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International audience; The design of photoinitiators of polymerization is an active research field and the development of initiators activable in the visible range and under low light intensity have been the focus of numerous research efforts from both the academic and industrial communities. Recently, two families of polyaromatic compounds, i.e. 1,8-naphthalic anhydride and naphthalimides, have been extensively studied by different research groups due to their easiness of synthesis and the possibility to easily tune the photophysical properties. Especially, panchromatic, crosslinkable or water-soluble photoinitiators could be easily developed starting from the benchmark and cheap 1,8-naphthalic anhydride. In this review, an overview of the different photoinitiators based on naphthalic anhydride or the naphthalimide scaffold is presented. Based on the diversity of structures reported in the literature, a structure-performance relationship could be established in this review.

The tailored synthesis of homo (A2) and hetero (AB) N-substituted peri-xanthenoxanthene diimides (PXXDIs) and peri-functionalized PXX monoimides (PXXMIs) from 3-hydroxy naphthalic anhydride is described. As A2-type PXXDIs could be synthesized in one step, AB-type PXXDIs and PXXMIs were prepared through a modular approach capitalizing on sequential Suzuki coupling, imidation, and Pummerer reactions with very high yields. In view of their potential applications as organic semiconductors, self-organization studies were performed through liquid deposition on surfaces, depicting the formation of islands, needles, and rods.

Room temperature phosphorescence (RTP) emission was achieved by host–guest recognition between γ-cyclodextrin (γ-CD) and a 4-bromo-1,8-naphthalic anhydride (BrNpA) polymer (poly-BrNpA), which can be controlled by the photo-isomerization of the azobenzene (Azo) unit of the other polymer (poly-Azo) in aqueous solution.

Two groups of new naphthalene-1,8-dicarboxylic acid derived compounds, 6-amino-1,8-naphthalic anhydride derivatives and 2-hydroxy-6-amino-1,8-naphthalimide derivatives, have been synthesized and characterized. The spectroscopic properties of all synthesized compounds were investigated in order to be used in the field of bio-imaging studies and as intermediates for the preparation of new fluorescent bioactive compounds. Positive solvatochromism was observed from non-polar to polar solvents and it was discussed using Catalan multilinear regression analysis. Comparative study of the photophysical characteristics of naphthalic anhydride and 1,8-naphthalimide derivatives was performed. The new naphthalic anhydride 6-(4-benzyl-piperazin-1-yl)benzo[de]isochromene-1,3-dione (3) presents the highest value of fluorescence quantum yield in solvents with lower polarities. The results demonstrate that the quantum yields values of naphthalic anhydride derivatives are higher than those of naphthalimide derivatives.

The liquid-phase oxidative carbonylation of aromatics leading to aromatic carboxylic acids is studied to develop new approaches to 2,6-naphthalenedicarboxylic acid (NDA) preparation. It is shown that the catalytic system Pd(OAc) 2 /K 2 S 2 O 8 allows the synthesis of naphthalic anhydride (NAn) by direct oxidative carbonylation of naphthalene under mild conditions (25 °С, 2 atm СО). The subsequent alkaline hydrolysis of NAn and isomerization of the obtained 1,8-naphthalenedicarboxylic acid salt is known to lead to NDA.

The reaction of (Z)-2-amino-N′-arylbenzimidamides with 1,8-naphthalic anhydride in ethyl alcohol under reflux conditions gave benzo[4,5] isoquinolino[2,1-a]quinazoline derivatives in good yield.

The quaternisation of tertiary amines (triethylamine, pyridine and 1, 4-diaza-[2, 2, 2] bicyclooctane) by cyclic anhydrides (phthalic, 4-nitro, 3-nitro-, 3, 5-dinitro, 3, 6-dichloro-and tetrachlorophthalic, naphthalic anhydride) is studied in aprotic media. It appears that the reaction is strongly dependent on substituent and solvent effects. In every case a charge-transfer complex is formed between the two reactants. This complex is a real intermediate on the reaction path. The activation parameters favour the resulting complex mechanism.

New sulfonated and non-sulfonated monomers — dinitro and diamino compounds — were prepared on the basis of 1,3,5-trinitrobenzene (TNB) which is the demethylation product of 2,4,6-trinitrotoluene (TNT). The sulfonated dinitrocompounds interacted with different binuclear bis-phenols under the conditions of aromatic nucleophilic nitrodisplacement reactions. Polyethers of moderate molecular weights were prepared on the basis of dinitrocompound containing electron-withdrawing 3,5-dinitrodiphenyl sulfone-4′-sulfonic acid “bridging” groups. Copolymers and blends with other sulfonated polymers were prepared to improve the film-forming properties of the polyethers developed on the basis of 3,5-dinitrodiphenyl sulfone-4′-sulfonic acid. High molecular weight sulfonated polynaphthylimides were prepared by the interaction of sulfonated diamine containing electron-donating ether group — 3,5-diaminodiphenyl ether-4′-sulfonic acid — with bis(naphthalic anhydride)s. The sulfonated polyethers and polynaphthylimides thus obtained contain sulfonic acid groups in the side chains.

The chemistry of formation of products of acenaphthene oxidation in the presence of the catalyst containing both manganese and cobalt bromides under batch conditions is discussed. The main reaction products are acenaphthene quinone, acenaphthenol-9, trans-acenaphthylene glycol, naphthalide, and naphthalic anhydride. The sequence of reactions leading to the final products is established. It is shown that the main oxidation product in the presence of the manganese-based catalyst is naphthalic anhydride, and the main product in the presence of the cobalt-based catalyst is acenaphthene quinone. The process and engineering techniques providing for the high overall and fractional yields of the desired products are discussed.

The liquid-phase oxidative carbonylation of aromatics leading to aromatic carboxylic acids is studied to develop new approaches to 2,6-naphthalenedicarboxylic acid (NDA) preparation. It is shown that the catalytic system Pd(OAc) 2 /K 2 S 2 O 8 allows the synthesis of naphthalic anhydride (NAn) by direct oxidative carbonylation of naphthalene under mild conditions (25 °С, 2 atm СО). The subsequent alkaline hydrolysis of NAn and isomerization of the obtained 1,8-naphthalenedicarboxylic acid salt is known to lead to NDA.

A new water-soluble saccharide receptor based on a naphthalic anhydride fluorophore was synthesized from 3-aminophenylboronic acid. The large change in fluorescence intensity (IIo=ca. 0.25) and measured pKa (7.7) make this compound a useful chemosensor at neutral pH.

In the presence of a strong Lewis base, such as Et3N, trithio-1,8-naphthalic anhydride (3) is easily oxidized. Two improved syntheses of trithio-1,8-naphthalic anhydride (3) are described. Trithio-1,8-naphthalic anhydride (3) undergoes Diels-Alder reactions with electron-deficient alkenes to give novel fused heterocyclic compounds (6–11) that then can undergo a novel, gradual desulfuration dimerization with triethyl phosphite to afford 12 and its analogs 13 and 14. The structures of 6–14 are confirmed by microanalysis, IR, and NMR spectroscopy, and MS. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 141–146, 1999

Derivatives of 1,8-naphthalic anhydride have been synthesized and their spectroscopic and photochemical properties studied. Whilst these compounds have a good photostability, only derivatives with a primary or secondary amino group, had a good fluorescence quantum yield.

Reaction of naphthalic anhydride (naphthalene-1,8-dicarboxylic anhydride) (1) or of 1,8-bis(hydroxymethyl)naphthalene (3) with LiAlH4 in refluxing THF yields the benzonorcaradiene derivatives 2 in yields of up to 50%. It is proposed that in the formation of this (strained) product an anti-hydroalumination reaction is involved, which is facilitated by the assistance of a neighbouring alkoxide function.

Hydrazine reacts with 1, 8-naphthalic anhydride to give, exclusively, the N-aminoimide which reacts further with cyclic anhydrides to yield stable bisimides containing an N-N linkage. Various bisanhydrides which contain the naphthalic anhydride moiety have been converted to the corresponding bis-N-aminoimides from which high molecular weight polyimides have been synthesized. The polyimides have very high glass transition temperatures but remain soluble. Polyimides derived from 3, 4, 9, 10-perylene tetracarboxylic dianhydride are intensely red in color and are fluorescent.

Three fluorescent brightening agents (FBA), imides of 4-methoxy-1,8-naphthalic anhydride, have been synthesized. The compounds contained, in the N-substituent, a triazine ring containing a substituent with a polymerizable centre, this allowing their copolymerization with styrene.

In the presence of a strong Lewis base, such as Et3N, trithio-1,8-naphthalic anhydride (3) is easily oxidized. Two improved syntheses of trithio-1,8-naphthalic anhydride (3) are described. Trithio-1,8-naphthalic anhydride (3) undergoes Diels-Alder reactions with electron-deficient alkenes to give novel fused heterocyclic compounds (6–11) that then can undergo a novel, gradual desulfuration dimerization with triethyl phosphite to afford 12 and its analogs 13 and 14. The structures of 6–14 are confirmed by microanalysis, IR, and NMR spectroscopy, and MS. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 141–146, 1999

New potent 5-HT3 antagonists were synthesized from naphthalic anhydride and racemic or (R) and (S) 3-aminoquinuclidines. In contrast to zacopride, the activity resided essentially in the (R) enantiomer. Conformational studies demonstrated the presence of a locked structure. The reduction of one carbonyl function yielded equipotent compounds with a loss of enantioselectivity.

New bis(naphthalic anhydrides) containing "hinge" groups and/or bulky substituents are considered. It has been shown that the majority of these monomers may be synthesised from derivatives of naphthalic anhydride or acenaphthene with subsequent oxidation of the bisacenaphthyls obtained. Reaction of these compounds with aromatic diamines and bis(o-phenylenediamines) gives polynaphthylimides and polynaphthoylenebenzimidazoles combining solubility in organic solvents with high thermal and chemical stability. The bibliography includes 154 references.

We studied the reaction kinetics, the change of copper salts catalyst and behaviour of DMF in the Ullmann condensation reaction of 4-chloro-1,8-naphthalic anhydride with DMF under the catalysis of CuSO4 by using u.v., e.s.r., n.m.r. and m.s. DMF is a good amination reagent, and its reducing effect to cupric salts accelerates the reaction.

Fluoresceine (C.I. 45350) is the best known representative of the class of hydroxy-xanthene dyes, and is obtained through the reaction between phthalic anhydride and resorcinol. In a similar way with the synthesis of fluoresceine, methods of synthesis were explored for obtaining novel xanthene structure compounds, starting from intermediates of the type anhydride with polyphenolic compound. Xanthene dyes are a very valuable class of organic compounds and have modern, non-conventional applications[1-4]. As oxidation agents Na2Cr2O7 and the peracetic acid are proposed, with the remark that in the case of naphthalic anhydride, oxidation was performed using sulfuric acid. At the same time it was tested the possibility to increase the reaction yield using a more diluted solution.

The products of the reactions of naphthalic anhydride and 1,4,5,8-naphthalenetetra-carboxylic acid dianhydride with anthranylamide were studied, and it was found that as a result of high temprature condensation in p-chlorophenol, mono and bis-napthoylenequinazolones are formed. Spectral-luminescent properties of the naphthoylene-quinazolones obtained were investigated.

A new series of N-substituted imide derivatives have been synthesized by treating phthalic anhydride, naphthalic anhydride and their substituted derivatives with 2-hydrazino-1-imidazoline hydrobromide, various para-substituted aryl amines, aminoglutethimide and 2,4-dinitrophenyl hydrazine. Compounds 9, 10, 12, 18, 19, 23, 24 and 34-36 have been selected and screened for antineoplastic activity by National Cancer Institute, Bethesda, USA. Some newer aminoglutethimide derivatives 37-39 have also been prepared in order to study the effect of N-substitution on its pharmacological profile for the treatment of carcinoma. These compounds (37-39) have exhibited weak inhibition of human placental aromatase as compared to aminoglutethimide.

3,4-Dihydro-1,2-Naphthalic Anhydride product: 3,4-Dihydro-1,2-naphthalic anhydride reactant: 50 g. (0.26 mole) of ethyl γ-phenylbutyrate solvent: 75 cc. of ligroin Keywords: annulation, carbocyclic-[6]; annulation, heterocyclic-[5]; condensation, ester-ester condensations; cyclization, condensation; potassium sand; sodium sand

1,2-Naphthalic anhydride solvent: 50 cc. of ligroin product: 1,2-Naphthalic anhydride Keywords: elimination, dehydrogenation

Unusual Pschorr cyclisation via naphthyl radical-induced intramolecular aromatic 1,5-hydrogen transfer using the corresponding diazonium salts as starting materials gave five- and six-membered oxacyclic-fused naphthalic anhydride isomers.

Heating 4-nitronaphthalic anhydride in an excess of 3(5)-methylpyrazole gives only 4-(3-methylpyrazolyl-1)naphthalic anhydride, which is converted by butylamine into the known N-butylimide of 4-(3-methylpyrazolyl-1)naphthalic acid.

1,2,3-Benzenetricarboxylic acid (hemimellitic acid) tritiated in position 5 has been labelled at a specific activity of 16.2 Ci/mmol, starting from 3-bromo naphthalic anhydride. Attempts at direct bromination of the acid followed by tritiodebromination, or of general labelling by hydrogen-tritium exchange gave poor results.

To improve the processing capacity of polynaphthoylene benzimidazoles an attempt has been made to increase the number of ether bonds in the elementary units of these polymers. For this purpose by oxidizing the corresponding bis-acenaphthene quinone we synthesized the dianhydride not previously described with three ether bonds—the dianhydride of 4,4(oxybis-( p -phenyleneoxy))dinaphthalene-1,8,1′,7′- tetracarboxylic acid— and by interacting it with bis-( o -phenylene diamines) in conditions of high temperature catalytic polycylization in phenolic solvents we obtained polynaphthoylene benzimidazoles which may be successflly processed to moulded products.

The fungus Verticillium lamellicola affords lamellicolic anhydride 1 (5 - methyl - 2,4.7 - trihydroxy -1,8 - naphthalic anhydride) together with small amounts of the quinone 2, the carbonate 3 and the chloro compound 4. Selective reactions of the functional groups in these and their derivatives have been used to interrelate these and effect conversion of 1 into 18, the anhydride obtained from Penicillium herquei.

A number of previously undescribed bis(1′,8′-naphthoylene-1,2-benzimidazoles) were obtained by reaction of bis(o-phenylenediamines) with various structures with naphthalic anhydride. Under the same conditions, the reaction of o-phenylenediamine with naphthalene-1,4,5,8-tetracarboxylic acid dianhydride leads to a mixture of cis and trans isomers of bisbenzimidazobenzophenanthrolinedione. The spectral and thermal characteristics of the synthesized compounds were studied.

The metabolites produced in liquid culture by the Ascomycetous fungus Gremmeniellaabietina (Lagerb.) Morelet, the causative agent of Scleroderris canker in pines, have been investigated. The major metabolite, which we have named sclerodin, is (−)-4,7-dihydroxy-2,3,3,9-tetramethyl-2,3-dihydronaphtho[1,2-b]furan-5,6-dicarboxylic anhydride (1), the enantiomer of the so-called "naphthalic anhydride from atrovenetin". Several highly colored compounds, including the enantiomer of atrovenetinone (3), the blue compound 6, the red acenaphthenequinone derivative 8 (sclerodione), and the yellow 8-hydroxysclerodin (12) were also obtained. The blue compound 6, named Scleroderris blue, has been prepared from 3, and sclerodione (8) has been transformed into sclerodin (1).

The synthesis of [14C-carboxyl] 1,8-naphthalic anhy-anhydride of high specific activity (31.8 mCi/mmol) is reported. The 14C was introduced by carbonation of the Grignard reagent, 8-bromo-1-naphthylmagnesium iodide, that was prepared from 8-bromo-1-iodonaphthalene. The overall radiochemical yield for the reaction scheme was 63.7% based on barium carbonate-14C.

Des naphto [1,8-cd] pyrannedithione-1,3 et thioxo-3 naphto [1,8-cd] pyrannone-1, naphto [1,8-cd] thiopyrannediones-1,3 et -dithiones-1,3 sont synthetisees; les additions de Diels-Alder de ces anhydrides avec le norbornene et l'acenaphtylene sont etudiees

Several minor pigments from cultures of Penicillium herquei are described. One of these has been identified as the naphthalic anhydride which is formed when atrovenetin is oxidized with alkaline peroxide. Evidence is presented which suggests that the characteristic green pigment found in this fungus is formed by a reaction analogous to that between ninhydrin and amino derivatives. In P. herquei the 1,2,3-trione is probably generated by mild oxidation of perinaphthenone pigments known to be produced by this organism.

The preparation of 5-nitroacenaphthene (2) using several nitrating agents resulted in a product which was found to be contaminated with 20–30% of the 3-nitro isomeride. Separation was accomplished by t.l.c. and the n.m.r. spectra of the isomers are now reported. A new synthesis of 4,5-dinitronaphthalic anhydride (5) and an improved preparation of the dimethyl and diethyl esters of 4-nitronaphthalic anhydride and 5 is described. The esters were converted to the corresponding diamino derivatives by high pressure hydrogen–Pd reduction.

A seven step synthesis of 1,8-diethynylnaphthalene (IX) from naphthalic anhydride (I) is described. Oxidation of IX with oxygen, cuprous chloride and ammonium chloride gave the very unstable “cyclic dimer” (XX), containing a conjugated 14-membered ring.

4-(5-Methyl-2-oxoazolyl)naphthalic anhydride was synthesized by condensation of 4-chloroformylnaphthalic anhydride with aminoacetone and subsequent cyclization of the resulting amide. Luminescing methyl-substituted N-phenylnaphthalimide and 1,8-naphthoylene-1′,2′-benzimidazple were obtained by condensation of this product with aniline and o-phenylenediamine, respectively. The relationship between the structures of the products and their electronic absorption and luminescence spectra was investigated.

The electronic nature of the substituent in naphthalic anhydride has a substantial effect on the isomeric composition of the naphthaloperinones formed in reactions with 1,8-naphthylenediamine. An electron-accepting substituent in the 4 position of naphthalic anhydride promotes predominant retention of the carbonyl group in the 1 position, while an electrondonating substituent promotes retention of the carbonyl group in the 8 position of the naphthalene ring. 10-Amino- and 11-amino-14H-benzo[4,5]isoquinolino[2,1-a]perimidin-14-ones were synthesized.

Herbicide antidotes in the past few years have gone from experimental curiosities to practical realities. Initial observations that led to the commercial products were 2, 4, 6- trichlorophenoxyacetic acid (2, 4, 6-T) antagonism of 2, 4-D on tomato and the total inactivation of barban by 2, 4-D. The development of a fast, cheap and accurate detection method for herbicide antidotes led to the development of l, 8-naphthalic anhydride as an antidote for thiocarbamate, chloroacetanilide and dithiocarbamate herbicides on corn. In addition to these families of chemicals 1, 8-naphthalic anhydride also has utility for antidoting alachlor on sorghum and rice, molinate on rice and barban on tame oats. Besides naphthalic anhydride some halogenated alkanoic acid amide-type chemicals have shown antidoting properties against several herbicides.