Perimidine derivatives

Bazureau described a tandem conjugate addition-intermolecular hetero-Diels-Al-der reaction of perimidine derivatives under solvent-free conditions with focused microwave irradiation [77]. The main feature of this reaction was attainment of complete addition in less than 8 min. When the reaction mixture was heated in an oil bath set at the same temperature for the same time the results were analogous (Scheme 9.27). 

Perimidine derivatives 1016 are best prepared from 1,8-naphthalenediamines 1015 by ring-closure methods <1981RCR816, 1995AQ151>, while benzo[g,4]perimidines 1017 are available in moderate yields from perimidines using Friedel-Crafts reaction conditions <2003CHE1417>. 

J. M. Herbert carried out his PhD research with associate professor P.D. Woodgate and Dr. W.A. Denny at the University of Auckland, into the synthesis and reactions of perimidine derivatives. He then carried out postdoctoral research with Dr. R.J.K. Taylor at the University of East Anglia on the reactions of pyrylium salts, before moving into Industry. He is presently a team leader in the Isotope Chemistry and Metabolite Synthesis Department of sanofi-aventis in Alnwick, UK. 

Amino-l,2-dimethylperimidinium mesitylsulfonate (26) reacted with DMAD in presence of base to afford with good yield pyrazolo[3,2-/>]perimidine derivative (27) in accordance with Scheme 3 (83CPB1378). 

Aromatization of dihydroperimidines 427 to perimidine derivatives 429-431 (X = NR) have been carried out (81UK1559). Benzologs of perimidine-6-ones, or so-called pyrimidinoanthrones (anthrapyrimidines) 441, are well-known dyes. The precursors of these compounds are usually A-(anthraquinonyl-l)-amidines 440, which are obtained from I-aminoanthraquinone 437, as described in the following paragraphs (83M11). 

The investigations by X-ray diffraction have been extended to other series such as fulgides and more recently developed series such as spriooxazines, 2H-chromenes and perimidine derivatives. 

Though both substrates have considerable positive charge character at the C-2 site, the values are significantly different (4.17 and 4.91 for the benzimidazole and perimidine derivatives, respectively), perhaps accounting for the difference in reactivity. 

Perimidinium imides 481 form with DMAD adducts 482, and the subsequent pathway to product for the latter compounds depends on the substituent R. If R = H, the corresponding pyrazole derivative 483 is formed as described earlier. However, if R = Me, elimination of a molecule of methane is observed, and pyrazolo[l,5-a]perimidine derivative 484 is formed (83CPB1378). 

Six-membered heterocyclic systems which have been synthesised by similar methods include l,6-methano[10]annulenopyridines (214) from (213), y-carblines (215), lavendamycin methyl ester,a range of functionalised 2,3-dihydropyrido[3 ,2 4,5]thieno[3,2-d]pyrimidines (216), and the quinazolino[3,4-a]perimidine derivatives (e.g. 218) from 1,2-dihydro-properimidine azide (217). The previously unreported 4-methylene-4H-3,l-benzozazine ring (219) has been prepared from o-azidoacetophenone and the zwitterionic heteropolycyclic uracils (220) have been synthesised by a three-component reaction of iminophosphorane, isocyanate, and substituted pyridine. ... 

In part 2.2 it was mentioned that the perimidine derivatives 124 are formed with high yields from the anhydrides 1 or 19 and 1,8-diaminonaphthalene. In the case of the anhydride 1 under these conditions the tetracyclic condensed compound 283 was also isolated with a yield of 5% [74],... 

This reaction has been modified for preparing oxazole, thiazole, and perimidine derivatives from the condensation of the corresponding o-aminophenol, o-aminobenzenethiol, and 1,8-naphthalenediamine with ketones. ... 

Hydroxy, thiol, and amino groups in pyrimidine exist in tautomeric equilibria with their oxo, thioxo, and imino forms. An amino group in an electrophilic position exists predominantly as such, and the compound is named as an amine. Pyrimidines with a hydroxy or thiol group in an electrophilic position are dominated by the oxo or thioxo forms and are named as such, or with -one or -thione suffixes, if these are the principal groups. In the benzenoid 5-position, these derivatives are mainly present in the hydroxy, thiol, or amino forms and are named as such. Similar considerations apply to the nomenclature of quinazolines and perimidines <1996CHEC-II(6)93>. 

Diazo coupling in quinazolines occurs in the benzene ring, with the normal benzene or naphthalene requirement for the presence of strongly electron-donating substituents. Perimidines couple readily in the 6(7)-position with diazonium salts to form blue azo derivatives. The reaction has been described for perimidine, 2-substituted derivatives, 6(7)-chloroperimidine, and 2-aminoperimidine <1981RCR816>. 

Benzotriazine and derivs 2 B86—B87 (benzo-1,2r3-triazine)-3-oxide 2 B86 (benzo-l,2,3-triazine)-4-oxide 2 B86—B87 1,2,3-benzotriazino-(3-4-a) perimidine see o-Amidophenylperimidine 2 A246 6-nitrobenzo-4-oxy-victriazine 2 B87... 

Monocyclic azines are very weak rr-donors and behave mostly as n-donors on interaction with electrophiles. However, ir-donor character is significantly increased in their benzo-derivatives. For instance, acridine forms with chloranil a highly colored 1 1 molecular complex. Perimidine is one of the strongest heterocyclic ir-donors which gives deeply colored molecular complexes with a variety of organic electron acceptors. On the other hand, the rr-acceptor ability of perimidine is moderate. 

Pseudo-bases derived from 2-unsubstituted 1,3-dialkylperimidinium salts disproportionate into 1,3-dialkylperimidones and l,3-dialkyl-2,3-dihydroperimidines, the former always predominate. By contrast, l-aroyl-3-alkylperimidinium salts (203), formed in situ from l-/ -perimidines and aroyl chlorides, produce pseudobases (204) which exist exclusively in the acyclic form (205). Interestingly, heating with alkali cleanly converted (205) into the corresponding 1,2-disubstituted perimidines (206). This reaction is of preparative significance for the introduction of aryl and heteroaryl groups in position 2 of perimidines (81RCR1559). 

Perimidine and its N-substituted derivatives on heating with sulfur undergo filiation to form perimidine-2-thiones in good yields (81RCR1559). Thiopyrimidines are prepared by the thiolysis of halopyrimidines. using sodium hydrogen sulfide, or thioureas. 

The nomenclature of peri-naphthalene heterocycles does not follow a common principle. In many original papers, the names of heterocyclic systems are derived from the corresponding peri-annelated hydrocarbon derivatives (1,2-diazaacenaphthylene, 1-oxaphenalene, etc.), from monoheterocycles with an indication of linked positions (naphtho[l,8-6c]furan, naphtho[l,8-de]azepine, etc.), and from benzoannelated heterocycles (benzo[o/]indole, benzo[heterocyclic systems and some compounds have trivial names, for instance, perimidine, naph-thostyryl, and naphtholactone. Moreover, it is necessary to remember some peculiarities in the electronic structure of peri-annelated heterocycles, namely the absence of independent existance of the 7r-closed-loop monoheterocycles which could be a fragment of peri-annelated heterocyclic systems. Therefore, the separation of a heterocycle from the united 7r-system is impossible. In this case, the simplest structure and the tt-electron unit is the whole peri-heterocyclic nucleus. 

Known compounds in this class include mainly 1,3-oxazine, 1,3-thiazine, 1,3-diazine (perimidine), and to a lesser extent 1,3-dithiine and 1,3-dioxine peri-annelated derivatives. The general strategy for constructing such systems is based on heterocyclization of 8-hydroxy-, 8-mercapto-, or 8-amino-substituted 1-naphthylamines 426 (X = NR)... 

Potassium cyanate, carbonic and chlorocarbonic esters, phosgene, or urea are used as cyclizing agents in the synthesis of perimidine-2-one 430 (X = X = NR, Y = O) and its derivatives from 1,8-naphthylene-diamines. Naphtho[substituted amino group in position 2 (X = Y = NH or Y = NR) are obtained on interaction of 1,8-naphthylenediamines with bromocyanogen, cyanoamide, 5-methylisothiourea, arylisothiocyanates, or dimethyltri-chloromethylamine. 

Perimidine and its N-substituted derivatives on heating with sulfur undergo thiation to form perimidine-2-thiones in good yields <1981RCR1559>. 

Syntheses of perimidine 109 and naphtho[l,8-<7, ]triazine 110 derivatives usually start from 1,8-diaminonaphthalene by procedures which are quite similar to the synthesis of benzimidazoles and benzotriazoles from 1,2-diaminobenzene <1995AQ151>. For example, 2-alkyl and 2-arylperimi-dines 112 can be readily obtained in good yield by heating carboxylic acids with 1,8-naphthalenediamine 111 under microwave conditions (Scheme 54) <2005ASJ2411>. 

Valence and prototropic tautomeric reactions are among the most important mechanisms that govern transformations of a broad variety of photochromic organic systems.1,2 Until recently, no examples of photochromic compounds have been reported whose photochromic behavior was due to a combination of these two tautomeric reactions. Such a combination, which is characteristic of ring-chain tautomerism3 has been implemented in the photochromic and thermochromic rearrangements of a novel type of heterocyclic photochromes, derivatives of 2,3-dihydro-2-spiro-4 -(2, 6 -di-iert-butylcyclohexadien-2, 5 -one)perimidine la and its analogs.4 The occurrence of a proton transfer step is in accord with the fact that the AvV -dimethyl derivative of la exhibits no photochromic properties. 

On prolonged passing of air through ethanol or acetonitrile solutions of 1 (R = H) in a quartz photoreactor with an immersed mercury lamp, 2, 3 -dihydro-2 -spiro-4-(2,6-di- ert-butylcyclohexadien-2,5-one)perimidin-4 -one 14 was isolated as the main product of the photooxidation reaction. With the A W -dimethyl derivative of 1, photooxidation results in the formation of the perimidinedione 15.12... 

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