Patent GB-349059-A (GB)
Title: Improvements in the manufacture and production of nitrogenous condensation products
IPC: C09B5/42
Filed: 1929-11-15
Abstract: Pyridino compounds.-High molecular pyridino compounds are obtained by condensing cyclic amino compounds having a condensed ring system containing at least four carbocyclic rings, which may contain further carbocyclic or heterocyclic rings, in which at least one position or ortho to the amino group is occupied by hydrogen or a group readily split off, with glycerine or a derivative thereof (e.g. epichlorhydrin) in sulphuric or phosphoric acid in the presence of dehydrogenating agents.  The products may be further condensed, halogenated or nitrated if desired.  As dehydrogenating agents may be used nitro compounds, such as nitrobenzene, nitrobenzenesulphonic acids and nitrotoluenesulphonic acids, arsenic acid, hydrogen peroxide, persulphuric acid, or ferric salts.  When sulphuric acid is used as the condensing agent, dehydrogenating agents may be dispensed with, but their addition is advantageous.  When glycerine and sulphuric acid are used for the condensation, it is possible to start from the cyclic nitro compounds instead of the corresponding amino compounds, part of the nitro compound being reduced and entering into reaction, while the remainder serves as dehydrogenating agent. Instead of using free amino compounds, derivatives thereof which react like the free amino compounds, for example, the corresponding azomethines or acylamino compounds, may be used as starting materials.  As cyclic amino compounds suitable for the purposes of the invention are specified amino derivatives of benzanthrones, benzanthraquinones, the various dianthrones, e.g. ms-benzdianthrones, ms-naphthodianthrones, allo-ms-naphthodianthrones and ms-anthradianthrones, pyranthrones, anthanthrones, anthraquinoneacridones, anthraquinonecarbazoles, anthraquinoneazines, perylenequinones and pyrenequinones.  The products obtained from initial materials capable of further condensation, for example by caustic alkali fusion or treatment with sulphuric acid or aluminium chloride, may be further condensed; thus the pyridino compounds obtained from benzanthrones containing hydrogen, halogen or hydroxy groups in the Bz1 and 2 positions yield pyridino-dibenzanthrones or -isodibenzanthrones on alkaline condensation, and the pyridino compounds obtained from ms-benz- and allo-ms-naphthodianthrones yield by treatment with aluminium chloride or by acid oxidation pyridino compounds of ms-naphtho and ms-anthradianthrones respectively.  The pyridino compounds may also be halogenated, and by the action of different halogens or halogenating agents, chlorobromo, chloroiodo and like derivatives may be obtained.  They may also be nitrated and the nitro compounds reduced to amino compounds, which may be condensed with organic halogen compounds, or the amino groups may be replaced by other substituents, such as halogen, cyano, thiocyano or hydroxy groups.  The products obtained are in some cases vat dyestuffs, and in others intermediate products for the dyestuff and pharmaceutical industries.  They may be purified by the usual methods, such as crystallization, sublimation, purification by way of their oxonium or ammonium salts, or treatment with oxidizing agents. They may also be employed in some cases as pigment dyestuffs or as dyestuffs for wool or acetate silk.  In examples (1) 6(N) : 5- and 6(N) : 7-pyridinobenzanthrones are obtained from 6-aminobenzanthrone and separated by fractional crystallization from chlorbenzene, and 8(N) : 7-pyridinobenzanthrone is obtained from 8-aminobenzanthrone; Bz-2-amino- and diaminobenzanthrones also yield the corresponding pyridino- and dipyridino-benzanthrones, (2) 8(N) : 7-pyridinobenzanthrone is fused with alcoholic potash; the product dyes cotton navy blue shades of good fastness to drops of water: the corresponding product from 6(N) :5-pyridinobenzanthrone dyes in violet-blue shades, (3) monoamino-allo-ms-naphthodianthrone (made by nitrating in nitrobenzene and reducing) yields a pyridino derivative (dyeing cotton in red shades), which on treatment with pyrolusite in sulphuric acid is converted into a pyridino-ms-anthradianthrone dyeing in orange shades; a pyridino-ms-anthradianthrone of similar dyeing properties may also be obtained directly from monoamino-ms-anthradianthrone (made by nitrating ms-anthradianthrone in nitrobenzene and reducing), (4) diamino-allo-ms-naphthodianthrone (made by reducing the nitro compound prepared by the action of fairly dilute nitric acid) yields a pyridino-derivative dyeing in blueish-red shades, (5) monoaminopyranthrone (made by nitration in nitrobenzene and reducing) yields a pyridino compound dyeing in blue red shades; the chloroaminopyranthrone obtained from monochlorpyranthrone (made by replacing the amino group in the monoaminopyranthrone by chlorine) by nitration in nitrobenzene and reduction yields a similar product, (6) diaminoanthanthrone (made by nitrating anthanthrone with concentrated nitric acid at room temperature) yields a dipyridino derivative dyeing in yellow shades; the product may be chlorinated by treating with chlorine in trichlorbenzene in the presence of iodine, or by treating with sulphuryl chloride in the presence of iodine and in the absence of any diluent, (7) monoamino-3 : 4 : 8 : 9-dibenzpyrene-5 : 10-quinone (obtained by nitrating in nitrobenzene and reducing) yields a pyridino derivative dyeing in orange-yellow shades, while the dipyridino derivative obtained from the diamino-3 : 4 : 8 : 9-dibenzpyrene-5 : 10-quinone made by reducing the nitro compound obtained by the action of concentrated nitric acid dyes in brown yellow shades; the pyridino derivative obtained from monoamino-4 : 5 : 8 : 9-dibenzpyrene-3 : 10-quinone dyes in red brown shades, (8) Bz2 : 3-dichlor-4-aminoanthraquinone-2 : 1-benzacridone yields the 4 : 3-pyridino derivative which dyes in violet shades, (9) 6(N) : 5-pyridinobenzanthrone is brominated or chlorinated, (10) pyridino-allo-ms-naphthodianthrone (example 3), pyridino-pyranthrone (example 5), and pyridino-ms-anthradianthrone (example 3) are halogenated; various chloro-, bromo- and mixed halogen derivatives are described, (11) pyridino-allo-ms-naphthodianthrone is nitrated; various products (which may be reduced to the corresponding amino compounds by sodium sulphide) are obtained according to the conditions, (12) monoaminoanthanthrone (made by nitrating anthanthrone in nitrobenzene and reducing) yields a pyridino derivative dyeing in golden-orange shades; on bromination in chlorsulphonic acid, a dibrom derivative is obtained, and on nitration a mononitro derivative, (13) monopyridino-3 : 4 : 8 : 9-dibenzpyrene-5 : 10-quinone is brominated in nitrobenzene, the monobrom derivative obtained dyes in orange-yellow shades, (14) monopyridinopyranthrone (example 5) is nitrated, the product dyes in blue-grey shades changed to brown by chlorine, and (15) monobrommonoaminoanthanthrone (made by brominating monoaminoanthanthrone in oleum) yields a pyridino compound dyeing in orange shades.