DE19718523A1 - Amino-di:aryl-azo compounds preparation - Google Patents
Amino-di:aryl-azo compounds preparationInfo
- Publication number
- DE19718523A1 DE19718523A1 DE1997118523 DE19718523A DE19718523A1 DE 19718523 A1 DE19718523 A1 DE 19718523A1 DE 1997118523 DE1997118523 DE 1997118523 DE 19718523 A DE19718523 A DE 19718523A DE 19718523 A1 DE19718523 A1 DE 19718523A1
- Authority
- DE
- Germany
- Prior art keywords
- formula
- compounds
- reduction
- mercapto
- carried out
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims description 15
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 6
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000987 azo dye Substances 0.000 claims description 4
- LFTMJBWNOFFSRW-UHFFFAOYSA-N 1,2-Butanedithiol Chemical compound CCC(S)CS LFTMJBWNOFFSRW-UHFFFAOYSA-N 0.000 claims description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 2
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 claims description 2
- KUODZPPJVMDYTK-UHFFFAOYSA-N 1-sulfanylbutan-2-ol Chemical compound CCC(O)CS KUODZPPJVMDYTK-UHFFFAOYSA-N 0.000 claims description 2
- FETFXNFGOYOOSP-UHFFFAOYSA-N 1-sulfanylpropan-2-ol Chemical compound CC(O)CS FETFXNFGOYOOSP-UHFFFAOYSA-N 0.000 claims description 2
- QNNVICQPXUUBSN-UHFFFAOYSA-N 2-sulfanylpropan-1-ol Chemical compound CC(S)CO QNNVICQPXUUBSN-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims 1
- -1 carboxy-alkyl mercaptans Chemical class 0.000 abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 2
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 abstract 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 abstract 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract 1
- 125000004055 thiomethyl group Chemical group [H]SC([H])([H])* 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- VMKJWLXVLHBJNK-UHFFFAOYSA-N cyanuric fluoride Chemical compound FC1=NC(F)=NC(F)=N1 VMKJWLXVLHBJNK-UHFFFAOYSA-N 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XSCFKJGIAYKLRV-UHFFFAOYSA-N n-naphthalen-1-ylnitramide Chemical compound C1=CC=C2C(N[N+](=O)[O-])=CC=CC2=C1 XSCFKJGIAYKLRV-UHFFFAOYSA-N 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012430 organic reaction media Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- 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
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/08—Preparation of azo dyes from other azo compounds by reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von Aminodi
arylazoverbindungen, dadurch gekennzeichnet, daß man Nitrodiarylazoverbindungen
mittels Verbindungen der Formel (I)
The present invention relates to a new process for the preparation of aminodi arylazo compounds, characterized in that nitrodiarylazo compounds by means of compounds of the formula (I)
H-S-CHR1-R (I),
HS-CHR 1 -R (I),
worin
R für CH2OH, CH(CH3)OH, COOH, CH2SH, C2H4OH, C2H4SH
und
R1 für H, CH3, C2H5 steht,
reduziert.wherein
R for CH 2 OH, CH (CH 3 ) OH, COOH, CH 2 SH, C 2 H 4 OH, C 2 H 4 SH
and
R 1 represents H, CH 3 , C 2 H 5 ,
reduced.
Bei den Aminodiarylazoverbindungen handelt es sich vorzugsweise um solche der
allgemeinen Formel (II)
The aminodiarylazo compounds are preferably those of the general formula (II)
worin
A und B unabhängig voneinander für Phenyl- oder Naphthylringe stehen, die
jeweils gegebenenfalls durch in der Azo-Farbstoffchemie übliche Reste
substituiert sind,
die durch erfindungsgemäße Reduktion der entsprechenden Nitrodiarylazover
bindungen (III)
wherein
A and B independently of one another represent phenyl or naphthyl rings, which are each optionally substituted by radicals customary in azo dye chemistry which are reduced by the inventive reduction of the corresponding nitrodiarylazo compounds (III)
worin
A und B die für Formel (II) angegebene allgemeine und spezielle Bedeutung
haben,
hergestellt werden.wherein
A and B have the general and special meaning given for formula (II),
getting produced.
Vorzugsweise handelt es sich bei den Aminodiarylazoverbindungen um Verbindungen der Formel (II), worin A und B unabhängig voneinander durch einen oder mehrere der folgenden Reste substituiert sind: SO3H, COOH, C1-C4-Alkyl, C1-C4-Alkoxy, OH, NH2, C1-C4-Mono- und -Dialkylamino, 2-Hydroxyethylamino, Sulfato-C1-C2-alkyl amino, CF3, F, Cl, Br, Acetylamino, Maleinylamino, Benzoylamino, Arylazo.The aminodiarylazo compounds are preferably compounds of the formula (II) in which A and B are independently substituted by one or more of the following radicals: SO 3 H, COOH, C 1 -C 4 alkyl, C 1 -C 4 Alkoxy, OH, NH 2 , C 1 -C 4 mono- and dialkylamino, 2-hydroxyethylamino, sulfato-C 1 -C 2 alkylamino, CF 3 , F, Cl, Br, acetylamino, maleinylamino, benzoylamino, Arylazo.
Beispiele für die als Substituenten für die Ringe A und B genannten Arylazoreste sind Phenylazo und Naphthylazo die jeweils gegebenenfalls durch einen oder mehrere Reste wie SO3H, COOH, CH3, C2H5, OCH3, OC2H5, OH, NH2, NHCH3, NHC2H4OH, CF3, F, Cl, Br, NHCOCH3, NHCOC2H2COOH, NHCOC6H5 weiter substituiert sind.Examples of the arylazo radicals mentioned as substituents for rings A and B are phenylazo and naphthylazo, each of which is optionally substituted by one or more radicals such as SO 3 H, COOH, CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , OH, NH 2 , NHCH 3 , NHC 2 H 4 OH, CF 3 , F, Cl, Br, NHCOCH 3 , NHCOC 2 H 2 COOH, NHCOC 6 H 5 are further substituted.
Beispiele für erfindungsgemäß einzusetzenden Reduktionsmittel der Formel (I) sind 2- Mercaptoethanol, 1-Mercapto-2-propanol, 1-Mercapto-2-butanol, 2-Mercapto-1- propanol, 2-Mercaptoessigsäure, 2-Mercapto-1-propionsäure, 1,2-Dimercaptoethan, 1,2-Dimercaptopropan, 1,2-Dimercaptobutan, 1,3-Dimercaptopropan, 3-Mercapto-1- propanol. Examples of reducing agents of the formula (I) to be used according to the invention are 2- Mercaptoethanol, 1-mercapto-2-propanol, 1-mercapto-2-butanol, 2-mercapto-1- propanol, 2-mercaptoacetic acid, 2-mercapto-1-propionic acid, 1,2-dimercaptoethane, 1,2-dimercaptopropan, 1,2-dimercaptobutane, 1,3-dimercaptopropan, 3-mercapto-1- propanol.
Die Reduktion erfolgt im allgemeinen in wäßrigem oder wäßrig-organischem Medium, vorzugsweise in Wasser, bei Temperaturen zwischen 300 und 105°C, vorzugsweise zwischen 500 und 100°C in schwach saurem, neutralem oder alkalischem Milieu, vorzugsweise bei pH-Werten zwischen 6 und 12.The reduction is generally carried out in aqueous or aqueous-organic Medium, preferably in water, at temperatures between 300 and 105 ° C, preferably between 500 and 100 ° C in weakly acidic, neutral or alkaline environment, preferably at pH values between 6 and 12.
Der Anteil des organischen Reaktionsmediums beträgt gegebenenfalls 0 bis 99%, vorzugsweise 0 bis 10%, wenn die zu reduzierende Nitrodiarylazoverbindung (III) mindestens eine SO3H- oder COOH-Gruppe enthält, vorzugsweise so bis 95%, wenn diese Gruppen fehlen. Als organische Lösemittel werden vorzugsweise C1-C6- Alkanole, Alkandiole, C4-C6-Lactame oder C2-C6-Sulfone verwendet. Solche Lösemittel sind beispielsweise Methanol, Ethanol, n-Propanol, Isopropanol, n- Butanol, N-Methylpyrolidon, ε-Caprolactam, Sulfolan.The proportion of the organic reaction medium is optionally 0 to 99%, preferably 0 to 10%, if the nitrodiarylazo compound (III) to be reduced contains at least one SO 3 H or COOH group, preferably up to 95% if these groups are absent. C 1 -C 6 alkanols, alkanediols, C 4 -C 6 lactams or C 2 -C 6 sulfones are preferably used as organic solvents. Such solvents are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, N-methylpyrolidone, ε-caprolactam, sulfolane.
Da es sich bei den Reduktionsmitteln der Formel (I) in wäßrigem Milieu um Säuren handelt, werden im allgemeinen bei der Durchführung des erfindungsgemäßen Ver fahrens Basen zur Kontrolle des pH-Wertes eingesetzt. Geeignete Basen sind z. B. die Hydroxide der Alkali- oder Erdalkalimetalle sowie ihre Carbonate oder Hydrogen carbonate oder auch Ammoniak, also beispielsweise LiOH, NaOH, KOH, Mg(OH)2, Ca(OH)2, Li2CO3, Na2DO3, NaHCO3, H2CO3, CaCO3.Since the reducing agents of the formula (I) are acids in an aqueous medium, bases for checking the pH are generally used when carrying out the process according to the invention. Suitable bases are e.g. B. the hydroxides of alkali or alkaline earth metals and their carbonates or hydrogen carbonates or ammonia, for example LiOH, NaOH, KOH, Mg (OH) 2 , Ca (OH) 2 , Li 2 CO 3 , Na 2 DO 3 , NaHCO 3 , H 2 CO 3 , CaCO 3 .
Aminodiarylazoverbindungen sind als Farbstoffe oder Farbstoffzwischenprodukte seit langem bekannt. Ein gängiges Herstellungsverfahren ist die selektive Reduktion von Nitrodiarylazoverbindungen mit Sulfid- oder Hydrogensulfid-Ionen (vergl. z. B. BIOS Final Report 1548, S. 107, 109, 128), wobei jederzeit die Gefahr des Auftretens und Entweichens von Schwefelwasserstoff, einem sehr giftigen Gas, gegeben ist. Bei dem erfindungsgemäßen Verfahren besteht diese Gefahr nicht.Aminodiarylazo compounds have been used as dyes or dye intermediates known for a long time. A common manufacturing process is the selective reduction of Nitrodiarylazo compounds with sulfide or hydrogen sulfide ions (see e.g. BIOS Final Report 1548, pp. 107, 109, 128), whereby the risk of occurrence and Escape of hydrogen sulfide, a very toxic gas. In which The method according to the invention does not pose this risk.
Bei dem erfindungsgemäßen Verfahren werden die gemäß Stand der Technik einge setzten Sulfid- oder Hydrogensulfid-Ionen durch die erfindungsgemäßen Reduktions mittel (I) ersetzt. Man verwendet in Abhängigkeit von den zu reduzierenden Nitro diarylazoverbindungen und den Parametern Temperatur und pH-Wert 2 bis 7 mol Reduktionsmittel der Formel (I) pro mol Nitrodiarylazoverbindung. Die Reihenfolge der Zugabe der Reaktionspartner zum Reaktionsmedium ist im Prinzip beliebig. Bei einer bevorzugten Variante wird die zu reduzierende Nitrodiarylazoverbindung zu nächst in dem Reaktionsmedium gelöst oder suspendiert; nach Erwärmung dieses Ge misches auf die Reaktionstemperatur wird zunächst der benötigte pH-Wert eingestellt, dann wird das Reduktionsmittel der Formel (I) zugegeben. Dabei werden ge gebenenfalls der pH-Wert und die Temperatur durch geeignete Maßnahmen konstant gehallen.In the method according to the invention, those according to the prior art are used set sulfide or hydrogen sulfide ions by the reduction according to the invention medium (I) replaced. It is used depending on the nitro to be reduced diarylazo compounds and the parameters temperature and pH 2 to 7 mol Reducing agent of formula (I) per mole of nitrodiarylazo compound. The chronological order In principle, the addition of the reactants to the reaction medium is arbitrary. At The nitrodiarylazo compound to be reduced becomes a preferred variant next dissolved or suspended in the reaction medium; after heating this Ge mix to the reaction temperature, the required pH is first set, then the reducing agent of formula (I) is added. Here are ge if necessary, the pH and the temperature can be kept constant by suitable measures echoed.
Der Fortschritt der Reduktion wird mit dem in der Azo-Farbstoffchemie üblichen Methode verfolgt, z. B. durch Dünnschichtchromatographie.The progress of the reduction is the usual in azo dye chemistry Method followed, e.g. B. by thin layer chromatography.
Nach Beendigung der Reduktion wird die Aminodiarylazoverbindung mit Hilfe eines der in der Azo-Farbstoffchemie üblichen Verfahrens isoliert, z. B. durch Ausfällung mit Hilfe eines Salzes, z. B. NaCl, KCl und/oder durch Änderung des pH-Wertes mit Säuren oder Laugen, wonach das Reduktionsprodukt abfiltriert wird. Weiterhin ist es auch möglich, das Reaktionsmedium durch Eindampfen oder Sprühtrocknen zu entfernen.After the reduction has ended, the aminodiarylazo compound is removed using a the usual method in azo dye chemistry isolated, for. B. by precipitation with the help of a salt, e.g. B. NaCl, KCl and / or by changing the pH with Acids or alkalis, after which the reduction product is filtered off. Furthermore it is also possible to the reaction medium by evaporation or spray drying remove.
Ebenso gut kann man in geeigneten Fällen auch unmittelbar eine weitere Umsetzung anschließen, ohne das Reduktionsprodukt zu isolieren, z. B. eine Diazotierung oder eine Acylierung, z. B. mit Phosgen oder eine Umsetzung mit einem der in der Reaktiv farbstoffchemie üblichen, durch Fluor, Chlor oder Brom substituierten Heterocyclus, z. B. mit 2,4,6-Trichlor- oder 2,4,6-Trifluor-1,3,5-triazin.In suitable cases, another implementation can also be carried out immediately connect without isolating the reduction product, e.g. B. a diazotization or an acylation e.g. B. with phosgene or a reaction with one of those in the reactive dye chemistry, heterocycle substituted by fluorine, chlorine or bromine, e.g. B. with 2,4,6-trichloro- or 2,4,6-trifluoro-1,3,5-triazine.
Die chemischen Ausbeuten bei der erfindungsgemäßen Reduktion sind ebenso gut wie bei der herkömmlichen Reduktion mittels Sulfid- oder Hydrogensulfid-Ionen.The chemical yields in the reduction according to the invention are as good as in the conventional reduction using sulfide or hydrogen sulfide ions.
Ein weiterer Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß im Gegensatz zur Sulfid-Ionen-Reduktion, das erfindungsgemäße Verfahren Produkte liefert, die frei von kolloidalem Schwefel sind, so daß die sonst nötige Behandlung zur Entfernung dieses Schwefels entfällt. Another advantage of the method according to the invention is that in Contrary to sulfide ion reduction, the process according to the invention products provides that are free of colloidal sulfur, so that the otherwise necessary treatment for Removal of this sulfur is not necessary.
Mit anderen Reduktionsmitteln ist diese selektive Reduktion, wenn überhaupt, nur mit geringen Ausbeuten durchzuführen.With other reducing agents, this selective reduction is, if at all, only with to carry out low yields.
Die zu reduzierenden Nitrodiarylazoverbindungen werden z. B. durch Kupplung der Diazoniumverbindungen von Nitroaminobenzol, Nitroaminonaphthalin oder ihren durch einen oder mehrere der o.a. Reste substitutierten Derivaten mit Kupplungskom ponenten aus der Reihe der mit einem oder mehreren der o.a. Reste substituierten Benzole oder Naphthaline erhalten.The nitrodiarylazo compounds to be reduced are e.g. B. by coupling the Diazonium compounds of nitroaminobenzene, nitroaminonaphthalene or their by one or more of the above Residues of substituted derivatives with coupling com components from the series with one or more of the above Residues substituted Obtained benzenes or naphthalenes.
Beispiele für Nitrodiarylazoverbindungen (III) sind
Examples of nitrodiarylazo compounds (III) are
Die folgenden Beispiele sollen das erfindungsgemäßen Verfahren erläutern.The following examples are intended to illustrate the process according to the invention.
48,5 g der Verbindung der Formel (IIIe) werden in 500 ml Wasser bei 80°C und
einem pH-Wert von 11,5 bis 12,0 mit 46,9 g 2-Mercaptoethanol versetzt. Nach
Beendigung der Reduktion wird der pH-Wert durch Zugabe von konz. Salzsäure auf
ca. 7 eingestellt. Die Aminodiarylazoverbindung der Formel
48.5 g of the compound of formula (IIIe) in 500 ml of water at 80 ° C. and a pH of 11.5 to 12.0 are mixed with 46.9 g of 2-mercaptoethanol. After the reduction has ended, the pH is increased by adding conc. Hydrochloric acid set to about 7. The aminodiarylazo compound of the formula
wird durch Zugabe von Salz ausgefällt und isoliert.is precipitated and isolated by adding salt.
46,8 g der Verbindung der Formel (IIIc) werden in 500 ml Wasser bei 80°C und einem pH-Wert von 6,5 bis 7,0 tropfenweise mit 46,9 g 2-Mercaptoethanol versetzt.46.8 g of the compound of formula (IIIc) in 500 ml of water at 80 ° C and 46.9 g of 2-mercaptoethanol were added dropwise to a pH of 6.5 to 7.0.
Nach Beendigung der Reduktion wird die Aminoazoverbindung der Formel
When the reduction is complete, the aminoazo compound of the formula
durch Zugabe von Salz ausgefällt und isoliert. precipitated and isolated by adding salt.
61,7 g der Verbindung der Formel (IIIb) werden in 500 ml Wasser bei 80°C und
einem pH-Wert von 7,0 bis 7,5 mit 93,8 g 2-Mercaptoethanol versetzt. Nach
Beendigung der Reduktion wird die Aminoazoverbindung der Formel
61.7 g of the compound of the formula (IIIb) in 500 ml of water at 80 ° C. and a pH of 7.0 to 7.5 are mixed with 93.8 g of 2-mercaptoethanol. When the reduction is complete, the aminoazo compound of the formula
durch Zugabe von Salz ausgefällt und isoliert.precipitated and isolated by adding salt.
49,2 g der Verbindung der Formel (IIIg) werden in 500 ml Wasser bei 80°C und
einem pH-Wert von 11,0 bis 11,5 mit 46,9 g 2-Mercaptoethanol versetzt. Nach
Beendigung der Reduktion wird der pH-Wert durch Zugabe von konz. Salzsäure auf
ca. 7 gebracht. Die Aminoazoverbindung der Formel
49.2 g of the compound of formula (IIIg) in 500 ml of water at 80 ° C and a pH of 11.0 to 11.5 are mixed with 46.9 g of 2-mercaptoethanol. After the reduction has ended, the pH is increased by adding conc. Brought hydrochloric acid to about 7. The aminoazo compound of the formula
wird durch Zugabe von Salz ausgefällt und isoliert. is precipitated and isolated by adding salt.
25,6 g der Verbindung der Formel (IIIl) werden in 500 ml Ethanol nach Zugabe von
46,9 g 2-Mercaptoethanol, 50,4 g Natriumhydrogencarbonat und 8 g Natrium
hydroxid zum Sieden erhitzt. Nach Beendigung der Reduktion werden ca. 450 ml
Ethanol unter vermindertem Druck abdestilliert. Nach Zugabe von 500 ml Wasser
wird die Diaminoazoverbindung der Formel
25.6 g of the compound of formula (IIIl) are heated to boiling in 500 ml of ethanol after addition of 46.9 g of 2-mercaptoethanol, 50.4 g of sodium hydrogen carbonate and 8 g of sodium hydroxide. After the reduction has ended, about 450 ml of ethanol are distilled off under reduced pressure. After adding 500 ml of water, the diaminoazo compound of the formula
isoliert.isolated.
54,8 g der Verbindung der Formel (IIIh) werden in 500 ml Wasser bei 80°C und
einem pH-Wert von 6,5 bis 7,0 tropfenweise mit 46,2 g Mercaptoessigsäure versetzt.
Nach Beendigung der Reduktion wird die Aminoazoverbindung der Formel
54.8 g of the compound of formula (IIIh) in 500 ml of water at 80 ° C and a pH of 6.5 to 7.0 are added dropwise with 46.2 g of mercaptoacetic acid. When the reduction is complete, the aminoazo compound of the formula
durch Zugabe von Salz ausgefällt und isoliert. precipitated and isolated by adding salt.
49,2 g der Verbindung der Formel (IIIg) werden in 500 ml Wasser bei 80°C und
einem pH-Wert von 11,0 bis 11,5 mit 18,4 g Mercaptoessigsäure versetzt. Nach
Beendigung der Reduktion wird der pH-Wert durch Zugabe von konz. Salzsäure auf
ca. 7 gebracht. Die Aminoazoverbindung der Formel
49.2 g of the compound of the formula (IIIg) in 500 ml of water at 80 ° C. and a pH of 11.0 to 11.5 are mixed with 18.4 g of mercaptoacetic acid. After the reduction has ended, the pH is increased by adding conc. Brought hydrochloric acid to about 7. The aminoazo compound of the formula
wird durch Zugabe von Salz ausgefällt und isoliert.is precipitated and isolated by adding salt.
Claims (7)
H-S-CHR1-R (I),
worin
R für CH2OH, CH(CH3)OH, COOH, CH2SH, C2H4OH, C2H4SH
und
R1 für H, CH3, C2H5 steht,
reduziert.1. A process for the preparation of aminodiarylazo compounds, characterized in that nitrodiarylazo compounds by means of compounds of the formula (I)
HS-CHR 1 -R (I),
wherein
R for CH 2 OH, CH (CH 3 ) OH, COOH, CH 2 SH, C 2 H 4 OH, C 2 H 4 SH
and
R 1 represents H, CH 3 , C 2 H 5 ,
reduced.
worin
A und B unabhängig voneinander für Phenyl- oder Naphthylringe stehen, die jeweils gegebenenfalls durch in der Azo-Farbstoffchemie übliche Reste substituiert sind und bei den Nitrodiarylazoverbindungen um solche der Formel (III)
worin
A und B die für Formel (II) angegebene allgemeine und spezielle Bedeutung haben,
handelt.2. The method according to claim 1, characterized in that the aminodiarylazo compounds are those of the formula (II)
wherein
A and B independently of one another represent phenyl or naphthyl rings which are each optionally substituted by radicals customary in azo dye chemistry and in the case of the nitrodiarylazo compounds are those of the formula (III)
wherein
A and B have the general and special meaning given for formula (II),
acts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1997118523 DE19718523A1 (en) | 1997-05-02 | 1997-05-02 | Amino-di:aryl-azo compounds preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1997118523 DE19718523A1 (en) | 1997-05-02 | 1997-05-02 | Amino-di:aryl-azo compounds preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19718523A1 true DE19718523A1 (en) | 1998-11-05 |
Family
ID=7828388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1997118523 Withdrawn DE19718523A1 (en) | 1997-05-02 | 1997-05-02 | Amino-di:aryl-azo compounds preparation |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19718523A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2008995A3 (en) * | 2007-06-29 | 2009-05-06 | Ricoh Company, Ltd. | Azo compound and method of preparing the azo compound |
| JP2013091722A (en) * | 2011-10-26 | 2013-05-16 | Sumitomo Chemical Co Ltd | Compound |
-
1997
- 1997-05-02 DE DE1997118523 patent/DE19718523A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2008995A3 (en) * | 2007-06-29 | 2009-05-06 | Ricoh Company, Ltd. | Azo compound and method of preparing the azo compound |
| US8232376B2 (en) | 2007-06-29 | 2012-07-31 | Ricoh Company, Ltd. | Azo compound and method of preparing the azo compound |
| US8541557B2 (en) | 2007-06-29 | 2013-09-24 | Ricoh Company, Ltd. | Azo compound and method of preparing the azo compound |
| JP2013091722A (en) * | 2011-10-26 | 2013-05-16 | Sumitomo Chemical Co Ltd | Compound |
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