Patent GB-1204522-A (GB)
Title: Substituted tetraazaphenalenes and their salts, a process for their production and compositions containing them
IPC: C07C63/68
Filed: 1967-10-02
Abstract: 1,204,522. Tetra-azaphenalenes. J. R. GIEGY A.G. 2 Oct., 1967 [3 Oct., 1966]; No. 44680/67. Heading C2C. [Also in Division A5] Compounds of the general formula and acid addition and quaternary ammonium salts thereof wherein R 1  represents the hyrazzino or phenylhydrazino radical or an amino radical corresponding to the Formula II: wherein R 5  represents hydrogen, a low alkyl group, a mononuclear aryl or aralkyl radical the aromatic nuclei of which can be substituted by halogen up to the atomic number 35, low alkyl, low alkoxy and trifluoromethyl, or R 5  and R 6  together with the adjacent nitrogen atom, represent a heterocyclic radical having 5 to 7 ring members and containing 4 to 6 carbon atoms, which radical also can contain oxygen or another nitrogen function in its ring, and can contain a fused, mononuclear aromatic carbocyclic ring optionally substituted by halogen up to the atomic number 35, low alkyl, low alkoxy or trifluoromethyl, and R 6  has the meaning of R 5  with the exception of hydrogen, R 2  represents hydrogen, a low alkyl group, the phenyl group or the benzyl group, R 3  represents hydrogen or the phenyl group, and R 4  represents hydrogen, halogen up to the atomic number 35, a low alkyl or alkoxy group, the hydroxy group or carboxyl group are prepared by reacting the compound of the general Formula III: wherein Y represents a chlorine or bromine atom or the mercapto group with a hydrazine, phenyl hydrazine or an amine of the formula HNR 5 R 6  in the presence of an acid binding agent and optionally with the formation of the desired salt except that when Y is mercapto and R 2 , R 3  and R 4  simultaneously are H, or when R 2  is phenyl and Y is halogen and R 3  and R 4  are H, hydrazine is not used. Compounds wherein R 1  is a group of Formula II above are novel. Compounds of the above general Formula III wherein Y represents the mercapto group are prepared by reacting a compound of the general Formula V with, for example, phosphorus pentasulphide. Compounds of the above Formula III wherein Y represents halogen may be prepared by reaction of the ketone of the last formula above with a phosphorus halide or oxyhalide, or by reaction of a halogen in the presence of an alkali metal salt of acetic acid with a compound of the general formula Compounds of the general Formula V wherein R 2  and R 3  represent hydrogen, can be produced e.g. from a 3-(alpha, alpha-dibromomethyl)- phthalic acid anhydride substituted according to the definition of R 4 , by reaction with at least double the molar amount of hydrazine or hydrazine hydrate. On treating these compounds with alkylating agents such as alkyl or benzyl halides in the presence of a base, compounds of the general Formula V are obtained therefrom wherein R 2  is a low alkyl group or the benzyl group and R 3  is hydrogen. 3-(Alpha, alpha - dibromomethyl) - phthalic acid anhydride can be obtained by brominating 3-methyl phthalic acid anhydride; compounds substituted corresponding to the definition of R 4  can be obtained analogously. Compounds of the general Formula V wherein R 2  is phenyl and R 3  is hydrogen can be obtained, e.g. from the 3-(alpha, alpha-dibromomethyl)- phthalic acid anhydrides mentioned above by first hydrolysing these, then reacting the 7 - carboxy - 3 - hydroxy - phthalides formed with phenyl hydrazine to form the 8-carbozy-2- phenyl-1(2H)-phthalazinones, esterifying these and reacting the 8-carbalkoxy-2-phenyl-1(2H)- phthalazinones with hydrazine to form the compounds of general Formula V wherein R 2  is phenyl and R 3  is hydrogen. Compounds of general Formula V wherein R 3  is phenyl and R 4  is hydrogen can be obtained by reacting an ester of 8-carboxy-4-phenyl-1(2H)- phthalazinone with hydrazine. Thus, for example, 8 - carboxy - 4 - phenyl - 1(2H) - phthalazinone, M.P. 257-259 C., is obtained from the known 3-benzoyl phthalic acid and hydrazine. On using an alkyl or phenyl hydrazine, 8 - carboxy - 4 - phenyl - 1(2H) - phthalazinones correspondingly substituted in the 2-position can be obtained in an analogous way. Esters of 8 - carbalkoxy - 4 - phenyl - 1(2H) - phthalazinones, e.g. the methyl or ethyl ester, are obtained by esterifying the 8-carboxy-4-phenyl-1(2H)- phthalazinones. "Low" as used above indicates groups containing up to 4 carbon atoms.