DE2152703C3 - Process for the production of basic dyes by catalytic oxidation - Google Patents
Process for the production of basic dyes by catalytic oxidationInfo
- Publication number
- DE2152703C3 DE2152703C3 DE19712152703 DE2152703A DE2152703C3 DE 2152703 C3 DE2152703 C3 DE 2152703C3 DE 19712152703 DE19712152703 DE 19712152703 DE 2152703 A DE2152703 A DE 2152703A DE 2152703 C3 DE2152703 C3 DE 2152703C3
- Authority
- DE
- Germany
- Prior art keywords
- hydrogen
- methyl
- carbon atoms
- parts
- chlorine
- 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.)
- Expired
Links
- 239000000981 basic dye Substances 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 5
- 230000003647 oxidation Effects 0.000 title claims description 5
- 238000007254 oxidation reaction Methods 0.000 title claims description 5
- 230000003197 catalytic Effects 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title description 5
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- -1 hydroxy, methoxy, ethoxy Chemical group 0.000 claims description 19
- 150000002431 hydrogen Chemical group 0.000 claims description 18
- 239000000460 chlorine Chemical group 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 14
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 9
- XOBKSJJDNFUZPF-UHFFFAOYSA-N methoxyethyl Chemical group CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005041 acyloxyalkyl group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 150000004054 benzoquinones Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- SCOAVUHOIJMIBW-UHFFFAOYSA-N phenanthrene-1,2-dione Chemical group C1=CC=C2C(C=CC(C3=O)=O)=C3C=CC2=C1 SCOAVUHOIJMIBW-UHFFFAOYSA-N 0.000 claims 1
- GRYBZNLNHVSHPY-UHFFFAOYSA-N sodium;4-hydroxy-5-[(6-oxocyclohexa-2,4-dien-1-ylidene)methylamino]naphthalene-2,7-disulfonic acid Chemical compound [Na+].C=12C(O)=CC(S(O)(=O)=O)=CC2=CC(S(O)(=O)=O)=CC=1NC=C1C=CC=CC1=O GRYBZNLNHVSHPY-UHFFFAOYSA-N 0.000 description 17
- 239000000975 dye Substances 0.000 description 11
- SMQUZDBALVYZAC-UHFFFAOYSA-N Salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- GEYOCULIXLDCMW-UHFFFAOYSA-N O-Phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- BXIXXXYDDJVHDL-UHFFFAOYSA-N 4-Chloro-ortho-phenylenediamine Chemical compound NC1=CC=C(Cl)C=C1N BXIXXXYDDJVHDL-UHFFFAOYSA-N 0.000 description 4
- 229960000583 Acetic Acid Drugs 0.000 description 4
- UGNWTBMOAKPKBL-UHFFFAOYSA-N Chloranil Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N Dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N Phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N 1,2-Diaminopropane Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N Diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 description 2
- 229940118019 Malondialdehyde Drugs 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HRKAMJBPFPHCSD-UHFFFAOYSA-N tris(2-methylpropyl) phosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 description 2
- PXQAZRQPYXELGS-UHFFFAOYSA-N 1,2,2,4-tetramethyl-3,4-dihydroquinoline Chemical compound C1=CC=C2C(C)CC(C)(C)N(C)C2=C1 PXQAZRQPYXELGS-UHFFFAOYSA-N 0.000 description 1
- BWVDOMYGBPMGKV-UHFFFAOYSA-N 1,2,2,4-tetramethylquinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)N(C)C2=C1 BWVDOMYGBPMGKV-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N 1,3-Diaminopropane Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1H-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- LWHDQPLUIFIFFT-UHFFFAOYSA-N 2,3,5,6-tetrabromocyclohexa-2,5-diene-1,4-dione Chemical compound BrC1=C(Br)C(=O)C(Br)=C(Br)C1=O LWHDQPLUIFIFFT-UHFFFAOYSA-N 0.000 description 1
- LPAGFVYQRIESJQ-UHFFFAOYSA-N 2,3-dihydro-1H-indole Chemical compound C1=CC=C2NCCC2=C1 LPAGFVYQRIESJQ-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-Dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- FABVMBDCVAJXMB-UHFFFAOYSA-N 3,5-dichloro-2-hydroxybenzaldehyde Chemical compound OC1=C(Cl)C=C(Cl)C=C1C=O FABVMBDCVAJXMB-UHFFFAOYSA-N 0.000 description 1
- KVBANSJOXDHNIW-UHFFFAOYSA-N 3-[benzyl(ethyl)amino]benzenesulfonic acid Chemical compound C=1C=CC(S(O)(=O)=O)=CC=1N(CC)CC1=CC=CC=C1 KVBANSJOXDHNIW-UHFFFAOYSA-N 0.000 description 1
- OFQBYHLLIJGMNP-UHFFFAOYSA-N 3-ethoxy-2-hydroxybenzaldehyde Chemical compound CCOC1=CC=CC(C=O)=C1O OFQBYHLLIJGMNP-UHFFFAOYSA-N 0.000 description 1
- RBYNJGKNRQUCJU-UHFFFAOYSA-N 3-nitrophenanthrene-1,2-dione Chemical group C1=CC=C2C(C=C(C(C3=O)=O)[N+](=O)[O-])=C3C=CC2=C1 RBYNJGKNRQUCJU-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N Chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M Crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- MLIREBYILWEBDM-UHFFFAOYSA-N Cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N Diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- PQAXGPJSVFSKAI-UHFFFAOYSA-N Hexadecachlorophthalocyanine Chemical compound C12=C(Cl)C(Cl)=C(Cl)C(Cl)=C2C(N=C2NC(C3=C(Cl)C(Cl)=C(Cl)C(Cl)=C32)=N2)=NC1=NC([C]1C(Cl)=C(Cl)C(Cl)=C(Cl)C1=1)=NC=1N=C1[C]3C(Cl)=C(Cl)C(Cl)=C(Cl)C3=C2N1 PQAXGPJSVFSKAI-UHFFFAOYSA-N 0.000 description 1
- OTBHHUPVCYLGQO-UHFFFAOYSA-N Norspermidine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 description 1
- JJVNINGBHGBWJH-UHFFFAOYSA-N Ortho-Vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N Triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- JVICFMRAVNKDOE-UHFFFAOYSA-M [4-[bis[4-(diethylamino)phenyl]methylidene]cyclohexa-2,5-dien-1-ylidene]-diethylazanium;chloride Chemical compound [Cl-].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 JVICFMRAVNKDOE-UHFFFAOYSA-M 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 1
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N ethanolamine Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M methanoate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 229940113083 morpholine Drugs 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic Effects 0.000 description 1
- 125000004430 oxygen atoms Chemical group O* 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- STOSPPMGXZPHKP-UHFFFAOYSA-N tetrachlorohydroquinone Chemical compound OC1=C(Cl)C(Cl)=C(O)C(Cl)=C1Cl STOSPPMGXZPHKP-UHFFFAOYSA-N 0.000 description 1
- ODGCEQLVLXJUCC-UHFFFAOYSA-N tetrafluoroborate Chemical compound F[B-](F)(F)F ODGCEQLVLXJUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Description
[ι 4-R5 [ι 4-R 5
N. N
R3' R4 R 3 'R 4
oderor
N
R1' R2 N
R 1 'R 2
R3 und R4 unabhängig voneinander Wasserstoff. Alkyl mit 1 bis 4 C-Atomen, Hydroxyalkyl mit 2 oder 3 C-Atomen, Cyanäthyl, Methoxyäthyl oder Äthoxyäthyl, R3 und R4 zusammen mit dem N-Atom einen heterocyclischen Rest oder R3 oder R4 verknüpft mit der o-Stellung des Benzolringes einen kondensierten Heterocyclus, R5 Wasserstoff, Chlor, Methyl, Methoxy, Äthoxy, Acylamino. Hydroxycarbonyl. Alkoxycarbonyl oder Hydroxysulfonyl und X ein Anion bedeutet.R 3 and R 4 independently of one another are hydrogen. Alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoethyl, methoxyethyl or ethoxyethyl, R 3 and R 4 together with the N atom are a heterocyclic radical or R 3 or R 4 linked to the o-position of the benzene ring is a condensed heterocycle, R 5 is hydrogen, chlorine, methyl, methoxy, ethoxy, acylamino. Hydroxycarbonyl. Alkoxycarbonyl or hydroxysulfonyl and X is an anion.
it. dadurch gekennzeichnet, daß man Gegenstand des Patents 21 38 931 ist ein Verfahrenit. characterized in that the subject of patent 21 38 931 is a method
ier Verbindungen der Formel zur Herstellung basischer Farbstoffe der allgemeinenier compounds of the formula for the preparation of basic dyes of the general
Formel IFormula I.
R1 R1 R 1 R 1
\ /=v / \ / = v / 40 R R2 40 RR 2
/ W \i/ \ NN/ W \ i / \ NN
R2 Y YR2 / V\A ,/\/'R 2 Y YR 2 / V \ A, / \ / '
lit Verbindungen der Formel AH zu Verbindunen der Formellit compounds of the formula AH to compounds of the formula
msetzt, wobei R1 Wasserstoff, Alkyl mit 1 bis C-Atomen, Hydroxyalkyl mit 2 oder 3 C-Atomen, 'yanäthyl. Carbalkoxyalkyl mit insgesamt 2 bis C-Atomen, Methoxyäthyl, Äthoxyäthyl, Alkaoyloxyalkyl mit insgesamt 4 bis 11 C-Atomen, 'yclohexyl, Benzyl, Phenyläthyl, Phenyl, durch Methyl, Methoxy oder Äthoxy substituiertes Pheyl, R2 Wasserstoff, Alkyl mit 1 bis 4 C-Atomen, iydroxyalkyl mit 2 oder 3 C-Atomen, Cyanäthyl, iethoxyäthyl oder Äthoxyäthyl, Y Wasserstoff, hlor, Methyl, Methoxy oder Äthoxy, A einenmsetzt, where R 1 is hydrogen, alkyl with 1 to C atoms, hydroxyalkyl with 2 or 3 C atoms, 'yanäthyl. Carbalkoxyalkyl with a total of 2 to 14 carbon atoms, methoxyethyl, ethoxyethyl, alkaoyloxyalkyl with a total of 4 to 11 carbon atoms, yclohexyl, benzyl, phenylethyl, phenyl, phenyl substituted by methyl, methoxy or ethoxy, R 2 hydrogen, alkyl with 1 to 4 C atoms, iydroxyalkyl with 2 or 3 C atoms, cyanoethyl, ethoxyethyl or ethoxyethyl, Y hydrogen, chlorine, methyl, methoxy or ethoxy, A one
R1 R 1
RJ R J
in der unabhängig voneinander R Wasserstoff, Alkyl mit 1 bis 4 C-Atomen, Hydroxyalkyl mit 2 oder 3 C-Atomen, Cyanäthyl, Carbalkoxyalkyl mit insgesamt 2 bis 5 C-Atomen, Methoxyäthyl, Äthoxyäthyl, Alkanoyloxyalkyl mit insgesamt 4 bis 11 C-Atomen, Benzyl, Phenyläthyl, Phenyl, durch Methyl, Methoxy oder Äthoxy substituiertes Phenyl oder einen Rest der Formelin which, independently of one another, R is hydrogen, alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms, cyanoethyl, carbalkoxyalkyl with a total of 2 to 5 carbon atoms, methoxyethyl, ethoxyethyl, Alkanoyloxyalkyl with a total of 4 to 11 carbon atoms, benzyl, phenylethyl, phenyl, methyl, methoxy or ethoxy-substituted phenyl or a radical of the formula
_ SO3H_ SO 3 H
R1 Wasserstoff. Alkyl mit 1 bis 4 C-Atomen, Hydroxyalkyl mit 2 oder 3 C-Atomen, Cyanäthyl, Methoxyäthyl, Äthoxyäthyl oder Phenyl, R2 dieselben Reste wie R, R3 dieselben Reste wie R1, X Wasserstoff, Chlor, Methyl, Methoxy oder Äthoxy, Y Wasserstoff, Chlor, Methyl, Methoxy oder Äthoxy, A Phenyl, durch Chlor. Methyl. Hydroxy, Methoxy, Äthoxy oder die Sulfonsäuregruppe mono- oder disubstituiertes Phe-R 1 is hydrogen. Alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoethyl, methoxyethyl, ethoxyethyl or phenyl, R 2 the same radicals as R, R 3 the same radicals as R 1 , X hydrogen, chlorine, methyl, methoxy or Ethoxy, Y hydrogen, chlorine, methyl, methoxy or ethoxy, A phenyl, through chlorine. Methyl. Hydroxy, methoxy, ethoxy or the sulfonic acid group mono- or disubstituted Phe-
nyl, einen heteroaromatischen Rest oder einen Rest wobei A1 gleich A oder ein Rest der Formeln
der Formeln nyl, a heteroaromatic radical or a radical where A 1 is A or a radical of the formulas
of the formulas
R1 R 1
R5 R 5
Y4 Y 4
R1 R 1
R5 R 5
f :i ' f: i '
oderor
R-'R- '
N-CHjN-CHj
R1 R 1
N-CH,N-CH,
ist.is.
R1 R 1
ί1 Η j!ί 1 Η j!
R2 R 2
R3 R 3
Es wurde nun gefunden, daß das Verfahren des Patents 21 38 931 ebenfalls sehr gut zur Herstellung basischer Farbstoffe der allgemeinen Formel IIt has now been found that the method of patent 21 38 931 is also very good for manufacture basic dyes of the general formula I
R: R :
R1 R 1
R2 R 2
R1 R 1
R4 Wasserstoff, Chlor. Methyl. Methoxy oder Athoxy, R5 Wasserstoff oder Chlor und X ein Anion bedeutet, das dadurch gekennzeichnet ist, daß man Verbindungen der allgemeinen Formel IIR 4 hydrogen, chlorine. Methyl. Methoxy or ethoxy, R 5 is hydrogen or chlorine and X is an anion which is characterized in that compounds of the general formula II
X (1)X (1)
R1 R 1
y c y c
Y XY X
Λ1 Λ 1
geeignet ist. in der unabhängig voneinander R1 50 Wasserstoff. Alkyl mit 1 bis 4 C-Atomen, Hydroxyalkyl mit 2 oder 3 C-Atomen. Cyanäthyl, Carbalkoxy- alkyl mit insgesamt 2 bis 5 C-Atomen, Methoxyäthyl. Äthoxyäthyl, Alkanoyloxyalkyl mit insgesamt 4 bi? R2 11 C-Atomen, Cyclohexyl, Benzyl, Phenyläthyl, Phe-suitable is. in which, independently of one another, R 1 50 is hydrogen. Alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms. Cyanoethyl, carbalkoxy alkyl having 2 to 5 carbon atoms, methoxyethyl. Ethoxyethyl, alkanoyloxyalkyl with a total of 4 bi? R 2 11 carbon atoms, cyclohexyl, benzyl, phenylethyl, Phe-
55 nyl. durch Methyl, Methoxy oder Äthoxy substituiertes Phenyl, R2 Wasserstoff, Alkyl mit 1 bis 4 C-Atomen Hydroxyalkyl mit 2 oder 3 C-Atomen. Cyanäthyl R-' (II) Methoxyäthyl oderÄthoxyathyl.Y Wasserstoff. Chlor55 nyl. phenyl substituted by methyl, methoxy or ethoxy, R 2 hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms. Cyanoethyl R- '(II) methoxyethyl or ethoxyethyl.Y hydrogen. chlorine
Methyl. Methoxy oder Äthoxy. A einen heteroaromatisehen Rest oder einen Rest der FormelnMethyl. Methoxy or ethoxy. A is a heteroaromatic Remainder or a remainder of the formulas
1 R5 1 R 5
mit durch Fluor. Chlor. Brom oder Cyan substituierten ßen/ochinoncn oder durch Nitro substituierten Phcnanthrenchinoncn in Gegenwart von Sauerstoff und Sauerstoff übertragenden komplex gebundenes Schwermetall enthaltenden Katalysatoren dehydrierl,with by fluorine. Chlorine. Bromine or cyano substituted ß / ochinoncn or substituted by nitro Phenanthrenequinone in the presence of oxygen and oxygen-transferring complex bound Heavy metal containing catalysts dehydrogenated,
R4 R 4
Heteroaromatische Reste A sind beispielsweise:Examples of heteroaromatic radicals A are:
1 -Methyl^-phenyl-indolyl-S, 2-Methyl-indolyl-3, 2-Phenyl-indolyl-3, 1-Cyanäthyl-2-methyl-indolyl-3, 1 - Phenyl-pyrazolyl-4,1 -Methyl ^ -phenyl-indolyl-S, 2-methyl-indolyl-3, 2-phenyl-indolyl-3, 1-cyanoethyl-2-methyl-indolyl-3, 1 - phenylpyrazolyl-4,
R1 R 1
R-R-
R' und R4 unabhängig voneinander Wasserstoff. Alkyl mit 1 bis 4 C-Atomen. Hydroxyalkyl mit 2 oder 3 C-Atomen. Cyanäthyl, Methoxyälhyl oder Äthoxyälhyl. R3 und R4 zusammen mit dem N-Atom einen heterocyclischen Rest oder R3 oder R4 verknüpft mit der o-Stcllung des Benzolringes einen kondensierten Heterocyclus. R5 Wasserstoff. Chlor, Methyl. Methoxy. Äthoxy. Acylamino. Hydroxycarbonyl. Alkoxycarbonyl oder Hydroxysulfonyl und X ein Anion bedeutet, wobei das Verfahren dadurch gekennzeichnet ist. daß man Verbindungen der allgemeinen Formel 2R 'and R 4 independently of one another are hydrogen. Alkyl with 1 to 4 carbon atoms. Hydroxyalkyl with 2 or 3 carbon atoms. Cyanoethyl, Methoxyälhyl or Äthoxyälhyl. R 3 and R 4 together with the N atom are a heterocyclic radical or R 3 or R 4 are linked to the o-position of the benzene ring to form a condensed heterocycle. R 5 is hydrogen. Chlorine, methyl. Methoxy. Ethoxy. Acylamino. Hydroxycarbonyl. Alkoxycarbonyl or hydroxysulfonyl and X is an anion, the process being characterized. that one compounds of the general formula 2
R1 R 1
R-R-
1.1.
R1 R 1
R2 R 2
(21(21
mit durch Fluor. Chlor. Brom oder Cyan substituierten Bcnzochinonen oder durch Nitrogruppen substituierten Phenanthrenchinonen in Gegenwart von Sauerstoff, sauerstoffaktivicrenden komplex gebundenes Schwermetall enthaltenden Katalysatoren und einer nucleophilen Verbindung der allgemeinen Formel 3with by fluorine. Chlorine. Bromine or cyano substituted benzoquinones or substituted by nitro groups Phenanthrenequinones in the presence of oxygen, oxygen-activating complex bound Heavy metal-containing catalysts and a nucleophilic compound of the general formula 3
AHAH
(3)(3)
3030th
3535
4040
5°5 °
dehydriert.dehydrated.
Außer den einzeln schon erwähnten Suhstituenten seien z. B. folgende Reste genannt:Besides the individually already mentioned Suhstituenten z. B. mentioned the following residues:
für R1:for R 1 :
Methyl. Äthyl. Propyl. Butyl. ,i-Hydroxyäihyl. ,.'-Hydroxypropyl. ,.'-Carbomethoxyäthyl. ,.-Carboäthoxyäthyl; Methyl. Ethyl. Propyl. Butyl. , i-hydroxyethyl. , .'-hydroxypropyl. , .'-carbomethoxyethyl. , .- carboethoxyethyl;
für R2, R3, R4:for R 2 , R 3 , R 4 :
Methyl. ÄthyL Propyl, Butyl, ^-Hydroxyäthyl oder /i-Hydroxypropyl;Methyl. Ethyl propyl, butyl, ^ -hydroxyethyl or / i-hydroxypropyl;
für einen heterocyclischen Rest aus R3 und R4 und dem N-Atom:for a heterocyclic radical consisting of R 3 and R 4 and the N atom:
der Rest des Morpholins, Piperidins, Piperazins oder Pyrrolidins;the remainder of the morpholine, piperidine, piperazine or pyrrolidine;
Tür einen kondensierten Heterocyclus. wenn R3 und R* mit der o-Stellung verknüpft ist:Door a condensed heterocycle. if R 3 and R * are linked to the o-position:
1,2,2,4-Tetramethyl-1,2-dihydrochinolin,
1,2.2,4-Tetramethyl-l ,2,3,4-tetrahydrochinolin,
2,2,4-Trimethyl-1,2-dihydrochinolin.
1 ^-Dimethyl^-dihydroindol.
1 -Butyl-a-hydroxy-T-methyl-l .2.3,4-tctrahydrochinolin.
1,2,2,4-tetramethyl-1,2-dihydroquinoline,
1,2,2,4-tetramethyl-1,2,3,4-tetrahydroquinoline,
2,2,4-trimethyl-1,2-dihydroquinoline.
1 ^ dimethyl ^ dihydroindole.
1-Butyl-a-hydroxy-T-methyl-1.2.3,4-t-tetrahydroquinoline.
1.4-Perimidin-yl-4 oder
Perimidon-yl-4.1,4-perimidin-yl-4 or
Perimidon-yl-4.
Bevorzugte Reste sind:
für R1:Preferred leftovers are:
for R 1 :
Wasserstoff, Methyl, Äthyl, Cyanäthyl, Phenyl, p-Methoxyphenyl oder p-Äthoxyphenyl;Hydrogen, methyl, ethyl, cyanoethyl, phenyl, p-methoxyphenyl or p-ethoxyphenyl;
für R2:for R 2 :
Wasserstoff, Methyl oder Äthyl; für R3:Hydrogen, methyl or ethyl; for R 3 :
Wasserstoff, Methyl, Äthyl oder Cyanäthyl; fürR4:Hydrogen, methyl, ethyl or cyanoethyl; forR 4 :
Wasserstoff. Methyl oder Äthyl; fürR5:Hydrogen. Methyl or ethyl; forR 5 :
Wasserstoff, Methyl. Methoxy. Äthoxy. Acetylamino. Carboxyl. Carbomethoxy. Carboäthoxy oder Hydroxysulfonyl:Hydrogen, methyl. Methoxy. Ethoxy. Acetylamino. Carboxyl. Carbomethoxy. Carboethoxy or hydroxysulfonyl:
für Y:for Y:
Wasserstoff;
für heteroaromatische Reste A:Hydrogen;
for heteroaromatic residues A:
die genannten lndolylreste.the indolyl radicals mentioned.
Anionen X sind beispielsweise: Bromid. Tetrafiuoroborat. Formiat, Methosulfat oder Äthosulfat und insbesondere Chlorid. Nitrat, Acetat oder Tetrachlorozinkat. Anions X are for example: bromide. Tetrafluoroborate. Formate, methosulphate or ethosulphate and especially chloride. Nitrate, acetate or tetrachlorozincate.
Als Schwermetall für die Oxidationskatalysatoren sind z. B. Kupfer. Vanadium. Molybdän und vorzugsweise Eisen und Kobalt zu nennen. Die Metalle liegen in den Katalysatoren in komplexer Bindung mit Stickstoff- und Sauerstoffatomen der ChelatbildnerThe heavy metal for the oxidation catalysts are, for. B. Copper. Vanadium. Molybdenum and preferably To mention iron and cobalt. The metals are in a complex bond with the catalysts Nitrogen and oxygen atoms of the chelating agents
45 vor.45 before.
6060
65 Im einzelnen seien beispielsweise folgende Verbindungen als Oxidationskatalysatoren genannt: 65 For example, the following compounds may be mentioned individually as oxidation catalysts:
Kupferkomplexverbindungen desCopper complex compounds of
1. 2-Aminoäthanols,1. 2-aminoethanol,
2. 1,2-Diaminoäthans,2. 1,2-diaminoethane,
3. 1,2-Diaminopropans,3. 1,2-diaminopropane,
Kobaltkomplexverbindungen desCobalt complex compounds of
4. Azomethins aus 1.2-Diaminoäthan + 2 Mol 2-Hydroxybenzaldehyd.4. Azomethine from 1,2-diaminoethane + 2 moles of 2-hydroxybenzaldehyde.
5. Azomethins aus 1,2-Diaminopropan + 2 Mol 2-Hydroxybenzaldehyd.5. Azomethine from 1,2-diaminopropane + 2 moles of 2-hydroxybenzaldehyde.
6. Azomethins aus 1,3-Diaminopropan6. Azomethine from 1,3-Diaminopropane
+ 2 Mol 2-Hydroxybenzaldehyd,+ 2 moles of 2-hydroxybenzaldehyde,
7. Azomethins aus 1,2-Diaminobenzol + 2 Mol 2-Hydroxybenzaldehyd,7. Azomethine from 1,2-diaminobenzene + 2 moles of 2-hydroxybenzaldehyde,
8. Azomethins aus l,2-Diamino-4-chlorbenzol + 2 Mol 2-Hydroxybenzaldehyd,8. Azomethine from 1,2-diamino-4-chlorobenzene + 2 moles of 2-hydroxybenzaldehyde,
9. Azomethins aus 1.2-Diaminobcnzol9. Azomethine from 1,2-diaminobenzene
+ 2MoI 2-Hydroxy-3,5-dichlorbenzaldehyd. 10. Azomethins aus l,2-Diamino-4-chlorbcnzol + 2 Mol 2-Hydroxy-3,5-dichlorbcn?.aldehyd.+ 2MoI 2-hydroxy-3,5-dichlorobenzaldehyde. 10. Azomethine from 1,2-diamino-4-chlorobenzene + 2 moles of 2-hydroxy-3,5-dichlorobenzene .aldehyde.
609 650/200609 650/200
11. Azomethins aus 1,2-Diaminoäthan11. Azomethine from 1,2-diaminoethane
+ 2 Mol 2-Hydroxy-5-nitrobenzaldehyd,+ 2 moles of 2-hydroxy-5-nitrobenzaldehyde,
12. Azomethins aus 1,2-Diaminoäthan12. Azomethine from 1,2-diaminoethane
+ 2 Mol 2-HydΓOxy-3-methoxybenzaldehyd,+ 2 moles of 2-Hydroxy-3-methoxybenzaldehyde,
13. Azomethins aus 1,2-Diaminoäthan13. Azomethine from 1,2-diaminoethane
+ 2 Mol 2-Hydroxy-3-äthoxybenzaldehyd,+ 2 moles of 2-hydroxy-3-ethoxybenzaldehyde,
14. Azomethins aus Bis-(3-aminopropyl)-amin
+ 2 Mol 2-Hydroxybenzaldehyd,14. Azomethines from bis (3-aminopropyl) amine
+ 2 moles of 2-hydroxybenzaldehyde,
15. Azomethins aus 1,2-Diaminobenzol15. Azomethine from 1,2-diaminobenzene
+ 2 Mol 2-Hydroxy-5-nitrobenzaldehyd,+ 2 moles of 2-hydroxy-5-nitrobenzaldehyde,
16. Azomethins aus 1,2-Diaminoäthan16. Azomethine from 1,2-diaminoethane
+ 2 Mol 2-Hydroxynaphthaldehyd-l,+ 2 moles of 2-hydroxynaphthaldehyde-1,
17. Azomethins aus 1,2-Diaminopropan
+ 2 Mol 2-Hydroxynaphthaldehyd-l,17. Azomethine from 1,2-Diaminopropane
+ 2 moles of 2-hydroxynaphthaldehyde-1,
18. Azomethins aus 1,2-Diaminobenzol18. Azomethine from 1,2-diaminobenzene
+ 2 Mol 2-Hydroxynaphthaldehyd-l,+ 2 moles of 2-hydroxynaphthaldehyde-1,
19. Azomethins aus l,2-Diamino-4-chlor-benzol
4- 2 Mol 2-Hydroxynaphthaldehyd-l,19. Azomethines from 1,2-diamino-4-chloro-benzene
4- 2 moles of 2-hydroxynaphthaldehyde-1,
20. Azomethins aus 1,2-Diaminobenzol
4- 2 Mol S-FormyM-methyl-S-cyan-2,6-dihydroxy-pyridin,
20. Azomethine from 1,2-diaminobenzene
4- 2 moles of S-FormyM-methyl-S-cyano-2,6-dihydroxypyridine,
21. Azomethins aus 1,2,4,5-Tetraminobenzol
+ 4 Mol 2-Hydroxybenzaldehyd,21. Azomethine from 1,2,4,5-tetraminobenzene
+ 4 moles of 2-hydroxybenzaldehyde,
22. Formazans aus Cyanessigsäure22. Formazans from cyanoacetic acid
4- 2 Mol Diazoverbindung von 4-Chlor- 25 Bei- Diphenyl-4- 2 moles of diazo compound of 4-chloro-25 bis-diphenyl
2-aminophenol-6-sulfosäure, spiel methan2-aminophenol-6-sulfonic acid, game methane
23. Tetraaza[14]annulens aus 1,2-Diaminobenzol23. Tetraaza [14] annulens from 1,2-diaminobenzene
+ Malondialdehyd, + Malondialdehyde,
24. Tetraaza[14]annulens aus l,2-Diamino-4-chlorbenzol 4- Malondialdehyd,24. Tetraaza [14] annulens from 1,2-diamino-4-chlorobenzene 4- malondialdehyde,
25. Phthalocyanins,25. phthalocyanine,
Eisenkomplexverbindungen desIron complex compounds of
26. Phthalocyanins (Fe"),26. phthalocyanine (Fe "),
Phthalocyanins (Fe1"), Hexadecachlor-phthalocyanins,
Phthalocyanin-tri(oder tetra)-sulfonsäure-(;< -dialkyiaminopropyl)-amids,
Hämatins,Phthalocyanine (Fe 1 "), hexadecachlorophthalocyanine,
Phthalocyanine tri (or tetra) sulfonic acid (; <-dialkyiaminopropyl) amides,
Hematins,
die Oxo-Vanadiumkomplexverbindung des Azo methins aus 1,2-Diaminoäthan + 2 Mol 2-Hy droxybenzaldehyd oderthe oxo-vanadium complex compound of azo methine from 1,2-diaminoethane + 2 moles of 2-Hy droxybenzaldehyde or
32. die Dioxo-Molybdänkomplexverbindung des
Azomethins aus 1,2-Diamino-äthan
4- 2 Mol 2-Hydroxybenzaldehyd.32. the dioxo-molybdenum complex compound des
Azomethines from 1,2-diaminoethane
4- 2 moles of 2-hydroxybenzaldehyde.
Technisch bevorzugt verwendet werden z. B. die Katalysatoren 4 bis 14, 23, 24, 26 oder 27.Technically preferred are z. B. the catalysts 4 to 14, 23, 24, 26 or 27.
Die Verbindungen der Formel 2 können als solche verwendet werden, sie können aber auch im Reaktionsgemisch aus den zugehörigen Ausgangsstoffen (z. B. Formaldehyd 4- Dialkylanilin) unter den erßndungsgemäßen Reaktionsbedingungen gebildet werden. The compounds of the formula 2 can be used as such, but they can also be used in the reaction mixture from the associated starting materials (e.g. formaldehyde 4-dialkylaniline) among those according to the invention Reaction conditions are formed.
Bezüglich aller weiteren Erläuterungen und Definitionen gelten die Angaben des Hauptpatents sinngemäß. With regard to all further explanations and definitions, the information in the main patent applies accordingly.
Gegenüber den aus den US-Patentschriften 16 94 057 und 25 42 544 bekannten katalytischen Verfahren zur Herstellung basischer Farbstoffe zeichnet sich das neue Verfahren durch sehr viel bessere Ausbeuten aus, es läßt sich zudem gegenüber herkömmlichen Methoden zur Herstellung basischer 6 desgl Farbstoffe in sehr umweltfreundlicher Weise durchführen. Compared to the catalytic processes known from US Patents 16 94 057 and 25 42 544 For the production of basic dyes, the new process is much better Yields from, it can also be compared to conventional methods for the production of basic 6 the same Perform dyes in a very environmentally friendly way.
In der US-Patentschrift 18 05 925 ist die Oxidation von Leukoverbindungen beschrieben, demgegenüber ermöglicht es das erfindungsgemäße Verfahren auf die oft aufwendige Herstellung der Lcukoverbindunger zu verzichten und statt dessen von leicht zugänglicher Ausgangsmaterialien auszugehen.In US Pat. No. 1,8 05,925, the oxidation of leuco compounds described, in contrast, it enables the method according to the invention to often to dispense with complex production of the Lcukoverbinder and instead of easily accessible Starting materials.
s B e i s ρ i e 1 1 s B eis ρ ie 1 1
Eine Mischung aus 254 Teilen 4,4'-Bisdimethyl aminodiphenylmethan, 121 Teilen Dimethylanilin lOTeilen Chloranil, lOTeilen des Komplexes Nr. 23 1480 Teilen Chloroform und 360 Teilen Eisessig werA mixture of 254 parts of 4,4'-bisdimethyl aminodiphenylmethane, 121 parts of dimethylaniline 10 parts of chloranil, 10 parts of complex no. 23 1480 parts of chloroform and 360 parts of glacial acetic acid
ίο den bei 50° C unter starkem Rühren in einer geschlosse nen Apparatur mit Sauerstoff behandelt. Die Sauer Stoffaufnahme kommt nach einem Verbrauch von 22,4 fast zum Erliegen. Aus der Reaktionsmischung win das Chloroform durch Abdestillieren entfernt. De Rückstand wird in 1200 Teilen Wasser bei 80 C ge löst, die Lösung wird filtriert und dann mit wenig konz Salzsäure versetzt. Nach Zugabe von konz. NaCl Lösung fällt der Farbstoff (Basic Violet 3) aus. Aus beute 343 g.ίο the at 50 ° C with vigorous stirring in a closed NEN apparatus treated with oxygen. The acidic substance uptake comes after a consumption of 22.4 almost to a standstill. The chloroform is removed from the reaction mixture by distillation. De The residue is dissolved in 1200 parts of water at 80 ° C., the solution is filtered and then treated with a little conc Hydrochloric acid added. After adding conc. NaCl solution precipitates the dye (Basic Violet 3). Out booty 343 g.
Auf gleiche Weise lassen sich folgende Diphenylme thane und Verbindungen der Formel 3 zu Triaryl methanfarbstoffen oxidieren.In the same way, the following Diphenylme thane and compounds of the formula 3 to triaryl oxidize methane dyes.
Verbindung der r-ormel 3Connection of the r-formula 3
2 4,4'-Bisdimethyl-
amino-2 4,4'-bisdimethyl-
amino
3 desgl.3 the same
--
4545
5050
5555
6060
4 desgl.4 the same.
Ausbeute yield
CH3 CH3 CH 3 CH 3
5 desgl.5 the same.
N CH3 XCH3 N CH 3 X CH 3
OC2H5 OC 2 H 5
1111th
Fortsetzungcontinuation
Bei- Diphenyl- Verbindung der Formel 3 spiel methanExample diphenyl compound of formula 3 play methane
7 4,4'-Bisdimethylamino- 7 4,4'-bisdimethylamino
8 desgl.8 the same.
9 desgl.9 the same.
10 desgl.10 the same.
11 desgl.11 the same.
12 desfel.12 desfel.
13 desgl. 13 the same.
NHCOCH3 NHCOCH 3
N CH3 CH3 N CH 3 CH 3
CO2HCO 2 H
/ \ CH3 CH3 / \ CH 3 CH 3
OC2H5 OC 2 H 5
Ν—Η Ν— Η
CH3 CH 3
N HOH4C2 C2H5 N HOH 4 C 2 C 2 H 5
spielat
game
methanDiphenyl
methane
C2H4OHN
C 2 H 4 OH
beuAu
beu
beuteOut
prey
methyl-
amino-4,4-bisdi
methyl-
amino
N
CH3 CH3 7th
N
CH 3 CH 3
30about
30th
16 desgl.16 the same
3535
17 desgl.17 the same.
4545
18 desgl.18 the same.
19 desgl.19 the same.
5555
6o6o
20 desgl.20 the same
N-CH3 N-CH 3
N-CH3 CH,N-CH 3 CH,
Λ/\Λ / \
NHNH
CH,CH,
/\ /N-CH3 O N / \ / N-CH 3 ON
PhPh
Fortsetzungcontinuation
Bei- Diphcnylspiel methanExample of a diphenyl game methane
1313th
Verbindung der FormetConnection of the Formet
22 desgl.22 the same.
23 desgl.23 the same
24 desel.24 desel.
25 desgl.25 the same.
CH,CH,
/γ/ γ
! H ! H! H ! H
\ ί: Η H3C H \ ί: Η H 3 CH
<i<i
1414th
bculeOut-
bcule
spielat
game
methanDiphenyl
methane
beul
1%)Out
dent
1%)
in30th
in
cyaniithyl-
meihyl-
amino-4.4'-to-
cyanithyl
meihyl-
amino
CH3 CH3 0
CH 3 CH 3
desgl.the same
3535
N C2H5 V1H5 N C 2 H 5 V 1 H 5
C2H5 C2H5 C 2 H 5 C 2 H 5
CH3 CH 3
26 4.4'-Bisdiäthylamino- 26 4.4'-bisdiethylamino
27 desgl.27 the same.
28 desel.28 desel.
29 des«!.29 of the «!.
N CH,N CH,
C2H5 HC 2 H 5 H
ü H ü H
H5C2OH 5 C 2 O
Ersetzt man im Beispiel 1 den Komplex Nr. durch andere Komplexverbindungen, so erhält nfolgende Ausbeuten:If complex no. Is replaced by other complex compounds in Example 1, the following is obtained Exploit:
Komplex-Nr.Complex no.
4545
>
6
7
8
9
10
H
12
13
14
15
16
17
18
19
20 >
6th
7th
8th
9
10
H
12th
13th
14th
15th
16
17th
18th
19th
20th
5555
6060
Ausbeute 1%)Yield 1%)
31 91 89 88 92 91 90 86 85 90 92 84 87 81 79 88 87 8531 91 89 88 92 91 90 86 85 90 92 84 87 81 79 88 87 85
Beispiel example
3838
Anilinaniline
C2H5 CH2-C 2 H 5 CH 2 -
Ausbeute yield
6868
IOIO
Eine Mischung aus 254 Teilen 4,4'-Bisdimethylamino-diphenylmethan, 121 Teilen Dimethylanilin, 5 Teilen Chloranil, 5 Teilen des Komplexes Nr. 23, 25 Teilen Spermölalkohol kondensiert mit 20 Mol Äthylenoxid, 20 Teilen Triisobutylphosphat, 175 Teilen Eisessig und 700 Teilen Wasser wird 8 Stunden in einer Umlaufapparatur durch eine Begasungsdüse bei 50 C mit Luft behandeil. Zu der Reaktionslösung gibt man anschließend 1500 Teile Wasser, erhitzt auf 80 C, filtriert ab, setzt etwas konz. Salzsäure zu und fällt den Farbstoff durch Zugabe von konz. NaCl-Losung. Ausbeute 377 Teile Farbstoff.A mixture of 254 parts of 4,4'-bisdimethylamino-diphenylmethane, 121 parts of dimethylaniline, 5 parts of chloranil, 5 parts of complex No. 23, 25 parts of sperm oil alcohol condensed with 20 moles Ethylene oxide, 20 parts of triisobutyl phosphate, 175 parts of glacial acetic acid and 700 parts of water is 8 hours in a circulating apparatus through a gas injection nozzle at 50 C with air. To the reaction solution then 1500 parts of water are added, the mixture is heated to 80 ° C., filtered off, and a little conc. Hydrochloric acid to and the dye falls by adding conc. NaCl solution. Yield 377 parts of dye.
3939
CH3 CH3 CH 3 CH 3
H CH, 71H CH, 71
ί Ίί Ί
2: 12: 1
Beispiel 35 ^0 Example 35 ^ 0
Eine Mischung aus 447 Teilen Diäthylanilin, 30 Teilen Paraformaldehyd, 10 Teilen Chloranil, 10 Teilen des Komplexes Nr. 4, 500 Teilen Eisessig und 1500 Teilen Äthylenchlorid wird bei 50 C unter heftigem Ruhren mit Luft begast. Nach 7 Stunden wird das Äthylenchlorid durch Destillation entfernt, der Rückstand in 1500 Teilen Wasser bei 80 C gelöst, die Lösung abfiltricrt. zum Filtrat etwas konz. Salzsäure zugegeben und der Farbstoff (CI. Basic Violet 4) mit konz. NaCl-Lösung gefällt. Ausbeute 377 Teile Farbstoff.A mixture of 447 parts of diethylaniline, 30 parts of paraformaldehyde, 10 parts of chloranil, 10 parts of complex No. 4, 500 parts of glacial acetic acid and 1500 parts Ethylene chloride is gassed with air at 50 C with vigorous stirring. After 7 hours the ethylene chloride is removed by distillation, the residue dissolved in 1500 parts of water at 80 ° C., the solution filtered off. slightly conc. to the filtrate. Hydrochloric acid was added and the dye (CI. Basic Violet 4) with conc. NaCl solution precipitated. Yield 377 parts of dye.
Auf gleiche Weise lassen sich folgende Aniline zu Triphenylmcthanfarbstoffen umsetzen:The following anilines can be converted into triphenyl methane dyes in the same way:
Beispiel example
Anilinaniline
CHj CH,CHj CH,
CH, C2H4CNCH, C 2 H 4 CN
Eine Mischung aus 254 Teilen N.N'-Bisdimethylamino-diphenylmethan, 121 Teilen Dimethylanilin, 10 Teilen Bromanil, 10 Teilen des Komplexes Nr. 27 aufgebracht auf Aktivkohle (Gewichtsverhältnis 1:1). 1480 Teilen Äthanol und 360 Teilen Propionsäure wird bei 50 C unter starkem Rühren in einer geschlossenen Apparatur mit Sauerstoff behandelt. Die Sauerstoffaufnahme kommt nach einem Verbrauch von 22 1 fast zum Erliegen. Durch Abdeslillieren wird das Äthanol von der Reaktionsmischung entfernt, der Rückstand wird in 1200 Teilen Wasser gelöst, die Lösung abfiltriert, mit etwas konz. Salzsäure versetzt und der Farbstoff durch Zugabe von konz. NaCl-Lösung ausgefällt. A mixture of 254 parts of N.N'-bisdimethylamino-diphenylmethane, 121 parts of dimethylaniline, 10 parts of bromanil, 10 parts of complex no. 27 applied to activated carbon (weight ratio 1: 1). 1480 parts of ethanol and 360 parts of propionic acid are closed at 50 C with vigorous stirring Apparatus treated with oxygen. The oxygen uptake comes after a consumption of 22 1 almost to a standstill. The ethanol is removed from the reaction mixture by distilling off, the residue is dissolved in 1200 parts of water, the solution is filtered off, with a little conc. Hydrochloric acid added and the Dye by adding conc. NaCl solution precipitated.
Ausbeute: 337 Teile.Yield: 337 parts.
Eine Mischung aus 254 Teilen N.N'-Bisdimethylamino-diphenylmethan. 121 Teilen Dimethylanilin. 10 Teilen Tetrachlorhydrochinon, 10 Teilen des Kondensationsproduktes aus 1 Mol o-Phenylendiamin mit 2 Mol Salicylaldchyd. 5 Teilen Co-Acctat. 2000 Tei-Auslen Äthylcnchlorid und 172 Teilen p-Toluolsulfon-A mixture of 254 parts of N.N'-bisdimethylamino-diphenylmethane. 121 parts of dimethylaniline. 10 parts of tetrachlorohydroquinone, 10 parts of the condensation product from 1 mole of o-phenylenediamine with 2 moles of salicylaldehyde. 5 parts of Co-acetate. 2000 Part-Auslen Ethyl chloride and 172 parts of p-toluenesulfone
hculc säure wird unter starkem Rühren 8 Stunden mil Luft Hculc acid is heated in air for 8 hours with vigorous stirring
Col 50 begast. Nach der Aufarbeitung gemäß Beispiel 1 erhält man 349 Teile Farbstoff.Col 50 fumigated. Obtained after work-up according to Example 1 349 parts of dye.
291 Teile N-Äthyl-N-benzylanilin-3-sulfonsäure werden in 1600 Teilen Wasser in wenig konz. Natronlauge gelöst. Man fügt dann 25 Teile des Anlagerungsproduktes aus 1 Mol Spermölalkohol und 20MoI Äthylenoxid sowie 25 Teile Triisobutylphosphat hinzu und anschließend eine Mischung aus 254 Teilen 4.4-Bis-dimethylamino-diphenylmethan. 400 Teilen Eisessig, 10 Teilen Chloranil und 10 Teilen des Komplexes Nr. 23. Die Reaklionsmischung wird bei 50 C 12 Stunden mit Luft begast. anschließend mil 2000 Teilen Wasser versetzt, auf 90 C erhil/l und nitriert. Der Farbstoff wird dann mit kon/. NaCl-Lösung gefälll. Ausbeute: 249 Teile.291 parts of N-ethyl-N-benzylaniline-3-sulfonic acid are concentrated in 1600 parts of water in a little. Sodium hydroxide solution dissolved. 25 parts of the adduct of 1 mol of sperm oil alcohol and 20 mol are then added Ethylene oxide and 25 parts of triisobutyl phosphate are added and then a mixture of 254 parts 4,4-bis-dimethylamino-diphenylmethane. 400 parts of glacial acetic acid, 10 parts of chloranil and 10 parts of the complex No. 23. The reaction mixture is gassed with air at 50 ° C. for 12 hours. then with 2000 parts Water added, erhil to 90 C / l and nitrated. the Dye is then used with kon /. NaCl solution fallen. Yield: 249 parts.
Claims (1)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE787210D BE787210A (en) | 1971-08-04 | PROCESS FOR THE CATALYTIC OXIDATION OF DI- AND TRI- (HETERO) -ARYL-METHANE COMPOUNDS | |
DE19712152703 DE2152703C3 (en) | 1971-10-22 | Process for the production of basic dyes by catalytic oxidation | |
CH1101272A CH585241A5 (en) | 1971-08-04 | 1972-07-24 | |
RO71776A RO61288A (en) | 1971-08-04 | 1972-07-28 | |
US00276108A US3828071A (en) | 1971-08-04 | 1972-07-28 | Catalytic oxidation of arylmethane compounds |
IT51940/72A IT965960B (en) | 1971-08-04 | 1972-08-02 | PROCEDURE FOR THE CATALYTIC OXIDATION OF COMPOUNDS OF AND TRI HETERO ARYLMETHANES |
SU1817941A SU530650A3 (en) | 1971-08-04 | 1972-08-02 | The method of obtaining di - or triarylmethane dyes |
DD164844A DD101176A5 (en) | 1971-08-04 | 1972-08-03 | |
JP7733472A JPS556665B2 (en) | 1971-08-04 | 1972-08-03 | |
GB3627872A GB1395627A (en) | 1971-08-04 | 1972-08-03 | Catalytic oxidation of di-arylmethane and tri-arylmethane compounds |
FR7228265A FR2149917A5 (en) | 1971-08-04 | 1972-08-04 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19712152703 DE2152703C3 (en) | 1971-10-22 | Process for the production of basic dyes by catalytic oxidation |
Publications (3)
Publication Number | Publication Date |
---|---|
DE2152703A1 DE2152703A1 (en) | 1973-04-26 |
DE2152703B2 DE2152703B2 (en) | 1975-11-20 |
DE2152703C3 true DE2152703C3 (en) | 1976-12-09 |
Family
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