DE1137816B - Process for the preparation of basic azo dyes - Google Patents
Process for the preparation of basic azo dyesInfo
- Publication number
- DE1137816B DE1137816B DEB50587A DEB0050587A DE1137816B DE 1137816 B DE1137816 B DE 1137816B DE B50587 A DEB50587 A DE B50587A DE B0050587 A DEB0050587 A DE B0050587A DE 1137816 B DE1137816 B DE 1137816B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- preparation
- dyes
- red
- alkyl
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 10
- 239000000987 azo dye Substances 0.000 title description 2
- 239000000975 dye Substances 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- -1 heterocyclic amines Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 239000002168 alkylating agent Substances 0.000 claims description 4
- 229940100198 alkylating agent Drugs 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 150000005840 aryl radicals Chemical class 0.000 claims description 3
- 239000000981 basic dye Substances 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 150000002790 naphthalenes Chemical class 0.000 claims description 3
- 150000003254 radicals Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 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
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- IPBRTIZQCXVAOA-UHFFFAOYSA-N 2-chloroethyl phenylmethanesulfonate Chemical compound ClCCOS(=O)(=O)CC1=CC=CC=C1 IPBRTIZQCXVAOA-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- HJELPNLGHMWKQT-UHFFFAOYSA-N 3-methoxy-n-methylpropan-1-amine Chemical compound CNCCCOC HJELPNLGHMWKQT-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- OXNSLTFQEONMAK-UHFFFAOYSA-N N1CCCCC1.N1C=NC=C1.NC1=CC=CC=C1 Chemical compound N1CCCCC1.N1C=NC=C1.NC1=CC=CC=C1 OXNSLTFQEONMAK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- ZYIFLKPDFLWFAE-UHFFFAOYSA-N aniline;toluene Chemical compound CC1=CC=CC=C1.NC1=CC=CC=C1 ZYIFLKPDFLWFAE-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C09B44/00—Azo dyes containing onium groups
- C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
- C09B44/16—1,3-Diazoles or hydrogenated 1,3-diazoles ; (Benz)imidazolium
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung basischer Azofarbstoffe Zusatz zum Patent 1098 642 Gegenstand des Patents 1098 642 ist ein Verfahren zur Herstellung kationischer Farbstoffe durch Behandeln sulfonsäuregruppenfreier Azoverbindungen der allgemeinen Formel worin n eine der Zahlen 1 oder 2, A im Falle von n = 1 den einwertigen und im Falle von zz = 2 den zweiwertigen Rest eines aromatischen diazotierbaren Amins bzw. tetrazotierbaren Diamins und Bi und Bz Wasserstoffatome, Alkyl, Cycloalkyl-, Aralkyl-und/oder Arylreste bedeuten oder Glieder eines gemeinsamen, nichtaromatischen Rings sein können, mit alkylierenden Mitteln.Process for the production of basic azo dyes Addition to patent 1098 642 The subject of the patent 1098 642 is a process for the production of cationic dyes by treating sulfonic acid group-free azo compounds of the general formula where n is one of the numbers 1 or 2, A in the case of n = 1 the monovalent and in the case of zz = 2 the divalent radical of an aromatic diazotizable amine or tetrazotizable diamine and Bi and Bz hydrogen atoms, alkyl, cycloalkyl, aralkyl and / or aryl radicals or can be members of a common, non-aromatic ring, with alkylating agents.
Es wurde nun gefunden, daß man einen Teil der im Hauptpatent beschriebenen katiönischen Farbstoffe auf vereinfachte Weise erhält; wenn man sulfonsäuregruppenfreie Azoverbindungen der allgemeinen Formel worin Bi und BZ die angegebenen Bedeutungen haben und Ar einen Rest der Benzol- oder Naphthalinreihe darstellt, der mindestens in einer o- oder der p-Stellung zur Azobrücke unsubstituiert ist, mit alkylierenden Mitteln behandelt und die erhaltenen Farbsalze zeit primären oder sekundären aliphatischen, araliphatischen oder, vorzugsweise nichtaromatischen, heterocyclischen Aminen zweckmäßig in Gegenwart von Oxydationsmitteln umsetzt.It has now been found that some of the cationic dyes described in the main patent are obtained in a simplified manner; if you use sulfonic acid group-free azo compounds of the general formula where Bi and BZ have the meanings given and Ar is a radical of the benzene or naphthalene series which is unsubstituted in at least one o- or p-position to the azo bridge, treated with alkylating agents and the resulting color salts are primary or secondary aliphatic, araliphatic or, preferably non-aromatic, heterocyclic amines, expediently reacted in the presence of oxidizing agents.
Die Ausgangsstoffe des Verfahrens lassen sich durch Diazotieren aromatischer Amine der Benzol-und Naphthalinreihe, die mindestens in einer o-oder der p-Stellung zur Aminogruppe unsubstituiert sind, und Kuppeln mit Imidazol oder dessen in 3- und/oder 4-Stellung entsprechend der allgemeinen Formel substituierten Derivaten gewinnen. Die hierbei verwendeten Diazokomponenten und die Substituenten Bi und BZ der allgemeinen Formei können beispielsweise Halogenatome, Alkyl-, Aralkyl-, Hydroxyl-, Alkoxyl ; Nitro-, Cyan-, primäre, sekundäre oder tertiäre Amino ; Acylamino-, Alkylsidfon-, Arylsulfon-, Carbonsäure-, Carbonsäureester- oder - gegebenenfalls substituierte - Carbonsäureamid-, Sulfonsäureantid- oder Arylazogruppen tragen.The starting materials of the process can be made more aromatic by diazotizing Amines of the benzene and naphthalene series which are in at least one o- or p-position are unsubstituted to the amino group, and coupling with imidazole or its in 3- and / or 4-position substituted derivatives according to the general formula to win. The diazo components used here and the substituents Bi and BZ of the general formula can, for example, halogen atoms, alkyl, aralkyl, Hydroxyl, alkoxyl; Nitro, cyano, primary, secondary or tertiary amino; Acylamino, Alkylsidfon-, arylsulfon-, carboxylic acid, carboxylic acid ester or - optionally substituted - Carboxamide, sulfonic acid or arylazo groups.
Als Alkylierungsmittel sind beispielsweise die Alkyl-, Aralkyl- oder Cycloalkylhaiogenide, wie Methylchlorid, Äthylbromid, Benzylchlorid, Phenacylchlorid, ferner Dialkylsulfate oder Alkylester aromatischer Sulfonsäuren wie Dimethylsulfat, Toluolsulfonsäuremethylester oder Toluolsuifonsäure-(2-chlor)-äthylester brauchbar. Die AIkylierung wird in wäßriger Lösung oder Suspension oder in organischen Lösungsmitteln bei normaler oder erhöhter Temperatur vorgenommen. Vorteilhaft arbeitet man in Gegenwart säurebindender Mittel, wie Alkalihydroxyden, Erdalkalioxyden oder -carbonaten. Gleichzeitig mit der Alkyherung des Imidazolrings lassen sich auch im Ausgangsstoff vorhandene, substituierbare Wasserstoffatome enthaltende Gruppen, wie Hydroxyl-, Carbonsäure- oder Aminogruppen, chemisch verändern, z. B. veräthern, verestern oder alkylieren.As alkylating agents, for example, the alkyl, aralkyl or Cycloalkyl halides, such as methyl chloride, ethyl bromide, benzyl chloride, phenacyl chloride, also dialkyl sulfates or alkyl esters of aromatic sulfonic acids such as dimethyl sulfate, Methyl toluenesulfonate or 2-chloroethyl toluenesulfonate can be used. The alkylation is carried out in aqueous solution or suspension or in organic solvents made at normal or elevated temperature. It is advantageous to work in the present acid-binding agents, such as alkali metal hydroxides, alkaline earth metal oxides or carbonates. Simultaneously with the alkylation of the imidazole ring can also be found in the starting material, groups containing substitutable hydrogen atoms, such as hydroxyl, carboxylic acid or amino groups, chemically change, e.g. B. etherify, esterify or alkylate.
Als für das Verfahren geeignete Amine seien beispiessweise genannt: Mono- oder Dimethylamin, Diäthylamin, Methyl 2-hydroxyäthylamin, 1-Amino-3-methoxypropan,1-Methylamino-3-methoxypropan, N,N-Dimethyl-i,3-diaminopropan, Pyrrolidin, Piperidin, Hexamethylenimin, Morpholin, Piperazin, Benzylamin, Benzylmethylamin. Die Umsetzung der quartären Farbsalze mit den genannten Aminen wird in wäßriger oder organischer Lösung, z. B. in Methanol, Äthanol, Aceton, Formamid, Dimethylformamid oder einfach in überschüssigem Amin als Lösungsmittel, im allgemeinen bei gewöhnlicher oder auch bei erhöhter Temperatur, vorgenommen. Als Oxydationsmittel sind beispielsweise Luftsauerstoff Wasserstoffperoxyd, Hypochlorite, Persulfate, Eisen(III)-, Kupfer(II)-, Quecksilber(II)-, Blei(IV)- oder Cer(M-salze und Hexacyanoferrate(III) zu nennen; gegebenenfals können auch Sauerstoffüberträger, z. B. Schwermetalle und ihre Salze, mitverwendet werden.Amines suitable for the process include: Mono- or dimethylamine, diethylamine, methyl 2-hydroxyethylamine, 1-amino-3-methoxypropane, 1-methylamino-3-methoxypropane, N, N-dimethyl-i, 3-diaminopropane, pyrrolidine, piperidine, hexamethyleneimine, morpholine, Piperazine, benzylamine, benzylmethylamine. Implementation of the Quaternary Color salts with the amines mentioned is in aqueous or organic solution, for. B. in methanol, ethanol, acetone, formamide, dimethylformamide or simply in excess Amine as solvent, generally at normal or also at elevated temperature, performed. Examples of oxidizing agents are atmospheric oxygen, hydrogen peroxide, Hypochlorite, persulfate, iron (III) -, copper (II) -, mercury (II) -, lead (IV) - or cerium (M salts and hexacyanoferrates (III); Oxygen carriers, e.g. B. heavy metals and their salts are also used.
Die amingruppenfreien Ausgangsfarbstoffe können in einer Lösung mit hoher Aminkonzentration auch selbst oxydierend wirken, so daß die Umsetzung auch ohne Zusatz von Oxydationsmitteln ausgeführt werden kann.The starting dyes free of amine groups can be in a solution with high amine concentration also have an oxidizing effect themselves, so that the implementation also can be carried out without the addition of oxidizing agents.
Nach Beendigung der papyrographisch leicht zu verfolgenden Umsetzung säuert man an und trennt gegebenenfalls unerwünschte Nebenprodukte, z. B. Blei(II)-salze, durch Ausfällen in Form der Carbonate, Sulfate oder Sulfide ab. Aus dem Filtrat wird dann der Farbstoff auf übliche Weise durch Aussahen oder durch Erzeugung weniger löslicher Salze isoliert. Im Falle der Oxydation mit I-lexacyanoferrat(III) erhält man die Farbstoffe beim Ansäuern als in Wasser weniger lösliche Hexacyanoferrate(II).After completion of the papyrographically easy to follow implementation is acidified and, if necessary, unwanted by-products, such. B. lead (II) salts, by precipitation in the form of carbonates, sulfates or sulfides. From the filtrate then the dye becomes in the usual way by looking or producing less soluble salts isolated. In the case of oxidation with I-lexacyanoferrate (III) is obtained the dyes are acidified as hexacyanoferrate (II), which is less soluble in water.
Eine weitere, besonders vorteilhafte Ausführungsform des Verfahrens besteht darin, daß man die in Wasser oder organischen Lösungsmitteln hergestellten quaternären Farbsalze, ohne sie zu isolieren, mit den Aminen umsetzt.Another, particularly advantageous embodiment of the method consists in that one prepared in water or organic solvents quaternary color salts, without isolating them, reacts with the amines.
Die nach dem Verfahren erhaltenen Farbstoffe besitzen die allgemeine Formel worin Ar, Bi und B2 die angegebenen Bedeutungen haben, X1 ein Wasserstoffatom oder eine Alkyl-oder Aralkylgruppe, X2 eine Alkyl- oder Aralkylgruppe ist und X1 und X2 gemeinsam Glieder eines vorzugsweise nichtaromatischen, heterocychschen Rings sein können, Z- ein Anion und R, und R2 Alkyl-, Cycloalkyl- oder Aralkylreste bedeuten. Sie lösen sich in Wasser mit orangeroter, roter oder violetter Farbe und können als basische Farbstoffe zum Färben von Gebilden, wie Fasern, Flocken, Fäden oder Gespinsten aus gebeizter Baumwolle, natürlichen oder synthetischen Polyamiden einschließlich Leder, oder von andern synthetischen Fasern, wie Polyurethanen, Celluloseestern, Polyestern oder von acrylnitrilhaltigen Polymerisaten dienen. Insbesondere auf Materialien aus Polyacrylnitril oder Acrylnitril enthaltenden Mischpolymerisaten erhält man durch Masse-, Spinn- oder Badfäden oder Bedrucken Färbungen in sehr echten und reinen Tönen.The dyes obtained by the process have the general formula where Ar, Bi and B2 have the meanings given, X1 is a hydrogen atom or an alkyl or aralkyl group, X2 is an alkyl or aralkyl group and X1 and X2 together can be members of a preferably non-aromatic, heterocyclic ring, Z- an anion and R, and R2 denotes alkyl, cycloalkyl or aralkyl radicals. They dissolve in water with an orange-red, red or purple color and can be used as basic dyes for dyeing structures such as fibers, flakes, threads or webs made of stained cotton, natural or synthetic polyamides including leather, or other synthetic fibers such as polyurethanes, Cellulose esters, polyesters or acrylonitrile-containing polymers are used. In particular on materials made from polyacrylonitrile or copolymers containing acrylonitrile, dyeings in very genuine and pure tones are obtained by mass, spun or bath threads or by printing.
Gegenüber der nach dem Verfahren des Hauptpatents vorgenommenen Herstellung der obigen Farbstoffe, bei der N-substituierte 1,2- oder 1,4-Diamino-Benzol- und' -naphthalinderivate, die gegen Luft-Sauerstoff empfindlich und deren Diazoverbindungen zudem wenig reaktionsfähig sind, weist das beanspruchte Verfahren den Vorteil auf, daß hier die in großer Zahl zugänglichen und leicht zu handhabenden, in einer o- oder der p-Stellung unsubstituierten Aminobenzole und primären oder sekundären Amine verwendet werden. Auch war die eintretende glatte Reaktion überraschend, da bekanntlich Wasserstoffatome am nicht aktivierten Arylrest im allgemeinen sehr fest gebunden sind.Compared to the production carried out according to the process of the main patent of the above dyes, in which N-substituted 1,2- or 1,4-diamino-benzene and ' -naphthalene derivatives, which are sensitive to atmospheric oxygen, and their diazo compounds are also not very reactive, the claimed method has the advantage that here those accessible in large numbers and easy to handle, in an o- or the p-position unsubstituted aminobenzenes and primary or secondary amines be used. The smooth reaction that occurred was also surprising, as is well known Hydrogen atoms on the non-activated aryl radical are generally very tightly bound are.
Die in den folgenden Beispielen genannten Teile sind Gewichtsteile. Beispiel 1 Zu der aus 9,3 Teilen Aminobenzol auf übliche Weise erhaltenen Diazoniumlösung gibt man nach und nach eine Lösung von 10 Teilen Imidazol in 150 Teilen Wasser und dann unter Außenkühlung noch 60 Teile 10%iger Natronlauge. Nach Beendigung der Kupplung wird mit Hilfe von 15 Teilen 30o/oiger Essigsäure neutralisiert, worauf man die ausgeschiedene gelbe Azoverbindung absaugt. Sie wird ohne Trocknung mit 250 Teilen Wasser angerührt. Dann werden 10 Teile Magnesiumoxyd, 250 Teile Eis und unter gleichzeitiger Außenkühlung 32 Teile Dimethylsulfat nach und nach zugegeben. Nach Beendigung der Methylierung filtriert man von etwa vorhandenem überschüssigem Magnesiumoxyd ab, setzt zum Filtrat 30 Teile Blei(IV)-oxyd und 50 Teile Piperidin und rührt das Reaktionsgemisch so lange bei gewöhnlicher Temperatur, bis kein Ausgangsfarbstoff mehr nachzuweisen ist. Dann wird mit 50 Teilen 30%iger Essigsäure angesäuert; schließlich gibt man 200 Teile gesättigter Natriumsulfatlösung zu, trennt den entstandenen Niederschlag von Bleiverbindungen ab, fällt den Farbstoff aus dem Filtrat durch Zusatz von 20 Teilen 50%iger Zinkchloridlösung und 1000 Teilen gesättigter Natriumchloridlösung aus und trocknet ihn. Er fällt als violettes, bronzeglänzendes Pulver an, das sich mit blaustichigroter Farbe in Wasser löst und Polyacrylnitrilmaterial in blaustichigroten Tönen von guten Echtheitseigenschaften färbt.The parts mentioned in the following examples are parts by weight. Example 1 To the diazonium solution obtained in the usual way from 9.3 parts of aminobenzene are gradually a solution of 10 parts of imidazole in 150 parts of water and then 60 parts of 10% sodium hydroxide solution with external cooling. After completing the coupling is neutralized with the help of 15 parts of 30% acetic acid, whereupon the Separated yellow azo compound sucks off. It is made with 250 parts without drying Touched water. Then 10 parts of magnesium oxide, 250 parts of ice and taking at the same time External cooling 32 parts of dimethyl sulfate were gradually added. After the Methylation is filtered off from any excess magnesium oxide present, add 30 parts of lead (IV) oxide and 50 parts of piperidine to the filtrate and stir the reaction mixture so long at normal temperature until no more starting dye can be detected is. Then it is acidified with 50 parts of 30% acetic acid; after all you give 200 parts of saturated sodium sulfate solution are added and the precipitate formed is separated of lead compounds, the dye falls out of the filtrate by adding 20 Parts of 50% zinc chloride solution and 1000 parts of saturated sodium chloride solution out and dry it. It falls as a purple, bronze-shining powder that is with a bluish-tinted red color dissolves in water and polyacrylonitrile material in a bluish-tinted-red color Dyes shades of good fastness properties.
Auf analoge Weise lassen sich unter Verwendung der folgenden Komponenten
basische Farbstoffe herstellen:
Eine Lösung von 16 Teilen des so erhaltenen Farbstoffs der Formel in 30 Teilen Wasser wird zu 100 Teilen Pyrrolidin gegeben. Das Gemisch rührt man bei gewöhnlicher Temperatur bis zur Beendigung der Umsetzung und läßt es dann in eine Mischung von 100 Teilen Eisessig und 3000 Teilen gesättigter Natriumchloridlösung unter Außenkühlung einfließen. Durch Zusatz von 50 Teilen 50%iger Zinkchloridlösung wird der Farbstoff als Zinkchloriddoppelsalz ausgefällt, abgesaugt und getrocknet. Man erhält ihn in Form eines dunklen, bronzeglänzenden Pulvers, das sich in Wasser mit blaustichigroter Farbe löst und Polyacrylnitrilfasern aus schwefelsaurem Bad in blaustichigroten Tönen von guten Echtheitseigenschaften färbt.A solution of 16 parts of the dye of the formula thus obtained in 30 parts of water is added to 100 parts of pyrrolidine. The mixture is stirred at ordinary temperature until the reaction has ended and is then allowed to flow into a mixture of 100 parts of glacial acetic acid and 3000 parts of saturated sodium chloride solution with external cooling. By adding 50 parts of 50% zinc chloride solution, the dye is precipitated as a zinc chloride double salt, filtered off with suction and dried. It is obtained in the form of a dark, bronze-shimmering powder which dissolves in water with a bluish-tinged red color and dyes polyacrylonitrile fibers from a sulfuric acid bath in bluish-tinged red shades with good fastness properties.
Entsprechende Farbstoffe können unter Verwendung der folgenden Komponenten
hergestellt werden
Entsprechend wurden die folgenden Farbstoffe erhalten
Claims (1)
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DEB50587A DE1137816B (en) | 1958-10-03 | 1958-10-03 | Process for the preparation of basic azo dyes |
CH7389059A CH391922A (en) | 1958-06-25 | 1959-06-02 | Process for the production of new basic dyes |
CH1128464A CH438527A (en) | 1958-06-25 | 1959-06-02 | Process for the production of new basic dyes |
CH1128564A CH441562A (en) | 1958-06-25 | 1959-06-02 | Process for the production of new basic dyes |
NL6609135A NL6609135A (en) | 1958-06-25 | 1966-06-30 |
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WO2005012437A1 (en) * | 2003-07-24 | 2005-02-10 | Ciba Specialty Chemicals Holding Inc. | Cationic direct dyes |
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FR1145751A (en) * | 1955-01-28 | 1957-10-29 | Geigy Ag J R | Water soluble dyestuff salts and method of preparation |
FR1145753A (en) * | 1955-01-28 | 1957-10-29 | Geigy Ag J R | Water-soluble dye salts and process for their preparation |
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FR1145751A (en) * | 1955-01-28 | 1957-10-29 | Geigy Ag J R | Water soluble dyestuff salts and method of preparation |
FR1145753A (en) * | 1955-01-28 | 1957-10-29 | Geigy Ag J R | Water-soluble dye salts and process for their preparation |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2005012437A1 (en) * | 2003-07-24 | 2005-02-10 | Ciba Specialty Chemicals Holding Inc. | Cationic direct dyes |
US7307155B2 (en) | 2003-07-24 | 2007-12-11 | Ciba Specialty Chemicals Corporation | Cationic direct dyes |
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