Perimidines, 2-amino

Thiol-thioxo tautomerism Amino-imino tautomerism Perimidine... 

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>. 

Pyrimidinethiones are S-acylated under mild or moderate conditions, but may be isomerized to the A -acyl isomers at higher temperature. Primary and secondary pyrimidinamines undergo acylation at the amino group. Aminoquinazolines and -perimidines react similarly. 

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). 

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. 

Thermal decomposition of l-amino-8-azido-naphthalene derivatives (229) gives rise to oxazoles (230) and perimidines (231)... 

The structural similarity to azoles and the resemblance of many physicochemical properties allow one to consider peri-codensed NH-heterocycIes of the perimidine type (236) as analogues of azolo heterocycles (85KGS867). Under the action of MSH, perimidine and its substituted derivatives give the quaternary salt 237 in good yield (80KGS93 83CPB1378). One of these salts was converted to l-methyl-3-amino-2,3-... 

Orthoesters annulate aminomethyl and amino groups to form a fused pyrimidine ring [2159]. Two amino groups in peri positions form a similar ring when treated with benzoic acid and. -diphenylphosphinyl-iV -methylpiperazine [3286] (see also Chapter 76, Section 1.1.A). 1,8-Naphthalenediamine is converted into perimidine by heating with 2-acylindanedione and 4-toluenesulphonic acid [2354]. Formic acid similarly cyclizes 4,5-quinolinediamine or the isomeric isoquinolinediamine in about 89VO yield [3338]. 

Primary and secondary pyrimidinamines undergo acylation at the amino group. Amino-quinazolines and -perimidines react similarly. 

A 2-amino group in perimidine reacts with ethoxymethylenemalonate with formation of (438). Thermal cyclization of the resultant 2-perimidinylaminomethylenemalonate by heating in diphenyl ether yielded 1 l-oxopyrimido[l,2-a]perimidine-10-carboxylate (439) <89AP(322)303>. 

Similarly, oxygenated amino groups in primary syntheses of quinazolines and perimidines yield the corresponding A-oxides. 

Stefanska, B., Dzieduszycka, M., Martelli, S., Tarasiuk, J., Bontemps-Gracz, M. and Borowski, E. (1993) 6-[(Aminoalkyl)amino]-substituted 7H-benzo[e ]perimidin-7-ones as novel antineoplastic agents. Synthesis and biological evaluation. J. Med. Chem. 36 38-41. 

Dihydro-lH-perimidines. A mixture of 1,8-diaminonaphthalene and 4-[bis-(2-chlorethyl) amino] benzaldehyde in abs. ethanol heated 20 min. on a steam... 

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