DE3246151A1 - Process for the preparation of 4-nitrodiphenylamines - Google Patents
Process for the preparation of 4-nitrodiphenylaminesInfo
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- DE3246151A1 DE3246151A1 DE19823246151 DE3246151A DE3246151A1 DE 3246151 A1 DE3246151 A1 DE 3246151A1 DE 19823246151 DE19823246151 DE 19823246151 DE 3246151 A DE3246151 A DE 3246151A DE 3246151 A1 DE3246151 A1 DE 3246151A1
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- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
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Abstract
Description
Verfahren zur Herstellung von 4-NitrodiphenylaminenProcess for the preparation of 4-nitrodiphenylamines
Die Erfindung betrifft ein Verfahren zur Herstellung von 4-Nitrodiphenylaminen durch Umsetzung von 4-Nitrohalogenbenzolen mit primären aromatischen Aminen in Gegenwart von Kaliumcarbonat und Kupferverbindungen.The invention relates to a process for the preparation of 4-nitrodiphenylamines by reacting 4-nitrohalobenzenes with primary aromatic amines in the presence of potassium carbonate and copper compounds.
Die Umsetzung von Halogennitrobenzolen mit aromatischen Aminen ist bereits seit langem bekannt. So ist aus der DE-PS 185 663 bekannt, die Umsetzung in Gegenwart von Alkalicarbonaten und Kupferverbindungen als Katalysatoren durchzuführen.The implementation of halonitrobenzenes with aromatic amines is known for a long time. The implementation is known from DE-PS 185 663 to be carried out in the presence of alkali carbonates and copper compounds as catalysts.
Außerdem ist bekannt, daß die außerordentlich langsam verlaufende Reaktion beschleunigt werden kann, wenn Kaliumcarbonat eingesetzt und das Reaktionswasser durch azeotrope Destillation entfernt wird.It is also known that the extremely slow The reaction can be accelerated if potassium carbonate is used and the water of reaction is removed by azeotropic distillation.
Gemäß Beispiel 1 der US-PS 2 927 943 wurde unter diesen Bedingungen in 21 Stunden Reaktionszeit mäßig reines 4-Nitrodiphenylamin in einer Ausbeute von 73 % der Theorie erhalten. Aus der US-PS 4 155 936 ist weiterhin bekannt, daß bei der Umsetzung von Halogennitrobenzolen mit primären aromatischen Aminen zu dem Nachteil langer Reaktionszeiten die Verunreinigung der Nitrodiphenylamine infolge Bildung nicht unerheblicher Mengen an Teeren und Nebenprodukten kommt, wie die Bildung von Nitrobenzol infolge reduktiver Enthalogenierung (vgl. US-PS 3 313 854, Spalte 3, Zeilen 64,65).According to Example 1 of US Pat. No. 2,927,943, under these conditions moderately pure 4-nitrodiphenylamine in a yield of 73% of theory received. From US-PS 4,155,936 it is also known that in the implementation of Halonitrobenzenes with primary aromatic Amines, the disadvantage of long reaction times, the contamination of the nitrodiphenylamines as a result of the formation of not inconsiderable amounts of tars and by-products, how the formation of nitrobenzene as a result of reductive dehalogenation (cf. US Pat. No. 3,313 854, column 3, lines 64,65).
Um diese Nachteile zu vermeiden, wurden dem Reaktionsgemisch polare Lösungsmittel als Cokatalysatoren zugesetzt. Allerdings sind auch die bislang eingesetzten polaren Lösungsmittel durchweg mit Nachteilen verbunden. So ist das Dimethylformamid, das gemäß der US-PS 3 055 940 eingesetzt wird, bei den Umsetzungsbedingungen flüchtig und bildet schwer abtrennbare Nebenprodukte. Hexamethyl-phosphorsäuretriamid, gemäß der US-PS 3 055 940 und Formanilid gemäß der US-PS 3 313 854 eingesetzt, besitzen in katalytischen Mengen in Gegenwart von Kupferverbindungen nur unbefriedigend beschleunigende Eigenschaften. Dimethylsulfoxid, Acetanilid sowie Salicylanilid, die gemäß der US-PS 3 277 175, der DE-AS 1 518 307 und der DE-AS 1 117 594 eingesetzt werden, ergeben ebenfalls nur geringe Effekte. Dies trifft auch für den Einsatz von N-Methylpyrrolidon gemäß DE-OS 2 633 811 oder &-Caprolactam gemäß JP 56/022 751 zu.In order to avoid these disadvantages, the reaction mixture became polar Solvents added as cocatalysts. However, the ones that have been used so far are also polar solvents are always associated with disadvantages. So is the dimethylformamide, which is used according to US Pat. No. 3,055,940, volatile under the reaction conditions and forms by-products that are difficult to separate. Hexamethyl-phosphoric acid triamide, according to U.S. Patent 3,055,940 and formanilide disclosed in U.S. Patent 3,313,854 only unsatisfactory accelerating in catalytic amounts in the presence of copper compounds Properties. Dimethyl sulfoxide, acetanilide and salicylanilide, which according to US Pat 3 277 175, DE-AS 1 518 307 and DE-AS 1 117 594 are used also only minor effects. This also applies to the use of N-methylpyrrolidone according to DE-OS 2 633 811 or & -caprolactam according to JP 56/022 751.
Auch der in der US-PS 4 155 936 beschriebene Zusatz von Polyethern ist mit Nachteilen verbunden. Je nach Aufarbeitungsweise verbleiben nämlich die Zusatzstoffe im Endprodukt oder im Abwasser.Also the addition of polyethers described in US Pat. No. 4,155,936 is associated with disadvantages. That is, depending on the method of work-up, the remaining Additives in the end product or in the wastewater.
In der US-PS 3 121 736 wird als weitere Möglichkeit zur Verminderung des Teeranfalls der Zusatz von Aminocarbonsäuren, von Alkyldiaminopolycarbonsäuren und ihren Salzen, von Disalicylaldiaminoalkanen, von o-Hydroxybenzalaminophenolen, von Polyphosphaten, Carboxymethyl-mercaptobernsteinsäure oder Schiff-Basen von Salicylaldehyden empfohlen.In US Pat. No. 3,121,736, a further possibility for reduction the tar accumulation, the addition of aminocarboxylic acids, of alkyldiaminopolycarboxylic acids and their salts, of disalicylaldiaminoalkanes, of o-hydroxybenzalaminophenols, of polyphosphates, carboxymethyl mercaptosuccinic acid or Schiff bases of salicylaldehydes recommended.
Aus dem Einsatz dieser Stoffe resultieren Probleme bei der Aufarbeitung.The use of these substances results in problems during work-up.
Es wurde nun ein Verfahren zur Herstellung von 4-Nitrodiphenylaminen der Formel (I) in der R1 R2 R3 und R4 R , R und R' gleich oder verschieden sind und für Wasserstoff oder einen Alkylrest mit 1 bis 9 Kohlenstoffatomen stehen, durch Umsetzung von Halogennitrobenzolen der Formel (II) in der X für Chlor oder Brom steht und in der R1 und R2 die obengenannte Bedeutung besitzen, mit primären aromatischen Aminen der Formel (III) in der R3 und R4 die obengenannte Bedeutung besitzen, in Gegenwart von Kaliumcarbonat und Kupferverbindungen gefunden, das dadurch gekennzeichnet ist, daß man Rubidium- oder Caesiumverbindungen oder Mischungen beider zusetzt.There has now been a process for the preparation of 4-nitrodiphenylamines of the formula (I) in which R1, R2, R3 and R4, R, R and R 'are identical or different and represent hydrogen or an alkyl radical having 1 to 9 carbon atoms, by reacting halonitrobenzenes of the formula (II) in which X stands for chlorine or bromine and in which R1 and R2 have the abovementioned meaning, with primary aromatic amines of the formula (III) in which R3 and R4 have the abovementioned meaning, found in the presence of potassium carbonate and copper compounds, which is characterized in that rubidium or cesium compounds or mixtures of both are added.
Als Alkylreste der Formel (I) kommen bevorzugt solche mit 1 bis 3 Kohlenstoffatomen in Frage.Preferred alkyl radicals of the formula (I) are those with 1 to 3 Carbon atoms in question.
Vorzugsweise wird das Verfahren zur Herstellung von 4-Nitrodiphenylamin aus 4-Nitrochlorbenzol und Anilin eingesetzt.Preferably the process is used to make 4-nitrodiphenylamine used from 4-nitrochlorobenzene and aniline.
Als Beispiele für die im erfindungsgemäßen Verfahren verwendbaren Kupferkatalysatoren seien Kupfer-(I)-jodid, Kupfer-(I)-chlorid, Kupfer-(II)-chlorid, Kupfer-(I)-bromid, Kupfer-(II)-bromid, Kupfer-(I)-cyanid, Kupfer-(I)-oxid, Kupfer-(II)-oxid, Kupfer-(II)-carbonat, basisches Kupfer-(II)-carbonat, Kupfer-(II)-sulfat, Kupfer-(II)-nitrat, Kupfer-(II)-formiat, Kupfer-(II)-acetat und organische und anorganische Kooordinationsverbindungen von ein- oder zweiwertigem Kupfer genannt. Bevorzugt werden sauerstoffhaltige Kupferverbindungen, wie Kupfer-(II)-oxid, Kupfer-(II)-carbonat, basisches Kupfer-(II)-carbonat oder Kupfer-(I)-oxid eingesetzt, wobei der Kupferkatalysator in einer Menge von 0,001 bis 0,1, bevorzugt 0,01 bis 0,05 Mol pro Mol eingesetztes Halogennitrobenzol eingesetzt wird. Die Kupferkatalysatoren können sowohl einzeln als auch im Gemisch untereinander eingesetzt werden.As examples of those which can be used in the process according to the invention Copper catalysts are copper (I) iodide, copper (I) chloride, copper (II) chloride, Copper (I) bromide, copper (II) bromide, copper (I) cyanide, copper (I) oxide, copper (II) oxide, Copper (II) carbonate, basic copper (II) carbonate, copper (II) sulfate, copper (II) nitrate, Copper (II) formate, copper (II) acetate and organic and inorganic coordination compounds of mono- or bivalent copper called. Oxygen-containing ones are preferred Copper compounds such as copper (II) oxide, copper (II) carbonate, basic copper (II) carbonate or copper (I) oxide used, the copper catalyst in an amount of 0.001 to 0.1, preferably 0.01 to 0.05 mol per mole of halonitrobenzene used is used. The copper catalysts can be used either individually or as a mixture are used among each other.
Als Halogennitrobenzole kommen beispielsweise 4-Nitrochlorbenzol, 4-Nitrobrombenzol, 4-Nitro-2-methyl-chlorbenzol und 4-Nitro-3-methyl-chlorbenzol in Frage.As halonitrobenzenes, for example 4-nitrochlorobenzene, 4-nitrobromobenzene, 4-nitro-2-methyl-chlorobenzene and 4-nitro-3-methyl-chlorobenzene in question.
Als primäre aromatische kommen zum Beispiel Anilin, o-Toluidin, m-Toluidin, p-Toluidin, 4-Ethylanilin, 4-Butylanilin, 4-Isopropylanilin, 3,5-Dimethylanilin und 2,4-Dimethylanilin in Frage.As primary aromatic, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 4-ethylaniline, 4-butylaniline, 4-isopropylaniline, 3,5-dimethylaniline and 2,4-dimethylaniline in question.
Selbstverständlich können die aromatischen Amine auch in Form von Gemischen, insbesondere Isomerengemischen, eingesetzt werden. Pro Mol Halogennitrobenzol werden im allgemeinen etwa 1 bis 6 Mol, bevorzugt 1,5 bis 3 Mol, besonders 1,7 bis 2,5 Mol, des aromatischen Amins eingesetzt.Of course, the aromatic amines can also be in the form of Mixtures, in particular isomer mixtures, are used. Per mole of halonitrobenzene are generally about 1 to 6 mol, preferably 1.5 to 3 mol, especially 1.7 to 2.5 mol, of the aromatic amine used.
Als Rubidium- oder Caesiumverbindungen kommen z.B. die Chloride, Bromide, Iodide, Sulfate, Oxide, Hydroxide, Carbonate, Hydrogencarbonate, Formiate, Acetate, Propionate, Cyanide und Phosphate in Frage, insbesondere jedoch die Salze von schwachen organischen oder anorgenischen Säuren, beispielsweise die Carbonate, Ace- tate, Formiate und Cyanide. Die Caesiumverbindungen sind bevorzugt. Die eingesetzten Salze können im Reaktionsgefäß aus den Hydroxiden und den entsprechenden Säuren oder geeigneten Säurederivaten gebildet werden.As rubidium or cesium compounds, e.g. the chlorides, bromides, Iodides, sulfates, oxides, hydroxides, carbonates, hydrogen carbonates, formates, acetates, Propionates, cyanides and phosphates in question, but especially the salts of weak organic or inorganic acids, for example the carbonates, acetic did, Formates and cyanides. The cesium compounds are preferred. The salts used can in the reaction vessel from the hydroxides and the corresponding acids or suitable Acid derivatives are formed.
Die Rubidium- und Caesiumverbindungen werden pro Mol Halogennitrobenzol in solchen molaren Mengen zugesetzt, die 0,05 bis 5 g, vorzugsweise 0,1 bis 1 g Caesiumcarbonat entsprechen.The rubidium and cesium compounds are halonitrobenzene per mole added in such molar amounts that 0.05 to 5 g, preferably 0.1 to 1 g Cesium carbonate.
Kaliumcarbonat kann in äquivalenter Menge oder im Uberschuß bis zur 1,5-fachen äquivalenten Menge eingesetzt werden.Potassium carbonate can be used in an equivalent amount or in excess up to 1.5 times the equivalent amount can be used.
Das während der Reaktion entstehende Wasser wird vorteilhafterweise aus dem Reaktionsgemisch unter Zuhilfenahme eines Schleppmittels durch Destillation entfernt. Als Schleppmittel kommen z.B. Xylol, Toluol, Benzol, Chlorbenzol, Chlortoluol, Anilin und/oder Toluidin in Frage, vorzugsweise Xylol oder Toluol.The water formed during the reaction is advantageous from the reaction mixture with the aid of an entrainer by distillation removed. Examples of entrainers are xylene, toluene, benzene, chlorobenzene, chlorotoluene, Aniline and / or toluidine are possible, preferably xylene or toluene.
Das erfindungsgemäße Verfahren kann, falls gewünscht, in Gegenwart von Verdünnungsmitteln, z.B. inerten organischen Kohlenwasserstoffen, beispielsweise in Gegenwart von Xylol, durchgeführt werden. Weiterhin können die aromatischen primären Amine selbst als Lösungsmittel eingesetzt werden.If desired, the process according to the invention can be carried out in the presence of diluents, e.g. inert organic hydrocarbons, e.g. in the presence of xylene. Furthermore, the aromatic primary Amines themselves can be used as solvents.
Die Reaktionstemperaturen des erfindungsgemäßen Verfahrens können in weiten Bereichen schwanken. Im all- gemeinen betragen sie 140 bis 2250C, vorzugsweise 180 bis 2100C.The reaction temperatures of the process according to the invention can fluctuate over a wide range. In space- common they are 140 to 2250C, preferably 180 to 2100C.
Die Durchführung des erfindungsgemäßen Verfahrens kann nach üblichen Methoden kontinuierlich oder diskontinuierlich erfolgen.The process according to the invention can be carried out according to customary Methods can be carried out continuously or discontinuously.
Die Aufarbeitung des Reaktionsgemisches kann ebenfalls nach verschiedenen Varianten erfolgen. Die im Reaktionsgemisch befindlichen Salze lassen sich bei erhöhter Temperatur auf physikalische Weise durch Zentrifugieren oder Filtrieren abtrennen. Nach Waschen mit warmem Xylol und Trocknen verbleibt ein hellgrauer pulvriger Feststoff.The work-up of the reaction mixture can also be carried out in various ways Variants are made. The salts in the reaction mixture can be reduced at increased Physically remove the temperature by centrifugation or filtration. After washing with warm xylene and drying, a light gray powdery solid remains.
Aus dem Filtrat können nicht-umgesetztes Halogennitrobenzol und primäres aromatisches Amin mit Wasserdampf ausgetrieben werden, wobei die Nitrodiphenylamine zumeist als Granulat anfallen. Eine andere Möglichkeit besteht darin, daß man das Filtrat im Vakuum teilweise destilliert und das Produkt dann im Rückstand erhält oder daß man die 4-Nitrodiphenylamine weitestgehend durch Kristallisation abtrennt und/oder daß man das Filtrat mit einem Fällungsmittel, z.B. Xylol, versetzt. Die 4-Nitrodiphenylamine fallen dabei in hochreiner Form an und können so direkt weiterverarbeitet werden.Unreacted halonitrobenzene and primary can from the filtrate aromatic amine can be driven off with steam, whereby the nitrodiphenylamines mostly occur as granules. Another possibility is that you can The filtrate is partially distilled in vacuo and the product is then obtained in the residue or that the 4-nitrodiphenylamines are largely separated off by crystallization and / or that a precipitant, e.g. xylene, is added to the filtrate. the 4-Nitrodiphenylamines are obtained in a highly pure form and can thus be further processed directly will.
Der Kupferkatalysator kann mehrfach verwendet werden.The copper catalyst can be used multiple times.
Gegebenenfalls wird ihm zur Erhaltung der vollen Aktivität eine geringere als die ursprünglich eingesetzte Katalysatormenge in frischer Form zugegeben. Zum Ausschleusen von Nebenprodukten wird im Bedarfsfall eine Teilmenge der anfallenden Mutterlauge abgetrennt. Das Reaktionsgemisch kann auch zur Entfernung der Salze vorzugsweise bei einer erhöhten Temperatur (85 bis 950C) mit der zum Lösen der Salze notwendigen Menge Wasser ausgerührt werden. Nach Phasentrennung wird die organische Schicht weiter aufgearbeitet, beispielsweise durch Wasserdampfdestillation oder durch Strippen der Bestandteile, die leichter flüchtig sind als das 4-Nitrodiphenylamin.If necessary, he will be given less activity to maintain full activity added in fresh form than the originally used amount of catalyst. To the If necessary, by-products will be discharged in part the resulting mother liquor separated. The reaction mixture can also be used for removal the salts preferably at an elevated temperature (85 to 950C) with that for dissolving the necessary amount of water to be stirred into the salts. After phase separation, the Organic layer further worked up, for example by steam distillation or by stripping the components which are more volatile than the 4-nitrodiphenylamine.
Nach dem erfindungsgemäßen Verfahren können 4-Nitrodiphenylamine in Ausbeuten von über 85 % und hohen Reinheiten bei kurzen Reaktionszeiten hergestellt werden.According to the process of the invention, 4-nitrodiphenylamines in Yields of over 85% and high purities with short reaction times will.
Die Bildung von Nebenprodukten findet bei dem erfindungsgemäßen Verfahren nur im geringen Ausmaß statt.The formation of by-products takes place in the process according to the invention only to a small extent.
Die nach dem erfindungsgemäßen Verfahren hergestellten 4-Nitrodiphenylamine können leicht nach bekannten Verfahren zu Aminodiphenylaminen reduziert werden und sind als solche wertvolle Zwischenprodukte für die Herstellung von beispielsweise Farbstoffen oder Stabilisatoren für Kautschuk (vgl. US-PS 3 163 616).The 4-nitrodiphenylamines produced by the process according to the invention can easily be reduced to aminodiphenylamines by known processes and are as such valuable intermediate products for the production of, for example Dyes or stabilizers for rubber (see US Pat. No. 3,163,616).
Beispiel 1 In einem 2 l-Dreihalskolben mit.Rührer und Destillationsaufsatz mit Wasserabscheider werden bei einer Rührgeschwindigkeit von 400 Upm 1 Mol 4-Chlornitrobenzol, 1,9 Mol Anilin, 1,25 Mol trockenes Kaliumcarbonat, 1/42 Mol Kupfer(II)-oxid, 1/950 Mol trockenes Caesiumcarbonat und 1/10 Mol Xylol vorgelegt.Example 1 In a 2 l three-necked flask with a stirrer and a distillation attachment with a water separator, 1 mol of 4-chloronitrobenzene, 1.9 moles of aniline, 1.25 moles of dry potassium carbonate, 1/42 mole of cupric oxide, 1/950 Submitted mol of dry cesium carbonate and 1/10 mol of xylene.
Das Reaktionsgemisch wird unter Rühren auf 1950C erhitzt.The reaction mixture is heated to 1950 ° C. while stirring.
Man hält den Kolbeninhalt solange bei dieser Temperatur, bis 10 bis 10,5 ml Wasser abgeschieden sind und bestimmt an einer Probe flüssigkeitschromatographisch den 4-Chlornitrobenzolgehalt. Liegt dieser unter 1,5 % der arsprünglichen Menge, wird die Reaktion durch Abkühlen abgebrochen; andernfalls fortgesetzt, bis dieser Wert erreicht ist.The contents of the flask are kept at this temperature until 10 to 10.5 ml of water are deposited and determined on a sample by liquid chromatography the 4-chloronitrobenzene content. If this is less than 1.5% of the original amount, the reaction is terminated by cooling; otherwise continue until this one Value is reached.
Die Gesamtdauer der Reaktion beträgt 5 bis 6 Stunden.The total duration of the reaction is 5 to 6 hours.
Bei 1000C werden 50 ml Wasser zugegeben und die flüchtigen Bestandteile mit Wasserdampf abgetrieben. Die wäßrige Phase des Kolbeninhaltes wird abgetrennt, die organische Phase erstarrt beim Abkühlen. Man erhält 216 g einer graugrünen körnigen Substanz, die nach flüssigkeitschromatographischer Analyse 86 Gew.-% 4-Nitrodiphenylamin enthält, entsprechend einer 87 %-igen Ausbeute bezogen auf 4-Chlornitrobenzol 4-Chlornitrobenzol.At 1000C 50 ml of water are added and the volatile constituents driven off with steam. The aqueous phase of the contents of the flask is separated off, the organic phase solidifies on cooling. 216 g of a gray-green granular are obtained Substance which, according to liquid chromatographic analysis, contains 86% by weight of 4-nitrodiphenylamine contains 4-chloronitrobenzene, corresponding to an 87% yield based on 4-chloronitrobenzene.
Beispiel 2 Beispiel 1 wird mit der Änderung, daß anstelle des Caesiumcarbonats 1/930 Mol Caesiumcyanid eingesetzt wird, wiederholt.Example 2 Example 1 is used with the change that instead of cesium carbonate 1/930 mol of cesium cyanide is used, repeated.
Man erhält 4-Nitordiphenylamin in 88,7 %-iger Ausbeute, bezogen auf eingesetzes 4-Chlornitrobenzol.4-Nitordiphenylamine is obtained in 88.7% yield, based on 4-chloronitrobenzene used.
Beispiel 3 Man führt Beispiel 1 mit 1,95 Mol Anilin, 1,3 Mol Kaliumcarbonat, 1/45 Mol Kupfer(II)-oxid, 1/850 Mol Caesiumacetat, 1/20- Mol Wasser und 1/12 Mol Xylol, ansonsten aber unverändert durch und treibt etwa 11 ml Wasser ab.Example 3 Example 1 is carried out with 1.95 mol of aniline, 1.3 mol of potassium carbonate, 1/45 mole cupric oxide, 1/850 mole cesium acetate, 1/20 mole water and 1/12 mole Xylene, but otherwise unchanged and drives off about 11 ml of water.
Die Ausbeute an 4-Nitrodiphenylamin beträgt, bezogen auf 4-Nitrochlorbenzol, 89,2 %.The yield of 4-nitrodiphenylamine, based on 4-nitrochlorobenzene, is 89.2%.
Claims (10)
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19823246151 DE3246151A1 (en) | 1982-12-14 | 1982-12-14 | Process for the preparation of 4-nitrodiphenylamines |
IN751/DEL/83A IN160179B (en) | 1982-12-14 | 1983-11-10 | |
KR1019830005642A KR910002370B1 (en) | 1982-12-14 | 1983-11-29 | Process for the preparation of 4-nitrodiphenyl amines |
JP58231624A JPS59112947A (en) | 1982-12-14 | 1983-12-09 | Manufacture of 4-nitrodiphenylamine |
DD83257811A DD215536A5 (en) | 1982-12-14 | 1983-12-12 | PROCESS FOR THE PREPARATION OF 4-NITRODIPHENYLAMINES |
CS839327A CS236898B2 (en) | 1982-12-14 | 1983-12-12 | Processing of 4-nitrodiphenylamine |
SU833673464A SU1158038A3 (en) | 1982-12-14 | 1983-12-12 | Method of obtaining 4-nitrodiphenylamine |
BR8306844A BR8306844A (en) | 1982-12-14 | 1983-12-13 | PROCESS FOR THE PREPARATION OF 4-NITRODIPENYLAMINS |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19823246151 DE3246151A1 (en) | 1982-12-14 | 1982-12-14 | Process for the preparation of 4-nitrodiphenylamines |
Publications (2)
Publication Number | Publication Date |
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DE3246151A1 true DE3246151A1 (en) | 1984-06-14 |
DE3246151C2 DE3246151C2 (en) | 1988-06-30 |
Family
ID=6180570
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Application Number | Title | Priority Date | Filing Date |
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DE19823246151 Granted DE3246151A1 (en) | 1982-12-14 | 1982-12-14 | Process for the preparation of 4-nitrodiphenylamines |
Country Status (8)
Country | Link |
---|---|
JP (1) | JPS59112947A (en) |
KR (1) | KR910002370B1 (en) |
BR (1) | BR8306844A (en) |
CS (1) | CS236898B2 (en) |
DD (1) | DD215536A5 (en) |
DE (1) | DE3246151A1 (en) |
IN (1) | IN160179B (en) |
SU (1) | SU1158038A3 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6235937B1 (en) | 1999-09-06 | 2001-05-22 | Bayer Aktiengesellschaft | Process for the preparation of nitrodiphenylamines |
EP1123916A1 (en) * | 2000-02-09 | 2001-08-16 | Bayer Ag | Process for the preparation of amino diphenylamines |
EP1437340A1 (en) | 2003-01-07 | 2004-07-14 | Bayer Aktiengesellschaft | Process for the preparation of aminodiphenylamines |
US6815562B2 (en) | 2003-01-07 | 2004-11-09 | Bayer Aktiengesellschaft | Process for the preparation of nitrodiphenylamines |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2502724C1 (en) * | 2012-10-22 | 2013-12-27 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | Method of producing nitrodiphenylamines |
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DE1056619B (en) * | 1956-11-29 | 1959-05-06 | Bayer Ag | Process for the preparation of 4-nitro-diarylamines |
US2927943A (en) * | 1955-12-07 | 1960-03-08 | Us Rubber Co | Preparation of p-nitrodiphenylamine |
DE1090225B (en) * | 1957-11-05 | 1960-10-06 | Us Rubber Co | Process for the preparation of p-nitrodiphenylamines |
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US4228103A (en) * | 1978-03-13 | 1980-10-14 | Monsanto Company | Effecting condensation of nitrohaloarene and formyl derivative of a primary aromatic amine with alkali metal hydroxide |
-
1982
- 1982-12-14 DE DE19823246151 patent/DE3246151A1/en active Granted
-
1983
- 1983-11-10 IN IN751/DEL/83A patent/IN160179B/en unknown
- 1983-11-29 KR KR1019830005642A patent/KR910002370B1/en not_active IP Right Cessation
- 1983-12-09 JP JP58231624A patent/JPS59112947A/en active Granted
- 1983-12-12 DD DD83257811A patent/DD215536A5/en not_active IP Right Cessation
- 1983-12-12 SU SU833673464A patent/SU1158038A3/en active
- 1983-12-12 CS CS839327A patent/CS236898B2/en unknown
- 1983-12-13 BR BR8306844A patent/BR8306844A/en not_active IP Right Cessation
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DE1056619B (en) * | 1956-11-29 | 1959-05-06 | Bayer Ag | Process for the preparation of 4-nitro-diarylamines |
DE1090225B (en) * | 1957-11-05 | 1960-10-06 | Us Rubber Co | Process for the preparation of p-nitrodiphenylamines |
US3155727A (en) * | 1960-07-25 | 1964-11-03 | Goodyear Tire & Rubber | Reaction of aromatic amines with para halo nitrobenzenes using copper cyanide condensation catalyst |
US3313854A (en) * | 1961-11-20 | 1967-04-11 | Universal Oil Prod Co | Preparation of para-nitrodiphenylamines utilizing a copper oxide catalyst |
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DE2855764A1 (en) * | 1977-12-27 | 1979-06-28 | Monsanto Co | METHOD OF PRODUCING NITRODIARYLAMINE USING A PROMOTOR |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6235937B1 (en) | 1999-09-06 | 2001-05-22 | Bayer Aktiengesellschaft | Process for the preparation of nitrodiphenylamines |
EP1123916A1 (en) * | 2000-02-09 | 2001-08-16 | Bayer Ag | Process for the preparation of amino diphenylamines |
US6316673B2 (en) | 2000-02-09 | 2001-11-13 | Bayer Aktiengesellschaft | Process for producing aminodiphenylamines |
EP1437340A1 (en) | 2003-01-07 | 2004-07-14 | Bayer Aktiengesellschaft | Process for the preparation of aminodiphenylamines |
US6815562B2 (en) | 2003-01-07 | 2004-11-09 | Bayer Aktiengesellschaft | Process for the preparation of nitrodiphenylamines |
CN100457713C (en) * | 2003-01-07 | 2009-02-04 | 朗盛德国有限责任公司 | Method for prudicing amino-diphenylamine |
Also Published As
Publication number | Publication date |
---|---|
KR910002370B1 (en) | 1991-04-20 |
SU1158038A3 (en) | 1985-05-23 |
IN160179B (en) | 1987-06-27 |
DE3246151C2 (en) | 1988-06-30 |
BR8306844A (en) | 1984-07-24 |
KR840007560A (en) | 1984-12-08 |
DD215536A5 (en) | 1984-11-14 |
JPS59112947A (en) | 1984-06-29 |
CS236898B2 (en) | 1985-05-15 |
JPS6323184B2 (en) | 1988-05-16 |
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