Patent GB-539078-A (GB)
Title: Process for the manufacture of new naphthalene derivatives
IPC: C07C309/51
Filed: 1940-04-05
Abstract: 539,078. Acylamino-naphthalene-sulphonic acids. SANDOZ, Ltd., (formerly CHEMISCHE FABRIK VORM SANDOZ). April 5, 1940, No. 6168. Convention date, April 5, 1939. [Class 2 (iii)] Naphthalene derivatives useful as dyestuff intermediates are prepared by treating with acylating agents 1-hydroxy-4-amino-naphthalene-3-sulphonic acids in which the 2-position is unsubstituted and which may contain other substituents with the exception of an unsubstituted or a mono-substituted amino group in the 5-position. The acylated products may if desired be partially saponified by treatment with alkaline saponifying agents to set free the hydroxyl group in the 1-position, and also if desired further treated with acid saponifying agents under moderated conditions so that the 4-acylamino group is not saponified. Suitable acylation agents mentioned include aliphatic, araliphatic, cycloaliphatic, aromatic and heterocyclic carboxylic acids, their halogenides and anhydrides such as formic acid, acetic anhydride, chloracetyl chloride, butyryl chloride, stearyl chloride, cinnamyl chloride, benzoyl chloride, p- or m-nitro-benzoyl chloride, naphthoyl chloride, the halogenides of organic' sulphonic acids, phosgene, thiophosgene or cyanuric chloride. Parent materials mentioned include 1-hydroxy-4:6-diaminonaphthalene-3- sulphonic acid, 1-hydroxy-4:7-diaminonaphthalene-3-sulphonic acid, 1-hydroxy-4:8-diaminonaphthalene-3-sulphonic acid, 1-hydroxy-4:7- diaminonaphthalene-3:6-disulphonic acid, 1- hydroxy - 4:8 - diaminonaphthalene-3:6-disulphonic acid, and their derivatives which are substituted in the amino group in the 6-, 7-, or 8-position by alkyl, aralkyl, aryl or acyl. Also halogenated 1-hydroxy-4-aminonaphthalene-3- sulphonic acids, such as 1-hydroxy-4-amino-6- chlornaphthalene-3-sulphonic acids, 1-hydroxy- 4-amino-8-chlornaphthalene-3-sulphonic acid as well as the corresponding disulphonic acids. These parent materials may be prepared by coupling negatively substituted diazo compounds with the corresponding 1-hydroxynaphthalene-3-sulphonic acids and subsequent reduction of the azo-dyestuffs. Alternatively, they may be made by introducing the nitrosogroup into the 4-position of the 1-hydroxynaphthalene-3-sulphonic acid and the subsequent reduction of the nitroso group. The acylation may be carried out in aqueous or anhydrous media, if desired in the presence of organic bases such as pyridine. In examples : (1) 1-hydroxy-4-aminonaphthalene-3-sulphonic acid is treated with acetic anhydride and then partially hydrolysed with 25 per cent. ammonia to give the corresponding 4-acetylamino-compound, which couples smoothly with diazo compounds to form azo-dyestuffs. (2) 1- hydroxy - 4-aminonaphthalene - 3:8-disulphonic acid is treated with acetic anhydride and partially hydrolysed with weak caustic alkali to give the 4-acetylamino derivative. The parent material is prepared by the reduction of the dyestuff formed from diazotized p-nitranilineo-sulphonic acid and 1-hydroxynaphthalene-3:8- disulphonic acid. (3) 1-hydroxy-4:8-diaminonaphthalene-3:6-disulphonic acid is treated with acetic anhydride and glacial acetic acid, and partly hydrolysed with sodium carbonate to give 1-hydroxy-4:8-diacetaminonaphthalene- 3:6-disulphonic acid. The parent 1-hydroxy- 4:8-diaminonaphthalene:3-6-disulphonic acid is prepared by reduction of the dyestuff prepared from diazotized p-nitraniline-o-sulphonic acid and H-acid. (4) 1-hydroxy-4-amino-7-chlornaphthalene-3-sulphonic acid prepared by the reduction of the dyestuff from diazotized pnitraniline-o-sulphonic acid and 1-hydroxy-7- chlor-naphthalene-3-sulphonic acid, is treated as in example (1). (5) 1-hydroxy-4-aminonaphthalene-3-sulphonic acid is treated with phosgene in the presence of sodium acetate. (6) 1-hydroxy-4-amino-7-acetylaminonaphthalene- 3-sulphonic acid is treated with acetic anhydride and sodium acetate to give 1-acetyloxy-4:7-di- (acetylamino )-naphthalene-3-sulphonic acid. The acetoxy group is removed with sodium carbonate to give 1-hydroxy-4:7-di-(acetylamino)-naphthalene-3-sulphonic acid. The 7- amino group may be saponified by treatment with dilute sulphuric acid. The parent 1- hydroxy-4-amino-7-autylaminonaphthalene - 3 - sulphonic acid is prepared by the reduction of the azodyestuff prepared by coupling 4-nitro-1- diazobenzene-2-sulphonic acid with 1-hydroxy- 7-acetylaminonaphthalene-3-sulphonic acid. (7) A pyridine solution of 1-hydroxy-4-amino-7- acetylaminonaphthalene-3-sulphonic acid is treated with benzoyl chloride to give 1-hydroxy- 4 - benzoylamino-7-acetylaminonaphthalene - 3- sulphonic acid. (8) 1-hydroxy-4-amino-7-acetylaminonaphthalene-3-sulphonic acid are treated with 4-nitrobenzoyl chloride in the presence of aqueous sodium acetate to give after partial hydrolysis with weak sodium carbonate 1- hydroxy-4 - (p - nitrobenzoylamino) - 7 - acetyl - aminonaphthalene-3-sulphonic acid. Instead of the 7-acetylamino compound there may be used the corresponding 6-acetylamino compound. (9) Phosgene is passed into a solution of sodium acetate and 1-hydroxy-4-amino-7- acetylamino-naphthalene-3-sulphonic acid to give the corresponding urea derivative. The corresponding 6-acetylamino-compound may also be used as starting material. (10) 1-hydroxy - 4 - amino-6-acetylaminonaphthalene-3-sulphonic acid is treated as in example (6) to give 1-hydroxy-4:6-di-(acetylamino)-naphthalene - 3- sulphonic acid. The parent material is obtained by reducing the dyestuff resulting from the coupling of paranitrodiazobenzene-sulphonic acid with N-acetyl-J-acid. (11) A pyridine solution of 1-hydroxy-4-amino-7-acetylaminonaphthalene-3-sulphonic acid is treated with p-toluenesulphochloride and partially saponified with sodium carbonate to give 1-hydroxy-4- (p-toluenesulphonyl) -amino - 7 - acetylamino-3- sulphonic acid. (12) 1-hydroxy-4:7-diaminonaphthalene-3:6-disulphonic acid is acylated with acetic anhydride and sodium acetate and the triacetyl compound treated with dilute aqueous or alcoholic alkali to give 1-hydroxy- 4:7-diacetylaminonaphthalene - 3:6 - disulphonic acid, which on hydrolysis with dilute mineral acid may itself be partially hydrolysed to split the 7-acetylamino group and to leave only the 4-acetylamino group unaltered. The parent 1-hydroxy-4:7-diaminonaphthalene - 3:6 - disul - phonic acid may be obtained by coupling 1- diazo-4-nitrobenzene-2-sulphonic acid with 1- hydroxy-7-acetylaminonaphthalene-3:6-disulphonic acid and filtering from the minor proportion of dyestuff which contains the azo group in position-2. The main proportion of dyestuff in which the azo group has entered position-4 is reduced with stannous chloride to give the required acid. If desired the separation of the dyestuffs may be avoided, and the mixture of 1-hydroxy-4:7-diaminonaphthalene-3:6-disulphonic acid and 1:4-diaminobenzene-2-sulphonic acid acylated and filtered hot, thus obtaining the triacetyl compound of the naphthalene derivative while the diacetyl benzene compound remains in solution. (13) 1-hydroxy-4-amino-7- phenylaminonaphthalene-3-sulphonic acid is acylated with acetic anhydride and sodium acetate, and partially hydrolyzed with sodium carbonate to give 1-hydroxy-4-acetylamino-7- phenylaminonaphthalene-3-sulphonic acid. The parent material is prepared by reducing the reaction product of 4-nitrodiazobenzene or 4-nitrodiazobenzene-2-sulphonic acid and 1- hydroxy-7-phenylaminonaphthalene-3-sulphonic acid.