DE622464C - Process for the preparation of dyes and dye intermediates - Google Patents

Description

Process for the preparation of dyes and dye intermediates The subject of the patent 6oo 6z6 is a process for the production of nitrogenous Condensation products; in the case of the pyridinonaphthalenes, which are attached to the pyridine ring isocyclic ring at least one oxygen atom in phenolic or ketone-like Binding contained in sulfuric acid medium with aerolein or compounds that how aeroleins are able to react are implemented. The compounds obtained are referred to there as pyrbenzanthrones. Since according to the guidelines of the International Union for Chemistry set up commission for reform of the nomenclature of organic chemistry (see reports of the German Chemical Society, Vol. 65 [193a], A. P. 15) the names of heterocyclic compounds of those the corresponding isocyelic compounds are to be derived in such a way that one should put the descriptions of the heteroatoms in front of them that end in a the compounds previously known as pyrbenzanthrones are referred to as azabenzanthrones will. The azabenzanthrones are therefore nitrogen isologues of the benzanthrone.

It has now been found that dyes and dye intermediates can be obtained if one is in the z. B. azabenzanthrones obtainable by the method of the patent mentioned introduces substituents by methods known per se. The substituents can take the place of hydrogen atoms or of substituents already present in the molecule; the latter can also be done by changing the substituents already present. The substitution products of azabenzanthrones obtainable in this way are in part with the after. The process of patent 6oo 6.26 is identical to azabenzanthrones obtainable by synthesis. In some cases, they represent new connections that were previously inaccessible or only very difficult to access.

By treating the azabenzanthrones with halogen or halogen donating Halogen derivatives are obtained, for example by bromination in inorganic ones or in organic media bromine derivatives, iodine derivatives by iodising in sulfuric acid; Mixed-halogenated azabenzanthrones are also light in the manner described accessible. By nitrating with nitric acid alone or in the presence of sulfuric acid, Nitrobenzene or glacial acetic acid, etc. one obtains nitroderivatives, which lead to the corresponding Amino derivatives can be reduced. When treating with pleum, more concentrated Sulfuric acid, chlorosulfonic acid or chlorosulfonic acid salts, sulfonic acids are obtained, in treatment with oxidizing agents, e.g. B. with manganese dioxide and sulfuric acid, oxy compounds are formed, by reaction with chlorosulfur there are mercapto compounds, by reaction with hydroxylamine in the presence of sulfuric acid amino compounds educated. The substituted by amino or sulfonic acid groups- Azabenzanthrones can easily be converted into oxyazabenzanthrones in a manner known per se transfer, which can then be alkylated or arylated if desired. the Aminoazabenzanthrorne can also be found via the diazo compounds according to Sandmeyer convert into halogen, cyano, rhodane and mercapto compounds.

The halogen derivatives of the azabenzanthrone series produced by the process of the patent 6oo 626 synthetically or according to the present process by direct Halogenation or by replacing the nitro groups of nitroazabenzanthrones can be, can be with compounds, which one to nitrogen, oxygen or Contain sulfur-bonded reactive hydrogen atom or metal atom; z. B. with ammonia, amines, e.g. B. aniline, or aminoketones, such as aminoanthraquinones, with phenol sodium, sulfur sodium, thiog @ ylcolic acid, etc., react. One can also the halogenazabenzanthrones by treatment with elemental sulfur or selenium or with selenium-oxygen compounds in sulfur or compounds containing selenium convict. The halogenazabenzanthrones give when heated with cyanide copper corresponding nitriles, which are converted to the corresponding carboxylic acids by the customary methods can be saponified. From azabenzanthrones and acid chlorides one obtains according to the Friedel-Crafts synthesis of ketone-like compounds. You can also do several Substituents simultaneously or one after the other in the molecule of the azabenganthrones introduce. -The reaction products are generally in very good yield and higher. Preserve purity, but can if necessary also by the usual methods, z. B. by crystallization, sublimation, boiling with solvents or over their salts or by treating them with oxidizing agents, cleaned or by the way resulting isomers, etc. are separated.

Example i -q: 6 parts of 8-azabenzanthrone of the formula (obtainable according to example i of patent 6oo 626) are suspended in 2.1 o parts of nitrobenzene with the addition of 1 part of iron and 2 parts of iodine, whereupon 75 parts of bromine are allowed to slowly flow in at 70 to 75%. The mixture is then heated to 70 to 75 minutes until a decrease in the free bromine content can no longer be determined. It is then allowed to cool, the yellow mass precipitated in crystalline form is filtered off with suction, the residue is heated to about 50 ° with dilute sodium hydroxide solution; sucks off and the residue recrystallizes from glacial acetic acid. A monobromazabenzanthrone with a melting point of 214 to 25 ° is obtained, which dissolves in concentrated sulfuric acid with a yellow color and yellow-green fluorescence.

One can also carry out the bromination in such a way that one can neutralize it the resulting hydrobromic acid to the reaction mixture from the outset calcium carbonate or similar active substances.

In an analogous manner, bromine derivatives can be prepared from the according to the process of the patent 6oo 626, Example 3, available azabenzanthrone or according to Example 2 of said patent obtainable methyl derivative of -B-azabenzanthrone produce. EXAMPLE 2 500 parts of 8-azabenzanthrone are heated in 2500 parts of nitrobenzene with the addition of 25 parts of iodine and 5 parts of iron with stirring to 170 °, leaves on it gradually flow in i5ooTeile bromine and then holds the reaction mixture up to completed bromination to 17o to 18o °. The reaction product deposited in crystalline form is worked up in the usual way and represents a dibromo-8-azabenzanthrone that crystallizes in felty yellow needles that melt above 300 °. In addition, even more highly brominated reaction products are obtained in small amounts, the melt above 36o °. The solution color of the bromazabenzanthrones thus obtained in concentrated sulfuric acid is yellow.

In an analogous way, by chlorinating the 8-azabenzanthrone, z. B. in trichlorobenzene, in the presence of iodine at 17o to 18o ° chlorine substitution products, z. B. a di- and a trichloro derivative. When treating with iodine in concentrated Sulfuric acid gives iodine derivatives.

From 8-azabenzanthrone is obtained by successive bromination and chlorination Chlorobromide derivatives, which can also be obtained by low-chlorination 8-azabenzanthrones subsequently treated with bromine. -The bromination can also take place in In the absence of diluents or in an aqueous suspension. example 3 23 parts of 8-azabenzanthrone are suspended in 180 parts of nitrobenzene and left at go ° gradually pour in 22 parts of 98% nitric acid while stirring. As soon as the The nitration is complete, the mixture is allowed to cool, filtered off with suction, washed with a little nitrobenzene after, the adhering nitrobenzene drives off with steam and crystallizes Reaction product from organic solvents, e.g. B. dichlorobenzene to. You get a mononitroazabenzanthrone in the form of orange-yellow needles that melt at 285 to 286 °.

Treated Iman the mononitro-8-azabenzanthrone thus obtained, which the Nitro group probably contains in the 2-position of the Bz nucleus, with reducing agents, z. B. aqueous sodium sulfur solution, a scarlet amino-8-azabenzanthrone is obtained, that melts at 267 to 268 °. Treatment with acetic anhydride gives from it an acetyl derivative, which changes into a bromine derivative when treated with bromine. The amino-8-azabenzanthrone can be diazotized and provides a diazonium compound, which when heated with water to 8o to go ° gives an oxy-8-azabenzanthrone. This Oxyazabenzantlirone is used when treating: with ethyl toluenesulfonate and potash converted into a methoxyazabenzanthrone in nitrobenzene solution at 20o °, the crystallized from glacial acetic acid in yellowish flakes.

In an analogous manner, one obtains from the isorneres of the 8-azabenzanthrone Azabenzanthrones, for example 5-azabenzanthrone or that according to example 3 of patent 60o 626 available azabenzanthrone, the corresponding nitro, amino and oxy derivatives etc. example q. 23 parts of 8-azabenzanthrone are slowly added to 35o parts 23o per cent Oleum and keeps on go until 100 °, until the sulfonation has ended, pour then on ice, dissolve the residue for cleaning in ammonia and fall with dilute Sulfuric acid. The 8-azabenzanthronesulfonic acid obtained is light in hot: water soluble, insoluble in methanol and melts above 300 °.

The sulfonic acid group can be used against other groups, e.g. B. against Oxy groups, or exchanging for halogen and by reduction into the mercapto group convict. Example 5 30 parts of 8-azabenzanthrone and 30 parts of benzoyl chloride are heated A few hours under reflux to boiling and then filtered in the Heat. When the filtrate cools, a brown mass separates out, which is then does not let it wither. It dissolves only slightly in boiling trichlorobenzene with yellow-green Fluorescence and, in its pure form, is a brick-red powder.

EXAMPLE 6 I5 parts of the according to Example i are heated in the autoclave available bromine-B-azabenzanthrons with 7 parts of copper cyanur in 30o parts of pyridine and holds at 150 to 155 ° until there is no more unchanged starting material is detectable, then sucks off and crystallizes the monocyanazabenzanthrone obtained from dichlorobenzene. around. It melts at 3o5 to 3o7 ° and delivers with the treatment Hydrochloric acid or sulfuric acid an azabenzanthronecarboxylic acid.

Example 7 150 parts of Bz-i-bromo-8-azabenzanthrone are obtained after the addition of 250 parts sodium sulphide and 100 parts sulfur in 100 parts butyl alcohol like this heated to the boil for a long time until everything has gone into solution. You then let it cool down and sucks after diluting with water and acidifying with acetic acid. The received The reaction product is a yellow powder and dissolves in alkali with a red-violet, in concentrated sulfuric acid with purple color.

Oxidation with hydrogen peroxide gives mari an alkali-insoluble one yellow reaction product, which is likely the corresponding disulfide.

Bz-i-bromo-8-azabenzanthrone and selenium are obtained in an analogous manner a selenium-containing reaction product. From Bz-i-halo-8-azabenzanthrone and thioglycolic acid a sulfur-containing substitution product is created .. Bz-i-halogen-8-azabenzanthrone gives with sodium methylate Bz-i-methoxy-8-azabenzanthrone and with phenol in the presence a phenoxy derivative from potash.

Example 8 150 parts of Bz-i-bromo-8-azabenzanthrone are in 2ooo. share Naphthalene after adding 100 parts of potash, 2 parts of copper carbonate and i30 Share a-aminoanthraquinone with stirring heated to boiling until one removed Sample is practically bromine-free. Then let it cool down a bit, suck it up, possibly afterwards Dilute with toluene or chlorobenzene, in the heat, removed from the residue the inorganic accompanying bodies by boiling with water or dilute acid and dries. Bz-i-a-Anthraquinonylamino-8-azabenzanthrone obtained in the form of felt needles dissolves in concentrated sulfuric acid with a green color and delivers a brown vat from which the vegetable fiber is colored pale purple-red.

From 1 mole of Bz-i-bromo-B-azabenzanthrone and% Mo1 1 # 5-diaminoanthraquinone a condensation product is obtained in the form of purple-brown crystals, which is in concentrated sulfuric acid with a green color.

Condensed with Bz-i-bromo-8-azal7enZ-anthrone with i-amino-q.-benzoylarninoanthraquinone, so, a crystalline violet condensation product is obtained with i-amino-5-benzoylaminoanthraquinone crystalline brown condensation product, with i Möl i # 5-diaminoanthraquinone a dark purple crystalline condensation product.

Instead of a-aminoanthraquinone, one can also use its substitution products, z. B. i-amino-4-methoxy- or i-amino-5-methoxyanthraquinone or i-amino-2-methylanthraquinone, i-amino-7-benzoylaminoanthraquinone, ß-Aminoanthraquinone and its derivatives, also Aminoanthraquinone acridones, Am.inoanthraquinone imidazoles, AminoanthraquinonthiazQle ,. Aminoanthrapyrimidines, Aminoanthrapyridones, Aminoanthrapyriinidones, Use aminobenzanthrone etc.

Bz-i-bromo-8-azabenzanthron delivers when treated with -Amixioniak an amino derivative under pressure. The dibromazabenzanthrone obtainable according to Example 2 on condensation with z moles of a-aminoanthraquinone gives a dark purple condensation product. Example 9 A mixture of 15 parts of Bz-i-bromo-8-azabenzanthrone is heated, 12 parts of pyrazole anthrone and 8 parts of potash in zoo parts of nitrobenzene are so long to boiling until no more unchanged starting material can be detected. Thereon one works up in the usual way. That obtained in the form of yellow crystals Condensation product dissolves in concentrated sulfuric acid with an orange color.

The dibromo-8-azabenzanthrone obtainable according to Example 2 is condensed with 1 mole of pyra: zolanthrone, a straw-yellow, crystalline, bromine-containing one is obtained Reaction product. Example 10 80 parts of the dibromo-8-azabenzanthrone obtainable according to Example z are with 45 parts of pyrazolanthrone and 6o parts of potash in 1500 parts of nitrobenzene Heated to the boil for several hours, then allowed to cool down a little, gives Sun. Share α-aminoanthraquinone, 50 parts calcined soda and 10 parts copper acetate and heated to the boil until the reaction has ended. That in the usual Way isolated condensation product is a brown crystalline powder, which Dissolves in concentrated sulfuric acid with a green color.

Claims (1)

PATENT CLAIM: Process for the production of dyes, substances and intermediate dyestuff products, characterized in that substituents are introduced into azabenzanthrones.