DE2427606A1 - Iron chelate oxidn catalyst - for use in dye prepn - Google Patents

Iron chelate oxidn catalyst - for use in dye prepn

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DE2427606A1
DE2427606A1 DE19742427606 DE2427606A DE2427606A1 DE 2427606 A1 DE2427606 A1 DE 2427606A1 DE 19742427606 DE19742427606 DE 19742427606 DE 2427606 A DE2427606 A DE 2427606A DE 2427606 A1 DE2427606 A1 DE 2427606A1
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formula
iii
methyl
iron
catalyst
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DE19742427606
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German (de)
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Helmut Dipl Chem Dr Kast
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BASF SE
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BASF SE
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Priority to DE19742427606 priority Critical patent/DE2427606A1/en
Priority to CH935274A priority patent/CH606278A5/xx
Priority to US05/486,677 priority patent/US4000135A/en
Priority to DD179789A priority patent/DD114828A2/xx
Priority to GB3029474A priority patent/GB1478338A/en
Priority to FR7423809A priority patent/FR2241589B2/fr
Priority to JP49078363A priority patent/JPS5929614B2/en
Priority to IT52020/74A priority patent/IT1046328B/en
Publication of DE2427606A1 publication Critical patent/DE2427606A1/en
Withdrawn legal-status Critical Current

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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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C09B11/18—Preparation by oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

In the catalytic oxidn. of cpds. of formula (I) (where Z'- Z4 are H or (cyclo)alkyl, aralkyl or aryl (opt. substd.) or Z' and Z2 or Z3 and Z4 may complete a N-heterocycle; Z5 and Z6 are H, halogen or alk(ox)yl; Z is H, opt. substd. aryl or heterocyclyl) by fluorinated-, chlorinated-, brominated-or CN-substd. benzoquinones or by nitrated phenanthraquinones, in the presence of oxygen and a heavy metal complex catalyst, the improvement is that the catalyst is a cpd. of formula (II) (where R'-R4 are H or methyl, R3 and R4 may also be phenyl, R' and R2 may complete a carbocyclic or heterocyclic ring; T is H or D-N=N-; D is an aromatic or heterocyclic gp.).

Description

Eisenkomplexe von Tetraazagl4gannulenen Die Erfindung betrifft Verbindungen der Formel I in der -R Wasserstoff oder Methyl, R2 Wasserstoff oder Methyl, R1 und R2 zusammen mit den sie verbindenden C-Atomen einen carbocyclischen oder heterocyclischen Rest und D den Rest einer Diazokomponente bedeuten.Iron Complexes of Tetraazagl4gannulenes The invention relates to compounds of the formula I. in which -R is hydrogen or methyl, R2 is hydrogen or methyl, R1 and R2 together with the C atoms connecting them are a carbocyclic or heterocyclic radical and D is the radical of a diazo component.

Die aus R1 und R2 zusammen mit den sie verbindenden C-Atomen gebildeten carbocyclischen Reste entsprechen vorzugsweise der Formel in der x Wasserstoff, Chlor, Brom, Methyl, Äthyl, Phenyl, Nethoxy, Nitro, Cyan, Methylsulfonyl oder Carbaloxy mit insgesamt 2 bis 5 C-Atomen, Y Wasserstoff, Chlor oder Methyl und X und Y zusammen einen ankondensierten Benzring, Tetramethylen oder o-Phthaloyl bedeuten.The carbocyclic radicals formed from R1 and R2 together with the carbon atoms connecting them preferably correspond to the formula in which x is hydrogen, chlorine, bromine, methyl, ethyl, phenyl, nethoxy, nitro, cyano, methylsulfonyl or carbaloxy with a total of 2 to 5 carbon atoms, Y is hydrogen, chlorine or methyl and X and Y together are a fused benzene ring, tetramethylene or mean o-phthaloyl.

Entsprechende heterocyclische Reste leiten sich beispielsweise von Diaminopyridinen, -chinoxalinen oder -benzimidazolen ab.Corresponding heterocyclic radicals are derived, for example, from Diaminopyridines, -quinoxalines or -benzimidazoles.

Die Reste D der Diazokomponenten entstammen vorwiegend der Benzol-, Benzthiazol-, Benzisothiazol-, Thiazol-, Thiadiazol-, Thiophe-, Triazol-, Indazol- oder Pyrazolreihe.The residues D of the diazo components come mainly from the benzene, Benzthiazole, benzisothiazole, thiazole, thiadiazole, thiophene, triazole, indazole or pyrazole series.

Bevorzugt sind Reste D, die sich von Anilinen und von Benzthiazolen ableiten.Radicals D which are different from anilines and from benzothiazoles are preferred derive.

Als Substituenten für die Reste D sind in der Anilinreihe beispielsweise Fluor, Chlor, Brom, Nitro, Cyan, Methylsulfonyl, Äthylsulfonyl, Phenylazo, Carbalkoxy mit 2 bis 5 C-Atomen, Trifluormethyl, Methyl, Äthyl, Methoxy, Äthoxy oder Acetylamino zu nennen.Substituents for the radicals D are, for example, in the aniline series Fluorine, chlorine, bromine, nitro, cyano, methylsulfonyl, ethylsulfonyl, phenylazo, carbalkoxy with 2 to 5 carbon atoms, trifluoromethyl, methyl, ethyl, methoxy, ethoxy or acetylamino to call.

In der heterocyclischen Reihe kommen z.Bt 2-Aminobenzthiazol, 2-Amino-5-methoxybenzthiazol, 2-Aminothiazol, 3-Aminotriazol, 3-Amino-5-phenyltriazol, )-Aminoindazol und 1-Phenyl-)-aminopyrazol als Diazokomponenten in Betracht.In the heterocyclic series there are e.g. 2-aminobenzothiazole, 2-amino-5-methoxybenzthiazole, 2-aminothiazole, 3-aminotriazole, 3-amino-5-phenyltriazole,) -aminoindazole and 1-phenyl -) - aminopyrazole as diazo components into consideration.

Zur Herstellung der Verbindungen der Formel I kann man Verbindungen der Formel II mit Diaminen der Formel III in Gegenwart einer Eisen abgebenden Verbindung umsetzen.To prepare the compounds of the formula I, compounds of the formula II can be used with diamines of the formula III react in the presence of an iron-releasing compound.

Die Verbindungen der Formel II kann man z.B. folgendermaßen herstellen: Cl e CH2=CH-OR + T¼l= C oder , N-CH=CH-CHO - A e e Vilsmeier Hydrolyse HC-CH=CH-OR OHC-CH-CHO e N N D-NX 2 r CH=O D-N=N-CH / \CH=O A e ist dabei ein Anion, R ist z.B. Alkyl mit 1 bis 4 C-Atomen.The compounds of the formula II can be prepared as follows, for example: Cl e CH2 = CH-OR + T¼l = C or, N-CH = CH-CHO - A e e Vilsmeier hydrolysis HC-CH = CH-OR OHC-CH-CHO e N N D-NX 2 r CH = O DN = N-CH / \ CH = O A e is an anion, R is, for example, alkyl with 1 to 4 carbon atoms.

Die Reaktionen sind im Prinzip bekannt und erfolgen anale, Einzelheiten können den Beispielen entnommen werden.The reactions are known in principle and take place anal, details can be found in the examples.

Diamine der Formel III sind z.B.: Athylendiamin, Propylendiamin, 1 ,2-Cyclohexylendiamin, 1,2-Phenylendiamin, 4-Chlor-1,2-phenylendiamin, 4-Methyl-1,2-phenylendiamin, 4,5-Dimethyl-1,2-phenylendiamin, 4,5-Dichlor-1,2-phenylendiamin, 4-Methoxy-1,2-phenylendiamin, 4-Methylsulfonyl-1,2-phenylendiamin' 4-Methoxycarbonyl-1,2-phenylendiamin, 4-Nitro-1,2-phenylendiamin, 4-Cyan-1,2-phenylendiamin, 4-Acetylamino-1,2-phenylendiamin, 1,2-Diamino-5,6,7,8-tetrahydronaphtalin, 1,2-Diaminonaphtalin, 2,3-Diaminonaphatlin, 2,3-Diaminoanthrachinon, 2,)-Diaminochinoxalin, 2-Methyl-5,6-diaminobenzimidazol, 5,6-Diaminobenzimidazol und ),4-Diaminopyridin.Diamines of the formula III are, for example: ethylenediamine, propylenediamine, 1 , 2-cyclohexylenediamine, 1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine, 4,5-dichloro-1,2-phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4-methylsulfonyl-1,2-phenylenediamine, 4-methoxycarbonyl-1,2-phenylenediamine, 4-nitro-1,2-phenylenediamine, 4-cyano-1,2-phenylenediamine, 4-acetylamino-1,2-phenylenediamine, 1,2-diamino-5,6,7,8-tetrahydronaphthalene, 1,2-diaminonaphthalene, 2,3-diaminonaphatlin, 2,3-diaminoanthraquinone, 2,) - diaminoquinoxaline, 2-methyl-5,6-diaminobenzimidazole, 5,6-diaminobenzimidazole and), 4-diaminopyridine.

Eisen abgebende Verbindungen sind beispielsweise: Eisensalze schwacher anorganischer oder organischer Säuren, wie basisches Fe-III-acetat, Fe-II-acetat, Fe-III-propionat, Fe-II-formiat, Fe-III-formiat, Fe-II-glykolat, Fe-III-lactat, Fe-III-malat, Fe-III-oxalat, Fe-II-oxalat, Fe-III-malonat, Fe-III-succinat, Fe-III-tartrat und Fe-III-citrat sowie Fe-II- und Fe-III-hydroxide. Bevorzugte Eisenverbindungen sind beispielsweise die Acetate und Hydroxide.Iron-releasing compounds are for example: Iron salts weaker inorganic or organic acids, such as basic Fe-III-acetate, Fe-II-acetate, Fe-III-propionate, Fe-II-formate, Fe-III-formate, Fe-II-glycolate, Fe-III-lactate, Fe-III-malate, Fe-III-oxalate, Fe-II-oxalate, Fe-III-malonate, Fe-III-succinate, Fe-III-tartrate and Fe-III citrate and Fe-II and Fe-III hydroxides. Preferred iron compounds are for example the acetates and hydroxides.

Die Umsetzung der Verbindungen der Formel II mit den Diaminen der Formel III wird zweckmäßigerweise so durchgerührt, daß man zu einer Lösung oder Suspension von Diamin und Eisen abgebender Verbindung in beispielsweise Alkoholen, Glykolen, Glykoläthern oder als Lösungsmittel üblichen Amiden bei erhöhter Temperatur die Verbindung der Formel II, vorzugsweise als Lösung zugibt.The implementation of the compounds of formula II with the diamines of the Formula III is expediently stirred so that a solution or Suspension of diamine and iron releasing compound in, for example, alcohols, Glycols, glycol ethers or amides customary as solvents at elevated temperature adding the compound of formula II, preferably as a solution.

Lösungsmittel für die Umsetzung sind im einzelnen z.B.Solvents for the reaction are in detail e.g.

Methanol, Äthanol, i-Butanol, Glykol, thylenglykolmonomethyl-, -äthyl- oder -butyläther, Dimethylformamid, Dimethylacetamid oder N-IIethylpyrrolidon.Methanol, ethanol, i-butanol, glycol, ethylene glycol monomethyl, ethyl or butyl ether, dimethylformamide, dimethylacetamide or N-IIethylpyrrolidone.

4ls Temperaturbereich für die Umsetzungen eignet sich der von ungefähr 20 bis IOOC, vorzugsweise 30 bis 1100C.The approximate temperature range for the reactions is suitable 20 to IOOC, preferably 30 to 1100C.

Nach beendeter Reaktion werden die schwerlöslichen Eisenkomplexe aus dem Reaktionsgemisch durch Filtration abgetrennt und können durch Waschen mit Lösungsmitteln und verdünnten wäßrigen Mineralsäuren oder Auskochen mit Lösungsmitteln gereinigt werden.After the reaction has ended, the sparingly soluble iron complexes are removed the reaction mixture separated by filtration and can by washing with solvents and diluted aqueous mineral acids or boiled with solvents will.

Die schwerlöslichen, rotbraunen bis schwarzen Eisenkomplexe sind in der Regel nicht analysenrein und enthalten angelagert bis zu 20 ß Sauerstoff. Ihre katalytische Aktivität ist jedoch ausgezeichnet.The poorly soluble, red-brown to black iron complexes are in usually not analytically pure and contain up to 20 ß oxygen. Her however, catalytic activity is excellent.

Für die Verwendung als Katalysatoren können die neuen Metallkomplexe noch Formierungsverfahren unterworfen werden, bei denen Zerkleinerungs-, Dispergier- oder Rekristallisationsprozesse ablaufen. Je nach Verwendungszweck können die Eisenkomplexe in reiner Form oder in Form von Zubereitungen auf bzw. in Trägermaterialien der verschiedensten Art, z.B.The new metal complexes can be used as catalysts are still subjected to formation processes in which comminution, dispersing or recrystallization processes take place. Depending on the intended use, the iron complexes in pure form or in the form of preparations on or in carrier materials of various kinds, e.g.

Aktivkohle, Ruß, Kieselgur, Kieselgel, Aluminiumoxid, verwendet werden.Activated carbon, carbon black, kieselguhr, silica gel, aluminum oxide can be used.

Die Verbindungen der Formel I sind vorzügliche Oxidationskatalysatoren, die sich z.B. für das in den deutschen Offenlegungsschriften 2 138 931, 2 152 703 oder der belgischen Patentschrift 737 210 beschriebene Verfahren eignen.The compounds of the formula I are excellent oxidation catalysts, which are e.g. for that in the German Offenlegungsschrift 2 138 931, 2 152 703 or Belgian patent 737 210 suitable.

Von besonderer technischer Bedeutung sind dabei Verbindungen der Formel I a in der X1 und Y1 unabhängig voneinander Wasserstoff, Methyl, Chlor oder Brom und D1 Phenyl, o-Tolyl, p-Tolyl, o-Anisyl, p-Anisyl, p-Athoxyphenyl, p-Chlorphenyl, o-Chlorphenyl oder 2,4-Dichlorphenyl bedeuten.Compounds of the formula I a are of particular industrial importance in which X1 and Y1 are independently hydrogen, methyl, chlorine or bromine and D1 is phenyl, o-tolyl, p-tolyl, o-anisyl, p-anisyl, p-athoxyphenyl, p-chlorophenyl, o-chlorophenyl or 2,4- Mean dichlorophenyl.

Beispiel 1 In eine Mischung aus 215 g o-Phenylendiamin, 220 g Eisen-III-acetat und 2 500 ml Isobutanol werden bei 7000 352 g Phenylazomalondialdehyd eingetragen, anschließend wird 4 Stunden bei ückflußtemperatur gerührt, wobei sich schon nach wenigen Minuten ein schwarzer Niederschlag bildet. Die Reaktionsmischung wird dann heiß filtriert und der Rückstand nacheinander mit Isobutanol, ungefähr 3 zeiger Schwefelsäure und Aceton gewaschen. Man erhält so 412 g einer schwarzbraunen Verbindung der Formel die eine vorzügliche katalytische Aktivität aufweist.EXAMPLE 1 352 g of phenylazomalondialdehyde are introduced into a mixture of 215 g of o-phenylenediamine, 220 g of iron (III) acetate and 2,500 ml of isobutanol at 7000, followed by stirring for 4 hours at reflux temperature, a black precipitate forming after a few minutes . The reaction mixture is then filtered hot and the residue is washed successively with isobutanol, about 3 times sulfuric acid and acetone. 412 g of a black-brown compound of the formula are obtained in this way which has excellent catalytic activity.

In der nachfolgenden Tabelle sind weitere Komponenten genannt, aus denen man analog die entsprechenden tetracyclischen Eisenkomplexe erhält: Bsp. Diamin (Formel III) Arylazomalondialdehyd Lösungsmittel (Formel II) 2 4-Chlor-1,2-phenylen- Phenylazo- Isobutanol diamin 3 4-Methyl-1,2-phanylen- " " diamin 4 4-Nitro-1,2-phenylen- " n diamin 5 4,5-Dimethyl-1s2-pheny- n 1I lendiamin 6 4,5-Dichlor-1,2-pheny- n n ft lendiamin 7 4-Cyan-1,2-phenylendiamin n n 8 Äthylendiamin " 4-Methoxy-1,2-phenylen- n Dimethylformamid diamin 10 4-Methylsulfonyl-1,2- " " phenylendiamin 11 2,3-Diaminonaphthalin n Isobutanol 12 2,3-Diamino-5,6,7,8- " " tetrahydronaphthalin Bsp. Diamin (Formel III) Brylazomalondialdehyd Lösungsmittel 13 2,3-Diaminochinoxalin Phenylazo- Dimethylform- amid 14 2-Methyl-5,6-diamino- " " benzimidazol 15 1,2-Phenylendiamin @ p-Chlorphenylazo- Methylglykol 16 fl p-Methoxyphenylazo- Isobutanol 17 n p-Methylphenylazo- " 18 n p-Äthoxyphenylazo- n 19 n p-Bromphenylazo- n 20 lt p-Nitrophenylazo- Dimethylformamid 21 n p-Cyanphenylazo- Isobutanol 22 n p-Methylsulfonyl- N-Nethylpyrro- phenylazo- lidon 23 lt p-Äthylphenylazo- Isobutanol 24 " p-Acetylphenylazo- " Bsp. Diamin (Formel III) Arylazomalondialdehyd Lösungsmittel (Formel II) 25 1,2-Phenylendiamin p-Fluorphenylazo- Isobutanol 26 " 2,4-Bis(methoxy)phenyl- " azo- 27 " 2,4-Dichlorphenylazo- " 28 " 3-Acetylaminophenylazo- " 29 " Benzthiazolazo-(2)- " 30 " Thiazolazo-(2)- " 31 " 1,2,4-Triazolazo-(3)- " 32 4-Methyl-1,2-phenylen- p-Chlorphenylazo- " diamin 33 n p-Tolylazo- Methanol 34 " p-Methoxyphenylazo- Äthanol 35 4-Chlor-1,2-phenylen- p-Methoxyphenylazo- Isobutanol diamin 36 2, 3-Diaminochinoxalin II " In Beispiel 1 kann Fe-III-acetat durch folgende eisenabgebende Mittel ersetzt werden: Bsp.The table below lists further components from which the corresponding tetracyclic iron complexes are obtained in an analogous manner: Ex. Diamine (formula III) arylazomalondialdehyde solvent (Formula II) 2 4-chloro-1,2-phenylene-phenylazo-isobutanol diamine 3 4-methyl-1,2-phanylene- "" diamine 4 4-nitro-1,2-phenylene- "n diamine 5 4,5-dimethyl-1s2-pheny- n 1I lenediamine 6 4,5-dichloro-1,2-pheny- nn ft lenediamine 7 4-cyano-1,2-phenylenediamine nn 8 ethylenediamine " 4-methoxy-1,2-phenylene-n-dimethylformamide diamine 10 4-methylsulfonyl-1,2- "" phenylenediamine 11 2,3-diaminonaphthalene n isobutanol 12 2,3-diamino-5,6,7,8- "" tetrahydronaphthalene E.g. diamine (formula III) brylazomalondialdehyde solvent 13 2,3-diaminoquinoxaline phenylazo- dimethylform- amide 14 2-methyl-5,6-diamino- "" benzimidazole 15 1,2-phenylenediamine @ p-chlorophenylazo-methylglycol 16 fl p-methoxyphenylazo-isobutanol 17 n p-methylphenylazo- " 18 n p-ethoxyphenylazo- n 19 n p-bromophenylazo- n 20 liters of p-nitrophenylazo-dimethylformamide 21 n p -cyanophenylazo-isobutanol 22 n p-methylsulfonyl- N-methylpyrro- phenylazolidone 23 liters of p-ethylphenylazo-isobutanol 24 "p-acetylphenylazo-" Ex. Diamine (formula III) arylazomalondialdehyde solvent (Formula II) 25 1,2-phenylenediamine p-fluorophenylazo-isobutanol 26 "2,4-bis (methoxy) phenyl-" azo- 27 "2,4-dichlorophenylazo-" 28 "3-acetylaminophenylazo-" 29 "Benzthiazolazo- (2) -" 30 "thiazolazo- (2) -" 31 "1,2,4-triazolazo- (3) -" 32 4-methyl-1,2-phenylene-p-chlorophenylazo- " diamine 33 n p -tolylazo-methanol 34 "p-methoxyphenylazo-ethanol 35 4-chloro-1,2-phenylene-p-methoxyphenylazo-isobutanol diamine 36 2,3-diamino quinoxaline II " In Example 1, Fe (III) acetate can be replaced by the following iron-releasing agents: Ex.

37 Fe-III-propionat 38 Fe-III-format 39 Fe-II-glykolat 40 Fe-III-lactat 41 Fe-III-oxalat 42 Fe-III-malonat 43 Fe-III-tartrat 44 Fe-III-citrat 45 Fe-II-hydroxid 46 Fe-III-hydroxid Beispiel 47 Eine Mischung aus 150 kg Vinylisobutyläther und 110 kg Dimethylformamid wird bei 75 bis 85°C unter gleichzeitigem Eingasen von 165 kg Phosgen kontinuierlich in eine Umlaufapparatur eingebracht, wobei entsprechend dem Zulauf Reaktionslösung abgenommen und in einem Nachreaktor eine Stunde auf 800C erhitzt wird. Das so erhaltene Produkt der Formel wird ohne weitere Reinigung direkt als Kupplungskomponente verwendet.37 Fe III propionate 38 Fe III format 39 Fe II glycolate 40 Fe III lactate 41 Fe III oxalate 42 Fe III malonate 43 Fe III tartrate 44 Fe III citrate 45 Fe -II-hydroxide 46 Fe-III-hydroxide Example 47 A mixture of 150 kg vinyl isobutyl ether and 110 kg dimethylformamide is continuously introduced into a circulation apparatus at 75 to 85 ° C. with simultaneous gassing of 165 kg phosgene, with the reaction solution being removed according to the feed and in a postreactor is heated to 80 ° C. for one hour. The product of the formula thus obtained is used directly as a coupling component without further purification.

Ausbeute : 377 kg.Yield: 377 kg.

Zu einer filtrierten Lösung von 253 g des wie angegeben hergestellten Formylierungsproduktes wird bei O bis 500 eine Diazoniumlösung aus 95 g Anilin in verdünnter Salzsäure zugetropft. Gleichzeitig wird durch eine ungefähr 30 Xige wäßrige Natriumacetatlösung der pH-Wert der Kupplungsmischung auf 4,3 bis 4,8 eingestellt. Über Nacht wird bei Raumtemperatur nachgerührt, dann wird der entstandene Niederschlag abfiltriert und mit Wasser ausgewaschen. Nach der Trocknung erhält man 131 g der Verbindung der Formel Schmp. nach dem Umkristallisieren aus ethanol 114 bis 1.1600.A diazonium solution of 95 g of aniline in dilute hydrochloric acid is added dropwise at 0 to 500 to a filtered solution of 253 g of the formylation product prepared as indicated. At the same time, the pH of the coupling mixture is adjusted to 4.3 to 4.8 using an approximately 30% aqueous sodium acetate solution. The mixture is stirred overnight at room temperature, then the precipitate formed is filtered off and washed out with water. After drying, 131 g of the compound of the formula are obtained After recrystallization from ethanol 114 to 1.1600.

Anlag erhält man mit den folgenden Diazokomponenten die entsprechenden Arylazomalondialdehyde : Diazokomponente Die Arylazomalondialdehyde können gemäß Beispiel 1 bzw. den Beispielen 2 bis 45 in die zugehörigen Eisenkomplexe überführt -werden.The corresponding arylazomalondialdehydes are obtained with the following diazo components: Diazo component The arylazomalondialdehydes can be converted into the associated iron complexes according to Example 1 or Examples 2 to 45.

Diazokomponente Beispiel 48 Eine Mischung aus 1 089 g Dimethylanilin, 90 g Paraformaldehyd und 1 391 Teilen Eisessig wird eine Stunde auf 700C erhitzt.Diazo component Example 48 A mixture of 1,089 g of dimethylaniline, 90 g of paraformaldehyde and 1,391 parts of glacial acetic acid is heated to 70 ° C. for one hour.

Zu der auf 500C abgekühlten Lösung gibt man dann 15 g Chloranil und 15 g der Verbindung der Formel zu und gast unter starkem Rühren 15 Stunden Luft ein. Danach werden unter vermindertem Druck ungefähr 800 g Eisessig abdestilliert, der Rückstand wird in 15 1 Wasser gelöst, die Lösung heiß filtriert und der Farbstoff aus dem Filtrat durch 5 000 g Natriumchlorid bei pH = 1,5 ausgefällt. Der kristal line Farbstoff wird abgesaugt und mit 3 000 ml verdünnter NaCl-Lösung (5 %ig) gewaschen.15 g of chloranil and 15 g of the compound of the formula are then added to the solution, which has been cooled to 50.degree and gas in air for 15 hours with vigorous stirring. About 800 g of glacial acetic acid are then distilled off under reduced pressure, the residue is dissolved in 15 1 of water, the solution is filtered hot and the dye is precipitated from the filtrate by 5000 g of sodium chloride at pH 1.5. The crystal line dye is filtered off with suction and washed with 3,000 ml of dilute NaCl solution (5%).

Ausbeute : 1 080 Teile Kristallvnolet.Yield: 1,080 parts of Kristallolet.

Beispiel 70 Eine Mischung aus 987 g Leukomalachitgrün, 1483 g Eisessig, 15 g Chloranil und 15 g der Verbindung der Formel wird unter starkem Rühren bei 45-50 °C, 8-10 Stunden mit Luft begast.Example 70 A mixture of 987 g of leuco malachite green, 1483 g of glacial acetic acid, 15 g of chloranil and 15 g of the compound of the formula is gassed with air with vigorous stirring at 45-50 ° C for 8-10 hours.

Tach der Oxidation werden ungefähr 800 g Eisessig unter vermindertem Druck abdestilliert, der Rückstand wird in-10 1 Wasser bei 95 °C gelöst und die Lösung heiß filtriert. Nach der Zugabe von 12 1 Xylol zum Filtrat wird mit 50 einer Natronlauge die Farbbase freigesetzt (pH = 10,5), die sich in Xylol löst. Die Xylolphase wird abgetrennt und durch Einleiten von 200 g Chlorwasserstoffgas wird aus ihr das Farbstoffchlorid ausgefällt. Nach dem Trocknen bei 6000 erhält man 1 125 g Malachitgrünchlorid.After the oxidation, about 800 g of glacial acetic acid are reduced Distilled off pressure, the residue is dissolved in 10 1 of water at 95 ° C and the Solution filtered hot. After the addition of 12 l of xylene to the filtrate is 50 with one Sodium hydroxide solution releases the color base (pH = 10.5), which dissolves in xylene. The xylene phase is separated off and by introducing 200 g of hydrogen chloride gas it becomes the Dye chloride precipitated. After drying at 6000, 1,125 g of malachite green chloride are obtained.

Claims (4)

Patentansprüche Claims Eisenkomplexe von Tetraaza[14]annulenen der Formel in der R1 Wasserstoff oder Methyl, R2 Wasserstoff oder Methyl, R1 und R2 zusammen mit den sie verbindenden C-Atomen einen carbocyclfschen oder heterocyclischen Rest und D den Rest einer Diazokomponenten bedeuten.Iron complexes of tetraaza [14] annulenes of the formula in which R1 is hydrogen or methyl, R2 is hydrogen or methyl, R1 and R2 together with the C atoms connecting them are a carbocyclic or heterocyclic radical and D is the radical of a diazo component. 2. Eisenkomplexe gemäß Anspruch 1 der Formel in der X1 und yl unabhängig voneinander Wasserstoff, Methyl, Chlor oder Brom und Dl Phenyl, o-Tolyl, p-Tolyl, o-Anisyl, p-Anisyl, p-Äthoxyphenyl, p-Chlorphenyl, o-Chlorphenyl oder 2,4-Dichlorphenyl bedeuten.2. iron complexes according to claim 1 of the formula in which X1 and yl are independently hydrogen, methyl, chlorine or bromine and Dl is phenyl, o-tolyl, p-tolyl, o-anisyl, p-anisyl, p-ethoxyphenyl, p-chlorophenyl, o-chlorophenyl or 2,4- Mean dichlorophenyl. 5. Verfahren zur Herstellung von Eisenkomplexen gemäß Anspruch 1, dadurch gekennzeichnet, daß man Verbindungen der Formel II mit Diaminen der Formel III in Gegenwart einer Eisen abgebenden Verbindung umsetzt.5. Process for the preparation of iron complexes according to claim 1, characterized in that compounds of the formula II with diamines of the formula III in the presence of an iron donating compound. 4. Die Verwendung der Eisenkomplexe gemäß Anspruch 1 als Oxidationskatalysatoren.4. The use of the iron complexes according to claim 1 as oxidation catalysts.
DE19742427606 1973-07-10 1974-06-07 Iron chelate oxidn catalyst - for use in dye prepn Withdrawn DE2427606A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE19742427606 DE2427606A1 (en) 1974-06-07 1974-06-07 Iron chelate oxidn catalyst - for use in dye prepn
CH935274A CH606278A5 (en) 1973-07-10 1974-07-08
US05/486,677 US4000135A (en) 1973-07-10 1974-07-08 Manufacture of basic dyes by catalytic oxidation
DD179789A DD114828A2 (en) 1973-07-10 1974-07-08
GB3029474A GB1478338A (en) 1973-07-10 1974-07-09 Catalytic oxidation of diarylmethane and triarylmethane compounds
FR7423809A FR2241589B2 (en) 1973-07-10 1974-07-09
JP49078363A JPS5929614B2 (en) 1973-07-10 1974-07-10 Method for producing basic dyes by catalytic oxidation
IT52020/74A IT1046328B (en) 1973-07-10 1974-07-10 PROCEDURE FOR THE PRODUCTION OF BASIC DYES THROUGH CATALYTIC OXIDATION

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DE19742427606 DE2427606A1 (en) 1974-06-07 1974-06-07 Iron chelate oxidn catalyst - for use in dye prepn

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2736679A1 (en) * 1977-08-16 1979-03-01 Basf Ag Process for the preparation of basic colorants
EP0659727A1 (en) * 1993-12-21 1995-06-28 Basf Aktiengesellschaft Process for the preparation of benzoquinones by oxidation of phenoles

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2736679A1 (en) * 1977-08-16 1979-03-01 Basf Ag Process for the preparation of basic colorants
EP0659727A1 (en) * 1993-12-21 1995-06-28 Basf Aktiengesellschaft Process for the preparation of benzoquinones by oxidation of phenoles
US5712416A (en) * 1993-12-21 1998-01-27 Basf Aktiengesellschaft Preparation of benzoquinones by oxidation of phenols

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