DE1817388A1 - Process for the carbazolization of anthrimides into derivatives of the diphthaloyl carbazoles - Google Patents

Description

Patent attorney

Dipl. Phys. DrAValther 3unius

. 3 Hanover, Abbeelr. 20th

December 27, 1968

Dr.j / Ha.

My act 1586

Vyzkumny ustav organickych syntez, Pardubice-Hybitvl

Process for the carbazolieation of anthrimides into derivatives of the diphthaloyl carbazoles

The invention relates to a process for the production of vat dyes based on diphthaloyl carbazoles by carbazolieation of anthrimides by the action of litantetrahalides (chlorides or Bromides) in a medium of organic solvents. '

Derivatives of diphthaloyl carbazoles form one of the main classes of vat dyes. You wise generally good coloristic properties and a wide range of shades from (JeIb and orange-yellow over there «brown, olive brown to gray, to khaki and black. Your manufacture consists of the so-called carbazolization of the antrhimids, which means a term, which in the

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Dye chemistry for dehydrogenation cyclization of the secondary amines of the anthraquinones used with the formation of a 5- or 6-membered nitrogen-containing heterocycle will. The carbazolization can essentially be carried out with three means: With sulfuric acid, Metal halides and alkali metal hydroxides, each of which has its own specific properties and has effects, which are usually due to the constitution of the starting substances is fixed.

Of the metal halides, it acquired the most universal and dominant position in industrial practice the aluminum chloride, which is either in the form of a melt with sodium chloride or in the form a solution in anhydrous organic bases (mainly pyridine) is used. From others Metal halides, the use of titanium tetra chloride has been described very often, which in the last fe years has become a generally accessible raw material is. In 1947 the American Cyanamid Company issued U.S. Patent 2,416,931 the use of titanium tetrachloride (at the same time as the use of titanium tetrabromide, zirconium tetrachloride and zirconium tetrabromide) for carbazoliiation of Most of the anthrimides used in practice are described. The manufacturing process consists of heating a suspension of anthrimides in an excess of titanium tetrachloride or better in one Dissolution of titanium tetrachloride in an inert solvent (in the Hegel in the halogen derivatives of

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Benzene) to temperatures of ^{100-200 0} O. Complex compounds of the resulting diphthaloyl carbazole derivatives with the metal halides used are obtained as primary products, which are isolated and processed further in various production methods into final dye products.

The real response can be broken down into three forms carry out.; By mixing the mixture of all components and heating to the required temperature, by heating the titanium tetrachloride solution in an inert solvent and by successively Dosage of a suspension of anthrimide in the same Solvent or by heating the suspension of anthrimide and by successively adding titanium tetrachloride solution. In this way one tries to remove the undesirable characteristics to cope with the given reaction technologically. The carbazolization does not proceed evenly and after in the course of heating, but only after reaching a certain critical temperature. Its level is mainly dependent on the constitution of the original anthrimide, but it has does not have a very precisely definable value and fluctuates within the limits between +5 to 10 ° C »Mach When the critical temperature is reached, the reaction begins abruptly, which then occurs usually very violent and practically uncontrollable. By forming a new bond In carbazolization, two hydrogen atoms are formed freed which from the reaction mixture in the form

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of hydrogen chloride escape. The chlorine is taken from the titanium tetrachloride present. This represents a significant technological problem when carrying out on a larger scale, in view of the violent course of the reaction mentioned. The successive metering of one component into the second component allows the reaction to be carried out in practice under the operating conditions, but it has some drawbacks. The very rapid course of Karbazolis'ation has the J ¹ cent, that in the reaction mixture practically from the beginning a certain ever increasing share of the product in addition to the previously reacted substance, under the relatively severe conditions of high temperature and the presence of Metal halides is located. This leads to a possible course of undesirable love reactions, which on the one hand worsen the quality of the product, on the other hand lower the yield of the desired product. The autocatalytic effect of the end product for the initiation (excitation) of the reaction, which was recommended as favorable by the authors of the method, was shown to be completely negative after a thorough examination.

By carefully studying the ILarbazolization reaction - in particular by precisely measuring their kinetic properties - has now been made possible by the invention found that these disadvantages can be avoided.

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The invention consists in that the suspension of the anthrimides and the titanium tetranalide in an inert, higher-boiling organic solvent is passed continuously with stirring through a heated zone, the actual reaction space, in which the actual reaction occurs, so that the product obtained is a complex compound of the diphthaloyl carbazole derivative with titanium halides. In this way it is achieved that the reaction components are only in the reaction space for a short time under the external reaction conditions, which is necessary to complete the reaction the Karbazolisation at a lower temperature than in the above-described method according to the US patent are performed, what still reported below. This provides the possibility of a Verlaufea of jJebenreaktionen to a minimum reduced ₃ which Sicla by improving the quality of products and by increasing the yields by about 5 ^c ß> noticeable.

From the technological point of view, this method of Karbazoliaation a great advantage in that it avoids the problems of a unbeherrschbarsn abrupt onset of the reaction and by the possibility of a continuous discharge of the hydrogen halide wes the risk sines explosive character of the reaction has borrowed, sat down

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Both unsubstituted substances can be used as starting substances Mono- and polyanthrimides (e.g. l, l '-, l, 2'- -Dianthrimide, 1,1 ', 4,1 "-, 1,1', 5, l" -issrianthrimid, 1,1 ', 4,1 ", 5,1'" IS,! "" - pentaanthrimide,) as their substituted derivatives (e.g. alkyl, alkoxy, halogen or acylamino derivatives) are also used will.

Titanium tetrahalides, such as titanium tetrachloride, titanium tetrabromide, are used in a length of 1.5 to 2.5 moles for a newly forming (forming) bond. A suitable medium for the cyclization are aromatic hydrocarbons of the benzene or liaphthalene series, which can be substituted with a wide variety of groups, provided they do not attach the titanium halides to themselves through firm complex bonds and do not interfere with their own reaction. Of the most suitable hydrocarbons, there can be mentioned benzene, toluene, xylenes, naphthalene, all their halogen derivatives, mainly o-dichlorobenzene, trichlorobenzene and others. Some higher-boiling halogen derivatives of aliphatic hydrocarbons, for example symmetrical tetrachloroethane, are also suitable for carrying out the carbazolization. And on the contrary: in a medium of aliphatic alcohols, ketones, low-boiling halogen derivatives or some heterocyclic compounds, e.g. 3. With pyridine ₉ , carbazolization does not take place.

The heating temperature of the reaction room depends

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ΘΑΟ ORIGINAL

of the constitution of the anthrimide and of the organic solvent used. ! The mechanism of participation of the solvent "in the reaction is not known; his influence as otherwise all Friedel-Crafts reactions, however, is visible, the reaction temperature can be defined in the range of 50 to 20O ⁰ C Its function is important.. At the beginning of the process it is advantageous to heat the mixture of the components to the maximum temperature, for example to the moderate boiling point of the solvent used, and to wait for the reaction to begin the first components react, it is _{advantageous}} to the temperature of at least 10 - 20 ⁰ C to lower, can be achieved whereby a good and technologically convenient reaction.

As soon as carbazolization occurs in the reaction mixture, a certain activated state develops, which autocatalytically influences the further course of the reaction in such a way that the reaction also takes place at a significantly lower temperature than was necessary for its initiation. For example, sufficient for Ι, Ι'-Dianthrimid have a temperature of 60 - 7O ⁰ C, for 1,1 ', 5,1' -Trianthrimid a temperature from 90 to 110 ⁰ G, for 1.1 *, 4.1 "- -Trianthrimid until a temperature of 110-120 ⁰ C. However, it is better in all cases, at higher temperatures by about 40 - 50 ⁰ C above this lower

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Limit to work, because by increasing the reaction temperature also the reaction rate increases, which leads to a faster passage of the reaction mixture through the heated Can take advantage of the reaction zone. It also supplies The maximum speed of reaction is another prerequisite for the most complete possible Reaction of the reaction mixture.

The flow rate is an important factor of the reaction mixture through the heated reaction zone. This rate is in given primarily with the constitution of the anthrimide, secondly with the reaction temperature. The influence of temperature has already been discussed and applies generally to all anthrimides. The influence of the anthrimide constitution cannot be defined in general terms. Obviously the Reaction fastest in the palle of 1,1 ', 4,1 "- -Triänthrimids, in which one mixes the reactions can be metered at such a rate that the filling (the content) of the actual reactor exchanged in 5 to 10 minutes; l, l'-Dianth3Jmid is about 1.5 to 2 times slower, 1,1 *, 5,1'-Trianthrimid dose about three to four times slower, among other things Limit the reaction mixture so that the content of the reactor exchanged in 5 to 60 minutes.

The actual implementation of the continuous carbazolization can be done in various ways

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bring about:

In the heated to a suitable temperature and provided with a good stirrer reaction chamber one doses either a homogenized G-emisoh of anthrimide or titanium tetrahalide at the necessary speed and organic solvent or the individual components independently. For example you can supply a suspension of anthrimide in an organic solvent and at the same time dose a solution of titanium tetrahalide in the same solvent in a certain ratio, as well as the halide, advantageously for example in the case of liquid titanium tetrachloride, dose independently.

The apparatus must have a suitable facility for discharging the hydrogen halide that is formed and the suspension of the complex compound of the dye are provided with the titanium halides.

The actual complex compounds can be distilled off in the usual way, e.g. by filtration of the solvent in a vacuum and the like. isolate. The decomposition of these complex compounds is carried out again in a generally known manner, for example according to the USA patent specification 2 41 6 931 or according to the Czechoslovak patent specification 123 732 by «,

The individual work processes and their implementation are illustrated in the following examples

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Example 1:

In a üeaktor 100 parts of o-dichlorobenzene, 2 parts of 1,1'-Dianthrimid and 2 parts Iltantetrachlorid (submitted, parts are liier everywhere (Jewichtsteile) and everything is heated to 150 ⁰ C. Ifech decay of the first Heaktion one starts with the Dosage of the components in a ratio of 4 parts!, L'-dianthrimide, 40 parts of titanium tetrachloride and 400 parts of o-dichlorobenzene at such a rate that the content of the reactor is exchanged in about 15 minutes of the reaction mixture, the temperature is allowed to drop to 120 ° C. and the temperature is then kept constant at this level. Diphthaloylcarbazole.Ti ₂ CIg is continuously filtered and the paste obtained is dried. By working up this primary product with the usual procedures, practically pure 1 is obtained 2,7,8-Diphthaloylcarbazole in a yield of at least 95% of theory.

Carbazolization gives the same result, when 40 parts of titanium tetrachloride are replaced by 73 »5 parts of titanium tetrabromide.

Example 2:

100 parts of trichlorobenzene are placed in a heater,

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2 parts of 1,1 ', 4,1 "-. Trianthrimid-and 2.5 parts titanium tetrachloride before, dae mixture was heated to 180 ⁰ C and this temperature is obtained up to the onset of the reaction After completion of the evolution of hydrogen chloride to start with the Dosage of the reaction component mixture in the following composition: 65 parts of 1,1 ', 4,1 "-Irianthrimid, 76 parts of titanium tetrachloride and 500 parts of trichlorobenzene at such a rate that the contents of the reactor are exchanged in about 10 minutes. The reaction temperature is allowed to spontaneously to 155 - decrease 160 ⁰ C and get them further at this altitude. The trichlorobenzene is distilled from the resulting suspension of a complex compound of the dye with the titanium chlorides in a kettle (Venulett) in vacuo. The solid product is processed in a known manner into the dye which is known under the trade mark Ostanthren brown RR. The results achieved are about $ 5 higher than with the known method.

Example 3;

In one. 100 parts of a technical reactor are heated Mixture of xylenes up to moderate boiling and into the xylene mixture are dosed at the same time on the one hand a suspension of 1,1 ', 5, l "-trianthrimide in the same solvent, on the other hand titanium tetrachloride in the proportion of 65 parts of anthri mid, 76 parts of titanium tetrachloride and 500 parts of solvent. The contents of the reactor are heated

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always to moderate boiling and regulates the dosage rate of the components so that the content of the reactor is exchanged in about JO - 40 minutes. By processing the derived Suspension of the product by the procedures as described in Example 1 or 2 a dye is obtained which is designated with the trademark Ostanthrengelb 3RT will, in a around 5? <> higher yield than in the synthesis according to the cited US patent.

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Claims (2)

- 13 claims : Process for the production of Eüpen dyes on the basis of diphthaloyl carbazoles by ICarbazolisation of anthrimides by action of iCitantetrahalogeniden (chlorides or bromides) in a medium of organic solvents, characterized, that the mixture of the reaction components, wel Ches 1.5 to "2.5 mol 'iitantetrahalogenid for a newly formed bond between the anthrimide molecules, is carried out continuously, advantageously with stirring, through a reaction zone (reaction space) which is at a temperature between 50 to 200 ^° C., the reaction mixture having to remain in the reaction chamber for the time necessary to complete the reaction of 5-60 minutes, whereupon the dye is isolated from the reaction product in a known manner 2. The method according to claim 1,
characterized, that one brings a homogenized mixture of all components in the necessary ratio to the reaction. Method according to claim 1, characterized, - that you have individual necessary components independently dosed to the reaction - 14 909848/09 5 7 Method according to claim. 1 to 3 »characterized, that one is aromatic as a solvent, optionally halo ^ enated iColilenv / a & cerfctoffe of the benzene or phthaline series or higher boiling halogenated aliphatic hydrocarbons used. y09848 / 0957