Patent GB-442129-A (GB)
Title: Manufacture of condensation products
IPC: F01L9/11
Filed: 1934-05-02
Abstract: Condensation products are prepared by subjecting a compound of the formula <FORM:0442129/IV/1> wherein X stands for hydrogen, the OH-group or the radicle of an acid, Y for oxygen, sulphur, an NH- or N-aryl group, and wherein there is contained a further benzene nucleus condensed in the 1.2-positions of the formula or in o-positions of the nucleus R, and, if desired, a further benzene nucleus condensed in the 7.8-positions or a substitution product thereof, to the action of a zinc chloride or aluminium chloride melt, or to the action of 1.4-benzoquinone in which case the reaction may be assisted by supplying energy in the form of heat or light or both. Inner ring closure appears to be effected to give condensed products which are dyes or intermediates.  In examples: (1) 9-(4<1>-methylphenyl)-dibenzoxanthenium chloride is heated with aluminium chloride at above 100 DEG  C. and subsequently at 200 DEG C. to give probably dehydro-9-(4<1>-methylphenyl)-1.2 : 7.8-dibenzoxanthenium chloride; (2) 9 - phenyl - 1.2 : 7.8 - dibenzoxanthenium perchlorate is heated with zinc chloride at 500 DEG C. to give probably a dehydro derivative; (3) 9-phenyldinaphthoacridine is heated with aluminium chloride at 200 DEG  C. to give a dehydro derivative; (4) p-nitrophenyldinaphthopyranol is heated with aluminium and sodium chlorides at 130--150 DEG  C. and a dehydro derivative obtained by precipitation of the aqueous filtrates with hydrochloric acid; this dyes cotton, tanned cotton, loaded and unloaded silk in red shades. Samples have been furnished under Sect. 2 (5) of products prepared (1) by heating ms-naphthylxanthenol with aluminium chloride at 200 DEG  C. and precipitating the product (presumed to be a dehydro derivative) as the perchlorate; (2) by condensing b .b -dinaphthylsulphide with benzoyl chloride in presence of aluminium chloride whereby ms - phenyl - 1.2 : 7.8 - dibenzothioxanthenium chloride is first formed and heating is then maintained at 200 DEG C. to give a dehydro derivative (dyes cotton and loaded silk in blue-green shades); (3) 9-phenyldibenzoxanthene in a mixture of acetic and hydrochloric acids is exposed to sunlight in presence of 1.4-benzoquinone to give a dehydro derivative which dyes unloaded silk in violet shades.  The Specification as open to inspection under Sect. 91 relates to the production of condensation products of carbenium compounds by treating carbenium compounds of any kind in the form of their salts, carbinols or methanes or substitution products thereof with oxygen in any form or by subjecting them to the action of another dehydrogenating agent.  As starting materials there are specified chromenium, flavenium or xanthenium compounds arylated in the 4-position of the heterocyclic pyrenium ring and the isologues of the sulphur, selenium, tellurium or NH-series; there are also specified carbenium compounds of the general formula <FORM:0442129/IV/2> wherein X stands for oxygen, sulphur selenium, tellurium or an imino- or substituted imino group, Y for hydrogen, a hydroxyl group or radicle of an acid, and R for an aryl group, and wherein in 1.2-position there may be condensed a further benzene nucleus. As dehydrogenating agents methylene blue and ferric salts are also specified.  In additional examples: (5) 9 phenyldibenzoxanthene is exposed to sunlight in a mixture of glacial acetic and hydrochloric acids at the boil and while introducing air or oxygen to give a dehydro derivative; (2) 9-phenyl - 7.8 - benzoxanthenium perchlorate is treated as in (5) to give a dehydro derivative; (3) phenyldinaphthoacridinium perchlorate is exposed to direct sunlight in nitrobenzene; (4) N-phenyl-ms-phenyl-1.2 : 7.8-dibenzoacridinium chloride is converted to a dehydro derivative by exposure to daylight or more rapidly to sunlight; (5) m-nitrophenyldinaphthopyrane is treated with a mixture of aluminium and sodium chlorides at 130 DEG  C. to give an aminated dehydro derivative which dyes cotton and tanned cotton green tints.  This subject-matter does not appear in the Specification as accepted.