CN1101060A - Preparation of Di- or triarylmethane dyes by oxidation - Google Patents
Preparation of Di- or triarylmethane dyes by oxidation Download PDFInfo
- Publication number
- CN1101060A CN1101060A CN93114187A CN93114187A CN1101060A CN 1101060 A CN1101060 A CN 1101060A CN 93114187 A CN93114187 A CN 93114187A CN 93114187 A CN93114187 A CN 93114187A CN 1101060 A CN1101060 A CN 1101060A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- hydrogen
- alkyl
- hydrogen peroxide
- group
- 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.)
- Granted
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000001003 triarylmethane dye Substances 0.000 title description 6
- 230000003647 oxidation Effects 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 title description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 150000004303 annulenes Chemical class 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 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 claims abstract description 6
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 5
- 150000001538 azepines Chemical class 0.000 claims description 19
- 239000000975 dye Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical class 0.000 claims description 8
- 230000000536 complexating effect Effects 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical group 0.000 claims description 6
- 150000002432 hydroperoxides Chemical class 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 abstract 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 abstract 1
- 239000001001 arylmethane dye Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- -1 hydroxyl sulfonyl-phenyl Chemical group 0.000 description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- SLXQRAMAAPBUQJ-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid;magnesium;hexahydrate Chemical compound O.O.O.O.O.O.[Mg].OOC(=O)C1=CC=CC=C1C(O)=O SLXQRAMAAPBUQJ-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical group CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- ZYHQGITXIJDDKC-UHFFFAOYSA-N 2-[2-(2-aminophenyl)ethyl]aniline Chemical compound NC1=CC=CC=C1CCC1=CC=CC=C1N ZYHQGITXIJDDKC-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- XWPSVCZJPUMSMF-UHFFFAOYSA-N C(C(=O)O)(=O)O.NCC(O)C(=O)O Chemical compound C(C(=O)O)(=O)O.NCC(O)C(=O)O XWPSVCZJPUMSMF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RYQWRHUSMUEYST-UHFFFAOYSA-N [14]annulene Chemical compound C1=CC=CC=CC=CC=CC=CC=C1 RYQWRHUSMUEYST-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FBDWCTWJJMORIU-UHFFFAOYSA-N magnesium;hexahydrate Chemical class O.O.O.O.O.O.[Mg] FBDWCTWJJMORIU-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010572 single replacement reaction Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
- C09B11/18—Preparation by oxidation
Abstract
The method for preparation of 2 or 3 aryl-methane dye is that the 2 or 3 aryl-methane oxidizing reaction is conducted under the existence of attenuant and oxygen transfusion catalyst containing complexed heavy metal ion. Said method includs using hydrogen peroxide, hydrogen peroxide donor compound, organo-hydrogen peroxide or percarboxylic acid as oxidant and using one of the group of porphyrin, tetrahetero annulene, phthalocyanine or tetraheterocycle tetradecane as oxygen transfusion catalyst.
Description
The present invention relates at thinner and contain in the presence of the oxygen transfer catalyst of heavy metal ion of complexing, by two or the oxidizing reaction of triarylmethane prepare two or the novel method of triarylmethane dye.
JP-A-74530/1978 discloses at mantoquita for example in the presence of copper sulfate (II) or the cupric chloride, prepares triarylmethane dye with the oxidizing reaction of triarylmethane and hydrogen peroxide.In addition, JP-A-57848/1981 disclose with hydrogen peroxide, chloranil, and metallic compound for example cupric bromide (I) or vanadium pentoxide carry out the method for oxidizing reaction.
According to the embodiment of JP-A-57848/1981, in the presence of iron(ic) chloride (II), manganous sulfate (II) and ethylenediamine tetraacetic acid (EDTA), triarylmethane that contains carbonyl and oxygen generation oxidizing reaction as oxygenant generate 2-benzo [C] furanone.
At last, EP-A-3005397 discloses in the presence of the azoic dyestuff cobalt complex, by make corresponding diarylmethanes generation oxygenizement with hydrogen peroxide, prepares 3, two (4-the dimethylamino phenyl)-6-dimethylaminos of 3--2-benzo [C] furanone.
The method for making that has been found that prior art still has shortcoming, and for example, the method for making of being mentioned is not all to be suitable for for preparation two or triarylmethane dye.
An object of the present invention is to provide the novel method of a kind of preparation two or triarylmethane dye, it is from corresponding two or triarylmethane, and carries out in the presence of the oxygen-transferance catalyzer of the heavy metal ion that contains complexing.This novel method will generate the purpose product with high yield and purity in simple mode.
We have found that purpose of the present invention is carried out a kind of method that oxidation prepares the dyestuff of formula I by the leucocompound with the general formula II and reached,
In the formula, R
1, R
2, R
3And R
4Be C independently of each other
1The alkyl of-C, this alkyl can be substituted and can form insert phenyl or C with the ether official with 1 to 3 Sauerstoffatom
1-C
4Alkyl phenyl.
R
5And R
6Be hydrogen or methyl independently of each other,
X is hydrogen, replaces or unsubstituted phenyl, or has replaced or unsubstituted naphthyl, and An
Be anionic equivalent,
R wherein
1, R
2, R
3, R
4, R
5, R
6And X each all as defined above.Oxygenizement thinner and contain complexing heavy metal ion the oxygen transfer catalyst in the presence of carry out.This method for making comprises uses hydrogen peroxide, hydrogen peroxide donor compound, organic hydroperoxide or percarboxylic acids as oxygenant with use a member in porphyrin, four azepines [14] (big ring) annulene, phthalocyanine or this group of tetraazacyclododecane decane as the oxygen transfer catalyst.
Any alkyl that appears in formula I and the II can be a straight or branched.
Any alkyl that has replaced that occurs in above-mentioned formula I and II contains following general formula base, for example hydroxyl, chlorine, cyano group, phenyl or hydroxyl sulfonyl-phenyl.
Any substituted-phenyl that occurs in above-mentioned formula I and II can contain following substituting group, methyl for example, chlorine, amino, C
1-C
4-alkylamino, or dialkyl amido, one or diphenyl amino, hydroxyl, C
1-C
4-alkoxyl group or hydroxyl alkylsulfonyl.
Any naphthyl that has replaced that occurs in above-mentioned formula I and II can contain following substituting group, and is for example amino, C
1-C
4-list or dialkyl amido, one or diphenyl amino, or the hydroxyl alkylsulfonyl.
Any alkyl that has replaced that occurs in above-mentioned general formula, phenyl or naphthyl generally is mono-substituted, dibasic or trisubstituted, preferred single replacement or dibasic.
Suitable R
1, R
2, R
3, R
4Group is a methyl for example, ethyl, propyl group; sec.-propyl, butyl, isobutyl-; the second month in a season-butyl, amyl group, isopentyl; neo-pentyl, uncle-amyl group, hexyl; heptyl, octyl group, 2-ethylhexyl; the 2-hydroxyethyl, 2-or 3-hydroxypropyl, 2 or the 4-hydroxybutyl; 2-chloro ethyl, 2-or 3-chloro propyl group, 2-or 4-chloro butyl; the 2-cyano ethyl, 2-or 3-cyano group propyl group, 2-or 4-cyano group butyl; benzyl, 1-or 2-phenylethyl, hydroxyl Sulphonylbenzyl; hydroxyl alkylsulfonyl phenylethyl, 2-methoxy ethyl, 2-ethoxyethyl group; 2-or 3-methoxy-propyl, 2-or 3-ethoxycarbonyl propyl, 2-or 4-methoxyl group butyl; 2-or 4-oxyethyl group butyl, 3,6-Er Evil heptyl; 3,6-Er Evil octyl group, 4; 8-Er Evil nonyl, 3,7-Er Evil octyl group; 3,7-Er Evil nonyl, 4; 7-Er Evil octyl group, 4,7-Er Evil nonyl; 4,8-Er Evil decyl, 5-hydroxyl-3-oxa-amyl group; 5-hydroxyl-1,4 dimethyl-3-oxa-amyl group, 8-hydroxyl-3; 6-Er Evil octyl group or 11-hydroxyl-3,6,9-trioxa undecyl phenyl; 1-, 2-or 3-aminomethyl phenyl or 1-, 2-or 3-ethylphenyl.
Suitable X is a phenyl for example; 2-, 3-or 4-aminomethyl phenyl, 2,4-3,5-dimethylphenyl; 2-, 3-or 4-chlorophenyl, 2,4-or 2; 6-dichloro-phenyl, 2-, 3-, or 4-aminophenyl; 2-, 3-or 4-one or dimethylaminophenyl, 2-; 3-, or 4-one or diphenyl amino phenyl, 2-; 3-or 4-hydroxy phenyl, 2-, 3-or 4-p-methoxy-phenyl; 2,4-Dimethoxyphenyl, 2-; 3-, or 4-hydroxyl alkylsulfonyl phenyl, 2; 4-sulfonyldioxy phenyl, 2,4-sulfonyldioxy-5-hydroxy phenyl; amino naphthyl, one or the dimethylamino naphthyl, one or diphenyl amino naphthyl or hydroxyl alkylsulfonyl naphthyl.
Suitable negatively charged ion is for example fluorine, chlorine, bromine, iodine, bisulfate ion, sulfate radical, tetrafluoro is for borate, formate, acetate moiety, propionate, one, two, or three chloro acetate moietys, lactate, methoxyacetic acid root, citrate, amber acid radical, methylsulphonic acid root, Phenylsulfonic acid root and 2-or 4-toluene sulfonic acide root.
When the dyestuff of formula I has the hydroxyl alkylsulfonyl, and be form with salt when existing, suitable counter ion is metal or ammonium ion.Metal ion is lithium, sodium or potassium ion particularly.Ammonium ion for the object of the invention, or that replaced or unsubstituted ammonium cation, the ammonium cation that has replaced be for example-alkyl-, dialkyl group-, trialkyl-, tetraalkyl or benzyl trialkyl ammonium positively charged ion, or by nitrogenous five or the resulting positively charged ion of hexa-atomic saturated heterocyclic compound, tetramethyleneimine for example, piperidines, morpholine, piperazine or N-alkylpiperazine positively charged ion or their N-monoalkyl or N, N-dialkyl group substitution product.Alkyl herein is interpreted as general straight or branched C
1-C
20Alkyl.They can be replaced by hydroxyl, and/or form ether functional group with the Sauerstoffatom insertion.
Sodium and potassium ion are preferred.
R wherein preferably
5And R
6Each is the preparation method of hydrogen, formula I dyestuff.
The preferred R that also has wherein
1, R
2, R
3, and R
4Each is to have replaced or unsubstituted C
1-C
4The C that-alkyl, particularly hydroxyl or hydroxyl alkylsulfonyl phenyl replace
1-C
4The preparation method of the formula I dyestuff of-alkyl.
Particularly preferably be wherein X and be hydrogen or replaced or the preparation method of the formula I dyestuff of the phenyl that unsubstituted phenyl, particularly chloro-or hydroxyl alkylsulfonyl replace.
The particularly preferred R that also has wherein
1, R
2, R
3And R
4Each is C
1-C
4-alkyl, C
2-C
4The preparation method of the formula I dyestuff of-hydroxyalkyl or hydroxyl Sulphonylbenzyl.
That should be mentioned that especially is R in the formula I
1And R
3Every kind is ethyl, R
2And R
4Every kind is the hydroxyl Sulphonylbenzyl, R
5And R
6Every kind is hydrogen, and X is the preparation method of the dyestuff of the phenyl that replaces of hydroxyl alkylsulfonyl.
That should be mentioned that especially is R in the formula I
1And R
3Every kind is ethyl, R
2And R
4Every kind is the hydroxyl Sulphonylbenzyl, R
5And R
6Every kind is hydrogen, and X is the preparation method of the dyestuff of the phenyl that replaces of hydroxyl alkylsulfonyl.
Shifting oxygen and containing the suitable catalyzer of complexation heavy metal ion is a member in porphyrin, four azepines [14] annulene, phthalocyanine pigment or this group of tetraazacycloalkane for example.
This heavy metal ion of complexing obtain by for example iron, manganese, cobalt or chromium, this heavy metal ion generally is 2-or 3-valency.
This compounds is early known, and is described in for example DE-A-2427606, WO-A-91/01985, and Kontakte 1985,38, or Chem.Lett.1991, in 1217.
They are consistent with for example following general formula:
Porphyrin:
P
1=hydrogen, methyl, ethyl, chlorine, or bromine
P
2, P
3, P
4, P
5=hydrogen, methyl, hydroxyl alkylsulfonyl or C
1-C
4-alkoxyl group
M=iron, manganese, cobalt or chromium.
Four azepines [14] (big ring) annulene:
L
1=hydrogen, C
1-C
8-alkyl, chlorine, C
1-C
4-alkoxyl group, replace or unsubstituted phenyl, replace or unsubstituted phenylazo C
1-C
4-alkoxyl group hydroxyl, or unsubstituted or use C
1-C
4Alkyl, hydroxyl, C
1-C
4The pyridine that-alkoxyl group hydroxyl or formamyl replace.
L
2, L
3=hydrogen, methyl, perhaps L
2And L
3Simultaneously=condensed benzo ring M=iron, manganese, cobalt or chromium
Phthalocyanine (dyestuff):
Q
1, Q
2=C
1-C
4-alkyl, chlorine, bromine, C
1-C
4-alkoxyl group, or Q
1And Q
2Together=a kind of condensed benzo ring
M=iron, manganese, cobalt or chromium
Tetraazacyclododecane four decane:
An
=a kind of anionic equivalent
M=iron, manganese, cobalt or chromium
Preferably use four azepines [14] (big ring) annulene or phthalocyanine pigment class as catalyzer.
Preferred also have use to contain the catalyzer of chelated iron ion.
Particularly preferred iron four azepines [14] (big ring) annulene or the iron-phthalocyanine (dyestuff) of being to use is as catalyzer.
Very particularly preferably be to use iron-5,14-dihydro-dibenzo [b, i] [5,9,14,18] four azepines [14]-(big ring) annulene or iron-phthalocyanine (dyestuff) are as catalyzer.
This catalyzer can use in solution equably or heterogeneously.Equally, they can be fixed on solid support material for example on silica gel or the ion exchange resin.
The oxygenant of Shi Yonging is a hydrogen peroxide in the methods of the invention, hydrogen peroxide donor compound, organic hydroperoxide or percarboxylic acids.
The hydrogen peroxide donor compound that is suitable for is for example alkali metal perborate or percarbonate.
The organic hydroperoxide that is suitable for is for example cumene hydroperoxide or alkyl hydroperoxide, particularly tertbutyl peroxide.
The percarboxylic acids that is suitable for is a peracetic acid for example, m-chloro benzoic acid, and two (monoperoxyphthalic acid) magnesium hexahydrate, and 1,12-12 diperacids.
It is preferred using hydrogen peroxide, tertbutyl peroxide or two (monoperoxyphthalic acid) magnesium hexahydrate.
If use hydrogen peroxide, generally be to use with the aqueous solution form of 10-70% weight concentration as oxygenant.
Organic hydroperoxide generally is to use with the form of about 70% weight concentration aqueous solution.
Two (monoperoxyphthalic acid) magnesium hexahydrate can use by solid form, as the aqueous solution or as aq suspension.
In some cases, this method for making is preferably in the compound that also has in addition a small amount of (calculate with the leucocompound II, generally be for up to 2 moles of %) can stablize this oxygenant carries out under existing, and this compound is an ethylenediamine tetraacetic acid (EDTA) for example, diethylenetriamine pentaacetic acid, nitrilotriacetic acid(NTA), β-An Jibingsuan oxalic acid, isoserine oxalic acid, ethylenediamine tetraacetic (methylene phosphonic acid), hexamethylene-diamine four (methylene phosphonic acid), Diethylenetriamine five (methylene phosphonic acid) or its alkaline metal salt, trimethylacetic acid, right-toluenesulphonic acids, water glass, acetate, Sodium Fluoride, cyanamide or xitix and/or certain nitrogenous aromatic heterocycle, imidazoles for example, the N-Methylimidazole, pyridine, pyrazoles, the pyrroles, or 1,3, the 4-triazole.
Leucocompound with respect to every mole of general formula III, the consumption of this oxygenant generally is by 1 to 5 mole, preferably by 1.5 to 4 moles, special preferably by 1.5 to 2.5 moles hydrogen peroxide, by 0.9 to 3 mole, be preferably by 1 to 2 mole, be preferably organic hydroperoxide especially by 1 to 1.5 mole, perhaps by 0.9 to 3 mole, preferred 1 to 2 mole percarboxylic acids (in each case, all be as the criterion calculate) with the peroxycarboxylic acidic group.
The general consumption of oxygen conveying person catalyzer that contains the heavy metal ion of complexing is to be that benchmark calculates by 1 to 3 mole of each percentage number average of % with the leucocompound II preferably by 0.1 to 5 mole of %.
Suitable thinner is a water for example, Glacial acetic acid, and chloroform, toluene, N, dinethylformamide, N-Methyl pyrrolidone, alcohols is methyl alcohol for example, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, di-alcohols is ethylene glycol for example, propylene glycol or its mixture.
Preferably make water, or water and Glacial acetic acid, the mixture of alcohols or di-alcohols.
Making water is particularly preferred as thinner.
Two-phase mixture for example by water and difficult and the miscible resulting mixture of solvent of water, also can provide with phase-transfer catalyst.The phase transition catalyzer that is suitable for is known commerical prod itself, as quaternary alkylammonium halides, or benzyl trialkyl ammonium halide, or hydrosulfate.
This novel method for making generally is under barometric point and at 20 to 100 ℃, preferably carries out under 40 to 90 ℃.It not only can carry out continuously, and may be carried out batchwise.
The method for making that this is novel is preferably undertaken by leucocompound II and thinner are added as initial admixture, and general, the weight ratio of leucocompound II and thinner is by 1: 10 to 2: 1, is preferably 3: 7 to 3.2.Add catalyzer then, subsequently, under thoroughly stirring, oxygenant or its aqueous solution are metered in the mixture.Then, under said temperature, oxidizing reaction takes place under agitation.
After oxygenant adds, this reaction generally promptly is through with, the temperature of reaction mixture is risen to 20-80 ℃, and restir 10-120 minute thereupon, isolate target product according to common mode then, for example, remove and desolvate to doing, or saltout with sodium sulfate, and if necessary, once more dissolving and again carry out reprecipitation.
Method for making of the present invention be simple, and can obtain high yield and highly purified general formula II dyestuff.In addition, the superior part of this novel method for making is that also oxygenant does not contain heavy metal, and the reaction times is short.
The dyestuff of this formula I is applicable to paper is dyeed and the environmental health protection.
The present invention will do more detailed explanation in the mode of embodiment.
Embodiment 1
To the 96.3g(50 mmole) 40% weight concentration 4; 4 " in the aqueous solution of two [N-ethyl-N-(3-hydroxyl Sulphonylbenzyl) amino] triphenyl methane-2-sulfonate sodium; add the 0.34g(1 mmole) iron-5; 14-dihydro-dibenzo [b; i] [5; 9; 14; 18] four azepines [14] (big ring) annulene, the 0.44g(1 mmole) ethylenediamine tetraacetic (methylene phosphonic acid) and 0.08g(1 mmole) the N-Methylimidazole, then; under vigorous stirring; under 80 ℃, in 25 minutes, drip the 11.4g(100 mmole) the aqueous hydrogen peroxide solution of 30% weight concentration.Reaction mixture is cooled to after 60 ℃,, filters then solution restir 1 hour.Filtrate is adjusted to PH4 with sodium hydroxide solution.Remove and anhydrate, dry thereupon, obtain the 43.5g dyestuff.
Embodiment 2
To the 96.3g(50 mmole) 40% weight concentration 4 '; 4 " in two [N-ethyl-N-(3-hydroxyl Sulphonylbenzyl) amino] triphenyl methane-2-sulfonate sodium aqueous solution; add the 0.34g(1 mmole) iron-5; 14-dihydro-dibenzo [b; i] [5; 9; 14,18] four azepines [14] (big ring) annulene, 0.28g(1 mmole) ethylenediamine tetraacetic acid (EDTA) and 0.08g(1 mmole) the N-Methylimidazole; then; at 40 ℃, in 25 minutes, under vigorous stirring; drip the 9.66g(75 mmole) tertbutyl peroxide (70% weight concentration, the aqueous solution).Reaction mixture 40 ℃ of following restir 1 hour, is filtered then.This solution is adjusted to PH4 with sodium hydroxide solution, removes and anhydrates, and is dry then, obtains the dyestuff of 45.3g.
Embodiment 3
To the 96.3g(50 mmole) 40% weight concentration 4 '; 4 " in two [N-ethyl-N-(3-hydroxyl Sulphonylbenzyl) amino] triphenyl methane-2-sulfonate sodium aqueous solution; add the 0.34g(1 mmole) iron-5; 14-dihydro-dibenzo [b; i] [5; 9; 14; 18] four azepines [14] (big ring) annulene; then, at 90 ℃, in 25 minutes; under vigorous stirring, drip the 24.19g(45 mmole in 200ml water) the solution of two (a peroxidation phthalic acid) magnesium hexahydrates (85% weight concentration).Reaction mixture is cooled to after 60 ℃, and restir 1 hour filters then.Add sodium sulfate to salt out dyestuff.Isolate precipitation while hot from water, dye-resin is dissolved in the water, this solution is adjusted to PH4 with sodium hydroxide solution, remove and to anhydrate, dry thereupon, obtain the salt dyestuff that contains of 52.8g.
The method for making of previous embodiment also can be used for the following leucocompound of oxidation general formula.
Claims (5)
1, a kind of method for preparing the formula I dyestuff
In the formula, R
1, R
2, R
3And R
4Be C independently of each other
1-C
8Alkyl, this alkyl can be substituted and can insert with 1 to 3 Sauerstoffatom becomes ether functional group, phenyl or C
1-C
4Alkyl phenyl,
R
5And R
6Be hydrogen or methyl independently of each other,
X is hydrogen, replaces or unsubstituted phenyl, or has replaced or unsubstituted naphthyl, and
An
-Be the negatively charged ion equivalent,
In this method for making, be the R with wherein
1, R
2, R
3, R
4, R
5, R
6And each of X is all as the leucocompound of above-mentioned defined general formula II
Thinner and contain complexing heavy metal ion the oxygen transfer catalyst in the presence of, carry out oxidizing reaction, it comprises uses hydrogen peroxide, hydrogen peroxide donor compound, organic hydroperoxide or percarboxylic acids as oxygenant with use a member in porphyrin, four azepines [14] (big ring) annulene, phthalocyanine pigment or this group of tetraazacyclododecane decane as the oxygen transfer catalyst.
2, a kind of method for making according to claim 1, wherein, R
5And R
6Every kind is hydrogen.
3, a kind of method for making according to claim 1, wherein, R
1, R
2, R
3And R
4Every kind is to have replaced or unsubstituted alkyl.
4, a kind of method for making according to claim 1, wherein, X is a hydrogen, or has replaced or unsubstituted phenyl.
5, a kind of method for making according to claim 1, wherein, the heavy metal ion of complexing is obtained by iron, manganese, cobalt or chromium in the oxygen transfer catalyst.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4211783A DE4211783A1 (en) | 1992-04-08 | 1992-04-08 | Process for the preparation of di- or triarylmethane dyes by oxidation |
| EP93105082A EP0568806B1 (en) | 1992-04-08 | 1993-03-27 | Method for producing diarylmethane or triarylmethane dyestuffs by oxidation |
| DE59306714T DE59306714D1 (en) | 1992-04-08 | 1993-03-27 | Process for the preparation of di- or triarylmethane dyes by oxidation |
| JP5080597A JPH0625544A (en) | 1992-04-08 | 1993-04-07 | Production of di- and triarylmethane dye |
| CN93114187A CN1047605C (en) | 1992-04-08 | 1993-09-27 | Preparation of Di- or triarylmethane dyes by oxidation |
| US08/615,065 US5659053A (en) | 1992-04-08 | 1996-03-13 | Preparation of Di- or triarylmethane dyes by oxidation |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4211783A DE4211783A1 (en) | 1992-04-08 | 1992-04-08 | Process for the preparation of di- or triarylmethane dyes by oxidation |
| CN93114187A CN1047605C (en) | 1992-04-08 | 1993-09-27 | Preparation of Di- or triarylmethane dyes by oxidation |
| US08/615,065 US5659053A (en) | 1992-04-08 | 1996-03-13 | Preparation of Di- or triarylmethane dyes by oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1101060A true CN1101060A (en) | 1995-04-05 |
| CN1047605C CN1047605C (en) | 1999-12-22 |
Family
ID=27179048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93114187A Expired - Fee Related CN1047605C (en) | 1992-04-08 | 1993-09-27 | Preparation of Di- or triarylmethane dyes by oxidation |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0625544A (en) |
| CN (1) | CN1047605C (en) |
| DE (1) | DE4211783A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111170A (en) * | 2019-06-21 | 2020-12-22 | 上海泰初化工技术有限公司 | Preparation method of triarylmethane color development material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6501689B2 (en) * | 2015-10-01 | 2019-04-17 | 公立大学法人大阪府立大学 | Process for producing di- and triarylmethane dyes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525746A (en) * | 1975-07-03 | 1977-01-17 | Kanzaki Paper Mfg Co Ltd | Novel process for preparation of triarymethane derivatives |
-
1992
- 1992-04-08 DE DE4211783A patent/DE4211783A1/en not_active Withdrawn
-
1993
- 1993-04-07 JP JP5080597A patent/JPH0625544A/en not_active Withdrawn
- 1993-09-27 CN CN93114187A patent/CN1047605C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111170A (en) * | 2019-06-21 | 2020-12-22 | 上海泰初化工技术有限公司 | Preparation method of triarylmethane color development material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1047605C (en) | 1999-12-22 |
| DE4211783A1 (en) | 1993-10-14 |
| JPH0625544A (en) | 1994-02-01 |
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