EP0578655A1 - Method of preparing halogenated indigo - Google Patents

Method of preparing halogenated indigo

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Publication number
EP0578655A1
EP0578655A1 EP92906628A EP92906628A EP0578655A1 EP 0578655 A1 EP0578655 A1 EP 0578655A1 EP 92906628 A EP92906628 A EP 92906628A EP 92906628 A EP92906628 A EP 92906628A EP 0578655 A1 EP0578655 A1 EP 0578655A1
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EP
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Prior art keywords
indigo
chlorine
thionyl chloride
bromine
reaction
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EP92906628A
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German (de)
French (fr)
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EP0578655B1 (en
Inventor
Reinhold Kohlhaupt
Udo Bergmann
Lothar Haas
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B7/00—Indigoid dyes
    • C09B7/02—Bis-indole indigos
    • C09B7/04—Halogenation thereof

Definitions

  • Vat Blue 5 is an important dye for dyeing and printing textiles in brilliant blue shades.
  • This dye is produced industrially by brominating indigo in glacial acetic acid as the reaction medium (Ullmann's Encyclopedia of Industrial Chemistry, fifth edition: Vol. A 14, p. 155; Indigo and Indigo Colorants) in the presence of a halogen-binding salt, e.g. Sodium acetate (DRP 237 262).
  • a halogen-binding salt e.g. Sodium acetate
  • the patent literature also describes the bro uring of indigo in nitrobenzene (DRP 193 438) and in dichlorobenzene or trichlorobenzene (DRP 208 471).
  • the object was therefore to develop a process for the production of Vat Blue 5 which does not have the disadvantages of the known processes.
  • halogenated indigo can be produced economically and ecologically advantageously in high yield and quality by reacting indigo with bromine and / or chlorine if thionyl chloride is used as the reaction medium.
  • bromine and / or chlorine if thionyl chloride is used as the reaction medium.
  • bromine only about half of the theoretical amount of bromine is used for the preparation of tetrabromoindigo because the hydrogen bromide formed is converted back into bromine by introducing chlorine into the reaction mixture.
  • the brominated indigo is finally oxidized to its yellow dehydroform by excess chlorine.
  • the dehydrotetrabromoindigo is finally treated with a reducing agent, e.g. Sodium thiosulfate, reduced to tetrabromo indigo.
  • a reducing agent e.g. Sodium thiosulfate
  • indigo in thionyl chloride in a weight ratio of 1: 1 to 1:10, preferably 1: 3 to 1: 7, and at 0 to 75 ° C., preferably at 20 to 40 ° C, with bromine in a molar ratio of 1: 0.5 to 1: 3.0, preferably 1: 2.2 to 1: 2.6 in 1-4 hours, preferably in 1.5-2.5 hours.
  • halogenation is carried out only with chlorine in thionyl chloride, with indigo being reacted with chlorine in a molar ratio of 1: 5 to 1:10, preferably 1: 8, then the resulting dehydrotetrachloroindigo 5, 7, 5 ', 7 is obtained after reduction '-Tetrachloroindigo with a chlorine content of 33.0 - 35.5%.
  • indigo is reacted in thionyl chloride with less bromine than is necessary for the production of Vat Blue 5, for example in a molar ratio of 1: 1, then after further reaction with chlorine and reduction of the dehydrotetrahalogenindigo initially obtained, 5,5'-dibromo, 7, 7'-dichloro indigo.
  • the halogenation of the indigo in thionyl chloride in a paddle dryer or in a rotary tube reactor made of special steel is particularly advantageous, because after the dehydrohalogeno indigo has formed, the thionyl chloride used for the synthesis can easily be distilled off from the reaction mixture and can be used again to halogenate Indigo can be used.
  • indigo powder (calc. 100%) are stirred into 250 g of thionyl chloride at 20-30 ° C. in about 10 minutes. After stirring for a further 10 minutes, 73 g of bromine are added in 15 minutes at a constant temperature with gentle cooling and the mixture is then stirred at 20-30 ° C. for a further hour. Then 81 g of chlorine are passed in at the same temperature in 8 hours. After stirring for another hour, the reaction mixture is introduced into a mixture of 1 kg of water and 0.5 kg of ice in a 4-1 stirred reactor. The suspension obtained is stirred for 1 hour, the dehydrotetrabromoindigo is filtered off on a suction filter and washed neutral with water at about 20.degree.
  • the moist filter material is then stirred into 1.5 kg of water in a 3-1 stirred reactor, brought to pH 7-7.5 by adding about 3 g of NaOH (50%) and stirred with 87 g of sodium thiosulfate in 15 minutes ( Na2S2 ⁇ 3 • H2O) added.
  • the mixture is then heated to 90-95 ° C. in the course of 30 minutes and stirring is continued for 2 hours at this temperature, a pH of 7.0-7.5 always being maintained by adding 37 g of NaOH (50%).
  • the reaction mixture is cooled to 70 ° C. and filtered on a suction filter.
  • the filter material is washed neutral with water and dried. 101 g of Vat Blue 5 are obtained with a content of 52.3% bromine and 0.5% chlorine, corresponding to a yield of 91.5% of theory. Th. (Calc. Tetrabromo indigo).
  • Example 2 Example 2
  • indigo powder 50 g of indigo powder (calc. 100%) are stirred into 250 g of thionyl chloride in a 500 ml stirred reactor. 73 g of bromine are added dropwise to the suspension at 20-30 ° C. in 15 minutes. After stirring at this temperature for one hour, 81 g of chlorine are passed into the reaction mixture at 20-30 ° C. in 6 hours. After stirring for a further 1 hour at constant temperature, the thionyl chloride is distilled off from the synthesis mixture, for example in a rotary evaporator, 220 g of the acid chloride originally used being recovered.
  • indigo powder 50 g of indigo powder (calc. 100%) are stirred into 300 g of thionyl chloride in a 500 ml stirred reactor. 73 g of bromine are added to the suspension obtained in 15 minutes at 20-30 ° C. After stirring for one hour at this temperature, the mixture is warmed to 50 ° C. and, after adding 1.5 g of iodine, 90 g of chlorine are gassed in at the same temperature in 6 hours. The reaction mixture is stirred for a further 1 hour at 50 ° C. and then added to a mixture of 1 kg of water and 0.5 kg of ice. After stirring for another hour, the suspended dehydrotetrabromoindigo is filtered off and washed neutral on the suction filter with water.
  • Example 4 As described in Example 1, the filter material is reduced to tetrabromoindigo with 87 g of sodium thiosulfate. After working up, 105.1 g of Vat Blue 5 with a content of 52.7% bromine and 0.6% chlorine, corresponding to a yield of 95.3% of theory. Th. Received (calc. Tetrabromoindigo).
  • indigo powder 50 g of indigo powder (calc. 100%) are suspended in 350 g of thionyl chloride in a 500 ml stirred reactor. In 5 hours, 107.5 g of chlorine are then introduced into the reaction mixture at 20 ° -30 ° C. and after stirring for another hour, it is stirred into 1.5 kg of ice water. The suspended dehydrotetrachloroindigo is filtered off and washed neutral with water. The reduction is carried out with 87 g of sodium thiosulfate, as described in Example 1. 57.8 g of tetrachloroindigo with a chlorine content of 34.5% are obtained, corresponding to a yield of 75.8% of theory. Th.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)

Abstract

Selon un procédé de préparation d'indigo halogéné par réaction d'indigo avec du brome et/ou du chlore, le cas échéant avec de l'iode comme catalyseur, on utilise comme milieu de réaction du chlorure de thionyle.According to a process for preparing halogenated indigo by reaction of indigo with bromine and/or chlorine, optionally with iodine as catalyst, thionyl chloride is used as reaction medium.

Description

Verfahren zur Herstellung von halogeniertem IndigoProcess for the production of halogenated indigo
Beschreibungdescription
Von der Vielzahl der literaturbekannten Halogenverbindungen des Indigos findet nur der 5, 7, 5', 7'-Tetrabromindigo industrielle Verwendung (Vat Blue 5, C.I. 73065). Vat Blue 5 ist ein wichtiger Farbstoff zum Färben und Bedrucken von Textilien in brillanten blauen Farbtönen.Of the multitude of halogen compounds of the indigo known from the literature, only the 5, 7, 5 ', 7'-tetrabromoindigo is used industrially (Vat Blue 5, C.I. 73065). Vat Blue 5 is an important dye for dyeing and printing textiles in brilliant blue shades.
Die technische Herstellung dieses Farbstoffs erfolgt durch Bromieren von Indigo in Eisessig als Reaktionsmedium (Ullmann's Encyclopedia of Industrial Chemistry, fifth edition: Vol. A 14, p. 155; Indigo and Indigo Colorants) in Gegenwart eines halogen- wasserstoffbindenden Salzes, z.B. Natriumacetat (DRP 237 262). In der Patentliteratur ist ferner die Bro ierung von Indigo in Nitrobenzol (DRP 193 438) und in Dichloi— oder Trichlorbenzol beschrieben (DRP 208 471).This dye is produced industrially by brominating indigo in glacial acetic acid as the reaction medium (Ullmann's Encyclopedia of Industrial Chemistry, fifth edition: Vol. A 14, p. 155; Indigo and Indigo Colorants) in the presence of a halogen-binding salt, e.g. Sodium acetate (DRP 237 262). The patent literature also describes the bro uring of indigo in nitrobenzene (DRP 193 438) and in dichlorobenzene or trichlorobenzene (DRP 208 471).
Die Durchführung der Halogenierung von Indigo in toxischen Löse¬ mitteln wie Nitrobenzol oder Chlorbenzol ist problematisch im Hinblick auf Arbeitsplatzhygiene, Abluft und Abwasser.The halogenation of indigo in toxic solvents such as nitrobenzene or chlorobenzene is problematic with regard to workplace hygiene, exhaust air and waste water.
Beim industriell genutzten Verfahren in Eisessig als Reaktions- medium gelangen, wenn nicht eine unwirtschaftliche Eisessig¬ regenerierung durchgeführt wird, pro kg Vat Blue 5 etwa 5 kg organisch gebundener Kohlenstoff in das Abwasser, so daß be¬ trächtliche Kosten für die Abwasserreinigung unumgänglich sind.In the industrially used process in glacial acetic acid as the reaction medium, unless an uneconomical regeneration of glacial acetic acid is carried out, about 5 kg of organically bound carbon per kg of Vat Blue 5 enter the wastewater, so that considerable costs for wastewater treatment are inevitable.
Es bestand daher die Aufgabe, ein Verfahren zur Herstellung von Vat Blue 5 zu entwickeln, das die Nachteile der bekannten Ver¬ fahren nicht aufweist.The object was therefore to develop a process for the production of Vat Blue 5 which does not have the disadvantages of the known processes.
Es wurde nun überraschenderweise gefunden, daß man halogenierten Indigo mit hoher Ausbeute und Qualität ökonomisch und ökologisch vorteilhaft durch Umsetzung von Indigo mit Brom und/oder Chlor herstellen kann, wenn man Thionylchlorid als Reaktionsmedium verwendet. In literaturbekannter Weise wird für die Herstellung von Tetra¬ bromindigo nur ungefähr die Hälfte der theoretischen Brommenge eingesetzt, weil man den entstehenden Bromwasserstoff durch Ein¬ leiten von Chlor in das Reaktionsgemisch wieder in Brom über¬ führt. Durch überschüssiges Chlor wird der bromierte Indigo schließlich noch zu seiner gelben Dehydroform oxidiert.It has now surprisingly been found that halogenated indigo can be produced economically and ecologically advantageously in high yield and quality by reacting indigo with bromine and / or chlorine if thionyl chloride is used as the reaction medium. In the manner known from the literature, only about half of the theoretical amount of bromine is used for the preparation of tetrabromoindigo because the hydrogen bromide formed is converted back into bromine by introducing chlorine into the reaction mixture. The brominated indigo is finally oxidized to its yellow dehydroform by excess chlorine.
Der Dehydrotetrabromindigo wird schließlich mit einem Reduktions- ittel, z.B. Natriumthiosulfat, zum Tetrabromindigo reduziert.The dehydrotetrabromoindigo is finally treated with a reducing agent, e.g. Sodium thiosulfate, reduced to tetrabromo indigo.
Je nach benutztem Reaktortyp hat es sich als vorteilhaft er¬ wiesen, Indigo in Thionylchlorid im Gewichtverhältnis 1:1 bis 1:10, bevorzugt 1:3 bis 1:7, einzutragen und bei 0 bis 75°C, bevorzugt bei 20 bis 40°C, mit Brom im Molverhältnis von 1:0,5 bis 1:3,0, bevorzugt 1:2,2 bis 1:2,6 in 1 - 4 Stunden, bevorzugt in 1,5 - 2,5 Stunden, umzusetzen. Durch anschließendes Einleiten von Chlor im Molverhältnis 1:1,5 bis 1:8, bevorzugt 1:5,5 bis 1:7, bei 0 - 75°C, bevorzugt bei 20 - 40°C, in 8 - 16 Stunden, bevorzugt in 11 - 13 Stunden, gegebenenfalls in Gegenwart von lod als Katalysator wird die Dehydroform von Vat Blue 5 erhalten. Anschließend kann das Reaktionsgemisch in Wasser eingetragen und der Dehydroindigo in literaturbekannter Weise zu Vat Blue 5 reduziert werden. Der Bromgehalt des hierbei erhaltenen, im Hinblick auf Koloristik und Echtheit hochwertigen Farbstoffes liegt bei 50,5 - 53,5 % bei einem Chlorgehalt von 0,5 - 2,5 %.Depending on the type of reactor used, it has proven advantageous to enter indigo in thionyl chloride in a weight ratio of 1: 1 to 1:10, preferably 1: 3 to 1: 7, and at 0 to 75 ° C., preferably at 20 to 40 ° C, with bromine in a molar ratio of 1: 0.5 to 1: 3.0, preferably 1: 2.2 to 1: 2.6 in 1-4 hours, preferably in 1.5-2.5 hours. Subsequent introduction of chlorine in a molar ratio of 1: 1.5 to 1: 8, preferably 1: 5.5 to 1: 7, at 0-75 ° C., preferably at 20-40 ° C., in 8-16 hours is preferred in 11-13 hours, if appropriate in the presence of iodine as catalyst, the dehydroform of Vat Blue 5 is obtained. The reaction mixture can then be introduced into water and the dehydroindigo reduced to Vat Blue 5 in a manner known from the literature. The bromine content of the dye obtained here, which is of high quality in terms of color and fastness, is 50.5-53.5% with a chlorine content of 0.5-2.5%.
Führt man die Halogenierung nur mit Chlor in Thionylchlorid durch, wobei Indigo mit Chlor im Molverhältnis 1:5 bis 1:10, bevorzugt 1:8, umgesetzt wird, dann erhält man nach Reduktion des zunächst anfallenden Dehydrotetrachlorindigos 5, 7, 5', 7'-Tetra- chlorindigo mit einem Chlorgehalt von 33,0 - 35,5 %.If the halogenation is carried out only with chlorine in thionyl chloride, with indigo being reacted with chlorine in a molar ratio of 1: 5 to 1:10, preferably 1: 8, then the resulting dehydrotetrachloroindigo 5, 7, 5 ', 7 is obtained after reduction '-Tetrachloroindigo with a chlorine content of 33.0 - 35.5%.
Setzt man Indigo in Thionylchlorid mit weniger Brom als zur Herstellung von Vat Blue 5 notwendig ist, z.B. im Molverhältnis 1:1 um, dann erhält man nach der weiteren Umsetzung mit Chlor und Reduktion des zunächst anfallenden Dehydrotetrahalogenindigos 5,5'-Dibrom, 7, 7'-Dichlorindigo. Besonders vorteilhaft ist die Halogenierung des Indigos in Thionylchlorid in einem Schaufeltrockner oder in einem Drehrohr¬ reaktor aus SpezialStahl, denn dann läßt sich nach der Bildung des Dehydrohalogenindigos das zur Synthese verwendete Thionyl¬ chlorid leicht aus dem Reaktionsgemisch abdesti 11 ieren und kann erneut zur Halogenierung von Indigo benutzt werden.If indigo is reacted in thionyl chloride with less bromine than is necessary for the production of Vat Blue 5, for example in a molar ratio of 1: 1, then after further reaction with chlorine and reduction of the dehydrotetrahalogenindigo initially obtained, 5,5'-dibromo, 7, 7'-dichloro indigo. The halogenation of the indigo in thionyl chloride in a paddle dryer or in a rotary tube reactor made of special steel is particularly advantageous, because after the dehydrohalogeno indigo has formed, the thionyl chloride used for the synthesis can easily be distilled off from the reaction mixture and can be used again to halogenate Indigo can be used.
Die Erfindung soll durch die folgenden Beispiele zusätzlich erläutert werden.The invention is illustrated by the following examples.
Beispiel 1example 1
In einem 500-ml-Rührreaktor werden in 250 g Thionylchlorid bei 20 - 30°C in ungefähr 10 Minuten 50 g Indigopulver (ber. 100 %) eingerührt. Nach 10-minütigem Weiterrühren läßt man bei gleich¬ bleibender Temperatur unter schwacher Kühlung in 15 Minuten 73 g Brom zufließen und rührt dann noch 1 Stunde bei 20 - 30°C weiter. Anschließend leitet man bei der gleichen Temperatur in 8 Stunden 81 g Chlor ein. Nach einstündigem Weiterrühren wird der Reak- tionsansatz in einem 4-1-Rührreaktor in ein Gemisch aus 1 kg Wasser und 0,5 kg Eis eingetragen. Man rührt die erhaltene Suspension 1 Stunde nach, filtriert den Dehydrotetrabromindigo auf einer Nutsche ab und wäscht ihn mit Wasser von etwa 20°C neutral .In a 500 ml stirred reactor, 50 g of indigo powder (calc. 100%) are stirred into 250 g of thionyl chloride at 20-30 ° C. in about 10 minutes. After stirring for a further 10 minutes, 73 g of bromine are added in 15 minutes at a constant temperature with gentle cooling and the mixture is then stirred at 20-30 ° C. for a further hour. Then 81 g of chlorine are passed in at the same temperature in 8 hours. After stirring for another hour, the reaction mixture is introduced into a mixture of 1 kg of water and 0.5 kg of ice in a 4-1 stirred reactor. The suspension obtained is stirred for 1 hour, the dehydrotetrabromoindigo is filtered off on a suction filter and washed neutral with water at about 20.degree.
Das feuchte Filtergut wird dann in einem 3-1-Rührreaktor in 1,5 kg Wasser eingerührt, durch Zugabe von ungefähr 3 g NaOH (50 %) auf pH 7 - 7, 5 gebracht und in 15 Minuten unter Rühren mit 87 g Natriumthiosulfat (Na2S2θ3 • H2O) versetzt. Dann erhitzt man in 30 Minuten auf 90 - 95°C und rührt 2 Stunden bei dieser Temperatur weiter, wobei durch Zugabe von 37 g NaOH (50 %) stets ein pH-Wert von 7,0 - 7,5 eingehalten wird. Nach weiterem Ein¬ rühren von 22 g NaOH (50 %) und 30-minütigem Nachrühren bei 90 - 95°C wird das Reaktionsgemisch auf 70°C gekühlt und auf einer Nutsche filtriert. Das Filtergut wird mit Wasser neutral gewaschen und getrocknet. Erhalten werden 101 g Vat Blue 5 mit einem Gehalt von 52,3 % Brom und 0,5 % Chlor, entsprechend einer Ausbeute von 91,5 % d. Th. (ber. Tetrabromindigo). Beispiel 2The moist filter material is then stirred into 1.5 kg of water in a 3-1 stirred reactor, brought to pH 7-7.5 by adding about 3 g of NaOH (50%) and stirred with 87 g of sodium thiosulfate in 15 minutes ( Na2S2θ3 • H2O) added. The mixture is then heated to 90-95 ° C. in the course of 30 minutes and stirring is continued for 2 hours at this temperature, a pH of 7.0-7.5 always being maintained by adding 37 g of NaOH (50%). After further stirring in 22 g of NaOH (50%) and stirring at 90-95 ° C. for 30 minutes, the reaction mixture is cooled to 70 ° C. and filtered on a suction filter. The filter material is washed neutral with water and dried. 101 g of Vat Blue 5 are obtained with a content of 52.3% bromine and 0.5% chlorine, corresponding to a yield of 91.5% of theory. Th. (Calc. Tetrabromo indigo). Example 2
In einem 500-ml-Rührreaktor werden in 250 g Thionylchlorid 50 g Indigopulver (ber. 100 %) eingerührt. Zur Suspension läßt man bei 20 - 30°C in 15 Minuten 73 g Brom zutropfen. Nach einstündigem Weiterrühren bei dieser Temperatur werden bei 20 - 30°C in 6 Stunden 81 g Chlor in das Reaktionsgemisch eingeleitet. Nach weiterem Rühren für die Dauer von 1 Stunde bei gleichbleibender Temperatur wird das Thionylchlorid aus dem Synthesegemisch, z.B. in einem Rotationsverdampfer, abdestilliert, wobei 220 g des ursprünglich eingesetzten Säurechlorides zurückgewonnen werden. Der verbleibende feste Destillationsrückstand wird mit 1500 g Wasser versetzt und mit 87 g Natriumthiosulfat (Na2S2θ3 • 5H20) wie bei Beispiel 1 beschrieben, zum Tetrabromindigo reduziert. Man erhält 102,1 g Vat Blue 5 mit einem Gehalt von 52,8 % Brom und 1,2 % Chlor, entsprechend einer Ausbeute von 92,1 % d. Th. (ber. Tetrabromindigo).50 g of indigo powder (calc. 100%) are stirred into 250 g of thionyl chloride in a 500 ml stirred reactor. 73 g of bromine are added dropwise to the suspension at 20-30 ° C. in 15 minutes. After stirring at this temperature for one hour, 81 g of chlorine are passed into the reaction mixture at 20-30 ° C. in 6 hours. After stirring for a further 1 hour at constant temperature, the thionyl chloride is distilled off from the synthesis mixture, for example in a rotary evaporator, 220 g of the acid chloride originally used being recovered. The remaining solid distillation residue is mixed with 1500 g of water and reduced to tetrabromoindigo with 87 g of sodium thiosulfate (Na2S2θ 3 • 5H 2 0) as described in Example 1. This gives 102.1 g of Vat Blue 5 with a content of 52.8% bromine and 1.2% chlorine, corresponding to a yield of 92.1% of theory. Th. (Calc. Tetrabromo indigo).
Beispiel 3Example 3
In einem 500-ml-Rührreaktor werden in 300 g Thionylchlorid 50 g Indigopulver (ber. 100 %) eingerührt. Die erhaltene Suspension wird in 15 Minuten bei 20 - 30°C mit 73 g Brom versetzt. Nach einstündigem Nachrühren bei dieser Temperatur wird auf 50°C erwärmt und nach Zugabe von 1,5 g Iod werden in 6 Stunden bei gleicher Temperatur 90 g Chlor eingegast. Das Reaktionsmgemisch wird noch 1 Stunde bei 50°C weitergerührt und dann in ein Gemisch aus 1 kg Wasser und 0,5 kg Eis eingetragen. Nach einstündigem Weiterrühren wird der suspendierte Dehydrotetrabromindigo ab- filtriert und auf der Nutsche mit Wasser neutral gewaschen. Das Filtergut wird, wie in Beispiel 1 beschrieben, mit 87 g Natrium¬ thiosulfat zum Tetrabromindigo reduziert. Nach der Aufarbeitung werden 105,1 g Vat Blue 5 mit einem Gehalt von 52,7 % Brom und 0,6 % Chlor, entsprechend einer Ausbeute von 95,3 % d. Th. erhalten (ber. Tetrabromindigo). Beispiel 450 g of indigo powder (calc. 100%) are stirred into 300 g of thionyl chloride in a 500 ml stirred reactor. 73 g of bromine are added to the suspension obtained in 15 minutes at 20-30 ° C. After stirring for one hour at this temperature, the mixture is warmed to 50 ° C. and, after adding 1.5 g of iodine, 90 g of chlorine are gassed in at the same temperature in 6 hours. The reaction mixture is stirred for a further 1 hour at 50 ° C. and then added to a mixture of 1 kg of water and 0.5 kg of ice. After stirring for another hour, the suspended dehydrotetrabromoindigo is filtered off and washed neutral on the suction filter with water. As described in Example 1, the filter material is reduced to tetrabromoindigo with 87 g of sodium thiosulfate. After working up, 105.1 g of Vat Blue 5 with a content of 52.7% bromine and 0.6% chlorine, corresponding to a yield of 95.3% of theory. Th. Received (calc. Tetrabromoindigo). Example 4
In einem 500-ml-Rührreaktor werden in 350 g Thionylchlorid 50 g Indigopulver (ber. 100 %) suspendiert. In 5 Stunden werden dann bei 20 - 30°C 107,5 g Chlor in das Reaktionsgemisch eingeleitet und nach einstündigem Weiterrühren wird es in 1,5 kg Eiswasser eingerührt. Der suspendierte Dehydrotetrachlorindigo wird ab¬ filtriert und mit Wasser neutral gewaschen. Die Reduktion wird mit 87 g Natriumthiosulfat, wie bei Beispiel 1 beschrieben, durchgeführt. Erhalten werden 57,8 g Tetrachlorindigo mit einem Chlorgehalt von 34,5 %, entsprechend einer Ausbeute von 75,8 % d. Th. 50 g of indigo powder (calc. 100%) are suspended in 350 g of thionyl chloride in a 500 ml stirred reactor. In 5 hours, 107.5 g of chlorine are then introduced into the reaction mixture at 20 ° -30 ° C. and after stirring for another hour, it is stirred into 1.5 kg of ice water. The suspended dehydrotetrachloroindigo is filtered off and washed neutral with water. The reduction is carried out with 87 g of sodium thiosulfate, as described in Example 1. 57.8 g of tetrachloroindigo with a chlorine content of 34.5% are obtained, corresponding to a yield of 75.8% of theory. Th.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung von halogeniertem Indigo durch Umsetzung von Indigo mit Brom und/oder Chlor gegebenenfa ls mit Jod als Katalysator, dadurch gekennzeichnet, daß man Thionylchlorid als Reaktionsmedium verwendet.1. A process for the preparation of halogenated indigo by reacting indigo with bromine and / or chlorine optionally with iodine as a catalyst, characterized in that thionyl chloride is used as the reaction medium.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man Indigo und Thionylchlorid im Gewichtsverhältnis 1:3 bis 1:7 einsetzt.2. The method according to claim 1, characterized in that indigo and thionyl chloride are used in a weight ratio of 1: 3 to 1: 7.
3. Verfahren gemäß Anspruch 1 und 2, dadurch gekennzeichnet, daß man Indigo mit Brom im Molverhältnis 1:2,2 bis 1:2,6 umsetzt und das Reaktionsgemisch anschließend mit Chlor im Molverhältnis 1:5,5 bis 1:6,5 reagieren läßt.3. Process according to Claims 1 and 2, characterized in that indigo is reacted with bromine in a molar ratio of 1: 2.2 to 1: 2.6 and the reaction mixture is then reacted with chlorine in a molar ratio of 1: 5.5 to 1: 6.5 can react.
4. Verfahren gemäß Anspruch 1 bis 3, dadurch gekennzeichnet, daß man die Umsetzung von Indigo mit Halogen bei 20 - 40°C durchführt.4. The method according to claim 1 to 3, characterized in that one carries out the reaction of indigo with halogen at 20 - 40 ° C.
Verfahren gemäß Anspruch 1 bis 4, dadurch gekennzeichnet, daß man die Umsetzung von Indigo mit Brom in 2 - 3 Stunden vornimmt und die anschließende Reaktion mit Chlor in 11 - 13 Stunden durchführt.Process according to Claims 1 to 4, characterized in that the reaction of indigo with bromine is carried out in 2-3 hours and the subsequent reaction with chlorine is carried out in 11-13 hours.
6. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man die Halogenierung von Indigo in Thionylchlorid in einem Schaufeltrockner oder einem Drehrohrreaktor vornimmt, bei Reaktionsende das Thionylchlorid abdestilliert und dieses weiter verwendet. 6. The method according to claim 1, characterized in that one carries out the halogenation of indigo in thionyl chloride in a paddle dryer or a rotary tube reactor, the thionyl chloride is distilled off at the end of the reaction and this is used further.
EP92906628A 1991-03-30 1992-03-19 Method of preparing halogenated indigo Expired - Lifetime EP0578655B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4110458 1991-03-30
DE4110458A DE4110458A1 (en) 1991-03-30 1991-03-30 METHOD FOR PRODUCING HALOGENED INDIGO
PCT/EP1992/000612 WO1992017547A1 (en) 1991-03-30 1992-03-19 Method of preparing halogenated indigo

Publications (2)

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EP0578655A1 true EP0578655A1 (en) 1994-01-19
EP0578655B1 EP0578655B1 (en) 1996-07-31

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US (1) US5380871A (en)
EP (1) EP0578655B1 (en)
JP (1) JPH06506008A (en)
BR (1) BR9205812A (en)
DE (1) DE4110458A1 (en)
WO (1) WO1992017547A1 (en)

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CN103897425A (en) * 2014-03-27 2014-07-02 重庆华彩化工有限责任公司 Preparation method of bromo indigo dye

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DE226319C (en) *
DE208471C (en) *
DE239314C (en) *
DE229304C (en) *
DE237262C (en) *
US2862930A (en) * 1955-03-18 1958-12-02 Ciba Ltd Halogenation of vat dyestuffs
US3530151A (en) * 1964-05-01 1970-09-22 Allied Chem Halogenation process
CH441253A (en) * 1964-08-17 1967-08-15 Sandoz Ag Process for halogenation

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See references of WO9217547A1 *

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EP0578655B1 (en) 1996-07-31
JPH06506008A (en) 1994-07-07
BR9205812A (en) 1994-06-28
WO1992017547A1 (en) 1992-10-15
US5380871A (en) 1995-01-10
DE4110458A1 (en) 1992-10-01

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