives ) in THF at room temperature allowed the preparation of the functionalized benzyllithium intermediate 331, which reacted with electrophiles at —78°C to give, after hydrolysis, the corresponding functionalized benzyl alcohols 332 (Scheme 97). When carbon dioxide was used as the electrophilic reagent, the corresponding 5-lactone was directly obtained . When carbonyl compounds were used as electrophiles, the cyclization of the resulting products 332 under acidic conditions (85% H3PO4) allows the synthesis of substituted isochromans. 

The attempted synthesis of [njcyclophenacenes has also been reported. Kuwata-ni and coworkers reported the synthesis of a pentabenzo[20]annulene, as a possible precursor to [10]cyclophenacene (Scheme 2.3) [16]. Light-induced electrocycli-zation of the precursor was unsuccessful because of isomerization of the (Z)-olefin into the (E)-olefin, which undergoes an undesirable transannular reaction [17]. St. Martin and Scott tried to synthesize [12]cyclophenacene, but attempts at the macrocyclic oligomerization of substituted naphthalene and phenanthrene building blocks by flash vacuum pyrolysis method were unsuccessful [18]. 

The first two transition-metal complexes of 2-naphthalyne78 have been prepared79 to be used as intermediates in the synthesis of polysubstituted naphthalenes. The naphthalyne intermediate 206, prepared from 205 [Eq. (31)], couples with a wide array of nitriles to give zirconocycles (207) that have been converted into substituted naphthalenes (208) by reaction with HC1 and iodonaphthalenes (209) by reaction with I2 followed by HC1. The... 

Electra-organic synthesis Chlorination of substituted naphthalenes. Toluene and aromatic hydrocarbon oxidation using Ce as a redoxmediator. Anthracene oxidation to anthraquinone using Mn as the redox medi ator. Forsyth et al. (1987) Pletcher Valdez (1988a,b) Chou etal. (1992)... 

Rate and Regioselectivity in the Nitration of (Trifluoromethyl)benzene 474 Substituent Effects in Electrophilic Aromatic Substitution Activating Substituents 476 Substituent Effects in Electrophilic Aromatic Substitution Strongly Deactivating Substituents 480 Substituent Effects in Electrophilic Aromatic Substitution Halogens 482 Multiple Substituent Effects 484 Retrosynthetic Analysis and the Synthesis of Substituted Benzenes 486 Substitution in Naphthalene 488 Substitution in Heterocyclic Aromatic Compounds 489... 

S.S. Chobe, R.D. Kamble, S.D. Patil, A.P. Acharya, S.V. Hese, O.S. Yemul, B.S. Dawane, Green approach towards synthesis of substituted pyrazole-l,4-dihydro-9-oxa-l,2,6,8-tetraazacyclopentano[i ]naphthalen-5-one derivatives as antimycobacterial agents, Med. Chem. Res. 22 (2013) 5197-5203. 

Synthesis of Substituted Benzenes The coupling reaction of zircona-cyclopentadiene with halogenated arenes provides a direct method of aromatic ring extension. As shown in Scheme 11.25, the reaction of zirconacyclopentadienes 4 with diiodobenzene in the presence of CuCl and DMPU afforded 1,2,3,4-tetra-substituted naphthalenes 60 in good yields. When tetraiodobenzene was used under similar conditions, 1,2,3,4,5,6,7,8-octa-substituted anthracene derivatives 61 could also be prepared [28]. 

Moreover, they are versatile building blocks for the synthesis of functionalized naphthalenes, anthracenes, and naphthacene natural products [8]. Recently, Rh-catalyzed C-H activation followed by nucleophilic addition to aldehydes emerged as a powerful alternative to access phthalides. In 2012, Li and coworkers developed a novel Rh(III)-catalyzed synthesis of three substituted phthalides from benzoic acids and aldehydes through carboxylate-directed ortho-C-H functionalization and subsequent intramolecular cyclization (Scheme 6.2a) [9]. In 2013, GooCen and coworkers described the straightforward synthesis of S-alkylidenephthalides from benzoic acids and aliphatic acids or anhydrides in the presence of [Rh(cod)Cl]2 and CsF (Scheme 6.2b) [10]. 

The first reaction was involved in a synthesis of morphine, the starting ketone being made by reduction of a substituted naphthalene O. Amer. Chem. Soc., 1950, 72, 3704). No doubt an epoxide could have been used as the electrophile. 

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. 

Although the sulfone activated biphenyl and the ketone activated naphthalene moiety for the displacement polymerization have been reported by Attwood et al. [11], these were rediscovered by Cummings et al. [12] and Hergenrother et al. [13], respectively, for the synthesis of poly(aryl ethers). Recently, Singh and Hay [14] reported polymers containing 0-dibenzoyl benzene (1,2,3) moiety by reaction between bis(O-fluorobenzoyl) benzene or substituted benzene with bisphenates of alkali metal salt in DMAC as follows ... 

Some thermal rearrangement reactions of 1-benzoxepins show the participation of the solvent in the formation of stable products, e.g. 6172,247 and 7.177 The synthesis of methoxy-substituted 1-benzoxepins by O-methylation of the anions generated by the deprotonation of the respective oxo derivative with ferf-butoxide is often limited by the rapid aromatization to methoxy-substituted naphthalenes, e.g. 816 and 9,173 under the reaction conditions.16,173... 

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... 

Isomerization of 1,3-dienes (12, 36).3 The 1,5-hydrogen shift in isomerization of 1,3-dienes catalyzed by (naphthalene)Cr(CO)3 (1) can be used for synthesis of aryl-substituted exocyclic alkenes, which are not readily available by coupling of aryl halides with exocyclic vinyl halides. 

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