Naphthalene-1-2-dicarboxylic acid anhydride

In polar solvents the excited state of sufficiently electron deficient arenes will accept an electron from donors. The fates of the radical ion pairs produced include formation of products of addition to the arene ring. A new example of this mode of reactivity is the photochemical reaction of 1,4-dicyanonaphthalene with benzyl methyl ether in acetonitrile. This yields stereoisomers of the addition product (120). The reaction most likely involves electron transfer from the ether to the naphthalene excited state and subsequent ionisation of a proton from the benzyl ether radical cation. This produces a benzyl ether radical which adds to the naphthalene derivative. An analogous sequence is proposed to explain the photochemical formation of (121)-(124) from ultra-violet light irradiated solutions of naphthalene-1,2-dicarboxylic acid anhydride in methanolic benzene or acetonitrile containing isobutene, 2-butene or 2-methyl-2-butene. Here it is suggested that the alkene radical cation, formed by electron transfer to the excited state of the naphthalene, is attacked by methanol deprotonation... 

Naphthalene dialdehyde, see Acenaphthylene Naphthalene-l,8-dicarboxylic acid, see Acenaphthene Naphthalene-2,3-dicarboxylic acid/anhydride, see... 

Also, when the reaction of 3,4-methylenedioxyphenylpropioIic acid 498 with DCC is conducted in dimethoxyethane below 0°C, it produces 6,7-methylenedioxy-l-(3, 4 -methylenedioxyphenyl)naphthalene-2,3-dicarboxylic acid anhydride 499." ... 

Acenaphthenequinone benzene, acetonitrile sun naphthalene-1,8-dicarboxylic acid anhydride 24)... 

Table 23 demonstrates the mesogenicity of polymers containing biphenylene-S j -tetracarboxylic imide. A comparison of series 9 and 10 in the table shows that replacement of pyromellitic dianhydride with BPTA in a copolymer with two moles of m-aminophenol and an aromatic diacid does not lead to mesogenic polymers. The assignment of an MI score of 4 compared to 2 for pyromellitic anhydride does however raise the MI as far as the borderline condition of MI=9.5 when 2,6-naphthalene dicarboxylic acid is the co-monomer. 

The addition of 4-aminophenol to compositions used commonly for poly-(ester)s allows the production of poly(ester amide)s. For example, a mixture of 2,6-naphthalene dicarboxylic acid, TPA, BP, HBA, and 4-aminophenol is condensed in the presence of acid anhydride. Such materials exhibit good soldering resistance so that they can be utilized as an electric or electronic material such as electric connectors, sockets for integrated circuits, etc. 

Naphthalene-1,8-dicarboxylic add, its nitro-substituted derivatives, and naphthalene- 1,4,5,8-tetracarboxyhc acid, on treatment with sulfur tetrafluoride at 0 °C, undergo dehydration to form quantitatively the corresponding anhydrides [218, 221] Unsubstituted and monomtrated monoanhydndes react further at 200-250 °C to give derivatives of 1,1,3,3-tetrafluoro-1H naph(lio[ 1,8 c,d]pyran Dmitronaphthalene-l,8-di-carboxyhc acid anhydrides and naphthalene 1,4,5,8 tetracarboxylic acid dianhydnde give the respective tetra- and octafluoroethers only in the presence of an excess of anhydrous hydrogen fluoride [2211 (equations 113 and 114)... 

A new class of diamine spacer was synthesised from a,co-diaminoalkanes and 4-nitrophthalic anhydride the resulting a, -bis(4-aminophthalimido)alkanes were polycondensed with one of the following acid chlorides terephthaloylchlo-ride, 2-phenylthioterephthaloylchloride, naphthalene-2,6-dicarboxylic acid or 4,4 -biphenyldicarboxylic acid chloride [40]. Thermotropic behaviour was con-... 

A reaction related to cleavage is aromatic ring degradation. Phthalic anhydride used to be prepared from naphthalene, and maleic anhydride from benzene, with air and V2O5 catalyst, losing 2 carbon atoms as CO2. More modern processes use o-xylene and butadiene (or -butane) respectively. However, the analogous formation of quinolinic (pyridine-2,3-dicarboxylic) acid from quinoline is still practised. Hypochlorite [94], hypochlorite or chlorite/Ru catalyst [95], or simply alkaline H2O2 [96] can be used. 

Anthraquinone itself is traditionally available from the anthracene of coal tar by oxidation, often with chromic acid or nitric acid a more modern alternative method is that of air oxidation using vanadium(V) oxide as catalyst. Anthraquinone is also produced in the reaction of benzene with benzene-1,2-dicarboxylic anhydride (6.4 phthalic anhydride) using a Lewis acid catalyst, typically aluminium chloride. This Friedel-Crafts acylation gives o-benzoylbenzoic acid (6.5) which undergoes cyclodehydration when heated in concentrated sulphuric acid (Scheme 6.2). Phthalic anhydride is readily available from naphthalene or from 1,2-dimethylbenzene (o-xylene) by catalytic air oxidation. 

Alkylacenaphthylenes (115), in which R is ethyl, n-propyl, or isopropyl, likewise give both dehydrogenation and bridging products on treatment with sulfur at 185°C the parent compound acenaphtho[l,2-b]thiophene 39), its 8-methyl (116, R = CH3 R = H m.p. 61.5°C) and 9-methyl derivative (116, R = H R = CH3 m.p. 127°C) are formed, respectively, in yields of 15%. 9 The methyl products were characterized by the formation of acetoxymercuri and benzoyl derivatives, wherein substitution was believed to occur in the thiophene ring. The structure of the 8-methyl-9-benzoyl derivative was verified by chromic acid oxidation to naphthalene-1,8-dicarboxylic anhydride. 

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