Synthesis of 1H-benzo[de]cinnolines (1H-1,2-diazaphenalenes)

Abstract

Manchester M13 9PL 8-Hydroxy-I -naphthyl ketones condense with hydrazine to give 1 H-benzo[de] cinnolines(1 H-I ,2-diazaphenalenes), whose conjugate bases are methylated a t postion 1. The oxime of 8-acetyl-1 -naphthol cyclises to 3rnethylnaphtho[l,8-de] -1.2-oxazine.present ring-c1osure reaction probably require '-proton-Condensations with Hyd,yaziM.--(a) 8-Acetyl-l-naphthol 9The diazaphenalenes (I) and (I1) give red hydrazine hydrate (99-100%; 1 ml.) and then boiled H. Duewell and T.

1H-Benzo[de]cinnolines: an interesting class of heterocycles

“…Simple 1H-benzo[de]cinnolines have been prepared by Lacy and Smith, Scheme 1(a) 5 and 1(b), 6 and by Aksenov, Aksenova et al, 7 Scheme 1(c). Using the methods represented in Scheme 1(a), a series of 1H-benzo[de]cinnolines have been prepared (Figure 2) by Mezheritskii et al, [8][9][10][11][12][13] A totally different method has been reported by Chenoweth et al, 8 (cited in 9 ).…”

New heteroaromatic bis-peri-fused azoxonium cation

“…The bis-acylation of 1,5-dimethoxynaphthalene (I) afforded compound II whose demethylation proceeded through intermediate A giving compound III with a methylenequinone structure which at heating both with 1 mol of ethylhydrazine and its double excess furnished monoheterocycle IV, whereas the 5-hydroxy-6-carbonyl peri-moiety was not affected in this process. This result seems rather unusual since the short heating in alcohol of peri-hydroxycarbonyl compounds with hydrazines is the easiest way of the preparation of peri-fused 1,2-diazines [4][5][6]. The short heating of diazine IV with perchloric acid in the acetic acid solution resulted in the dehydration of the peri-hydroxycarbonyl moiety with the closure of a fi ve-membered ring and the formation of perchlorate V. The closure of the fi ve-membered furylium ring and the formation of cation V is confi rmed by the disappearance of the bands of carbonyl and hydroxy groups in the IR spectra, by the appearance of intensive yellow-orange fl uorescence with λ max 538 nm (quantum yield μ 0.65) at the irradiation with light of λ max 320 nm, and also by the considerable downfi eld shift of all proton signals in its 1 H NMR spectrum compared to the spectra of precursor IV due to the formation of the 14π-electron heteroaromatic circuit on the periphery of the bis-peri-fused framework in cation V.…”

Synthesis of 1,2-Diazaphenalenes under Microwave

“…4,8 The three fused cycles of the monoazaphenalene framework are found in natural and semi-synthetic products such as apomorphine (I), holdine (2) and melosmine (3) (Scheme 1)y These aporphinolds exhibit considerable phamacological activitie~.~ Most of them display promising effects in large clinical trials on animals (NCS antidepressant, dopaminergic agonist and antagonist, antifungus cholagogue ...).9 Apomorphine is a potential Parkinson's desease therapeutic? It has been reported that substituted 1H-l,2-diazaphenalenes were obtained by heating 8-hydroxy-I-naphthaldehyde or 6acetyl-(or benzoy1)-I-naphthol with hydrazine in boiling ethylene glyco1.4.s Although 1H-azaphenalenes decompose rather quickly,6.7 1H-1,3-diazaphenalenes and 1H-l,2-diazaphenalenes are more stable in air.…”