Patent GB-461425-A (GB)
Title: Carboxylic acid amides derived from aza compounds
IPC: C07D215/40
Filed: 1935-06-11
Abstract: Carboxylic acid amides derived from aza compounds are prepared by heating aza compounds having at least 2 condensed rings and no nuclear keto groups, and no other hetero atom besides nitrogen in the molecule, the aza-nitrogen standing in a 6-membered ring, and which contain at least one reactive hydrogen atom attached to nitrogen, with esters of enolizable keto-carboxylic acids Suitable starting materials on the one hand are primary or secondary amino compounds of azanaphthalenes, azaphenanthrenes (cf. Specification 451,932), azanthracenes, diazaphenanthrenes, azatriphenylene, diaza- and triaza-triphenylenes, azachrysenes, benzazapyrenes, azaperylenes, azacarbazoles and azabenzanthracenes; and on the other hand carboxylic acid esters of the formulae R.CO.CHR<1>.X or <FORM:0461425/IV/1> wherein R is any organic radicle combined to the CO group by means of carbon, R<1> is hydrogen or an organic radicle, and X is an esterified carboxylic group.  Reaction is preferably effected in a diluent.  In examples the following pairs of compounds are reacted together: acetoacetic ethyl ester and 9-amino-4-azaphenanthrene, 10-amino-4-azaphenan - threne, 9-amino-1-azaphenanthrene, 5-amino-4-azaphenanthrene, 6-amino-4-azaphenanthrene, 7-amino-4-azaphenanthrene, 8-amino-4-azaphenanthrene, 3-methyl-9-amino-4-azaphenanthrene, 2-methyl-5-amino-1-azaphenanthrene, amino-3-azaphenanthrenes, 9-methylamino-4-azaphenanthrene, 5-amino-2-azanaphthalene, 3-methylamino-1-azanaphthalene, 3-8-diamino-1-azanaphthalene, 8-amino-5-nitro-1-azanaphthalene, tetrahydro-1-azanaphthalene, 7-amino-1-azaphenanthrene, monamino-6.12-diazachrysene, monaminodiazatriphenylene, 2-amino-6.7-benzo-3.5.8.10-tetrazapyrene, monamino-5.11-dimethyl-4.10-diazaperylene, 3-amino-1-azanaphthalene, 9-amino-4.8-diazaphenanthrene, or the condensation product obtained by condensing 9-amino-4-azaphenanthrene with p-nitrobenzoylacetic ester and reducing; p-chlorbenzoylacetic ester and 9-amino-4-azaphenanthrene; p-nitrobenzoylacetic ester and 9-amino-4-azaphenanthrene; 2.5-dichlorbenzoylacetic ester and 9-amino-4-azaphenanthrene; benzoylacetic ester and 5-amino-2-azanaphthalene, the reduced condensation product of acetoacetic ester and 8-amino-5-nitro-1-azanaphthalene, 9-amino-4-azaphenanthrene, 9-amino-4.8-diazaphenanthrene, amino-1-azacarbazole, monamino-6.12-diazachrysene, 2 - amino - 6.7 - benzo - 3.5.8.10 - tetrazapyrene, 8 - amino - 4 - azaphenanthrene, or 3 - amino - 1 - azanaphthalene; terephthaloyl-bis-acetic ester and 10-amino-4-azaphenanthrene, 3-, 5-, 6-, 7-, 8- or 9-amino-4-azaphenanthrene, 5-, 6- or 8-amino-1-azaphenanthrene, amino-2-azaphenanthrene, amino 1.8-diazatriphenylene, 5-amino-2-azanaphthalene, a mixture of 9-amino- and 10-amino-4-azaphenanthrenes, or a mixture of p-toluidine and 9-amino-4-azaphenanthrene; nitroterephthaloyl-bis-acetic ester and 10-amino-4-azaphenanthrene; isophthaloyl-bis-acetic ester and 10-amino-4-azaphenanthrene, 5-nitroisophthaloyl-bis-acetic ester and 10-amino-4-azaphenanthrene; chlorisophthaloyl - bis - acetic ester and amino - 9-chloro-1-azanthracene; naphthoylene - 1.5 - bis - acetic ester and 10-amino-4-azaphenanthrene or 8-amino-2-methyl-1-azanaphthalene.  Aza compounds.--Aminodiazaphenanthrenes are prepared by a Skraup synthesis from mononitro or monohalogen derivatives of phenylenediamines having a reactive o-position to each of the amino groups and reducing the nitro group or replacing the halogen atom of the resulting diazaphenanthrene by the amino group. Aminoazatriphenylenes are prepared by a Skraup synthesis from 9- or 10-aminophenanthrenes, nitration and reduction; aminodiaza- and -triaza-triphenylenes are similarly prepared from 9- or 10-aminomono- or diazaphenanthrenes.  Aminoazachrysenes are prepared by a Skraup synthesis from 1.5-, 1.6-or 2.6-diaminonaphthalene, nitration and reduction. Aminobenzazapyrenes are prepared by condensing 1.4-diaminoanthraquinones with acetone, nitration and reduction of the resulting product; 2-amino-6.7-benzo-3.5-8.10-tetrazapyrene is prepared by reacting 2.4-diamino-1.9-anthrapyrimidine with formamide. Aminoazaperylenes are prepared by condensing 1.5-diaminoanthraquinones with acetone and nitrating and reducing; thus 5.11-dimethyl-4.10-diazaperylene is prepared by condensing 1.5-diaminoanthraquinone with acetone in an alkaline medium and may then be nitrated and reduced.  Aminoazacarbazoles are prepared by dehydrating by means of copper at elevated temperature the hexahydrocarbazoles described in Specification 360,027; an amino-1-azacarbazole is prepared by nitrating and reducing 1-azacarbazole.  Aminoazabenzanthracenes are prepared by treating pyridinoanthraquinones with reducing agents and treating the products with ammonia.  An amino-2-azaphenanthrene is prepared by sulphonation, replacement of the sulpho group by hydroxy and the latter by the amino group.  Ketocarboxylic acid esters.--Terephthaloylbis-acetic ester, p nitroterephthaloyl-bis-acetic ester, isophthaloyl-bis-acetic ester, 5-nitroisophthaloyl-bis-acetic ester and naphthoylene-1.5-bis-acetic ester are prepared by condensing the corresponding acids with acetoacetic ester in presence of alkali.