Patent GB-451932-A (GB)
Title: Improvements in the manufacture and production of amino-aza-phenanthrenes
Filed: 1935-01-10
Abstract: Amino derivatives of mono- and di-azaphenanthrenes (azaphenanthrenes being compounds wherein a --CH = group of the phenanthrene ring is replaced by nitrogen) are prepared by reacting a compound of the formula <FORM:0451932/IV/1> wherein X is a reactive hydrogen atom, R1 is hydrogen or an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic group, R2 is hydrogen, hydroxyl, amino, or an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic group or wherein <FORM:0451932/IV/2> is a heterocyclic ring system, with a hydroxy compound of a mono- or di-azaphenanthrene.  A diluent may be present in the reaction which may in some cases be preferably carried out in presence of a reducing agent or under pressure.  In examples the following compounds are reacted together: 9-oxy-4-azaphenanthrene (prepared by a Skraup condensation of naphthionic acid with glycerine and alkali fusion of the resulting sulphonic acid) with ammonia, hydrazine hydrate, phenylhydrazine, benzylamine, ethylamine, dimethylamine, phenylethylamine, dodecylamine, octodecylamine, octodecenylamine, o -aminomethylnaphthalene cyclohexylamine and its halogen, alkyl or aryl substitution products, 8 - aminoquinoline, 5-amino-1,9-anthrapyrimidine (dyes cotton lilac shades) and 1-aminoanthraquinone (dyes cotton rose shades); 10-hydroxy-4-azaphenanthrene (prepared by a Skraup condensation of 1-aminonaphthalene-3-sulphonic acid with glycerin and alkali-fusion of the resulting sulphonic acid) with ammonia, hydrazine hydrate, hydroxylamine hydrochloride, aniline, toluidines, xylidines, aminobenzoic acids and esters thereof, aminonaphthalenes, aminoanthracenes, aminophenanthrenes, aminopyrenes, aminochrysenes, aminoperylenes and their carboxylic acids and acid esters, and 8-aminoquinoline; 8-hydroxy-4-azaphenanthrene (prepared by a Skraup condensation of 1-aminonaphthalene-5-sulphonic acid with glycerine and alkali-fusion of the resulting sulphonic acid) with ammonia and hydrazine hydrate; 7-hydroxy-4-azaphenanthrene (prepared by a Skraup condensation of 1-aminonaphthalene-6-sulphonic with glycerine and alkali fusion of the resulting sulphonic acid) with ammonia, 8-aminoquinoline, aminopyridines, aminolutidines, aminoisoquinolines, aminocarbazoles, aminodiphenylene oxides, aminodiphenylenesulphides, piperidine, pyrrolidine, lupetidine, tetrahydroquinoline and tetrahydroisoquinoline; 6-hydroxy-4-azaphenanthrene with ammonia and 8 - aminoquinoline; 5 - hydroxy - 4 - azaphenanthrene with 8-aminoquinoline; 5. 10-dihydroxy-4-azaphenanthrene (derived from 1-aminonaphthalene - 3,8 - disulphonic acid and glycerin, followed by an alkali-fusion of the resulting disulphonic acid) with ammonia; 1,3-dihydroxy-4-azaphenanthrene (prepared by heating 1-aminonaphthalene with malonic ester in nitrobenzene) with ammonia; bromo-8-hydroxy - 4 - azaphenanthrene (derived by brominating the oxy-compound in acetic acid) with ammonia; 7-hydroxy-1-azaphenanthrene (derived by a Skraup condensation of 2-aminonaphthalene-6-sulphonic acid with glycerine and alkali fusion of the resulting sulphonic acid) with ammonia.  References are also made in the examples to the amination with ammonia of 9-hydroxy-4-azaphenanthrenes containing chlorine, bromine, iodine (prepared by the action of the respective halogens on the 9-oxy derivative), nitro groups (prepared by nitration), fluorine (prepared by reduction of the nitro derivatives, diazotization and treatment with boron hydrofluoric acid), sulphonic groups (prepared by sulphonation), alkyl or aralkyl groups (prepared similarly to the 9-oxy derivative from the appropriate alkyl- or aralkyl-1-aminonaphthalene-4-sulphonic acids) or carboxylic acid or acid ester or acid amide groups (prepared by oxidizing the appropriate alkyl-4-azaphenanthrene-9-sulphonic acids followed by alkali fusion with further esterification &c. as necessary), 3-methyl-10-hydroxy-4-azaphenanthrene (prepared by condensing 1-aminonaphthalene - 4 - sulphonic with crotonaldehyde followed by alkali-fusion), 10-hydroxy-4-azaphenanthrene-3-carboxylic acid (prepared by oxidation of the above 3-methyl compound), 4-azaphenanthrene-7,10-hydroxysulphonic acid (prepared by fusing the 7,10-disulphonic acid with alkali), 7-hydroxy-2-methyl-1-azaphenanthrene (prepared by condensing crotonaldehyde with 2-aminonaphthalene-6-sulphonic acid and alkali-fusing the product), 3-, 5-, 6-, 9- or 10-hydroxy - 1 -azaphenanthrenes (the 3-oxy-derivative is prepared by brominating the azaphenanthrene and treating with alkali; the 5-, 6-, 9- and 10-oxy-derivatives are derived from the appropriate 2-aminonaphthalene sulphonic acids by a Skraup condensation followed by alkali fusion), hydroxy-1-azaphenanthrene carboxylic acid (prepared by the action of carbon dioxide on the hydroxy-1-azaphenanthrene), 10-hydroxy-1,5-diazaphenanthrene (prepared by a Skraup condensation on 1.3-diaminobenzene-4-sulphonic acid and alkali-fusion), 3,5.10-trihydroxy-4-azaphenanthrene (alkali fusion of 4-azaphenanthrene-5,10-disulphonic acid while leading in air), hydroxy-3-azaphenanthrene (alkali-fusion of the sulphonation product of 3-azaphenanthrene), 8-hydroxy-4-azaphenanthrene - 7 - carboxylic acid, acid amide and acid anilide (prepared by the action of carbon dioxide on 8-hydroxy-4-azaphenanthrene); to the amination with substitution products of cyclohexylamine of halogen, nitro or alkyl-9-hydroxy-4-azaphenanthrenes; to the amination with 8-aminoquinoline of hydroxy-2-, 3-, 9- or 10-azaphenanthrenes (hydroxy-2- and 3-azaphenanthrenes are derived by catalytic reduction of o -cyano-2- and -1-methylnaphthalenes respectively with formaldehyde or formic acid, sulphonation and alkali fusion).