Patent GB-512841-A (GB)
Title: Process for the manufacture of condensation products of the anthraquinone series
IPC: C09B5/36
Filed: 1938-03-17
Abstract: 512,841. Dyes. I.G. FARBENINDUSTRIE AKT.-GES. March 17, 1938, No. 8318. Convention date, March 17, 1937. Sample furnished. [Class 2 (iii)] Dyes are made by heating aromatic amines containing at least one hydrogen atom attached to nitrogen with alpha-arylamino-anthraquinone- 2.1-(N)-1<1>.2<1>-(N)-acridones which contain a - COX group in the aryl nucleus (X being halogen) and correspond to the formula. Aalpha-NH-aryl-COX wherein A stands for an anthraquinone-benzacridone and alpha indicates that the nitrogen atom is attached to the anthraquinone nucleus of A in an alpha-position thereof. Amines specified are aminoanthraquinones, and when aminoanthraquinones containing in o-position to the amino group a hydroxy, mercapto or NHR group (R being hydrogen, alkyl, or aryl) are used, an oxazole, thiazole, or imidazole ring system is formed on further heating'. The acridone starting materials are made by reacting an alpha-aminoanthraquinone-2.1-(N)-1<1>.2<1>-(N)-acridone with a halogen-benzoic acid ester, followed by saponification and treatment with an acid chloride forming agent such as thionyl chloride. The reaction is carried out in excess of the amine or in a solvent such as o-dichlorbenzene, trichlorbenzene, nitrobenzene, chlornaphthalene or ethyl-carbazole. Products prepared from anthraquinone-acridones having the arylamino radicle in 4-position dye cotton yellowish-green shades, in 5- or 8-position violet-brown to black-brown shades ; they can be recrystallized from quinoline. In examples : (1) 3.<1>5<1>- dichloro-anthraquinone-2.1 (N)-1<1>.2<1>-(N)-benzene - acridone - 4 - (anilido -pcarboxylic acid chloride) is reacted with 1-aminoanthraquinone (green shades on cotton), 1-amino-5-benzoylaminoanthraquinone (yellow-green), 4-amino- 1.9-anthrapyrimidine (olive-green), 4-amino- 5<1>-chloro-anthraquinone-2.1-(N)-1<1>.2<1>-(N)- benzene acridone (greenish-blue) ; (2) 3.5<1>-dichloroanthraquinone-2.1-(N)-1<1>-2<1>-(N) - benzene - acridone-4-(anilido-m-carboxylic acid chloride) is reacted with 1-aminoanthraquinone ; (3) 5<1>- chloro-anthraquinone-2.1 (N)-1<1>.2<1>-(N)-benzeneacridone-4-(anilido-p-carboxylic acid chloride) is heated with 2.3-aminohydroxy-anthraquinone, 1-amino-2- hydroxyanthraquinone, 2-amino- 3-mercaptoanthraquinone or 1-anilido-2-aminoanthraquinone to give the corresponding acridone-oxazole, acridone-thiazole, and acridoneimidazole bodies ; (4) 41-chloroanthraquinone- 2.1 - (N) - 1<1>.2<1> - (N) - benzene - acridone - 4 - (anilido-p-carboxylic acid chloride) is reacted with 2-amino-3-mercaptoanthraquinone to give a thiazole. A sample has been furnished under Sect. 2 (5) of an acridone-oxazole prepared from anthraquinone - 2.1 - (N) - 1<1>.2<1> (N) - benzene - acridone-5-(anilido-p-carboxylic acid chloride) and 1-amino-2-hydroxyanthraquinone 31.51 - Dichloro - anthraquinone - 2.1 - (N) - 1<1>.2<1> - (N) - benzene - acridone 4 - (anilido - p - carboxylic acid chloride) is prepared by condensing 4-amino-3<1>.5<1>-dichloro - anthraquinone - 2.1 (N)-1<1>.2<1>-(N)-benzene-acridone with pbromobenzoic acid methyl ester, followed by saponification of the product in an alkaline medium to the free acid, which is then reacted with thionyl chloride in trichlorobenzene. The 51-chloro body is similarly prepared. The Specification as open to inspection under Sect. 91 also refers to starting materials prepared by reacting an anthraquinone-1.4-dihalogen-2- carboxylic acid with 1 mol. of an aminobenzoic acid ester to give an anthraquinone benzacridone containing a carbethoxy group in the benzene nucleus, which may then be reacted with an arylamine, followed by saponification of the carbethoxy group, and conversion of the carboxylic acid to the acid chloride. Two mols. of the same aminobenzoic ester may be employed, or 1 mol. each of two different esters. A schedule further specifies as starting materials, on the one hand, anthraquinone- 2.1(N)- 1<1>.2<1> - (N) - benzene - acridone - 5 - (anilido - p - carboxylic acid chloride) or its Bz.-3.5-dichloroderivative, and anthraquinone-2.1(N)-11.21- (N)-naphthacridone - 5 - (anilido - p - - carboxylic acid chloride, and on the other hand, 1-amino-2- hydroxyanthraquinone, 1-hydroxy-2-aminoanthraquinone, 1-amino-2-mercaptoanthraquinone, 2-amino-3-hydroxyanthraquinone, 1-mercapto-2-aminoanthraquinone ; it also describes the reaction of 5<1>-chloroanthraquinone-2.1(N)- 1<1>.2<1> - (N) - benzeneacridone - 4 - (anilido - p - carboxylic acid chloride) with dehydrothiotoluidine. This subject matter does not appear in the Specification as accepted.