DE2165660A1 - Acridanone derivatives and processes for their preparation - Google Patents

Description

te and process for their manufacture "

The invention relates to novel Acridanonderivate and in particular new 3-Alkorycarbonyl-2-K'-arylamino-1 _t 4-dihydro-9 ~ acridanone and a method for preparing these Acridanonderivate.

The invention relates to new acridanone derivatives from Iforüiel

gHH

COOIi ₂

H H

in which E ^ is a material or halogen atom or a lower alkyl or alkoxy radical, Rp e5.n is a lower alkyl radical and K _{7 is} a hydrogen or halogen atom or a lower alkyl or alkoxy radical.

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The invention is based on dex ⁿ realization that by heating a solution of a 1, 'l-Dialkoxycarbcnyl- ^ ß-di-l'T- »* arylamino-1' + - cyclohexadiene of the formula

in which E ^, E ~ ^{un <} ^ - R * have the meaning given above, in an organic solvent in an inert atmosphere, new acridanone derivatives of the general formula I are obtained, the characteristic IE absorption bands at wavelengths in the vicinity of 6, 0, 9i3, 13.2, 6.1, 6.2, and 6.3 η as well as strong UV absorption bands at wavelengths in the range of 242 and 320 ΐημ

For example, using 1,4-diethoxycarbonyl-2,5-dianilino-1 , ^ - cyclohexadiene "after the above (new) according to the invention obtained according to the described method of the invention Acridanone derivative of the formula I that in Figure ri ΙΕ-absorption spectrum and has the following elemental analysis data:

SAD

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found % calculated %

3-Athoxycaj'bonyl-2-anilino-1,4-dihydio-9acridanone

C 73.9 74.2
H 5.65 5.65

H 7.83 7.86

In the IR absorption spectrum reproduced in FIG These results show that the compound in question is an ester.The presence of a group of the formula -RH- / 3 is indicated by the absorption band at 14.3 η, which is characteristic of mono-substituted benzenes, and the The absorption band at 12.9 u, which can be assigned to EH deformation vibrations, is confirmed. Furthermore, in this IR absorption spectrum there is a very strong and characteristic absorption band at 13.2 u, which can be ascribed to the CH deformation vibrations of 1,2-disubstituted benzene in an acridanone framework, as well as for acridanone characteristic absorption bands at 6.1, 6.2 and 6.3 ii noted. in ¹ U In the V spectrum, two strong absorption bands can be observed at A max. 242 mn and 320 mu, the K absorption due to conjugated double bonds OC-C = ~ 0)

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are to be assigned or correspond. In the mass spectrum of this compound, a Stamiu peak appears at in / e - 360 and two characteristic spectra or bands corresponding to M-29 and M-46 at m / e = 331 and m / e = 314. These peaks or maxiiaa or bands can be assigned to the splitting off of ethyl residues and ethanol from 3-ethoxycarbonyl-2-anilino-1 _i 4-dihydro-9acridanone. This is a serious iridir, for the presence of an ethyl ester bond or group in the compound in question. Accordingly, it is confirmed from the above-mentioned results of elemental analysis, the above-mentioned infrared absorption spectrum, UV spectrum and mass spectrum that the one obtained from 1,4-diethoxycarbony-2,5dianilino-1,4-cyclohexadiene as a starting material is confirmed new compound is 3-ethoxycarbonyl-2-anilino-1, 4dihydro-9-acr, idanone.

Corresponding analysis results are generally in the case of new compounds according to the invention or Acrj.danonderivaten determine those from other 1,4-dialkoxycarbonyl-2,5-di-N-arylamino-1,4-cyclohexadienes as 1,4-diethoxycarbonyl-2,5-dianilino-1,4-cyclohexadiene will be received »

It can therefore be concluded that the new, according to the invention Acrylic acid derivatives 3-alkoxycarbonyl-2-N-arylamino-1,4-dihydro-9-acridarione of the general formula I.

BATH ORIGINAL 209830/1181

In the process of the invention, a partial cyclization _{reaction presumably takes place, which can be illustrated by the following reaction equation in the case of using 1 i} 4-diethoxycarbonyl-2,5-dianilino-1,4-cyclohexadiene as starting material

^E *

This partial cycling is carried out in an organic solvent at a temperature of 190-250 ° C preferably 200 - 230 ° 0 carried out

Regarding the reaction medium used in the process of the invention There is only the following restrictive selection rule for organic solvents to be used: The solvents must be inert and can dissolve the starting material. Examples alone or as a mixture as a reaction medium for the process Solvents to be used in the invention are aromatic hydrocarbons such as benzene, toluene or the like, paraffinic hydrocarbons “Like pentane, hexane, octane or the like. And Kerosene, petroleum naphtha, liquid paraffins, squalene or the like.

Regarding the amount of these organic solvents to be used there is no particular limit. Become common however, these organic solvents

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BATH ORIGINARY

Gangsmaterialjin a 3-15 ⁿ al, preferably 7 - ΊΟ η "al larger amount by weight.

The reaction system is "in the process of the invention, as already mentioned, in an inert gas atmosphere such as nitrogen, carbon dioxide or the like. To avoid oxidation of the reactants. Depending on the boiling point of the particular organic solvent used, the pressure is the inert gas atmospheres sphere so _eingestellt that a reaction temperature of 190 - 250, preferably 200 - 2 John ⁰ C is maintained Reaktionstempez'aturen than 2 ^ 0 ° C should be avoided in order to further cyclization of the result Eden in the method of the invention, reaction products Dihydrcdriinacridonen to. Sometimes it is advisable to convert the 1,4-dialkoxycarbonyl-2,5-di-IT-arylainino- T ^ -cyclohexas & en to the desired product 3-alkoxycarbonyl-2,5-di-arylamino- 1,4 ~ dihydro-9-acr; ldanone to a somewhat lower value in order to obtain a purer product Achieve a desired product by repeating the reaction and using the 1,4-dialkoxycarbonyl-2,5-di-N-arylamino-1,4-cyclohexadiene as starting material or as part of the starting material used, which can easily be extracted from the respective re-

BATH ORIGINAL

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Recover action product mixture as a filtrate in high yield can. The new Acrd.danonderivate of the invention are in the organic solvents used as reaction media essentially insoluble, while the 1,4-dialkoxycarbonyl-2,5-di-N-arylainino ~ 1., ^ - cyclohexadienes in organic solvents Temperatures above 60 ° C are soluble. One can therefore use the new acridanone derivatives resulting from the process of the invention of the invention can be easily separated from the sauce by filtering the reaction product mixture while hot. That included The new acridanone derivative of the invention obtained is in the case of 5-ethoxycarbonyl-2-anilino-1,4-dihydro-9-acridanone recrystallized by precipitating it from a solution in tetrahydrofuran with water as the displacing solvent, pink crystals are obtained, while recrystallization from a solution in N-methyl-2-pyrrolidone, Dimethylformamide or Dimethylsulfoxjd orange crystals are obtained.

The new acridanone derivatives of the invention are very valuable Intermediate products for organic syntheses, in particular because they are produced by subsequent oxidation and cyclization can be converted into quinacridone homologues "make red pigments.

BATH ORIGINAL

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The following examples explain the invention, but are not to be understood as a limitation. In the examples, "parts" and "%" always relate to weight.

example 1

In an autoclave, a mixture of 100 parts of 1,4-diethoxycarbonyl-2 _t 5-dianilino ™ 1, ^ -cyclohexadiene and 300 parts of toluene is heated to 230 ° G in a nitrogen atmosphere with stirring within 50 minutes, then 2 1/2 Stirred for hours at this temperature and then cooled. The reaction product, which is insoluble in toluene, is filtered off at 60.degree. C. and washed with hot toluene until the toluene used as washing liquid no longer shows any noticeable yellow coloration, and the unreacted 1,4-diaphoxycarbonyl-2,5-dianilino-1,4 ~ remove cyclohexadiene. The pale yellow crystals obtained in this way are dried at 60.degree. The infrared absorption spectrum of this crystalline product is shown in FIG. It has key absorption bands which are identical to those of 3-ethoxycarbonyl-2-anilino-1,4-dihydro-9-acridanone, as has already been explained in detail above. The compound obtained in this way is therefore, on the basis of its IR spectrum, 3-xthoxycarbonyl-2-anilino-1,4-dihydro-9-acridanone. The yield is 57 »5 parts, corresponding to 65 % of theory.

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Example 2

A mixture of 100 parts of 1,4-Diäthoxycarbonyl _T-2 5-dianilino-1,4-cyclohexadiene and η-hexane 300 parts is stirred in an autoclave in a nitrogen atmosphere for 2.5 hours at 230 ° C and then at 60 ° G cooled down. The precipitate formed is filtered off, washed with η-hexane and dried. The compound thus obtained is identified as the same substance as the pale yellow crystals obtained in Example 1. The yield is 66.5 parts, corresponding to 75 % of theory.

Example 3

A mixture of 100 parts of 1,4-diabhoxycarbonyl-2,5-dianilino-T ^ 4 -cyclohexadiene and 300 parts of squalene is heated to 240 ° C. in a reactor with stirring in a stream of nitrogen and kept at this temperature for 3 hours, during which the resulting reaction is distilled off ethyl alcohol forming. The reaction mixture is then cooled, with the formation of yellow crystals which are filtered off, washed with hot toluene and dried. 63 parts of 3- & thoxycarbonyl-2-anilino-1,4-dihydro-9-acridanone are obtained, corresponding to a yield of 71 % of theory.

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Example "4

In an autoclave, a mixture of 100 parts of 1,4-diethpxycarT3onyl-2 _i 5-d-ianilino-1,4-cyclohexadiene and 100 parts of benzene is stirred in a nitrogen atmosphere for 5 hours at 220.degree. C., whereupon it is heated to 60.degree cools down. The crystals formed are filtered off, washed with hot benzene and dried. 46.8 parts of 3-A "thoxycarbonyl-2-anilino-1, ^ - dihydro-S-acridanone are obtained, corresponding to a yield of 55 % oil Theory.

Example 5

Example 3 is made using a mixture of 100 parts of 1,4-dimethoxycarbonyl-2,5-dianilino-1,4-cyclohexadiene and 300 parts of squalene repeated, making 78 parts 3-methoxycarbonyl-2-anilino-1,4-dihydro-9-acridanone, correspondingly a yield of 85% of theory is obtained.

tr

Example 6

Example 3 is repeated using a mixture of 1,4-diethoxycarbonyl-2,5-di-N- (4-methylphenyl) amino-1,4-cyclohexadiene and 300 parts of squalene, 74 parts of 3-ethoxycarbonyl-2- N- (4-methylphenyl) amino-7-methyl-1,4-dihydro-9-acridanone, corresponding to a yield of 83 % of theory, is obtained.

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Example 7

A mixture of 100 parts of 1,4-diet _/ hoxycarbonyl-2,5-di-N- (4-chloiuphenyl) amino-1,4-cyclohexadiene and 600 parts of diphenyl ether is under. Stir in a nitrogen atmosphere, heated to 240 ° C for 30 minutes and then cooled to 70 ° C. The crystals formed are filtered off, washed with hot toluene and recrystallized from N-iiethylpyriSlidon. 55 parts of 3-iithoxycarbonyl-2-Xi- (4-chloro-phenyl) -amino-7-chloro-1 ^ -dihydro-S-acridanone are obtained, corresponding to a yield of 63 % of theory.

Example 8

Example 7 is repeated using a mixture of 100 parts of 1,4-diethoxycarbonyl-2,5-Ä.iN- (4-methoxyphenyl) amino-1,4-cyclohexadiene and 600 parts of diphenyl ether, 50 parts of 3- ^ thoxycarbonyl-2-N- (4-methoxyphcnyl) -amino-7-methoxy-1 ^^ - dihydro-S-acridanone, corresponding to a yield of 60 % of theory, is obtained.

Example 9

A mixture of 100 parts of 1,4-dietoxycarbonyl-2,5-dianilino-1,4- cyclohexadiene and 300 parts of toluene

209 8 3 0/1181 B ^AD ORIGINAL

one hour at 255 C (in a nitrogen atmosphere) · stirred, after which it is cooled to 60 ° C. The precipitate formed is filtered off, washed with hot toluene and dried. 36 parts of 3- & thoxycarbonyl-2-N-anilino-1,4-dihydro-9-acridanone are obtained, corresponding to a yield of 40% of theory. The washing liquid and the filtrate obtained by filtering off the product are purified and subjected to steam distillation, 50 parts of unreacted 1,4-diethoxycarbonyl-2,5-dianilino-1,4-cyclohexadiene (90 %) being recovered.

A mixture of the 1,4-diabhoxycarbonyl-2,5-dianilino-1,4-cyclohexadiene (50 parts) and 150 parts of toluene is treated as described above. This gives 18 parts of 3- & thoxycarbonyl-2-N-anilino-1,4-dihydro-9-acridanone, corresponding to a yield of 40 % of theory,

BATH ORIGINAL

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Claims (7)

in the E ,, a hydrogen or Hrilogenatom or a lower Alkyl or alkoxy radical, Rp a lower alkyl radical and E-, is hydrogen or halogen, or lower alkyl or alkoxy. 2. Acridanone derivatives of the formula I according to. Claim 1, characterized in that IL and E _{7 are} each a hydrogen atom and Ro is the methyl or ethyl radical. 3. acridanone derivatives of the formula I according to claim 1, characterized in that R ^ and R ^ Je is a chlorine atom and R ^ is the methyl or the ethyl radical. WSPSCTED 209830/1181 η -: 4-, acridanone derivatives of the formula I according to claim 1, characterized in that R ^ and R _{7 are} each a methyl or methoxy radical and Ep is a methyl or ethyl radical. 5. Process for the preparation of acridanone derivatives of the formula I according to at least one of claims Ibis 4, characterized in that at least one 1,4-dialkoxycarbonyl-1-di-N-arylamino-1, 4-cyclohexadiene the formula in which R ^, Rp and R, the meaning given in claim 1 own heated. 6. The method according to claim 5i, characterized in that the reaction at a reaction temperature of 190 to 250 ⁰ C is carried out. 7. The method according to claim 5 or 6, characterized in that the reaction is carried out in an inert gas atmosphere. ORIGINAL INSPECTED 209830/1181 8 «, method according to isiil.ti.decter · '; c :: i; iem of claims 5 "to 7, characterized in that the 1,4-DIaIkO ^ CyCQr bonjl-2 <-. ^r ; - & i ~ N ~ aryl amine 1,4-cyclohexadiene of the formula II is heated in an inert organic solution. 209830/1181 Blank page