Naphthalene 1,2 dicarboxylic, anhydride

Photolysis of aromatic lactones and anhydrides, such as naphthalene-1,2-dicarboxylic anhydride (339), gives arynes (in this case 340)1039 as reactive intermediates.1040 Matrix isolation spectroscopy (Section 3.10) then allows their study along with other exotic molecules, which are formed as primary or secondary (photo)products (Scheme 6.150). 

With cyclic materials in which the CO groups form part of a five-membered ring, the influence of ring strain induces a shift to higher frequencies, similar to that found in cyclic ketones and lactones with five-membered rings. Succinic anhydride [ 1 ], for example, absorbs at 1865 cm" and 1782 cm". In cyclic materials also, conjugation lowers these values to some extent, so that differentiation between an a 3-unsaturated cychc anhydride and a saturated open-chain anhydride is not always possible on the basis of the carbonyl absorptions alone. Typical values for unsaturated cyclic products are 1845 cm" and 1775 cm" for phthalic anhydride [4], and 1848 cm" and 1790 cm" for maleic anhydride [4]. Naphthalene-1 2-dicarboxylic anhydride and some substituted derivatives [7] absorb at 1848—1845 cm" and 1783—1779 cm". In the case of cyclic six-membered ring anhydrides condensed to aromatic systems a much smaller separation... 

Products from Naphthalene Dicarboxylic Anhydrides with Benzene... 

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. 

The list of suitable substituents includes acylamino groups, but especially halogen atoms such as chlorine or bromine. Halogenated derivatives are obtained from tetrahalogen phthalic anhydride or naphthalene-2,3-dicarboxylic anhydride, by... 

Other aromatic anhydrides also exhibit parallel behavior upon electrou impact and pyrolysis. The mass spectra of naphthalene-2,3-dicarboxylic anhydride and 1,8-naphthalic anhydride are qualitatively similar (Fields and Meyerson, 1967d) ... 

The ions of mass 126 from naphthalene-2,3- and -1,8-dicarboxylic anhydrides in the mass spectrometer may well be identical. At one atmosphere pressure in the vapor phase, however, the analogous neutral... 

Both naphthalene-1,8- and -2,3-dicarboxylic anhydrides sequentially lose carbon dioxide and carbon monoxide upon electron impact to give an ion of mass 126, nominally naphthalyne, as was shown in Section C. In addition, both spectra show a peak of moderate intensity at mass 76, corresponding to an ion having at least the elemental composition of benzyne, suggesting the sequence ... 

Anthracnose caused by infection with a fungus Colletotrichum musae is a common disease of banana, Musa acuminata. The unripe green fruit of banana shows resistance to the growth of fungal hyphae, and the pathogen is quiescent until the fruit ripens. Phytoalexins produced by the unripe fruit were isolated by Hirai et al., and 2-(4-hydroxyphenyl)naphthalene-l,8-dicarboxylic anhydride (44, Figure 2.29) was identified as the major and the strongest component of the phytoalexins.93... 

Figure 2.29 Synthesis of 2-(4-hydroxyphenyl)naphthalene-1,8-dicarboxylic anhydride, a banana phytoalexin...

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. 

Thiophen Analogues of Polycyclic Aromatic Hydrocarbons Analogues of Anthracene and Phenanthrene. - Keto-enol tautomerism in a naphtho- and several anthra-thiophen systems [such as (241) (242)] has been studied. The system (241) (242) was obtained via the Friedel-Crafts reaction of thiophen with naphthalene-2,3-dicarboxylic anhydride followed by ring-closure. A [c] -fused system was similarly obtained by starting from... 

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. 

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. 

ClaHi6O3, 1,2,3,4,4a,5,6,7,8,8a-Decahydro-1,4,5,8-exo,endo-dimeth-anonaphthalene-4a,8a-dicarboxylic anhydride, 46B, 320 ClaHi6O3, 1,2,3,4,4a,5,6,7,8,8a-Decahydro-1,4,5,8-exo,exo-dimethano-naphthalene-4a, 8a-dicarboxylic anhydride, 46B, 320 ClaHi6O3 f 4-Methoxy-6-(1, 2 -dihydrostyryl)-5,6-dihydro-a-pyrone, 38B, 335... 

Naphthalene-1,8-dicarboxylic add, its nitro-substituted derivatives, and naphthalene-1,4,5,8 tetracarboxylic acid, on treatment with sulfur tetrafluoride at 0 C, undergo dehydration to form quantitatively the corresponding anhydrides [218, 221] Unsubstituted and mononitrated monoanhydndes react further at 200-250 °C to give derivatives of 1,1,3,3-tetrafluoro-l// naphtho[I,8 c,d]pyran Dinitronaphthalene-l,8-di-carboxyhc acid anhydndes 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 [221] (equabons 113 and 114)... 

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

On the basis of the formal similarity between 1,8-diamino-naphthalene and 3,4-diaminothienothiophene (1) the latter might be able to form a fused pyrimidine system on reaction with orthoformic ester or formamide. However, heating dimethyl 3,4-diaminothieno[2,3-6]-thiophene-2,5-dicarboxylate with acetic anhydride gave the corresponding MiV -diacetyl derivative, while 3,4-diacyloxy derivatives resulted from analogous reaction of dimethyl 3,4-dihydroxythieno-[2,3-6]thiophene-2,5-dicarboxylate with orthoformic ester and acetic anhydride."... 

Benzo[Z> jthiophene 1,1-dioxide cycloadds to acetylenedicarboxylic ester to yield naphthalene-1,2-dicarboxylic ester after extrusion of S02. However, maleic anhydride and benzoquinone are reported not to react with benzo[Z>]thiophene dioxide (70AHC(ll)l77). 

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." ... 

---