DE1445956A1 - Carbazole derivatives and processes for their preparation - Google Patents

Description

Carbazole derivative; e and process for their preparation The present Invention relates generally to organic compounds and, more particularly, to new substituted ones Carbazoles, such as, for example, 9- (3-butenyl) carbazole and 9-g-4-monohalobutyl) carbazoles, and their manufacture.

Carbazole is a well-known nitrogen-containing organic compound, which is also called dibenzopyrrole or diphenyleneimine and has the structural formula is equivalent to.

Carbazole has a melting point of around 244-2460c and a boiling point from 352 - 3540C and is soluble in alcohol and ether and insoluble in water. It is used technically for the production of dyes of the carbazole type and also as chemical Reagent used in various types of reactions. This is how it is in production of explosives, insecticides, fungicides, glidants and lubricants, antioxidants for rubber and the like. Used as an odor inhibitor for detergents.

Carbazole can be made from raw anthracene cake by selective dissolution of Phenanthrene with crude solvent naphtha and subsequent removal of the phenanthrene by converting it into a sulfonic acid derivative and then extracting it with Water can be obtained. Carbazole is also obtained synthetically from o-aminodiphenyl nen. Carbazole derivatives have also already become known. So was the making of 9-vinylcarbazole by reacting carbazole with B-chloroethyl-p-toluenesulfonac in Acetonldaung in the presence of sodium hydroxide and subsequent treatment with methyl alcohol Potash lye described.

Considering the increasing use of carbazole for various Reactions. including various syntheses and the like, it is extraordinary desirable to have carbazole derivatives available, the new chemical products with suitable chemical, physical and electrical properties capital.

The present invention, therefore, is primarily concerned with providing new reactive carbazole derivatives.

The present invention further relates to the provision of new carbazole derivatives chemically selected to form new products with physical and chemical properties can react.

These and other objects are achieved in accordance with the invention by providing new compounds such as 9- (3-butenyl) .- carbazole and 9- (4-monohalobutyl) -carbazole, achieved.

The new compounds according to the invention are substituted carbazolo of the formula in which X is a butenyl radical or a monohalogenated butyl radical in which the halogen is chlorine, bromine or iodine.

Attempts have been made to obtain 9- (3-butenyl) carbazole by condensation (Elimination of hydrogen halide) from sodium carbazole n; it 4-bromobutene (1) manufacture. However, these incinerations are due to the formation of butadiene from the 4-bromobutene- (1) was not successful due to catalysis by sodium carbarol. Self in carrying out such a reaction over a wide range of temperatures and even when using lithium arbazole instead of sodium carbazole Favoring the desired condensation reaction instead of the dimerization reaction 9- (3-buteryl) -earbazole could not be produced in an appreciable amount.

It has now been found that 9- (3-butenyl) -carbazole is easy and effective Meadow in considerable yield through condensation of sodium carbazel and 1,4-dichlorobutene or 1,4-dibromobutane and subsequent elimination of nalohydrogen from the Kendensationspredukt can be produced. for example, sodium arbazole was mixed with 1,4-dichlorobutane in a gesigeton reaction medium (tetrahydrofuran) at reflux temperature the new prebond 9- (4-chlorobutyl) -carbazole replaced. From the 9- (4-chlorobutyl) carbazole obtained was then melogen hydrogen using potassium tert.-buthlate as a hydrogen splitting agent (Hydrogen halide acceptor) split off under reflux conditions, including the 9- (4-chlorobutyl) carbazole in a suitable reaction medium (tert -butyl alcohol) was present in order to achieve a considerable Yield of the new compound 9- (3-butyenyl) carbazole to be obtained. It should be noted that 9- (4-chlorobutyl) -carbazole and similar new 9- (4-monohalobutyl) -carbazoles can also be produced as intermediates in the production of the 9- (3-butenyl) carbazoles and other substituted carbazoles and other compounds are valuable.

It was found that the 9- (3-butenyl) carbazole itself is responsible for CinO Pure of uses is extremely suitable. So it is as a starting point or Intermediate product in the production of various new chemicals, including new types of polishing materials, valuable, gate insulation purposes, coatings and coatings and the like and also for the production of suitable polymer-containing Products, for example photo providers and the like. Are useful.

1. It has also been found that 9- (3-butenyl) -oarbasol is suitable for use in the production of agricultural chemicals, including insecticides, Fungicides and the like, of pharmaceutical preparations or other chemical products, also suitable.

9- (3-butenyl) carbazole is highly reactive, which is partly due to the presence of the double bond is conditional on both chemical reactions of the type of reactions involving free radicals as well as the reactions can be of the ionic type. In addition, the double bond can cause polymerization occur and active substitution can take place on the aromatic nucleus. In addition, the nitrogen atom of 9- (3-butenyl) carbazole can easily be oxidized. For example, 9- (3-butenyl) carbazole can have one dye site or a plurality of dye sites in a polymer, such as polypropylene or the like., introduce. As a result, 9- (3-butenyl) carbazole has proven to be a new and valuable one chamic connection for the production of selected chemical products with selected physical and chemical properties proven.

According to another aspect of the invention, as already mentioned, provided novel halogen-substituted carbazoles that are suitable for use in the H.rstellwig of 9- (3-butenyl) carbazole and other compounds are suitable.

The protruding and other objectives, features and advantages of the present Invention are from the following more detailed description of preferred embodiments of the invention can be seen.

According to the invention, an alkali metal carbazole is condensed with a dihalogenated butane. The product can then be subjected to hydrogen halide cleavage to produce 9- (3-butanyl) carbazole. The alkali metal arbazole is preferably A sodium carbazole, but can also be potassium carbazole or lithium carbazole if desired. The alkali carbazole can be obtained in any suitable manner, for example by adhesion of carbazole with a selected alkali hydride in the presence of a suitable solvent at room temperature. Such a solvent can be, for example, tetrahydrofuran or the like. The reaction can be represented as follows: > + B2 ii) r XEi s2 zn-erte- N # N X R 1 wherein X is sodium, potassium or lithium.

The dihalogenated butanes are commercially available and currently belong to 1,4-type ans So the butane 1,4-dichlorobutane, 1,4-dibromobutane, 1-chloro-4-bromobutane, 1-iodo-4-chlorobutane, 1,4-diiodobutane or the like. The halogen atoms of the dihalogenated Butanes are from the group of chlorine, bromine and iodine atoms and the mixtures of these chosen. The halogen atoms on the butane in the 11 and 4 positions can be the same Type or any two of the specified three types of halogen atoms.

The condensation of the sodium or another alkali metal carbazole with the 1,4-diahogenated butanes is preferably carried out at reflux temperatures or at any other suitable temperature, for example at 70-75 ° C., with the reaction components in a suitable organic solvent, for example tetrahydrofuran or the like. , are dissolved, and in the presence of a catalyst, such as sodium iodide or the like., carried out to obtain the new 9- (4-halobutyl) carbazoles. The reaction is carried out for a period of 16-18 hours, for example, until the practical completion. The reaction can be represented by the following equation: in which X is sodium, potassium or lithium and Y is a chlorine, bromine or iodine atom0 For example, the sodium of sodium carbazole reacts with one of the chlorine atoms of 14-dichlorobutane under condensation of the butane with the carbazole to form monochlorobutylcarbazole, namely 9- (4-chlorobutyl) carbazole.

The spalling off of hydrogen halide from 9- (4-monohalobutyl) carbazole, i.e. 9- (4-chlorobutyl) carbazole, 9- (4-Bromobutyl) -carbazole or 9- (4-J @ dbutyl) -carbazole is prepared using either suitable hydrogen halide elimination catalyst or any hydrogen halide acceptor carried out, whereby the desired product is obtained in a satisfactory yield will.

However, it has been found to be harsh conditions for most purposes are required and that metal alkylates, such as potassium tert-butoxide in tert-butyl alcohol or the like, as hydrogen halide cleavage catalysts or hydrogen halide acceptors are preferred for use under reflux conditions are.

The hydrogen halide elimination reaction takes place during a suitable Period of time, for example about 66 hours, and in a suitable organic Medium, for example tert-p-butyl alcohol. Other suitable media include Diglyme (diethylene glycol dimethyl ether) or other suitable high-boiling solvents. During the elimination of hydrogen halide, the 9- (4-monohalgoenbutyl) -carbazole by removing the halogen atom together with a hydrogen atom from a carbon atom, that is adjacent to the one carrying the halogen atom, with the formation of a double bond practically converted into 9- (3-butenyl) carbazole.

After the reaction has ended, the desired product, 9- (3-butenyl) carbazole, of the reaction components and the solvent or organic reaction medium in each in any suitable manner, for example by evaporation of the solvent and crystallization from a suitable medium or by evaporation of the solvent, ether extraction and crystallization and the like., Separated. So For example, the solvent can partially evaporate and the mixture then cool left, poured into water and extracted with Xther, the obtained Ether extracts are then combined, dried and freed from the solvent in order to to obtain pure 9- (3-butenyl) carbazole.

It was also found that the method described ohPn works also on the preparation of 9- (3-butenyl) carbazoles, the substituents, in particular Have alkyl and / or aryl and / or alkaryl substituents on the butenyl chain, can apply.

The following examples illustrate the invention without restricting it.

Example 1 Sodium carbazole is obtained by reacting 8.3 g (0.050 mol) Carbazole in 55 ml of tetrahydrofuran with 2.8 g (0.061 mol) of sodium hydride (53.1% strength Dispersion in mineral oil) in 60 ml of tetrahydrofuran at room temperature within 2 hours made. The product is then heated to reflux temperature in Covered a dropping funnel and added dropwise to a mixture of 73.0 g (0.57 Mol) 1,4-dichlorobutane in 60 ml of tetrahydrofuran and a small one Amount of potassium iodide was added with stirring, the mixture then being kept at 70-75 ° C will. Stir heating is continued for an additional 18 hours.

The cooled reaction mixture is then poured into 500 ml of water and extracted three times with 60 ml of Xther each time. The combined ether extracts become then dried over anhydrous magnesium sulfate. The solvent is then put together removed with unreacted 1,4-dichlorobutane by vacuum distillation, and the solid residue is recrystallized from 300 ml of methanol, 8.2 g (63.6% strength Yield) of a pale brown Festsübstanz with a temperature of 92-95 ° C. By Vacuum sublimation (at 1300C and 0.1 mm Hg) of this product is finally obtained a white product from. F = - 97 ° C, identified by chemical analysis as 9- (4-chlorobutyl) -oarbazole is identifiable, Analysis:: Calculated C 74.55 H 6.26 N 5.43 Cl 13.76% found 74.81 5.79 5.45 13.48% This analysis reveals the identity of the product with 9- (4-chlorobutyl) carbazole.

The 9- (4-chlorobutyl) -carbazole then undergoes the elimination of halohydrogen subject. This is done by mixing 1.0 g (0.004 moles) 9- (4-chlorobutyl) carbazole obtained with 0.35 g (0.009 mol) of potassium and 20 ml of tert-butyl alcohol, whereby you mixture 66 hours or so long until the hydrogen halide elimination reaction is practically has ended, is maintained at the reflux temperature.

The mixture is poured into 80 ml of water and then twice with each 40 ml of diethyl ether extracted. The extracts are combined and dried over anhydrous dried magnesium sulfate. The Xther is then vaporized into the thick remaining yellow oil is distilled. The boiling point is 145 ° C at 0.1 mm Hg.

The product is subjected to combustion analysis, NMR analysis and analysis by infrared spectrography. The results show that the product is about 80% by weight of 9- (3-butenyl) carbazole (about 50% yield9 and 20% by weight of # -tert-butoxy-Nn-butylcarbazole of the formula contains. The 9- (3-butenyl) -carbazole is practically completely separated from the # 6J-tert-butoxy-Nn-butylcarbazole by conventional gas chromatographic separation. Example 2 9- (3-butenyl) -oarbazole is prepared by first 4.1 g (0.025 mol) of carbazole in 30 ml of tetrahydrofuran are reacted with sodium hydride. The sodium hydride is present at a concentration of 1.4 g (0.034 mol) as a 53.1% suspension in mineral oil in 30 ml of tetrahydrofuran. The mixture is kept at room temperature for 2 hours.

The sodium arbazole formed is then heated to reflux temperature, transferred to a dropping funnel and added dropwise to a mixture of 54.0 g (0.25 Mol) 1,4-dibromobutane, which is present in 25 ml of tetrahydrofuran, was added with stirring.

The resulting mixture becomes during the reaction, which over a period of time of about 18 hours, held at reflux temperature. Then the reaction mixture is cooled and poured into 500 ml of water and extracted three times with 60 ml of Xther each time. The combined Xether extract is dried over anhydrous Magnesium sulfate dried, and the solvent is combined with unreacted 1,4-dibromobutane removed by vacuum distillation. The pale yellow solid substance obtained is in an amount of 6.2 g (83.0%). By vacuum sublimation at a table at 140 ° C and a pressure of 0.2 mm S a white product of F = 104 is obtained - 106 ° C.

Analysis: 9- (4-bromobutyl) carbazole calculated: C 63.58 H 5.34 N 4.64 Br 26.44% found t 63.76 5.57 4.63 26.32% This analysis shows that the product 9-94-bromobutyl) carbazole.

You 9-A (4-bromobutyl) -carbazole is then put together in an amount of 1.2 g with a hydrogen bromide splitting agent to produce the desired end product 5, 9 - (3-butenyl) carbazole, is used. The procedure for this stage is convenient identical to that described in Example 1.

1.2 g of 9- (4-bromobutyl) carbazl are mixed with 0.35 g of potassium and 20 ml of tert-butyl alcohol mixed. The mixture is held at reflux temperature for about 66 hours, after which the hydrogen halide release reaction has ended.

The recovery and purification of the desired 9- (3-butenyl) carbazole are obtained in the same manner as in Example 1. The 9- (3-butenyl) carbazole is in about 50% yield together with # -tert. -Butyoxy-N-n-butylcarbazole before [about 70% by weight of 9- (3-butenyl) carbazole and about 30% by weight of the above-mentioned ether]. The separation of 9- (3-butenyl) -carbazole from the named ether takes place in gaseous form State by usual gas chromatographic separation using helium performed.

There can also be a carrier gas-liquid separation by liquid chromatography Separation methods can be made.

The production of 9- (3-butenyl) carbazole can also be successfully carried out under application of practically the same procedure as in Examples 1 and 2, but using other 1,4-dihalogenated butanes, such as 1,4-diiodobutane, 1-chloro-4-bromobutane and 1-bromo-4-iodobutane.

An alternative procedure according to the invention for the production of 9- (3-butenyl) carbazole involves the preparation of a dimethylamine derivative from 9- (4-monohalobutyl) carbazole and subsequent oxidation of the Amine and pyrolysis of the oxide obtained to give the desired 9- (3-butenyl) carbazole.

This manufacturing process is characterized by the lack of education unexpected by-products. The above examples clearly show that the new 9- (3-butenyl) -oarbazole in an effective manner by the process according to the invention can be produced. As already mentioned, the method according to the invention comprises also the production of 9- (4-monohalobutyl) -carbazoles.

So substituted carbazoles of the formrel produced, in which X is a butenyl substituent or a monohalogenated butyl substituent, in particular a 3-butenyl substituent or 4-monohalobutyl substituent, the halogen atoms being selected from the group of chlorine, bromine and iodine atoms, preferably chlorine and bromine atoms. These substituted carbazoles are produced by the process according to the invention by reacting carbazole substituted by an alkali metal with a 1,4-dihalobutane under condensation / hydrogen halide spalling conditions.

The 9- (4-monohalobutyl) -carbazoles are used as starting or

Intermediates in the manufacture of 9- (3-butenyl) carbazole and other compounds are valuable, while the 9- (3-butenyl) carbazole see for use as starting point or

Intermediate product in the production of various neurochemicals Compounds, including polymers, copolymers, polyemers Products, fungi, pharmaceutical products and the like., Is suitable.

As in more detail in patent application J 26 448 IVd / 39e on the here is incorporated by reference in its entirety, 9- (3-butenyl) carbazole is described due to its double bond to form polymers of different molecular weights a multiplication of the monomer units of about 10-1000, for example 70 - 1000, polymerized Such polymers can be homopolymers or copolymers, block copolymers and the like in isotactic, syndiotactic or atactic form, depending on the polymerisation conditions. So can 9- (3-butenyl) carbazole for example with diethyl aluminum chloride and titanium trichloride, in a ratio of the carbazole to the polymerization catalyst of 20 200: 1 - 3 at temperatures from 0 - 70 ° C, while it is in a suitable organic solvent, such as a benzene series aromatic solvent is dissolved.

The reaction product can, depending on its properties, be in fibers Overfilled or for insulation, coating compounds, binders and adhesives and the like. Can be used.

For example, 9- (3-butenyl) carbazole can form a crystalline Polymer with a length of 70-1000 monomers can be polymerized this polymer can with a selected class of compounds, such as a quinone or the like, e.g. B. 2,5-diphenylquinone in 3% concentration, the to form complexes with the aromatic one side of the same unite capable of being sensitized, being a crystalline product with a charge transfer absorption band is obtained in the near ultraviolet and / or visible region of the spectrum. such a product is applied to an aluminum carrier plate and the folded one Film with a corona unit up to a suitable tension, e.g. 280 volts, when charged, a subsequent exposure to visible light radiation leads to for example from a mercury arc lamp, uz a discharge of about 1/2 the tension in about 16.7 mseo. such photoconductors are for use in a wide variety of suitable for electrical and mechanical devices.

9- (3-But @ nyl0-carbazole is therefore a new and valuable chemical Compound chense such as the 9- (4-Monohalegenbutyl) -zarbazols, which according to the invention Process can be produced. Other advantages have already been indicated above.

Claims (1)

P atent claims 1. Substituted carbazoles of the formula in which X is a butenyl radical or a monohalogenated butyl radical in which the halogen is chlorine, bromine or iodine. 2. Substituted carbazoles according to claim 1, characterized in that , since the butenyl substituent is a 3-butenyl substituent and the monohalogenated butyl substituent is a 4-monohalogenated butyl substituent. 3. 9- (3-butenyl) carbazole of the formula 4. 9- (4-monohalobutyl) carbazoles of the formula in which Y is a chlorine, bromine or iodine atom. 5. 9- (4-chlorobutyl) carbazole of the formula 6. 9- (4-bromobutyl) carbazole of the formula 7. Process for the preparation of compounds of the formula in which X denotes a butenyl or monohalogenated butyl substituent, characterized in that a carbazole substituted by an alkali metal is condensed with a 1,4-dihalogenated butane, the halogen atoms of which can be chlorine, bromine or iodine atoms or mixtures of these, and optionally the resultant Subjects the product to the elimination of hydrogen halide. 8. The method according to claim 7, characterized in that one as through an allca. Limetall substituted carbazole sodium carbazole is used. 9. The method according to claim 7 or 8, characterized in that the condensation reaction is carried out in tetrahydrofuran. 10. The method according to any one of claims 7 to gd, characterized in that that the elimination of hydrogen halide is carried out in tert-butyl alcohol. 11. The method according to any one of claims 7 to 10, characterized. that the elimination of hydrogen halide in the presence of Metallalkyla t; s, in particular Potassium tert. -butylate, through. 12. Modification of the procedure according to claim 7, characterized in that that one obtained by the condensation 9- (4-Monohalcgenbutyl'-carbazole in transferred to a dimethylamine derivative. this is oxidized and the Oyxd obtained is pyrolyzed.