CA1111032A - Process for the separation of dinitroanthraquinone mixtures - Google Patents
Process for the separation of dinitroanthraquinone mixturesInfo
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- CA1111032A CA1111032A CA285,064A CA285064A CA1111032A CA 1111032 A CA1111032 A CA 1111032A CA 285064 A CA285064 A CA 285064A CA 1111032 A CA1111032 A CA 1111032A
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- dinitroanthraquinone
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Abstract
ABSTRACT OF THE DISCLOSURE
A process has been developed for the separation isomers of 1,5-dinitroanthraquinone (particularly 1,8-dinitroanthraquinone) from 1,5-dinitroanthraquinone which comprises a) treating 1 part by weight of a dinitroanthraquinone mixture with 4.5-9 parts by weight of nitrobenzene and/or with the solution obtained after the separation of 1,5-dinitroanthraquinone according to step b) and/
or the solution obtained after the separation of the 1,X- (X = 5, 6, 7 and 8)-dinitroanthraquinone mixture at a temperature of 100 to 200°C and then separating off the unsoluble constituents at 100 - 150°C, b) treating the residue which is obtained according to step a) and essentially consists of 1,5-dinitroanthraquinone, with 1-4 parts by weight of nitrobenzene at a temperature from 140°C to the boiling point, then cooling the mixture to 90 to 130°C and separating the 1,5-dinitroanthra-quinone which is not dissolved, c) cooling the solution obtained after the separation of the unsoluble constituents according to step a) to 90 to 120°C and separating off the 1,8-dinitroanthraquinone which has crystallised out.
A process has been developed for the separation isomers of 1,5-dinitroanthraquinone (particularly 1,8-dinitroanthraquinone) from 1,5-dinitroanthraquinone which comprises a) treating 1 part by weight of a dinitroanthraquinone mixture with 4.5-9 parts by weight of nitrobenzene and/or with the solution obtained after the separation of 1,5-dinitroanthraquinone according to step b) and/
or the solution obtained after the separation of the 1,X- (X = 5, 6, 7 and 8)-dinitroanthraquinone mixture at a temperature of 100 to 200°C and then separating off the unsoluble constituents at 100 - 150°C, b) treating the residue which is obtained according to step a) and essentially consists of 1,5-dinitroanthraquinone, with 1-4 parts by weight of nitrobenzene at a temperature from 140°C to the boiling point, then cooling the mixture to 90 to 130°C and separating the 1,5-dinitroanthra-quinone which is not dissolved, c) cooling the solution obtained after the separation of the unsoluble constituents according to step a) to 90 to 120°C and separating off the 1,8-dinitroanthraquinone which has crystallised out.
Description
In the dinitration of an-thraquinone, mixtures are obtained, as is known, which essentially consist of l,5-. l,8-, l,6- and l "-dinitroanthraquinone. Various methods for the separa-tion of such mixtures are described in the literature With oleum, for example, the separation is carried out accord-ing to German Offenlegungsschrift (German Publi~hed Specification) ~,143,253, wi-th monohydrate (= 100 ~ stren~th sulphuric acid) it is carried out according to Helv. chim. Acta 14, 1404 (l93l), with N-methylpyrrolidone it is carried out according to ~ lO German Offenlegungsschrift 2,334,713, with nitrobenzene :. it is carried out according to Japanese Laid-open Published Specification 49-76,~51 and with ni~ro-benzene and/or nitrotoluene it is carried out according to German Offenlegungsschrift 2,248,70~.
However, these processes are unsatisfactory with .. regard to the quality and/or the yield and are actually only suitable for the isolation of l,5-dinitroanthraquinone, l,5-dinitroanthraquinone obtained by this separation process still . containing, however, about 5/0 of l,8-dinitroanthraquinone (com-pare, for example, German Offenlegungsschrift . 2,248,/`04).
Such a content of l,8-dinitroanthraquinone in the l,5-dinitroanthraquinone is very troublesome, however, in the preparation of secondary products, for example of industrially important l,5-diamino-anthraquinone and of l-amino-5-benzoyl-amino-anthraquinone. Thus, in the preparation of l,5-diamino-anthraquinone, the l,8-dinitroanthraquinone is also reduced and is -then present in the l,5-diamino-anthraquinone as l,8-diamino-anthraquinone. During the monobenzoylation reaction, the l,8-diamino-anthraquinone is converted into l-benzoylamino-8-aminoanthraquinone and l,8-dibenzoylamino-anthraquinone and is ; Le A ll 371 - 2 -__ present in this form in -the l-amino-5-benzoylaminoanthraquinone.
The removal of the undesired secondary products of 1,8-dinitro-anthraquinone can be effected only with difficulty and necessi-tates complicated and wasteful operations. If the 1,8-isomeric by-products are not removed, these have a disadvantage-ous effect on yields and/or shades and/or fastness properties in the preparation of dyestuffs which are prepared from l-amino-5-benzoylaminoanthraquinone. Thus as complete a separation as possible of the 1,8-dinitroan-thraquinone in the 1,5-dinitroanthraquinone is of great industrial importance.
The separation processes described above are com-pletely unsuitable for the preparation of pure 1,8-dinitro-anthraquinone, which is also a valuable dyestuff intermediate product. Thus, for example, a 1.8-dinitroanthraquinone which contains 15% of 1,5-dinitroanthraquinone as an impurity is obtained by the process in German Offenlequnqs~chrift
However, these processes are unsatisfactory with .. regard to the quality and/or the yield and are actually only suitable for the isolation of l,5-dinitroanthraquinone, l,5-dinitroanthraquinone obtained by this separation process still . containing, however, about 5/0 of l,8-dinitroanthraquinone (com-pare, for example, German Offenlegungsschrift . 2,248,/`04).
Such a content of l,8-dinitroanthraquinone in the l,5-dinitroanthraquinone is very troublesome, however, in the preparation of secondary products, for example of industrially important l,5-diamino-anthraquinone and of l-amino-5-benzoyl-amino-anthraquinone. Thus, in the preparation of l,5-diamino-anthraquinone, the l,8-dinitroanthraquinone is also reduced and is -then present in the l,5-diamino-anthraquinone as l,8-diamino-anthraquinone. During the monobenzoylation reaction, the l,8-diamino-anthraquinone is converted into l-benzoylamino-8-aminoanthraquinone and l,8-dibenzoylamino-anthraquinone and is ; Le A ll 371 - 2 -__ present in this form in -the l-amino-5-benzoylaminoanthraquinone.
The removal of the undesired secondary products of 1,8-dinitro-anthraquinone can be effected only with difficulty and necessi-tates complicated and wasteful operations. If the 1,8-isomeric by-products are not removed, these have a disadvantage-ous effect on yields and/or shades and/or fastness properties in the preparation of dyestuffs which are prepared from l-amino-5-benzoylaminoanthraquinone. Thus as complete a separation as possible of the 1,8-dinitroan-thraquinone in the 1,5-dinitroanthraquinone is of great industrial importance.
The separation processes described above are com-pletely unsuitable for the preparation of pure 1,8-dinitro-anthraquinone, which is also a valuable dyestuff intermediate product. Thus, for example, a 1.8-dinitroanthraquinone which contains 15% of 1,5-dinitroanthraquinone as an impurity is obtained by the process in German Offenlequnqs~chrift
2,248,7O4.
A process for the separation of dinitroanthraquinone mixtures using nitrobenzene has now been found, which comprises the steps of a) treating I part by weiqht of a dinitroanthraquinone mixture with 4.5-9 parts by weight of nitrobenzene and/or with the solution ob-tained after the separation of 1,5-dinitroanthraquinone according to step b) and optionally wash liquid recycled from step b) and/or with the solution obtained after the separation of 1,X (X = 5, 6, 7 and 8)-dinitroanthraquinone at a temperature of 100 -to 200C and then separating off the unsoluble constituents at 100 - 150C, b) treating the residue, which is obtained according to step a) and essentially consists of 1,5-dinitroanthraquinone, with 1-4 parts by weight of nitrobenzene at a -temperature from 140C to the boiling point, then cooling the mixture to 90 to 130C and separating off Le A 17 371 - 3 -" and optionally washing wi-th ni-trobenzene the 1,5-dinitroanthra-quinone which is not dissolved, c) cooling the solu-tion obtained after the separation of the un-soluble constituents according to step a) -to 90 to 120C and se-parating off and optionally washing with nitrobenzene the 1,8-dinitroanthraquinone which has crystallised out.
The process of the present invention makes possible the isolation of 1,5-dinitroanthraquinone in purities of over 96 %
with a separation yield of over 80 ~. After separating off the 1,5-dinitroanthraquinone, 1,8-dinitroanthra~uinone can be obtained in a similar purity to the 1,5-dinitroanthraquinone.
rn ~eneral, the 1,5-dinitroanthraquinone and 1,8-dinitroanthra-quinone isolated by the process according to the invention con-tain less than 2%, often less than 1 %, of the other isomer.
1,5- and 1,8-dinitroanthraquinone of such quality is certainly obtained when the products separated off according to steps b) and c) of the inventive process are washed with nitrobenzene. In cases where the separated products have a high content of solids, for example more than 70%, espe-cially more than 80%, products of such purities can also be obtained often without washing with nitrobenzene.
A preferred embodiment of step a) of the inventive process comprises one or more of the following process features and can be carried out, for example, by treating 1 part by weight of a dinitroanthraquinone mixture with 5.5 to 8 parts by weight of nitrobenzene at a temperature of 110 to 200C and then separating off the unsoluble constituents at 110 to 130C.
By heating to a temperature above the temperature at which the separation is carried out, preferably to a temperature above Le A 17 371 _ 4 _ : ~
160C, one achieves a considerable coarsening of -the undis-- solved portions and of those portions which have been precipi~
tated during the cooling; because of this the separation period and the moisture remaining in the residue (= part of the mother-liquor) are greatly diminished. After a period of 1/2 - 1 hour of stirring preferably at 110 to 130C the crystallisation equilibrium is reached to an extent that these advan-tages are obtained upon separation. Heating to temperatures above the temperature at which the separation is carried out one achieves further a higher content of 1,5-dinitroanthraquinone in -the separated unsoluble constit-uents and normally a higher purity of 1,5-dinitroanthraquinone separated in the following step b).
` The residue obtained according to step a), which essentially consists of 1~5-dinitroanthraquinone, is treated with 2 to 3 parts by weight of nitrobenzene at a temperature of 150 to `~ 200C, preferably of 160 to 180C, the mixture is then cooled : to 100 to 110C and the 1,5-dinitroanthraquinone which precipi-tates is separated off and optionally washed with 0.3 to 1 part by weight of nitrobenzene.
The solution obtained after separating off the unsoluble ` constituents according to step a) is cooled to 90 to 110C, preferably to 100 to 110C, and the 1,8-dinitroanthraquinone which has crystallized out is separated off and optionally washed with 0.3 to 1 part by weight of nitrobenzene.
The solution obtained after the separation of the 1,8-optionally combined with the washing liquid from the washing of 1,8-dinitroanthraquinone is cooled to 5 to 85C, a 1,X-di-nitroanthraquinone mixture (X - 5, 6, 7 and 8) separating out.
Le A 17 371 - 5 -:
-. ~
The mixture is separated off and some of the remaining solution is used again for separating the starting dinitroanthraquinone mixture employed and some is concentrated by distillation in vacuo to separate the X,Y-dinltroanthraquinone (X = 5, 6, 7 and 8;
Y = 1 or 2). It is possible to wash the separated 1,X-dinitro-anthraquinone with nitrobenzene, however, this gives normally no special advantages because the desired qualities can be ob-tained without carrying out a washing. It is possible to separate out the 1,X-dinitroanthraquinone mixture from all of the solution obtained after the separation of the 1,8-dinitroanthraquinone or only from a part of this solution. It is possible to isolate separately the remaining dinitroanthraquinone portions from this ;- solution out of the separation of 1,8-dinitroanthraquinone and out of the solution obtained after the separation of 1,X-dinitro-anthraquinone by distilling off nitrobenzene. However, it is advantageous to work up both solutions jointly by distilling off nitrobenzene. Dependent from the amount of the solution out of the separation of 1,8-dinitroanthraquinone which is used for the isolation of 1,X-dinitroanthraquinone X, Y-dinitroanthraquinone mixtures of different composition can beobtained. In this manner, further dinitroanthraquinones can also be obtained, such as 1,6-, 1,7-, 2,6- and 2,7-dinitro-anthraquinone, in addition to the 1,5- and 1,8-dinitroanthra-quinone which remained. The temperature to which the solution out of the 1,8-dinitroanthraquinone separation, optionally to-gether with the wash liquid from the washing of 1,8-dinitroanthra-quinone, are cooled is decisive for the composition of -the 1,X-dinitroanthraquinone mixture obtained. If, for example, the Le A 17 371 - 6 -.'
A process for the separation of dinitroanthraquinone mixtures using nitrobenzene has now been found, which comprises the steps of a) treating I part by weiqht of a dinitroanthraquinone mixture with 4.5-9 parts by weight of nitrobenzene and/or with the solution ob-tained after the separation of 1,5-dinitroanthraquinone according to step b) and optionally wash liquid recycled from step b) and/or with the solution obtained after the separation of 1,X (X = 5, 6, 7 and 8)-dinitroanthraquinone at a temperature of 100 -to 200C and then separating off the unsoluble constituents at 100 - 150C, b) treating the residue, which is obtained according to step a) and essentially consists of 1,5-dinitroanthraquinone, with 1-4 parts by weight of nitrobenzene at a -temperature from 140C to the boiling point, then cooling the mixture to 90 to 130C and separating off Le A 17 371 - 3 -" and optionally washing wi-th ni-trobenzene the 1,5-dinitroanthra-quinone which is not dissolved, c) cooling the solu-tion obtained after the separation of the un-soluble constituents according to step a) -to 90 to 120C and se-parating off and optionally washing with nitrobenzene the 1,8-dinitroanthraquinone which has crystallised out.
The process of the present invention makes possible the isolation of 1,5-dinitroanthraquinone in purities of over 96 %
with a separation yield of over 80 ~. After separating off the 1,5-dinitroanthraquinone, 1,8-dinitroanthra~uinone can be obtained in a similar purity to the 1,5-dinitroanthraquinone.
rn ~eneral, the 1,5-dinitroanthraquinone and 1,8-dinitroanthra-quinone isolated by the process according to the invention con-tain less than 2%, often less than 1 %, of the other isomer.
1,5- and 1,8-dinitroanthraquinone of such quality is certainly obtained when the products separated off according to steps b) and c) of the inventive process are washed with nitrobenzene. In cases where the separated products have a high content of solids, for example more than 70%, espe-cially more than 80%, products of such purities can also be obtained often without washing with nitrobenzene.
A preferred embodiment of step a) of the inventive process comprises one or more of the following process features and can be carried out, for example, by treating 1 part by weight of a dinitroanthraquinone mixture with 5.5 to 8 parts by weight of nitrobenzene at a temperature of 110 to 200C and then separating off the unsoluble constituents at 110 to 130C.
By heating to a temperature above the temperature at which the separation is carried out, preferably to a temperature above Le A 17 371 _ 4 _ : ~
160C, one achieves a considerable coarsening of -the undis-- solved portions and of those portions which have been precipi~
tated during the cooling; because of this the separation period and the moisture remaining in the residue (= part of the mother-liquor) are greatly diminished. After a period of 1/2 - 1 hour of stirring preferably at 110 to 130C the crystallisation equilibrium is reached to an extent that these advan-tages are obtained upon separation. Heating to temperatures above the temperature at which the separation is carried out one achieves further a higher content of 1,5-dinitroanthraquinone in -the separated unsoluble constit-uents and normally a higher purity of 1,5-dinitroanthraquinone separated in the following step b).
` The residue obtained according to step a), which essentially consists of 1~5-dinitroanthraquinone, is treated with 2 to 3 parts by weight of nitrobenzene at a temperature of 150 to `~ 200C, preferably of 160 to 180C, the mixture is then cooled : to 100 to 110C and the 1,5-dinitroanthraquinone which precipi-tates is separated off and optionally washed with 0.3 to 1 part by weight of nitrobenzene.
The solution obtained after separating off the unsoluble ` constituents according to step a) is cooled to 90 to 110C, preferably to 100 to 110C, and the 1,8-dinitroanthraquinone which has crystallized out is separated off and optionally washed with 0.3 to 1 part by weight of nitrobenzene.
The solution obtained after the separation of the 1,8-optionally combined with the washing liquid from the washing of 1,8-dinitroanthraquinone is cooled to 5 to 85C, a 1,X-di-nitroanthraquinone mixture (X - 5, 6, 7 and 8) separating out.
Le A 17 371 - 5 -:
-. ~
The mixture is separated off and some of the remaining solution is used again for separating the starting dinitroanthraquinone mixture employed and some is concentrated by distillation in vacuo to separate the X,Y-dinltroanthraquinone (X = 5, 6, 7 and 8;
Y = 1 or 2). It is possible to wash the separated 1,X-dinitro-anthraquinone with nitrobenzene, however, this gives normally no special advantages because the desired qualities can be ob-tained without carrying out a washing. It is possible to separate out the 1,X-dinitroanthraquinone mixture from all of the solution obtained after the separation of the 1,8-dinitroanthraquinone or only from a part of this solution. It is possible to isolate separately the remaining dinitroanthraquinone portions from this ;- solution out of the separation of 1,8-dinitroanthraquinone and out of the solution obtained after the separation of 1,X-dinitro-anthraquinone by distilling off nitrobenzene. However, it is advantageous to work up both solutions jointly by distilling off nitrobenzene. Dependent from the amount of the solution out of the separation of 1,8-dinitroanthraquinone which is used for the isolation of 1,X-dinitroanthraquinone X, Y-dinitroanthraquinone mixtures of different composition can beobtained. In this manner, further dinitroanthraquinones can also be obtained, such as 1,6-, 1,7-, 2,6- and 2,7-dinitro-anthraquinone, in addition to the 1,5- and 1,8-dinitroanthra-quinone which remained. The temperature to which the solution out of the 1,8-dinitroanthraquinone separation, optionally to-gether with the wash liquid from the washing of 1,8-dinitroanthra-quinone, are cooled is decisive for the composition of -the 1,X-dinitroanthraquinone mixture obtained. If, for example, the Le A 17 371 - 6 -.'
3~
solution is cooled to a -tempera-ture which is above 60 - 70C, a 1,5- and 1,8-dinitroanthraquinone mixture is obtained which contains only about 2 to 5% of 1,6- and 1,7-dini-troanthraquinone, whilst at lower tempera-tures a dinitroanthraquinone mixture is isolated which can contain up to 40% of 196- and 1,7-dini-tro-anthraquinone. In the residual solution, some of which, as mentioned above, can be used again for the separation of the di-nitroanthraquinone mixture employed, there are the remaining nitroanthraquinone compounds which have not been separated off, mainly residual 1,5- and 1,8-dlnitroanthraquinone, in addition to the majority of the 1,6/1,7-dinitroan-thraquinone contained in the material employed. This X,Y-dinitroanthraquinone (X = 5, 6, 7 and 8; Y = 1 or 2) can be isolated by distilling off the - nitrobenzene to dryness, preferably under reduced pressure.
~` 15 When the nitrobenzene used is re-employed in the form of a part of the solution obtained after separating off 1,X-dinitro-anthraquinone for the dinitroanthraquinone separation, care mus-t be taken that no more than 0.25 par-t by weight of dinitroanthra-quinones, relative to 1 part by weight of the dinitroanthra-quinone mixture employed, is recycled with the nitrobenzene. The separations mentioned above, which are separations of solids from liquids, can be carried out by applying customary methods, for example by filtration, dekantation or in a hydro-cyclone. The preferred measures and features stated above can be applied separately; for example the relative amounts of substances and temperatures given for a preferred separating operation can be independent;ly from one another.
It is an essential characteristic of the present invention that the dinitroanthraquinone mixture employed is initially 3~ pretreated with nitrobenzene, preferably in the form of a solution obtained after carrying out step b) and/or after sepa-rating 1,X--dinitroanthraquinone, whilst hot, and -the resulting Le A 17 37 !
- crude 1,5-dinitroanthraquinone, which still contains about 6 to 30%, preferably 8 to 20%, of 1,8-dinitroanthraquinone, is again after-treated with pure nitrobenzene. The solution ob-tained after carrying out step b) can be used in total or par-tially, the solution obtained after separating 1,X-dinitroanthra-quinone is preferably partially used for the separation of di-nitroanthraquinone mixtures. Only by a double treatment with nitrobenzene, in which the starting dinitroanthraquinone mixture is also treated with the solution obtained after carrying out step b), is a 1,5-dinitroanthraquinone obtained in separation yields of over 80% and purities over 96%, with a 1,8 `~ dinitroanthraquinone proportion of less than 2%, often less than 1%.
Furthermore, it is important for the process according to the invention that in the separation of dinitroanthraquinone mixtures at least about 75%, blt preferably about 80 to 86%, of the l,5-dinitroanthraquinone presentare separated off before the l,8-dinitroanthraquinone crystallises ou-t or that, relative to the l,8-dinitroanthraquinone, only a maximum of 25%, prefer-ably a maximum of 20%, of l,5-dinitroanthraquinone is sti~l present. The isolation of l,8-dinitroanthraquinone which only still contains less than 2% of l,5-dinitroanthraquinone is otherwise no longer possible or only possible in very low yields.
The recycling, which takes place by the process according to the invention, of the nitrobenzene solutions obtained in the 1,5- and 1,X-dinitroanthraquinone separation, especially the recycling of the solution obtained from the fine purification of 1,5-dinitroanthraquinone and also the recycling of solution Le A 17 371 - 8 -, . .
obtained after the separation of 1,X-dinitroan-thraquinone~ into the dinitroanthraquinone separation effects ~i- a significant rise in the separation yield in the separation of 1,5- and 1,8-dinitroanthraquinone. Furthermore, these ~` 5 measures make it possible to carry out the process accor-ding to the invention particularly economically, since ; only a proportion of the amounts of solvent used must be -~ purified by distillation.
The dinitroanthraquinone containing mixtures subjected to the separation process can contain some water, for example in form of a precipitate obtained in the dinitration process of anthraquinone after filtration and washing with water until neutral. Before subjecting such water containing mixtures to the separation process the water is to be removed, for example by azeotropic distillation at normal or reduced pressure. The small amount of nitro-benzene which distills off together with water is to be replaced by fresh nitrobenzene. Preferahly the nitrobenzene obtained after cooling and phase separation of the azeotropic distillate is used for this purpose. It is also possible to subject dinitroanthraquinone containing mixtures to the ` separation process which contain up to 2 % by weight of sulfuric acid without getting worse results with respect to quality and yield.
Virtually all dinitroanthraquinone mixtures accessible by industrial routes can be employed in the process acc-rding to the invention. Thus, for examp e, dinitroanthraquinone mixtures can be separated which are obtained by the nitration of an'hraquinone ln highly-concentrated nitric acid, by the Le A 17 371 - 9 -.
;
:
nitration of anthraquinone using a mixture of highly-concentrated nitric acid and 0.75 to 2 parts hy weight of sulphuric acid, relative to the weigl1t of nitric acid, or by thc nitration of anthraquinone in exces~ sulphuric acid, which optionally contains S03, or hydrofluoric acid or organic solvents. It is also possible te cmploy those dini-tration products which have bcen obtained by the nitration of 1-nitroanthraquinone, which may contain other nitroanthraquinones as impurities.
The 1-nitroanthraquinone to be nitrated can contain anthra-quinone, 2-nitroanthraquinone and the various dinitro-anthraquinone isomers as impurities, especially if it has been obtained as the residual product in the purification of 1-nitroanthraquinone by crystallisa-tion or distillation.
Furthermore, those dinitroanthraquinone mixtures which are obtained by mixing any desired products, solutions or suspensions of any desired origin eontaining 1,5- and 1,8-dinitroanthraquinone ean also be employed in the process aeeording to the invention. The eontent of any 1,6- and 1,7-dinitroanthraquinone whieh may be present and the ratio of 1,5-dinitroanthraquinone to 1,8 dinitroanthraquinone are of minor importanee.
The proeess aeeording to the invention ean be earried out both diseontinuously and partly or entirely eontinuously.
Le ~ 17 371 - 10 -~ . .
Th- 1,5- and 1,8-dinitroanthraqui~one obtained according to the inve~tion can be con~erted directly into the correspon~ing amino compoun,1 and then further processed to giv~ anthraquinone ~- dyest,lffs 'compare, for example, Friedlaender, Fortschri-tte der Teerfarben-Fabri]iation (~dvances in the Manufacture of Aniline Dyes), 22nd part(1935), page 1014; Fiat Final Report 1313, German Dyestuffs and Interm~diates, II, page 26).
The examples which follow are intend-d to illus ra~e further the process according to the invenlion. The - 10 analyses in the examples are based ~n high pressure liquidchroDatogiaplly and on semi-qua;ltitative thin layer chromatography.
Examples s 1. Separation of a dinitroanthraquinone mixture having the composition: 0.5% of 2,6-dinitroanthraquinone, 0.4 % of 2,7-15 dinitro~nthraquinone, 1.8% of l-nitroan~hraqlinone, 9.8% of 1,6-dinitroanthraqlinone, 9.6% of l,l-dinitroanthraquin~ne, . 33 9~ of 1,5-dinitroanthraquinone and 36.6% of 1,8-dinitro-anthraquinone, obtained during the nitration of 20~ g of anthra-quinone with a mixture of 424 g of 98% strength nitric acid and 500 g of sulphuric acid monohydrate, the mixture having been stirred initially at 4~C (l an hour), then at 50C (-1- an hour).
The instructions which follow refer to a crystallisation with recycling of -the mother liquor after all the crystallisation - e~uilibria are established For starting up, pure nitrobenzene is used instead of recycled mother liquor.
1.1 Isolation of -the 1,5-dinitroanthraquinone 65.0 ~ of the above dinitroanthr~quinone mixture to~ether with 252 g of recycled mother liquor from 1.3. and 252 q of re-cycled mother-liquor from the fine purification described below 30 are warmed to 120~C for 0.5 hours, whilst stirring, and the mix-ture is then filtered a-t 120C. The fil-trate is used for Le A 17 371 - 11 -further pro~essing -to give 1,8-dinitroanthraquinone according to 1.2 The moist filter cake is war~ed to 160C with 18~ g of ~itrobenzene for 0.5 hour , whilst stirring. The mixture is then cooled to 10~C in the course o~ 0.2~ hour, and after stirring for 0.5 hour at 100C, is fil-tered. The residue is was'~ed with 60 g of nitrobenzene, heated to 10~C, in portions. The combined filtrates of the fine pariflca-tion which still con-tain dissolved dinitroanthraquinorle and/o~
mononitroanthraquinone are used for the next 1,5-dinitroanthra-q~inone cry~tallis~tion After drying the residue in vacuo atlOnC, the~ are obtained.22 4 g of 1,5-dinitro~nthraquinone (97.7 -~ of l,~-dinitroanthraquinone, 1 1% of 1,8-dinitroanthraquinone, 0.2~ of 1,6-dinitroanthraquinone and 0.1% of l,~-dinitroantnra-quinone).
Separation yield 84.1%.
., .
1 2. Isolation of the 1,8-dinitroanthraquinone The filtrate from the 1,5-dinitroanthraquinone separa-;'~ tion (about 510 g) is cooled to 105C, after it has been warmed, if appropriate, to 140C in order to achieve a clear solu~ion, and seeded with a few rystals of 1,8-dinitroanthraquinone and the mixture is stirred for 2 hours at 105C. It is filtered and the residue is washed with 48 g of cold nitrobenzene and dried in vacuo at 100C: 7.3 g of 1,8-dinitroanthraquinone (98 5% of 1,8-dinitroanthraquinone an-l ).6% of i,5--dinitro-anthraquinone).
Separa-~jon yield 30,2%.
The combined filtrates are used for the separation of the l,X-dinitroanthraquinone mixture according to 1.3.
1.3. Isolation of the l,X-dinitroanthraquinone (X = 5,6, 7 and 8) The combined filtrates from the 1,8-dinitroanthraquinone separation (about 540 g) are warmed to 120C until the solution Le A 17 371 _ 12 -. .
becomes clear. It is then cooled to 25C and stirred atthis temperature for 3 hours. The product which has ~; crystallised out is then filtered off and dried in vacuo at 100C: 21.0 g of l,X-dinitroanthraquinone (6.'/% of 1,6-di-nitroanthraquinone, 15.6% of l,','-dinitroanthraquinone, 10.8%
of 1,5-dinitroanthraquinone and 60.','% of 1,8-dini-troanthra-'~ quinone and 2.2% of l-nitroanthraquinone).
1.4. Isolation of the X,Y-dinitroanthraquinone (Y=l and 2, X =
' 5, 6, ',' and 8) The filtrate from 1.3. (about 504 g) is divided, about 252 g being recycled to 1.1 for the next crystallis-ation. The remainder is distilled to dryness in vacuo:
11.1 g of X,Y-dinitroanthraquinone (2.0% of 2,6-dinitroanthra-quinone, 1.9% of 2,'7-dinitroanthraquinone, 3r7 ~ 5% of 1,6-dinitro-anthraquinone, 22.1% of l,~-dinitroan-thraquinone, 6.1% of 1,5-; dinitroanthraquinone and 14.4% of 1,8-dinitroanthraquinone and ~' 3.6% of l-nitroanthraquinone).
The nitrobenzene which has distilled off is used again " in 1.1. and 1.2.
2. Separation of a dinitroanthraquinone mixture having ~` the composition of Example 1 (for establishing the crystallisat-ion equilibria, compare Example 1).
2.1. Isolation of the 1,5-dinitroanthraquinone 65.0 g of the dinitroanthraquinone mixture having the composition as in Example 1, together with 216 g of nitrobenzene and 252 g oE recycled Eiltra-te an~ ~Jashing liquid Erom the fine purification described below,are warmed to 120C for 0.5 hour, whilst stirring, and the mixture is then filtered at 120C. The filtrate is used for the further processing to give 1,8-dinitro-anthraquinone according to 2.2. The moist residue iswarmed -to 180C with 180 g of nitrobenzene for 0.5 hour, whilst Le A 17 371 - 1~-stirring The mixture is then cooled to 100C in -the - course of 025 hour and, after stirring for 0.5 hour at 100C, the product which has crystallised out is filtered off. The material on the filter is washed with 60 g of hot nitrobenzene in portions. The combined filtrates of this fine purifica-- tion are used for the next 1,5-dinitroanthraquinone crystallisa-tion. After drying the residue in vacuo at 100C, there are obtained: 21., g of 1,5-dinitroanthraquinone (98.8% of 1,5 dinitroanthraquinone and 1.1% of 1,8-dinitroanthraquinone).
- 10 Separation yield 82.f%.
2.2. Isolation of the 1,8-dinitroanthraquinone ` The filtrate from 2.1. is cooled to 100C and stirred a-t 100C for 2 hours. The crystals are filtered off, washed with 48 g of nitrobenzene and dried in vacuo at 100C: 6.8 g of 1,8-dinitroanthraquinone (9/.5% of 1,8-dinitroanthraquinone and 0.1% of 1,5-dinitroanthraquinone).
; Separation yield 2-7.9%.
2.3. Isolation of the l,X-dinitroanthraquinone (X = 5, 6, I
and 8) The combined filtrates from the 1,8-dinitroanthraquinone separation are cooled to 25C and stirred for 3 hours at this temperature. The precipitate is then filtered off and dried at 100C in vacuo: 16.1 g of l,X-dinitroanthraquinone (2.6% of 1,6-dinitroanthraquinone, 4.9% of 1,7-dinitroanthraquinone, 12.6% of 1,5-dinitroanthraquinone and 74.4% of 1,8-dinitroanthra-quinone).
2.4. Isolation of the X,Y-dini-troanthraquinone (Y = 1 and 2, X = 5,6, l and 8) The filtrate from 2.3. is distilled to dryness in vacuo:
19.5 g of X,Y-dinitroanthraquinone (1.5% of 2,6-dinitroanthra-quinone, 1.5% of 2,7-dinitroanthraquinone, 30.8% of 1,6-dinitro-Le A 17 ~71 - 14 --anthraquinone, 28,2% of l"'-dinitroanthraquinone, 7.8% of 1,5-dinitroanthraquinone and 16.1% of 1,8-dini-troanthraquinone and
solution is cooled to a -tempera-ture which is above 60 - 70C, a 1,5- and 1,8-dinitroanthraquinone mixture is obtained which contains only about 2 to 5% of 1,6- and 1,7-dini-troanthraquinone, whilst at lower tempera-tures a dinitroanthraquinone mixture is isolated which can contain up to 40% of 196- and 1,7-dini-tro-anthraquinone. In the residual solution, some of which, as mentioned above, can be used again for the separation of the di-nitroanthraquinone mixture employed, there are the remaining nitroanthraquinone compounds which have not been separated off, mainly residual 1,5- and 1,8-dlnitroanthraquinone, in addition to the majority of the 1,6/1,7-dinitroan-thraquinone contained in the material employed. This X,Y-dinitroanthraquinone (X = 5, 6, 7 and 8; Y = 1 or 2) can be isolated by distilling off the - nitrobenzene to dryness, preferably under reduced pressure.
~` 15 When the nitrobenzene used is re-employed in the form of a part of the solution obtained after separating off 1,X-dinitro-anthraquinone for the dinitroanthraquinone separation, care mus-t be taken that no more than 0.25 par-t by weight of dinitroanthra-quinones, relative to 1 part by weight of the dinitroanthra-quinone mixture employed, is recycled with the nitrobenzene. The separations mentioned above, which are separations of solids from liquids, can be carried out by applying customary methods, for example by filtration, dekantation or in a hydro-cyclone. The preferred measures and features stated above can be applied separately; for example the relative amounts of substances and temperatures given for a preferred separating operation can be independent;ly from one another.
It is an essential characteristic of the present invention that the dinitroanthraquinone mixture employed is initially 3~ pretreated with nitrobenzene, preferably in the form of a solution obtained after carrying out step b) and/or after sepa-rating 1,X--dinitroanthraquinone, whilst hot, and -the resulting Le A 17 37 !
- crude 1,5-dinitroanthraquinone, which still contains about 6 to 30%, preferably 8 to 20%, of 1,8-dinitroanthraquinone, is again after-treated with pure nitrobenzene. The solution ob-tained after carrying out step b) can be used in total or par-tially, the solution obtained after separating 1,X-dinitroanthra-quinone is preferably partially used for the separation of di-nitroanthraquinone mixtures. Only by a double treatment with nitrobenzene, in which the starting dinitroanthraquinone mixture is also treated with the solution obtained after carrying out step b), is a 1,5-dinitroanthraquinone obtained in separation yields of over 80% and purities over 96%, with a 1,8 `~ dinitroanthraquinone proportion of less than 2%, often less than 1%.
Furthermore, it is important for the process according to the invention that in the separation of dinitroanthraquinone mixtures at least about 75%, blt preferably about 80 to 86%, of the l,5-dinitroanthraquinone presentare separated off before the l,8-dinitroanthraquinone crystallises ou-t or that, relative to the l,8-dinitroanthraquinone, only a maximum of 25%, prefer-ably a maximum of 20%, of l,5-dinitroanthraquinone is sti~l present. The isolation of l,8-dinitroanthraquinone which only still contains less than 2% of l,5-dinitroanthraquinone is otherwise no longer possible or only possible in very low yields.
The recycling, which takes place by the process according to the invention, of the nitrobenzene solutions obtained in the 1,5- and 1,X-dinitroanthraquinone separation, especially the recycling of the solution obtained from the fine purification of 1,5-dinitroanthraquinone and also the recycling of solution Le A 17 371 - 8 -, . .
obtained after the separation of 1,X-dinitroan-thraquinone~ into the dinitroanthraquinone separation effects ~i- a significant rise in the separation yield in the separation of 1,5- and 1,8-dinitroanthraquinone. Furthermore, these ~` 5 measures make it possible to carry out the process accor-ding to the invention particularly economically, since ; only a proportion of the amounts of solvent used must be -~ purified by distillation.
The dinitroanthraquinone containing mixtures subjected to the separation process can contain some water, for example in form of a precipitate obtained in the dinitration process of anthraquinone after filtration and washing with water until neutral. Before subjecting such water containing mixtures to the separation process the water is to be removed, for example by azeotropic distillation at normal or reduced pressure. The small amount of nitro-benzene which distills off together with water is to be replaced by fresh nitrobenzene. Preferahly the nitrobenzene obtained after cooling and phase separation of the azeotropic distillate is used for this purpose. It is also possible to subject dinitroanthraquinone containing mixtures to the ` separation process which contain up to 2 % by weight of sulfuric acid without getting worse results with respect to quality and yield.
Virtually all dinitroanthraquinone mixtures accessible by industrial routes can be employed in the process acc-rding to the invention. Thus, for examp e, dinitroanthraquinone mixtures can be separated which are obtained by the nitration of an'hraquinone ln highly-concentrated nitric acid, by the Le A 17 371 - 9 -.
;
:
nitration of anthraquinone using a mixture of highly-concentrated nitric acid and 0.75 to 2 parts hy weight of sulphuric acid, relative to the weigl1t of nitric acid, or by thc nitration of anthraquinone in exces~ sulphuric acid, which optionally contains S03, or hydrofluoric acid or organic solvents. It is also possible te cmploy those dini-tration products which have bcen obtained by the nitration of 1-nitroanthraquinone, which may contain other nitroanthraquinones as impurities.
The 1-nitroanthraquinone to be nitrated can contain anthra-quinone, 2-nitroanthraquinone and the various dinitro-anthraquinone isomers as impurities, especially if it has been obtained as the residual product in the purification of 1-nitroanthraquinone by crystallisa-tion or distillation.
Furthermore, those dinitroanthraquinone mixtures which are obtained by mixing any desired products, solutions or suspensions of any desired origin eontaining 1,5- and 1,8-dinitroanthraquinone ean also be employed in the process aeeording to the invention. The eontent of any 1,6- and 1,7-dinitroanthraquinone whieh may be present and the ratio of 1,5-dinitroanthraquinone to 1,8 dinitroanthraquinone are of minor importanee.
The proeess aeeording to the invention ean be earried out both diseontinuously and partly or entirely eontinuously.
Le ~ 17 371 - 10 -~ . .
Th- 1,5- and 1,8-dinitroanthraqui~one obtained according to the inve~tion can be con~erted directly into the correspon~ing amino compoun,1 and then further processed to giv~ anthraquinone ~- dyest,lffs 'compare, for example, Friedlaender, Fortschri-tte der Teerfarben-Fabri]iation (~dvances in the Manufacture of Aniline Dyes), 22nd part(1935), page 1014; Fiat Final Report 1313, German Dyestuffs and Interm~diates, II, page 26).
The examples which follow are intend-d to illus ra~e further the process according to the invenlion. The - 10 analyses in the examples are based ~n high pressure liquidchroDatogiaplly and on semi-qua;ltitative thin layer chromatography.
Examples s 1. Separation of a dinitroanthraquinone mixture having the composition: 0.5% of 2,6-dinitroanthraquinone, 0.4 % of 2,7-15 dinitro~nthraquinone, 1.8% of l-nitroan~hraqlinone, 9.8% of 1,6-dinitroanthraqlinone, 9.6% of l,l-dinitroanthraquin~ne, . 33 9~ of 1,5-dinitroanthraquinone and 36.6% of 1,8-dinitro-anthraquinone, obtained during the nitration of 20~ g of anthra-quinone with a mixture of 424 g of 98% strength nitric acid and 500 g of sulphuric acid monohydrate, the mixture having been stirred initially at 4~C (l an hour), then at 50C (-1- an hour).
The instructions which follow refer to a crystallisation with recycling of -the mother liquor after all the crystallisation - e~uilibria are established For starting up, pure nitrobenzene is used instead of recycled mother liquor.
1.1 Isolation of -the 1,5-dinitroanthraquinone 65.0 ~ of the above dinitroanthr~quinone mixture to~ether with 252 g of recycled mother liquor from 1.3. and 252 q of re-cycled mother-liquor from the fine purification described below 30 are warmed to 120~C for 0.5 hours, whilst stirring, and the mix-ture is then filtered a-t 120C. The fil-trate is used for Le A 17 371 - 11 -further pro~essing -to give 1,8-dinitroanthraquinone according to 1.2 The moist filter cake is war~ed to 160C with 18~ g of ~itrobenzene for 0.5 hour , whilst stirring. The mixture is then cooled to 10~C in the course o~ 0.2~ hour, and after stirring for 0.5 hour at 100C, is fil-tered. The residue is was'~ed with 60 g of nitrobenzene, heated to 10~C, in portions. The combined filtrates of the fine pariflca-tion which still con-tain dissolved dinitroanthraquinorle and/o~
mononitroanthraquinone are used for the next 1,5-dinitroanthra-q~inone cry~tallis~tion After drying the residue in vacuo atlOnC, the~ are obtained.22 4 g of 1,5-dinitro~nthraquinone (97.7 -~ of l,~-dinitroanthraquinone, 1 1% of 1,8-dinitroanthraquinone, 0.2~ of 1,6-dinitroanthraquinone and 0.1% of l,~-dinitroantnra-quinone).
Separation yield 84.1%.
., .
1 2. Isolation of the 1,8-dinitroanthraquinone The filtrate from the 1,5-dinitroanthraquinone separa-;'~ tion (about 510 g) is cooled to 105C, after it has been warmed, if appropriate, to 140C in order to achieve a clear solu~ion, and seeded with a few rystals of 1,8-dinitroanthraquinone and the mixture is stirred for 2 hours at 105C. It is filtered and the residue is washed with 48 g of cold nitrobenzene and dried in vacuo at 100C: 7.3 g of 1,8-dinitroanthraquinone (98 5% of 1,8-dinitroanthraquinone an-l ).6% of i,5--dinitro-anthraquinone).
Separa-~jon yield 30,2%.
The combined filtrates are used for the separation of the l,X-dinitroanthraquinone mixture according to 1.3.
1.3. Isolation of the l,X-dinitroanthraquinone (X = 5,6, 7 and 8) The combined filtrates from the 1,8-dinitroanthraquinone separation (about 540 g) are warmed to 120C until the solution Le A 17 371 _ 12 -. .
becomes clear. It is then cooled to 25C and stirred atthis temperature for 3 hours. The product which has ~; crystallised out is then filtered off and dried in vacuo at 100C: 21.0 g of l,X-dinitroanthraquinone (6.'/% of 1,6-di-nitroanthraquinone, 15.6% of l,','-dinitroanthraquinone, 10.8%
of 1,5-dinitroanthraquinone and 60.','% of 1,8-dini-troanthra-'~ quinone and 2.2% of l-nitroanthraquinone).
1.4. Isolation of the X,Y-dinitroanthraquinone (Y=l and 2, X =
' 5, 6, ',' and 8) The filtrate from 1.3. (about 504 g) is divided, about 252 g being recycled to 1.1 for the next crystallis-ation. The remainder is distilled to dryness in vacuo:
11.1 g of X,Y-dinitroanthraquinone (2.0% of 2,6-dinitroanthra-quinone, 1.9% of 2,'7-dinitroanthraquinone, 3r7 ~ 5% of 1,6-dinitro-anthraquinone, 22.1% of l,~-dinitroan-thraquinone, 6.1% of 1,5-; dinitroanthraquinone and 14.4% of 1,8-dinitroanthraquinone and ~' 3.6% of l-nitroanthraquinone).
The nitrobenzene which has distilled off is used again " in 1.1. and 1.2.
2. Separation of a dinitroanthraquinone mixture having ~` the composition of Example 1 (for establishing the crystallisat-ion equilibria, compare Example 1).
2.1. Isolation of the 1,5-dinitroanthraquinone 65.0 g of the dinitroanthraquinone mixture having the composition as in Example 1, together with 216 g of nitrobenzene and 252 g oE recycled Eiltra-te an~ ~Jashing liquid Erom the fine purification described below,are warmed to 120C for 0.5 hour, whilst stirring, and the mixture is then filtered at 120C. The filtrate is used for the further processing to give 1,8-dinitro-anthraquinone according to 2.2. The moist residue iswarmed -to 180C with 180 g of nitrobenzene for 0.5 hour, whilst Le A 17 371 - 1~-stirring The mixture is then cooled to 100C in -the - course of 025 hour and, after stirring for 0.5 hour at 100C, the product which has crystallised out is filtered off. The material on the filter is washed with 60 g of hot nitrobenzene in portions. The combined filtrates of this fine purifica-- tion are used for the next 1,5-dinitroanthraquinone crystallisa-tion. After drying the residue in vacuo at 100C, there are obtained: 21., g of 1,5-dinitroanthraquinone (98.8% of 1,5 dinitroanthraquinone and 1.1% of 1,8-dinitroanthraquinone).
- 10 Separation yield 82.f%.
2.2. Isolation of the 1,8-dinitroanthraquinone ` The filtrate from 2.1. is cooled to 100C and stirred a-t 100C for 2 hours. The crystals are filtered off, washed with 48 g of nitrobenzene and dried in vacuo at 100C: 6.8 g of 1,8-dinitroanthraquinone (9/.5% of 1,8-dinitroanthraquinone and 0.1% of 1,5-dinitroanthraquinone).
; Separation yield 2-7.9%.
2.3. Isolation of the l,X-dinitroanthraquinone (X = 5, 6, I
and 8) The combined filtrates from the 1,8-dinitroanthraquinone separation are cooled to 25C and stirred for 3 hours at this temperature. The precipitate is then filtered off and dried at 100C in vacuo: 16.1 g of l,X-dinitroanthraquinone (2.6% of 1,6-dinitroanthraquinone, 4.9% of 1,7-dinitroanthraquinone, 12.6% of 1,5-dinitroanthraquinone and 74.4% of 1,8-dinitroanthra-quinone).
2.4. Isolation of the X,Y-dini-troanthraquinone (Y = 1 and 2, X = 5,6, l and 8) The filtrate from 2.3. is distilled to dryness in vacuo:
19.5 g of X,Y-dinitroanthraquinone (1.5% of 2,6-dinitroanthra-quinone, 1.5% of 2,7-dinitroanthraquinone, 30.8% of 1,6-dinitro-Le A 17 ~71 - 14 --anthraquinone, 28,2% of l"'-dinitroanthraquinone, 7.8% of 1,5-dinitroanthraquinone and 16.1% of 1,8-dini-troanthraquinone and
4.2% of l-nitroan-thraquinone).
' The nitrobenzene which has distilled off can be used again in 2.1. and 2.2.
` ;. Separation of a dinitroanthraquinone mixture having the ~' composition: 0.4% of 2,6-dinitroanthraquinone, 0.5% of 2,7-,~ dinitroanthraquinone, 1.','% of l-nitroanthraquinone, 10.6% of ~..
1,6-dinitroanthraquinone, 10.8% of l,'~-dinitroanthraquinone, :6.5% o~ 1,5-dinitroanthraquinone, ~4.7% of 1,8-dinitroanthra-, quinone and 0,1% of anthraquinone, obtained during the nitration ' of 188 g of anthraquinone, 145 g of a mother liquor product of a l-nitroanthraquinone pre-purification and 87 g of a distillation - residue from a l-nitroanthraquinone distillation (composition of : 15 the mixture: 48,4% of anthraquinone, 5.5% of 1,5~dinitroanthra-quinone, 5,1% of 1,8-dinitroanthraquinone, 1,5% of l,'l-dinitro-anthraquinone and 1,4% of 1,6-dinitroanthraquinone, 26.7% of 1-nitroanthraquinone and ~.1% of 2-nitroanthraquinone) wi-th 62'l g of 98% strength nitric acid and '102 g of 96% strength sulphuric acid at temperatures of ~0C (1- an hour), which were then raised to 50C (~ an hour) and 60C (1 an hour), The instructions which follow refer to a crystallisation with nitrobenzene recycling after all the equilibria are established, For startin~ u~ pure nitrobenzene is used ins-tead of recycled mother liquor.
~,1, Isolation of the 1,5-dinitroanthraquinone 70.7 g of the above dinitroanthraquinone mixture together with 252 g of recycled filtrate and wash liquid from the fine purification of 1,5-dinitroanthraquinone described further below, 72 g of ; 30 pure nitrobenzene and 180 g of recycled filtrate from 3.3 are warmed to 120C for 1 hour, whilst stirring, and the mixture Le A 17 371 _ 15 _ is then filtered at 120C. The ~iltrate is used for the further processing to give 1,8-dinitroanthraquinone according to 3.2. The moist fil-ter cake is warmed to 180C with 180 g of nitrobenzene for 0.5 hour, whilst stirring, the mix-ture , is then cooled to 100C and filtered after stirring for -~ an hour at 100C and the residue is washed with 60 g of nitro-benzene, heated to 100C, in portions, and dried at 100C.
rl`~lere are obtained: 22.9 g of 1,5-dinitroanthraquinone (9/ 8%
of 1,5-dinitroanthraquinone, 1.8% of 1,8-dini-troanthraquinone - 10 and 0.~% of l-nitroanthraquinone).
Separation yield 86.8%.
-~.2. Isolation of the 1,8-dinitroanthraquinone In this process, in the manner described in Example 1.2., the filtrate from 3.1. is crystallised at 100-102C and the crystals are then worked up: 9.5 g of 1,8-dinitroanthra-quinone (9,`.8% of 1,8-dinitroanthraquinone and 0 3% of 1,5-` dinitroanthraquinone) Separation yield 38%.
The combined filtrates are used for the separation, according to 3.3., of a l,X-dinitroanthraquinone mixture.
3 3 Isolation of the l,X-dinitroanthraquinone (X = 5, 6, 7 and 8) The combined filtrates from the 1,8-dinitroanthraquinone separation in 3 2. are stirred at 60C for 3 hours, after they had been brought into solution again by warming briefly to ~` lS0C The precipitate is then filtered off and dried at 100C: 13 2 g of l,X-dinitroanthraquinone (1.5% of l-nitro-anthraquinone, 2 1% of 1,6-dinitroanthraquinone, 4.0% of 1,7-dinitroanthraquinone, 16 9% of 1,5-dinitroanthraquinone and 7S.3% of lJ8-dinitroanthraquinone).
3.4 Isolation of the X,Y-dinitroanthraquinone (Y = 1 and 2, Le A 17 37]; - 16 --`~
`,:
` X = 5, 6, 7 and 8) Af-ter separa-tlng off 180 g for recycling -to -i.l., the fil-trate from ~ 3 is dis-tilled to dryness.
;:
21.9 g of X,Y-dinitroanthraquinone (~ 8% of l-nitro-anthraquinone, l.2% of 2,6-dinitroanthraquinone, l 3% of 2,7-dinitroanthraquinone, ~0.7% of l,6-dinitroanthraquinone 7 26.2%
of l" -dinitroanthraquinone, 5 5% of l,5-dinitroanthraquinone and 2l.2~o of l,8-dinitroanthraquinone).
4. Separation of a dinitroanthraquinone mix-ture having the composition: 0.5% of 2,6-dinitroanthraquinone, 0.4% of 2,7-dinitroanthraquinone, l.2% of l-nitroanthraquinone, lO.3% of l,6-dinitroanthraquinone, lO.2% of l,l-dinitroanthraquinone, 38.1% of l,5-dinitroanthraquinone, 34.60/o of l~8-dinitroanthra-quinone and 0.1% of anthraquinone, obtained after nitrating a mixture of ,`2.6 g of anthraquinone, 56.1 g of the mother liquor product of a l-nitroanthraquinone pre-purification, 31.l g of the sump product of a l-nitroanthraquinone distillation having the composition: (48.3% of anthraquinone, 5.2% of l,5-dinitro-anthraquinone, 5.6% of l,8-dinitroanthraquinone, l.3% of l,6-dinitroanthraquinone, l.4% of l,l-dinitroanthraquinone, 26.7%
of l-nitroanthraquinone, 9.9% of 2-nitroanthraquinone and 0.5%
of 2,6- and 2 "-dinitroanthraquinone) with 226 ml of nitric acid (98% strength) and 213 ml of sulphuric acid (85% strength) a-t an initial temperature of 30C (l hour), which was then increased to 40C (l hour) and to 50C (2 hours).
The instructions which follow refer to a crystallisation with filtrate recycling aEter all the equilibria are establishecl.For starting up, pure nitrobenzene is used instead of recyclecl filtrate.
4.l. Iso].ation of the l,5-dinitroanthraquinone 70,7 g of the above dinitroanthraquinone mixture toge-ther Le A 17 37~ - 17 - ~
with 252 g of recycled filtrate from the fine purification of the 1,5-dinitroanthraquinone described further below and 256 ~ of recycled moth~r liquor from ~.3 are warmed to 120C ror 1 hour, whilst stirrin~, and the mixture is then filtered at 120~C. The filtrate is used for the further processing to give l,8-dinitroanthraquinone . according to 4.2. The moist filter cake is warmed to 180C
with 180 g of nitrobenzene for 5 hours, whilst stirring, and then cooled to 100C and, after stirring at 100C for l an hour, the precipitate is filtered off, washed wi-th 60 g of nitrobenzene, heated to 100C, in portions and dried at 100C.
There are obtained: 2~.3 g of 1,5-dinitroanthraquinone (97.6%
of 1,5-dinitroanthraquinone, 1.~% of 1,8-dinitroanthraquinone and 0.3% of l-nitroanthraquinone).
Separation yield 84.4%.
4.2, Isolation of the 1,8-dinitroanthraquinone In this process, in the manner described in Example 1.2., the filtrate from 4.1. is crystallised at 95C in the course of 6 hours and then worked up: 11.l g of 1,8-dinitroan-thraquinone (98.0~ of 1,8- and 1,3 ~ of 1,5-dinitroanthraquinone).
Separation yield 46.9%.
The combined filtrates are used for the separation, according to 4.3., of a l,X-dinitroanthraquinone mixture.
4.3. Isolation of the l,X-dinitroanthraquinone (X = 5, 6, 7 and 8) The combined filtrates from the 1,8-dinitroanthraquinone separation in 4.2. are stirred at 25C for 5 hours after they had been brought into solution again by briefly warming to 130C.
The precipitate is then filtered off and dried at 100C: 21.0 g of l,X-dinitroanthraquinone (1 8% of l-nitroanthraquinone, 11.9% of 1,6-dinitroanthraquinone, 22.8% of 1,7-dinitroanthra-Le A 17 37I - 18 -,' , : .
' ~ ' ' ' - ' ; '.
: `
quinone, 1~.1% of 1,5-dini-troanthraquinone and 4'/.f% of 1,8-dinitroanthraquinone).
About half of the filtrate (about 256 g) is recycled to 4.1.
.4. Isolation of the X,Y-dinitroanthraquinone (Y = 1 and 2, X = 5, 6, '7 and 8) :
` The remaining filtrat;e from 4.~. is distilled to dry-ness in vacuo at 150C: 12.5 g of X,Y-dinitroanthraquinone :
- (2.~% of l-nitroanthraquinone, 1.8% of 2,6-dinitroanthraquinone, . ~ lQ 1.1% of 2,''-dinitroanthraquinone, 36.~% of 1,6-dinitroanthra-' quinone, 19.0% of l,~-dinitroanthraquinone, 6.2% of 1,5-di-: nitroanthraquinone and 15.1% of 1,8-dinitroanthraquinone).
' The nitrobenzene which has distilled off can be used again in 2.1. and 2.2.
` ;. Separation of a dinitroanthraquinone mixture having the ~' composition: 0.4% of 2,6-dinitroanthraquinone, 0.5% of 2,7-,~ dinitroanthraquinone, 1.','% of l-nitroanthraquinone, 10.6% of ~..
1,6-dinitroanthraquinone, 10.8% of l,'~-dinitroanthraquinone, :6.5% o~ 1,5-dinitroanthraquinone, ~4.7% of 1,8-dinitroanthra-, quinone and 0,1% of anthraquinone, obtained during the nitration ' of 188 g of anthraquinone, 145 g of a mother liquor product of a l-nitroanthraquinone pre-purification and 87 g of a distillation - residue from a l-nitroanthraquinone distillation (composition of : 15 the mixture: 48,4% of anthraquinone, 5.5% of 1,5~dinitroanthra-quinone, 5,1% of 1,8-dinitroanthraquinone, 1,5% of l,'l-dinitro-anthraquinone and 1,4% of 1,6-dinitroanthraquinone, 26.7% of 1-nitroanthraquinone and ~.1% of 2-nitroanthraquinone) wi-th 62'l g of 98% strength nitric acid and '102 g of 96% strength sulphuric acid at temperatures of ~0C (1- an hour), which were then raised to 50C (~ an hour) and 60C (1 an hour), The instructions which follow refer to a crystallisation with nitrobenzene recycling after all the equilibria are established, For startin~ u~ pure nitrobenzene is used ins-tead of recycled mother liquor.
~,1, Isolation of the 1,5-dinitroanthraquinone 70.7 g of the above dinitroanthraquinone mixture together with 252 g of recycled filtrate and wash liquid from the fine purification of 1,5-dinitroanthraquinone described further below, 72 g of ; 30 pure nitrobenzene and 180 g of recycled filtrate from 3.3 are warmed to 120C for 1 hour, whilst stirring, and the mixture Le A 17 371 _ 15 _ is then filtered at 120C. The ~iltrate is used for the further processing to give 1,8-dinitroanthraquinone according to 3.2. The moist fil-ter cake is warmed to 180C with 180 g of nitrobenzene for 0.5 hour, whilst stirring, the mix-ture , is then cooled to 100C and filtered after stirring for -~ an hour at 100C and the residue is washed with 60 g of nitro-benzene, heated to 100C, in portions, and dried at 100C.
rl`~lere are obtained: 22.9 g of 1,5-dinitroanthraquinone (9/ 8%
of 1,5-dinitroanthraquinone, 1.8% of 1,8-dini-troanthraquinone - 10 and 0.~% of l-nitroanthraquinone).
Separation yield 86.8%.
-~.2. Isolation of the 1,8-dinitroanthraquinone In this process, in the manner described in Example 1.2., the filtrate from 3.1. is crystallised at 100-102C and the crystals are then worked up: 9.5 g of 1,8-dinitroanthra-quinone (9,`.8% of 1,8-dinitroanthraquinone and 0 3% of 1,5-` dinitroanthraquinone) Separation yield 38%.
The combined filtrates are used for the separation, according to 3.3., of a l,X-dinitroanthraquinone mixture.
3 3 Isolation of the l,X-dinitroanthraquinone (X = 5, 6, 7 and 8) The combined filtrates from the 1,8-dinitroanthraquinone separation in 3 2. are stirred at 60C for 3 hours, after they had been brought into solution again by warming briefly to ~` lS0C The precipitate is then filtered off and dried at 100C: 13 2 g of l,X-dinitroanthraquinone (1.5% of l-nitro-anthraquinone, 2 1% of 1,6-dinitroanthraquinone, 4.0% of 1,7-dinitroanthraquinone, 16 9% of 1,5-dinitroanthraquinone and 7S.3% of lJ8-dinitroanthraquinone).
3.4 Isolation of the X,Y-dinitroanthraquinone (Y = 1 and 2, Le A 17 37]; - 16 --`~
`,:
` X = 5, 6, 7 and 8) Af-ter separa-tlng off 180 g for recycling -to -i.l., the fil-trate from ~ 3 is dis-tilled to dryness.
;:
21.9 g of X,Y-dinitroanthraquinone (~ 8% of l-nitro-anthraquinone, l.2% of 2,6-dinitroanthraquinone, l 3% of 2,7-dinitroanthraquinone, ~0.7% of l,6-dinitroanthraquinone 7 26.2%
of l" -dinitroanthraquinone, 5 5% of l,5-dinitroanthraquinone and 2l.2~o of l,8-dinitroanthraquinone).
4. Separation of a dinitroanthraquinone mix-ture having the composition: 0.5% of 2,6-dinitroanthraquinone, 0.4% of 2,7-dinitroanthraquinone, l.2% of l-nitroanthraquinone, lO.3% of l,6-dinitroanthraquinone, lO.2% of l,l-dinitroanthraquinone, 38.1% of l,5-dinitroanthraquinone, 34.60/o of l~8-dinitroanthra-quinone and 0.1% of anthraquinone, obtained after nitrating a mixture of ,`2.6 g of anthraquinone, 56.1 g of the mother liquor product of a l-nitroanthraquinone pre-purification, 31.l g of the sump product of a l-nitroanthraquinone distillation having the composition: (48.3% of anthraquinone, 5.2% of l,5-dinitro-anthraquinone, 5.6% of l,8-dinitroanthraquinone, l.3% of l,6-dinitroanthraquinone, l.4% of l,l-dinitroanthraquinone, 26.7%
of l-nitroanthraquinone, 9.9% of 2-nitroanthraquinone and 0.5%
of 2,6- and 2 "-dinitroanthraquinone) with 226 ml of nitric acid (98% strength) and 213 ml of sulphuric acid (85% strength) a-t an initial temperature of 30C (l hour), which was then increased to 40C (l hour) and to 50C (2 hours).
The instructions which follow refer to a crystallisation with filtrate recycling aEter all the equilibria are establishecl.For starting up, pure nitrobenzene is used instead of recyclecl filtrate.
4.l. Iso].ation of the l,5-dinitroanthraquinone 70,7 g of the above dinitroanthraquinone mixture toge-ther Le A 17 37~ - 17 - ~
with 252 g of recycled filtrate from the fine purification of the 1,5-dinitroanthraquinone described further below and 256 ~ of recycled moth~r liquor from ~.3 are warmed to 120C ror 1 hour, whilst stirrin~, and the mixture is then filtered at 120~C. The filtrate is used for the further processing to give l,8-dinitroanthraquinone . according to 4.2. The moist filter cake is warmed to 180C
with 180 g of nitrobenzene for 5 hours, whilst stirring, and then cooled to 100C and, after stirring at 100C for l an hour, the precipitate is filtered off, washed wi-th 60 g of nitrobenzene, heated to 100C, in portions and dried at 100C.
There are obtained: 2~.3 g of 1,5-dinitroanthraquinone (97.6%
of 1,5-dinitroanthraquinone, 1.~% of 1,8-dinitroanthraquinone and 0.3% of l-nitroanthraquinone).
Separation yield 84.4%.
4.2, Isolation of the 1,8-dinitroanthraquinone In this process, in the manner described in Example 1.2., the filtrate from 4.1. is crystallised at 95C in the course of 6 hours and then worked up: 11.l g of 1,8-dinitroan-thraquinone (98.0~ of 1,8- and 1,3 ~ of 1,5-dinitroanthraquinone).
Separation yield 46.9%.
The combined filtrates are used for the separation, according to 4.3., of a l,X-dinitroanthraquinone mixture.
4.3. Isolation of the l,X-dinitroanthraquinone (X = 5, 6, 7 and 8) The combined filtrates from the 1,8-dinitroanthraquinone separation in 4.2. are stirred at 25C for 5 hours after they had been brought into solution again by briefly warming to 130C.
The precipitate is then filtered off and dried at 100C: 21.0 g of l,X-dinitroanthraquinone (1 8% of l-nitroanthraquinone, 11.9% of 1,6-dinitroanthraquinone, 22.8% of 1,7-dinitroanthra-Le A 17 37I - 18 -,' , : .
' ~ ' ' ' - ' ; '.
: `
quinone, 1~.1% of 1,5-dini-troanthraquinone and 4'/.f% of 1,8-dinitroanthraquinone).
About half of the filtrate (about 256 g) is recycled to 4.1.
.4. Isolation of the X,Y-dinitroanthraquinone (Y = 1 and 2, X = 5, 6, '7 and 8) :
` The remaining filtrat;e from 4.~. is distilled to dry-ness in vacuo at 150C: 12.5 g of X,Y-dinitroanthraquinone :
- (2.~% of l-nitroanthraquinone, 1.8% of 2,6-dinitroanthraquinone, . ~ lQ 1.1% of 2,''-dinitroanthraquinone, 36.~% of 1,6-dinitroanthra-' quinone, 19.0% of l,~-dinitroanthraquinone, 6.2% of 1,5-di-: nitroanthraquinone and 15.1% of 1,8-dinitroanthraquinone).
- 5. Separation of a dinitroanthraquinone mixture having -the composition: 0.4% of 2,6-dinitroanthraquinone, 0.4% of 2,~-dinitroanthraquinone, 1.7% of l-nitroanthraquinone, 10.6% of 1,6-dinitroanthraquinone, 10.8% of 1,1-dinitroanthraquinone, 36.~% of 1,5-dinitroanthraquinone, 34.'1% of 1,8-dinitroanthra-quinone and 0.10% of an-thraquinone, obtained according to the nitration instructions given in Example 3.
; 20 The instructions which follow refer to a crystallisation with filtrate recyclin~ after all the equilibria are established.For starting up, pure nitrobenzene is used instead of recycled filtrate.
5.1. Isolation of the 1,5-dinitroanthraquinone '70.7 g of the above dinitroanthraquinone mixture together ~: with 260 ~ of recycled filtrate from the fine purification of the 1,5-dinitroanthraquinone described further below and 73 ~ of recycled filtrate from 5.3. are warmed to 170C for 1 hour, cooled to 120 C, stirred for 1 hour 120C and the mixture is then filtered at 120C. The filtrate is used for the further processing to give 1,8-dinitroanthraquinone according to 5.2. The Le A 1? 371 - 1 9 moist filter cake is warmed to 160~C with 180 g of nitro-benzene for 0.5 hour, whilst stirring, the mixture is then cooled to 100C and, af-ter stirring at 100C for 1/2 an hour, - -the precipitate is sharply succed off, and dried at 100C.
5 There are obtained: 22.5 g of 1,5-dinitroanthraquinone (97.6 % of 1,5-dinitroanthraquinone, 0.8 % of 1,8-dinitro-anthraquinone and 0.3 % of 1-nitroanthraquinone.
Separation yield 85.-L%.
5.2 Isolation of the 1,8-dinitroanthraquinone The filtrate from the 1,5-dinitroanthraquinone separa-tion is warmed to 1~0C with 183 q of recycled filtrate from 5.3., ~hilst stirring, until a clear solution is obtained and the solution is then cooled to 100C and allowed to crystallise out in the course of 1.5 hours. The crystals are filtered off, sharply succed and dried at 120C: 9.0 g of 1,8-dinitroanthraquinone (98.2% pure~
containing 1.0% of 1,5-dinitroanthraquinone, 0.3% of 1,6-dinitroanthraquinone and 0.3% of 1,7-dini-troanthraquinone).
Separation yield 36 1%
` The combined filtrates are used for the separation, according to 5 3., of the l,X-dinitroanthraquinone mixture.
; 5.3. Isolation of the l,X-dinitroanthraquinone (X = 5, 6, 7 and 8) The filtrates from 5.2. are cooled -to 10C and s-tirred at this temperature for 3 hours. The precipitate is then ; filtered off and dried in vacuo: 28.6 g of l,X-dinitroanthra-quinone containing l,8-dinitroanthraquinone as the main com-ponent (50-60%) and 5-10% of 1,5-dinitroanthraquinone, 20-25%
of 1,7-dinitroanthraquinone and about 15% of 1,6-dinitroan-thra-quinone.
Le A 17 371 - 20 -,, About half o~ the filtrate is recycled to 5 1 and 5.2.
; 20 The instructions which follow refer to a crystallisation with filtrate recyclin~ after all the equilibria are established.For starting up, pure nitrobenzene is used instead of recycled filtrate.
5.1. Isolation of the 1,5-dinitroanthraquinone '70.7 g of the above dinitroanthraquinone mixture together ~: with 260 ~ of recycled filtrate from the fine purification of the 1,5-dinitroanthraquinone described further below and 73 ~ of recycled filtrate from 5.3. are warmed to 170C for 1 hour, cooled to 120 C, stirred for 1 hour 120C and the mixture is then filtered at 120C. The filtrate is used for the further processing to give 1,8-dinitroanthraquinone according to 5.2. The Le A 1? 371 - 1 9 moist filter cake is warmed to 160~C with 180 g of nitro-benzene for 0.5 hour, whilst stirring, the mixture is then cooled to 100C and, af-ter stirring at 100C for 1/2 an hour, - -the precipitate is sharply succed off, and dried at 100C.
5 There are obtained: 22.5 g of 1,5-dinitroanthraquinone (97.6 % of 1,5-dinitroanthraquinone, 0.8 % of 1,8-dinitro-anthraquinone and 0.3 % of 1-nitroanthraquinone.
Separation yield 85.-L%.
5.2 Isolation of the 1,8-dinitroanthraquinone The filtrate from the 1,5-dinitroanthraquinone separa-tion is warmed to 1~0C with 183 q of recycled filtrate from 5.3., ~hilst stirring, until a clear solution is obtained and the solution is then cooled to 100C and allowed to crystallise out in the course of 1.5 hours. The crystals are filtered off, sharply succed and dried at 120C: 9.0 g of 1,8-dinitroanthraquinone (98.2% pure~
containing 1.0% of 1,5-dinitroanthraquinone, 0.3% of 1,6-dinitroanthraquinone and 0.3% of 1,7-dini-troanthraquinone).
Separation yield 36 1%
` The combined filtrates are used for the separation, according to 5 3., of the l,X-dinitroanthraquinone mixture.
; 5.3. Isolation of the l,X-dinitroanthraquinone (X = 5, 6, 7 and 8) The filtrates from 5.2. are cooled -to 10C and s-tirred at this temperature for 3 hours. The precipitate is then ; filtered off and dried in vacuo: 28.6 g of l,X-dinitroanthra-quinone containing l,8-dinitroanthraquinone as the main com-ponent (50-60%) and 5-10% of 1,5-dinitroanthraquinone, 20-25%
of 1,7-dinitroanthraquinone and about 15% of 1,6-dinitroan-thra-quinone.
Le A 17 371 - 20 -,, About half o~ the filtrate is recycled to 5 1 and 5.2.
6. 1,5- and 1,8-dinitroanthraquinone can be obtained in very si~ilar qualities and with very similar separation yields, iE Example 4 is repeated, however using instead of 70.7 g dinitroanthraquinone of the given composition ; a) 76 ~ of a dinitroanthraquinone mixture of followinq compo-sition: 0.7 ~ 2,6-; 0.7 % 2,7-; 12.9 % 1,6-; 12.6 ~ 1.7-;
35.3 ~ 1.5-; 32.6 % 1,8-dinitroanthraquinone and 1.4 ~ 1-nitro-anthraquinone.
Such a dinitroanthraquinone mixture can be obtained as follows:
A mixture containing 7 % anthraquinone, 9.8 % 1,5-, 9.2 ~ 1,8-, 2.7 % 1,6-, 2.7 % 1,7-dinitroanthraquinone, 48.4 % 1~ and 16.4 %
2-nitroanthraquinone is nitrated with a mixed acid consisting of the 1.23 fold amount by weight of 98 % nitric acid and the 1.4 fold amount by weight of 96 % sulfuric acid at 40, 50 and 60C (each temperature is maintained for 30 minutes). After dilution with water the nitration product is isolated in customary manner. The starting material for such nitration can be obtained by mixing the product obtained in the working up of the mother liquor of the purification of 1-nitroanthraquinone by crystallisation and the product obtained as residue in the distillation of 1-nitroanthraquinone.
b) 61.2 g of a dinitroanthraquinone mixture of following composition: 2 % 1-nitroanthraquinone, 3.4 % 1,6-, 3.5 ~ 1,7-, 47.2 % 1,5- and 39.1 % 1,8-dinitroanthraquinone.
` Such a dinitroanthraquinone mixture can be obtained as follows:
A mixture containing 20.5 % 1,5-, 13.9 % 1,8-, 0.5 ~ 1,6-, 0.4 ~ 1.7-dinitroanthraquinone, 59.8 ~ 1- and 0.1 % 2-nitro-anthraquinone is nitrated with a mixed acid consisting of the Le A 17 37:L j - 21 -?
3~
" 1.4 fold amount by weight of 98 % nitric acid and of the 1.67 fold amount by wei~ht of 96 % sulfuric acid at 40, 50 and 60C
(cach temperature is maintained for 30 ~inutes). Af-ter dilution with water the nitration product is isolated in cus-tomary manner. The startinq material for such ni-tration can be obtained as a residue in the distillation of 1-nitroanthraquinone.
c) 8.15 g of a dinitroanthraquinone mixture of followin~
composition: 1.0 % 1-nitroanthraquinone, 1.3 ~ 2,7-, 1.1 %
2,6-, 18.4 % 1,6-, 17.9 % 1,7-, 27.9 % 1,5- and 28.7 % 1,8-dinitroanthraq~inone.
Such a dinitroanthraquinone mixture can be obtained asfollows: ~ mixture containing 11.2 ~ anthraquinone, 3.4 %
1,5-, 6.4 % 1,8-, 4 % l,6-, 4 % 1,7-dinitroanthraquinone, 41.4 % 1- and 26.2 % 2-nitroanthraquinone is nitrated with a mixed acid consisting of the 1.4 fold amount by weight of 98 %
nitric acid and the 1.67 fold amount by weight of 96 % sulEuric acid at 40, 50 and 60C (each temperature is maintained for 30 minutes). After dilution with water the nitration product is isolated in customary manner. The startin~ material for such nitration can be obtained in the working up of the mother liquor of the pre-purification of 1-nitroanthraquinone by crystallisation.
35.3 ~ 1.5-; 32.6 % 1,8-dinitroanthraquinone and 1.4 ~ 1-nitro-anthraquinone.
Such a dinitroanthraquinone mixture can be obtained as follows:
A mixture containing 7 % anthraquinone, 9.8 % 1,5-, 9.2 ~ 1,8-, 2.7 % 1,6-, 2.7 % 1,7-dinitroanthraquinone, 48.4 % 1~ and 16.4 %
2-nitroanthraquinone is nitrated with a mixed acid consisting of the 1.23 fold amount by weight of 98 % nitric acid and the 1.4 fold amount by weight of 96 % sulfuric acid at 40, 50 and 60C (each temperature is maintained for 30 minutes). After dilution with water the nitration product is isolated in customary manner. The starting material for such nitration can be obtained by mixing the product obtained in the working up of the mother liquor of the purification of 1-nitroanthraquinone by crystallisation and the product obtained as residue in the distillation of 1-nitroanthraquinone.
b) 61.2 g of a dinitroanthraquinone mixture of following composition: 2 % 1-nitroanthraquinone, 3.4 % 1,6-, 3.5 ~ 1,7-, 47.2 % 1,5- and 39.1 % 1,8-dinitroanthraquinone.
` Such a dinitroanthraquinone mixture can be obtained as follows:
A mixture containing 20.5 % 1,5-, 13.9 % 1,8-, 0.5 ~ 1,6-, 0.4 ~ 1.7-dinitroanthraquinone, 59.8 ~ 1- and 0.1 % 2-nitro-anthraquinone is nitrated with a mixed acid consisting of the Le A 17 37:L j - 21 -?
3~
" 1.4 fold amount by weight of 98 % nitric acid and of the 1.67 fold amount by wei~ht of 96 % sulfuric acid at 40, 50 and 60C
(cach temperature is maintained for 30 ~inutes). Af-ter dilution with water the nitration product is isolated in cus-tomary manner. The startinq material for such ni-tration can be obtained as a residue in the distillation of 1-nitroanthraquinone.
c) 8.15 g of a dinitroanthraquinone mixture of followin~
composition: 1.0 % 1-nitroanthraquinone, 1.3 ~ 2,7-, 1.1 %
2,6-, 18.4 % 1,6-, 17.9 % 1,7-, 27.9 % 1,5- and 28.7 % 1,8-dinitroanthraq~inone.
Such a dinitroanthraquinone mixture can be obtained asfollows: ~ mixture containing 11.2 ~ anthraquinone, 3.4 %
1,5-, 6.4 % 1,8-, 4 % l,6-, 4 % 1,7-dinitroanthraquinone, 41.4 % 1- and 26.2 % 2-nitroanthraquinone is nitrated with a mixed acid consisting of the 1.4 fold amount by weight of 98 %
nitric acid and the 1.67 fold amount by weight of 96 % sulEuric acid at 40, 50 and 60C (each temperature is maintained for 30 minutes). After dilution with water the nitration product is isolated in customary manner. The startin~ material for such nitration can be obtained in the working up of the mother liquor of the pre-purification of 1-nitroanthraquinone by crystallisation.
7. Separation of a dinitroanthraquinone mixture having the composition: 0.4 % of 2,6-dini-troanthraquinone, 0.4 % of 2,7-dinitroanthraquinone, 1.7 % of 1-nitroanthraquinone, 10.6 % of 1,6 dinitroanthraquinone, 10.8 % of 1,7-dinitroanthraquinone, 36.5 % of 1,5-dinitroanthraquinone, 34,7 % of 1,8-dinitroanthra-quinone and 0.10 % of anthraquinone, obtained according to the nitration instructions given in Example 3.
The instructions which follow refer to a crystallisa-tion with recycling of mother liquor after all the equilibria are Le A 17 371 - 22 -.
$~ 3~
:
established. Fc>r starting up, pure nitrohenzene is used ins-tead of recycled mother-liquor.
7.1 rsolation of the 1,5-dinitroan-thraquinone 70.7 g of the above dinitroanthraquinone mixture together with 247 g of recycled mother-liquor from the fine purification of the 1,5-dinitroan-thraquinone described further below and - all of the mother-liquor from 7.3. are warmed to 180C for 3 hours, whilst stirring, then cooled to 120C during 30 minutes by means of vaporization cooling of nitrobenzene at reduced pressure, then stirred for 1 hour at 120C. The mixture is then filtered at 120C. The filtrate is used for the further processing to give 1,8-dinitroanthraquinone according to 7.2. The moist filter cake is warmed to 160 C with 180 g of nitrobenzene for 0.5 hour, whilst stirring, the mixture is then cooled to 100C
and, after stirring at 100C for 1/2 an hour, the precipitate is filtered off, washed with 60 g of cold nitrobenzene in portions, and dried at 100C. There are obtained: 22.4 g of 1,5-dinitro-anthraquinone (98~9% of 1,5-dinitroanthraquinone, 0.6% of 1,8-dinitroanthraquinone and 0.1 % of 1-nitroanthraquinone).
Separation yield 85. 9 %
7.2 Isolation of the 1,8-dinitroanthraquinone The filtrate from the 1,5-dinitroanthraquinone separation is warmed -to 140C whilst stirring, until a clear solution is obtained and the solution is then cooled to 100C and allowed to crystallize out in the course of 1.5 hours. The crystals are filtered off, washed with 48 g of cold nitrobenzene and dried at 120C: 8.3 g of 1,8-dinitroanthraquinone (97.4 % pure, containing 0.8 % of 1,5-dinitroanthraquinone, 0.4 % of 1,6-dinitroanthxaquinone and 0.5 ~6 of 1,7-dinitroanthraquinone).
Separation yield 82.9 %.
Le A 17 371 - 23 , part of the combined filtrates are used for the separation, accordir.g to 7.3., of the l,X-dinitroanthraquinone mixture.
7.3. Isolation of the l,X-clinitroanthraquinone (X = 5, 6, 7 and 8) Half of the filtrates from 7.3 ~about 200 g) are cooled to 60C
and stirred at this temperature for 3 hours. Tlle precipitate is then filtered off and dried in vacuo: 9.5 g of l,X-dinitro-anthraquinone containing 64.6 % og 1,8-dinitroanthraquinone and 13.5 % of 1,5-dinitroanthraquinone, 13.0 % of 1,7-dinitroanthra-quinone and about 4.1 % of 1,6-dinitroan-thra~uinone.
: 7.4 Isolation of X, Y-dinitroanthraquinone (X = 1 and 2, Y = 5, 6, 7 and 8).
Half of the filtrate from 7.2 is freed of nitrobenzene in vacuo:
30.0 g X, Y-dinitroanthraquinone cor.taining 30.9 % of 1,8-,
The instructions which follow refer to a crystallisa-tion with recycling of mother liquor after all the equilibria are Le A 17 371 - 22 -.
$~ 3~
:
established. Fc>r starting up, pure nitrohenzene is used ins-tead of recycled mother-liquor.
7.1 rsolation of the 1,5-dinitroan-thraquinone 70.7 g of the above dinitroanthraquinone mixture together with 247 g of recycled mother-liquor from the fine purification of the 1,5-dinitroan-thraquinone described further below and - all of the mother-liquor from 7.3. are warmed to 180C for 3 hours, whilst stirring, then cooled to 120C during 30 minutes by means of vaporization cooling of nitrobenzene at reduced pressure, then stirred for 1 hour at 120C. The mixture is then filtered at 120C. The filtrate is used for the further processing to give 1,8-dinitroanthraquinone according to 7.2. The moist filter cake is warmed to 160 C with 180 g of nitrobenzene for 0.5 hour, whilst stirring, the mixture is then cooled to 100C
and, after stirring at 100C for 1/2 an hour, the precipitate is filtered off, washed with 60 g of cold nitrobenzene in portions, and dried at 100C. There are obtained: 22.4 g of 1,5-dinitro-anthraquinone (98~9% of 1,5-dinitroanthraquinone, 0.6% of 1,8-dinitroanthraquinone and 0.1 % of 1-nitroanthraquinone).
Separation yield 85. 9 %
7.2 Isolation of the 1,8-dinitroanthraquinone The filtrate from the 1,5-dinitroanthraquinone separation is warmed -to 140C whilst stirring, until a clear solution is obtained and the solution is then cooled to 100C and allowed to crystallize out in the course of 1.5 hours. The crystals are filtered off, washed with 48 g of cold nitrobenzene and dried at 120C: 8.3 g of 1,8-dinitroanthraquinone (97.4 % pure, containing 0.8 % of 1,5-dinitroanthraquinone, 0.4 % of 1,6-dinitroanthxaquinone and 0.5 ~6 of 1,7-dinitroanthraquinone).
Separation yield 82.9 %.
Le A 17 371 - 23 , part of the combined filtrates are used for the separation, accordir.g to 7.3., of the l,X-dinitroanthraquinone mixture.
7.3. Isolation of the l,X-clinitroanthraquinone (X = 5, 6, 7 and 8) Half of the filtrates from 7.3 ~about 200 g) are cooled to 60C
and stirred at this temperature for 3 hours. Tlle precipitate is then filtered off and dried in vacuo: 9.5 g of l,X-dinitro-anthraquinone containing 64.6 % og 1,8-dinitroanthraquinone and 13.5 % of 1,5-dinitroanthraquinone, 13.0 % of 1,7-dinitroanthra-quinone and about 4.1 % of 1,6-dinitroan-thra~uinone.
: 7.4 Isolation of X, Y-dinitroanthraquinone (X = 1 and 2, Y = 5, 6, 7 and 8).
Half of the filtrate from 7.2 is freed of nitrobenzene in vacuo:
30.0 g X, Y-dinitroanthraquinone cor.taining 30.9 % of 1,8-,
8.3 ~ of 1.5-, 21.2 ~ cf 1,7-, 24.4 ~ of 1,6-, 1 ~ 2,6-, 1 ~ 2,7-dlnitroanthraquinone and 2.7 ~ 1-nitroanthr~quinone.
`:
.
Le A 17 371 - 24 -
`:
.
Le A 17 371 - 24 -
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1) Process for the separation of dinitroanthraquinone mixtures using nitrobenzene, characterised in that a) treating 1 part by weight of a dinitroanthraquinone mixture with 4.5 - 9 parts by weight of nitro-benzene and/or with the solution obtained after the separation of 1,5-dinitroanthraquinone according to step b) and optionally wash liquid recycled from step b) and/or with the solution obtained after the separation of 1,X (X= 5, 6, 7 and 8)-dinitroanthraquinone at a temperature of 100 to 200°C and then separating off the unsoluble constituents at 100 - 150°C, b) treating the residue, which is obtained according to step a) and essentially consists of 1,5-dinitroanthraquinone, with 1 - 4 parts by weight of nitrobenzene at a temperature from 140°C in the boiling point, then cooling the mixture to 90 to 130°C and separating off and optionally washing with nitrobenzene the 1,5-dinitroanthraquinone which is not dissolved, c) cooling the solution obtained after the separation of the unsoluble constituents according to step a) to 90 to 120°C and separating off and optionally washing with nitrobenzene the 1,8-dinitro-anthraquinone which has crystallised out.
2) Process according to claim 1, characterised in that in step a) 1 part by weight of a dinitroanthraquinone mixture is treated with 5.5 to 8 parts by weight of nitrobenzene.
3) Process according to claim 1, characterised in that in step a) the separation of unsoluble constituents is carried out at a temperature of 110 to 130°C.
4. Process according to claim 1, characterised in that in step b) the residue obtained according to step a) is treated with 2 to 3 parts by weight of nitrobenzene.
5. Process according to claim 1, characterised in that in step b) the process is carried out at a temperature of 150 to 200°C.
6. Process according to claim 1, characterised in that in step b) and/or in step c) the mixture is cooled to 100 to 110°C.
7. Process according to claim 1, characterised in that in steps b) and c) the 1,5-dinitroanthraquinone (b) and 1,8-dinitroanthraquinone (c) which have been separated off are washed with 0.3 to 1 part by weight of nitrobenzene.
8. Process according to claim 1, 2 or 3, characterised in that in order to separate the 1,X-dinitroanthraquinone (where X denotes the 5, 6, 7 and 8 ring position) the solution obtained after separation of the 1,8-dinitroanthraquinone optionally combined with the washing liquid from the washing of 1,8-dinitroanthraquinone is cooled to 5 to 85°C and the mixture which crystallises out is separated off.
9. Process according to claim 1, 2 or 3, characterised in that in order to separate the X,Y-dinitroanthraquinone (where Y denotes the 1 and 2 and X denotes the 5, 6, 7 and 8 ring positions) the remaining solution from the 1,X-dinitro-anthraquinone separation is distilled to dryness under reduced pressure.
10. Process according to claim 1, 2 or 3, characterised in that the solution obtained after carrying out step b) is used for treating the dinitroanthraquinone mixture in step a).
11. Process according to claim 1, 2 or 3, characterised in that the solution obtained after carrying out step b) is used in total or partially and the solution obtained after separating 1,X-dinitroanthraquinone is partially used for the separation of dinitroanthraquinone mixtures.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2637733.3 | 1976-08-21 | ||
| DE19762637733 DE2637733C3 (en) | 1976-08-21 | 1976-08-21 | Process for the separation of dinitroanthraquinone mixtures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1111032A true CA1111032A (en) | 1981-10-20 |
Family
ID=5986033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA285,064A Expired CA1111032A (en) | 1976-08-21 | 1977-08-19 | Process for the separation of dinitroanthraquinone mixtures |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5325549A (en) |
| AT (1) | AT350542B (en) |
| BE (1) | BE857926A (en) |
| CA (1) | CA1111032A (en) |
| CH (1) | CH634038A5 (en) |
| DE (1) | DE2637733C3 (en) |
| FR (1) | FR2362111A1 (en) |
| GB (1) | GB1564373A (en) |
| IT (1) | IT1079921B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2458536A2 (en) * | 1978-07-27 | 1981-01-02 | Ugine Kuhlmann | Purificn. of mixed di:nitro anthraquinone(s) - to obtain 1,5 and 1,8 isomers, by treating with specified acetic acid ester(s) |
| FR2432014A1 (en) * | 1978-07-27 | 1980-02-22 | Ugine Kuhlmann | PROCESS FOR OBTAINING HIGH PURITY A, A'-DINITRO-ANTHRAQUINONES |
| DE2854427A1 (en) * | 1978-12-16 | 1980-06-26 | Bayer Ag | METHOD AND APPARATUS FOR THE RECOVERY OF DRY 1,5- AND / OR 1,8- DINITROANTHRAQUINONE FROM SUSPENSIONS CONTAINING SOLID 1,5- AND / OR 1,8-DINITROANTHRAQUINONE AND LIQUID NITROBENZENE |
| DE3329453A1 (en) * | 1983-08-16 | 1985-03-07 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING PURE 1-NITROANTHRACHINONE |
| JPH0811251B2 (en) * | 1984-08-18 | 1996-02-07 | 愛知製鋼株式会社 | Overload prevention device in cold roll forming |
| NL1035539C1 (en) * | 2008-06-04 | 2008-06-20 | Adriaan Johannes Stoffelen | Shovel for use in lawn, has shark fin-like extra cutting section with specific angle at front and back, and T-shaped incision to manually remove lumps of earth |
| US20170350621A1 (en) * | 2016-06-06 | 2017-12-07 | Frontline Aerospace, Inc | Secondary solar concentrator |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE167699C (en) * | ||||
| BE789702A (en) * | 1971-10-07 | 1973-02-01 | Sumitomo Chemical Co | PROCESS FOR THE PREPARATION OF DINITROANTHRAQUINONS |
| JPS4976851A (en) * | 1972-12-05 | 1974-07-24 | ||
| JPS511709A (en) * | 1974-06-25 | 1976-01-08 | Mitsubishi Heavy Ind Ltd | Renzokusokoshijono itotooshihoho |
| DE2524747C3 (en) * | 1975-06-04 | 1980-12-18 | Basf Ag, 6700 Ludwigshafen | Process for the isolation of 1,5- / 1,8-dinitroanthraquinone with a high content of a, a '-duutro compounds |
-
1976
- 1976-08-21 DE DE19762637733 patent/DE2637733C3/en not_active Expired
-
1977
- 1977-08-16 CH CH1002877A patent/CH634038A5/en not_active IP Right Cessation
- 1977-08-17 GB GB3451777A patent/GB1564373A/en not_active Expired
- 1977-08-19 IT IT5072077A patent/IT1079921B/en active
- 1977-08-19 CA CA285,064A patent/CA1111032A/en not_active Expired
- 1977-08-19 AT AT603577A patent/AT350542B/en not_active IP Right Cessation
- 1977-08-19 FR FR7725463A patent/FR2362111A1/en active Granted
- 1977-08-19 JP JP9879977A patent/JPS5325549A/en active Granted
- 1977-08-19 BE BE2056176A patent/BE857926A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2362111B1 (en) | 1981-09-04 |
| JPS5325549A (en) | 1978-03-09 |
| DE2637733B2 (en) | 1981-07-30 |
| BE857926A (en) | 1978-02-20 |
| AT350542B (en) | 1979-06-11 |
| GB1564373A (en) | 1980-04-10 |
| FR2362111A1 (en) | 1978-03-17 |
| JPS5546382B2 (en) | 1980-11-22 |
| DE2637733A1 (en) | 1978-02-23 |
| ATA603577A (en) | 1978-11-15 |
| DE2637733C3 (en) | 1982-05-06 |
| IT1079921B (en) | 1985-05-13 |
| CH634038A5 (en) | 1983-01-14 |
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