EP1603902A1 - New heterocyclic compounds, a process for their preparation and their use as dyes and pigments - Google Patents
New heterocyclic compounds, a process for their preparation and their use as dyes and pigmentsInfo
- Publication number
- EP1603902A1 EP1603902A1 EP04741425A EP04741425A EP1603902A1 EP 1603902 A1 EP1603902 A1 EP 1603902A1 EP 04741425 A EP04741425 A EP 04741425A EP 04741425 A EP04741425 A EP 04741425A EP 1603902 A1 EP1603902 A1 EP 1603902A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- hydrogen
- printing
- compound
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 49
- 239000000975 dye Substances 0.000 title description 13
- 239000000049 pigment Substances 0.000 title description 7
- 150000002391 heterocyclic compounds Chemical class 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 87
- -1 nitro, cyano, amino, carboxy Chemical group 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
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- 239000004033 plastic Substances 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 15
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 14
- 150000002367 halogens Chemical group 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
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- 150000001408 amides Chemical class 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 125000005110 aryl thio group Chemical group 0.000 claims abstract description 7
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims abstract description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical group 0.000 claims abstract 10
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
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- FXJBHVJHXKVCQM-UHFFFAOYSA-N 4-phenyl-3h-1,3-oxazol-2-one Chemical class O1C(=O)NC(C=2C=CC=CC=2)=C1 FXJBHVJHXKVCQM-UHFFFAOYSA-N 0.000 description 3
- LCGIQDHXIAOOCB-UHFFFAOYSA-N 4-phenylimidazol-2-one Chemical class O=C1N=CC(C=2C=CC=CC=2)=N1 LCGIQDHXIAOOCB-UHFFFAOYSA-N 0.000 description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical group CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920003825 Ultramid® B3K Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical compound NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000549 coloured material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VHILMKFSCRWWIJ-UHFFFAOYSA-N dimethyl acetylenedicarboxylate Chemical compound COC(=O)C#CC(=O)OC VHILMKFSCRWWIJ-UHFFFAOYSA-N 0.000 description 1
- 150000005125 dioxazines Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- FKEHEUVXUIVPLY-UHFFFAOYSA-N ethyl 2-oxo-5-phenyl-1,3-dihydropyrrole-4-carboxylate Chemical compound N1C(=O)CC(C(=O)OCC)=C1C1=CC=CC=C1 FKEHEUVXUIVPLY-UHFFFAOYSA-N 0.000 description 1
- VHDKUDINYGOVKE-UHFFFAOYSA-N ethyl 5-(4-methylphenyl)-2-oxo-1,3-dihydropyrrole-4-carboxylate Chemical compound N1C(=O)CC(C(=O)OCC)=C1C1=CC=C(C)C=C1 VHDKUDINYGOVKE-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 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 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 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
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- MQUPWTBHHPUUMC-UHFFFAOYSA-N isoindole Chemical compound C1=CC=C[C]2C=NC=C21 MQUPWTBHHPUUMC-UHFFFAOYSA-N 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical class C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical class C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000000025 natural resin Substances 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
- 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 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000485 pigmenting effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical class C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/36—One oxygen atom
- C07D263/40—One oxygen atom attached in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
Definitions
- the present invention relates to new compounds, to their preparation and to their use in the production of coloured plastics or polymeric colour particles
- R-i is hydrogen, hydroxy, halogen, nitro, cyano, ammo, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy
- R' ⁇ is hydrogen, hydroxy, halogen, nitro, cyano, ammo, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy
- X is -0-, -S-, -NH- or -N(alkyl)-
- X' is -0-, -S-, -NH- or -N(alkyl)-
- Y is hydrogen or carboxylic ester
- Y' is hydrogen or carboxylic ester
- Z ⁇ s C-
- n 0, 1 , 2 or 3
- m 0, 1 , 2 or 3
- B is a phenyl ring
- W is a heterocyclic, or linear or polycondensed aromatic group which is unsubstituted or substituted by alkyl, halogen, hydroxy, alkoxy, alkylthio or amino
- R 2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino.
- an alkyl is for example a straight-chain or branched C ⁇ alkyl as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl or octyl, preference being given to a C 1-4 alkyl.
- an alkylthio is for example methylthio, ethylthio, propylthio, butyl- thio, heptylthio or hexylthio.
- an alkoxy is for example a straight-chain or branched C 1-8 alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert. butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1 ,1 ,3,3-tetramethylbutoxy or 2-ethylhexyloxy.
- an aryloxy is to be understood as being for example a C 6 . 24 aryl- oxy, preferably a C 6- ⁇ 2 aryloxy radical, for example phenoxy or 4-methylphenoxy.
- an arylthio is for example phenylthio or napthylthio.
- W as aromatic group includes, for example, phenylene, naphthalene, acenaphthylene, anthracene, phenanthrene, naphthacene, chrysene, pyrene or perylene.
- W is preferably phenylene, naphthalene, anthracene, phenanthrene, perylene or pyrene, and most preferably phenylene or naphthalene.
- W as heterocyclic group is, for instance, pyhdine, pyrazine, pyrimidine, pyridazine, indole iso- indole, quinoline, isoquinoline, carbazole, phenothiazine, benzimidazolone, benzothiazole, pyrrolo, imidazole, pyrrolidine, piperidine, piperazine, morpholine or pyrazole.
- an ester is for example methyl-, ethyl-, propyl- or butylester.
- preferred compounds of formula (1 ) are a) compounds of phenyl-butyrolactams of formula
- preferred compounds of formula (1 ) are e) compounds of phenyl-carboethoxy-butyrolactams of formula
- n 0, 1 or 2
- the compounds of formula (1 ) according to the invention are prepared, for example, by reacting 2 mol of compound of formula
- R 1 , R ⁇ , X, X , Y, Y , Z, Z, x and y are as defined above for formula (1), n is 0, 1 , 2 or 3, m is 0, 1 , 2 or 3, B is a phenyl ring, R 2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino and R 3 is hydrogen, C C 12 alkyl or CN, at elevated temperature or by oxidation 2 mol of compound of formula (50) at elevated temperature or by oxidation 1 mol of compound of formula (50) and 1 mol of compound of formula (51 ) at elevated temperature.
- Ph means phenyl and Ac 2 0 means acetic anhydride
- the compound of formula (1 ) can be symmetrical or asymmetrical and can contain one or more water soluble groups (sulfonic, carboxylic or cationic groups).
- Water soluble derivatives of compounds of formula (1 ) can be used as dyestuffs for textile application, coloration of cotton, wool, polyamide and polyacrylonitrile using all the well known dyeing processes.
- Such dyes are useful for dyeing and printing manufactured natural polymer and especially synthetic hydrophobic fibre materials, especially textile materials.
- Textile materials composed of blend fabrics comprising such manufactured natural polymer or synthetic hydrophobic textile materials are likewise dyeable or printable with the dyes of the invention.
- Useful manufactured natural polymer textile materials are especially cellulose acetate and cellulose triacetate.
- Synthetic hydrophobic textile materials are especially linear aromatic polyesters, for example polyesters formed from a terephthalic acid and glycols, particularly ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hydroxymethyl)cyclohexane; polycarbonates, for example those formed from ⁇ , ⁇ -dimethyl-4,4-dihydroxydiphenylmethane and phosgene; or fibres based on polyvinyl chloride or polyamide.
- linear aromatic polyesters for example polyesters formed from a terephthalic acid and glycols, particularly ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hydroxymethyl)cyclohexane
- polycarbonates for example those formed from ⁇ , ⁇ -dimethyl-4,4-dihydroxydiphenylmethane and phosgene
- fibres based on polyvinyl chloride or polyamide are especially linear aromatic polyesters, for example polyesters formed from a terephthalic acid
- polyester fibres are exhaust dyed from an aqueous dispersion in the presence of customary anionic or nonionic dispersants with or without customary carriers at temperatures between 80 and 140°C.
- Cellulose acetate is preferably dyed at between about 65 to 85°C and cellulose triacetate at up to 1 15°C.
- the above dyes are also useful for dyeing by the thermosol, exhaust and continuous processes and for printing processes.
- the exhaust process is preferred.
- the liquor ratio depends on the apparatus, the substrate and the make-up form. However, the liquor ratio can be chosen to be within a wide range, for example in the range from 4:1 to 100:1 , but it preferably is between 6:1 to 25:1.
- the textile material mentioned may be present in the various processing forms, for example as a fibre, yarn or web or as a woven or loop-formingly knitted fabric. It is advantageous to convert the dyes into a dye preparation before use for this, the dyes are ground so that their particle size is on average between 0.1 and 10 microns. The grinding may be effected in the presence of dispersants. For example, the dried dye is ground with a dispersant or kneaded in paste form with a dispersant and then dried under reduced pressure or by spray drying. The preparations thus obtained can be used to prepare print pastes and dyebaths by adding water.
- Printing utilizes the customary thickeners, for example modified or nonmodified natural products, for example alginates, British gum, gum arabic, crystal gum, carob bean flour, traga- canth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof or polyvinyl alcohols.
- the above dyes confer on the materials mentioned, especially on polyester material, level shades having very good service fastnesses, such as in particular good light fastness, especially a very good hot light fastness, fastness to dry heat setting and pleating, chlorine fastness and wet fastness such as fastness to water, perspiration and washing; the dyeings are further characterized by good rub fastness and heat stability.
- Water insoluble derivatives of compounds of formula (1) can be used as disperse dyes for coloration of PET by exhaustion or pigments for mass coloration of plastics or can be used for inks and paints. These products can also be used for coloration of wood and metals and they are also suitable as functional dyes for special applications such as optical information storage, or display devices or printed circuit boards.
- the present invention relates also to a process for the production of coloured plastics or polymeric colour particles, which comprises mixing together a high molecular weight organic material and a tincto ally effective amount of at least one compound of formula (1 ).
- the present invention further relates to the use of the compounds of formula (1 ) individually as colourants, especially for colouring or pigmenting organic or inorganic, high-molecular- weight or low-molecular-weight material, especially high-molecular-weight organic material. It is also possible, however, for the compositions according to the invention comprising compounds of formula (1 ) to be used in the form of mixtures, solid solutions or mixed crystals.
- Compounds of formula (1 ) can also be combined with colourants of another chemical class, for example with dyes or pigments, for example those selected from the group of the diketo- pyrrolopyrroles, quinacridones, perylenes, dioxazines, anthraquinones, indanthrones, fla- vanthrones, indigos, thioindigos, quinophthalones, isoindolinones, isoindolines, phthalocyani- nes, metal complexes, azo pigments and azo dyes.
- dyes or pigments for example those selected from the group of the diketo- pyrrolopyrroles, quinacridones, perylenes, dioxazines, anthraquinones, indanthrones, fla- vanthrones, indigos, thioindigos, quinophthalones, isoindolinones, isoindolines, phthalocyani- nes, metal
- the high-molecular-weight material may be organic or inorganic and may be synthetic and/or natural material.
- the high-molecular-weight organic material usually has an average molecular weight of 10 5 -10 7 g/m°l. It may be, for example, a natural resin or a drying oil, rubber or casein or a modified natural material, such as chlorinated rubber, oil-modified alkyd resins, viscose, or a cellulose ether or ester, such as ethylcellulose, cellulose acetate, propionate or butyrate, cellulose acetobutyrate or nitrocellulose, but is especially a completely synthetic organic polymer (duroplasts and thermoplasts) as may be obtained by polymerisation, for example by polycondensation or polyaddition.
- the class of polymers includes, for example, polyolefins, such as polyethylene, polypropylene, polyisobutylene, and substituted polyole- fins, such as polymerisates of monomers such as vinyl chloride, vinyl acetate, styrene, acry- lonitrile, acrylates, methacrylates, fluoropolymers, such as polyfluoroethylene, polytrifluoro- chloroethylene or tetrafluoroethylene/hexafluoropropylene mixed polymerisate, and copoly- merisates of the mentioned monomers, especially ABS (acrylonitrile/butadiene/styrene) or EVA (ethylene/vinyl acetate).
- polyolefins such as polyethylene, polypropylene, polyisobutylene
- substituted polyole- fins such as polymerisates of monomers such as vinyl chloride, vinyl acetate, styrene, acry-
- condensation products of formaldehyde with phenols the so-called phenoplasts, and condensation products of formaldehyde and urea or thiourea, also melamine, the so-called aminoplasts
- the polyesters used as surface coating resins either saturated, such as alkyd resins, or unsaturated, such as maleic resins, and also linear polyesters, polyamides, polyurethanes, polycarbonates, polyphenylene oxides or silicones, and silicone resins.
- the mentioned high-molecular-weight compounds may be present individually or in mixtures in the form of kneadable compounds, melts or in the form of spinning solutions.
- They may also be present in the form of their monomers or in the polymerised state in dissolved form as film-formers or binders for paints or printing inks, such as, for example, boiled linseed oil, nitrocellulose, alkyd resins, melamine resins and urea-formaldehyde resins or acrylic resins.
- film-formers or binders for paints or printing inks such as, for example, boiled linseed oil, nitrocellulose, alkyd resins, melamine resins and urea-formaldehyde resins or acrylic resins.
- Low-molecular-weight materials are, for example, mineral oils, waxes or lubricating greases.
- the present invention further relates, therefore, to the use of the compounds of formula (1) for the production of inks, for printing inks in printing processes, for flexographic printing, screen printing, the printing of packaging, security colour printing, intaglio printing or offset printing, for preliminary printing stages and for textile printing, for office and home use or for graphics, such as, for example, for paper goods, for ball-point pens, felt-tip pens, fibre-tip pens, paperboard, wood, (wood) stains, metal, stamp pads or inks for impact printing processes (with impact printing ink ribbons), for the production of colourants, for paints, for use in industry or advertising, for textile decoration and industrial labelling, for roll coating or powder coating compositions or for automobile paints, for high-solids (low-solvent), water-containing or metallic paints or for pigmented formulations for aqueous paints, for mineral oils, lubricating greases or waxes, for the production of coloured plastics for coatings, fibres, plates or moulded substrates, for
- the present invention further relates to inks comprising high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
- the inks can be produced by mixing the compounds according to the invention with polymeric dispersants.
- the mixing of the compounds according to the invention with the polymeric dispersant is preferably carried out by generally known mixing methods, such as stirring or mixing, and the use of an intensive mixer, such as an Ultraturax, is especially to be recommended.
- the weight ratio of the compounds according to the invention to ink is advantageously selected to be in the range of from 0.0001 to 75 % by weight, preferably from 0.001 to 50 % by weight, based on the total weight of the ink.
- the present invention therefore relates also to a process for the production of inks which comprises mixing high-molecular-weight organic material with a colour-producing amount of the compound of formula (1 ).
- the present invention further relates to colourants comprising high-molecular-weight organic material and a compound according to the invention of formula (1 ) in a colour-producing amount.
- the present invention relates, in addition, to a process for the preparation of colourants which comprises mixing a high-molecular-weight organic material and a colour-producing amount of the compound according to the invention of formula (1 ).
- the present invention further relates to coloured or pigmented plastics or polymeric coloured particles comprising high-molecular-weight organic material and compound of formula (1 ) in a colour-producing amount.
- the present invention relates, in addition, to a process for the preparation of coloured or pigmented plastics or polymeric coloured particles which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula
- the colouring of high-molecular-weight organic substances with the colourants of formula (1 ) is carried out, for example, by mixing such a colourant, optionally in the form of a master batch, into those substrates using roll mills or mixing or grinding apparatus, whereby the colourant is dissolved or finely distributed in the high-molecular-weight material.
- the high-molecular-weight organic material with the admixed colourant is then processed according to procedures known per se, such as, for example, calendering, compression moulding, extrusion moulding, coating, spinning, casting or injection-moulding, whereby the coloured material acquires its final form.
- Admixing of the colourant can also be carried out immediately prior to the actual processing step, for example by continuously metering a powdered colourant according to the invention and a granulated high-molecular-weight organic material, and optionally also additional ingredients, such as additives, directly into the inlet zone of an extruder simultaneously, where mixing takes place just before the processing operation.
- additional ingredients such as additives
- plasticisers it is often desirable for the purpose of producing non-rigid mouldings or reducing the brittle- ness thereof to incorporate so-called plasticisers into the high-molecular-weight compounds before shaping.
- plasticisers for example, esters of phosphoric acid, phthalic acid or sebacic acid.
- the plasticisers can be incorporated into the polymers before or after the incorporation of the colourant.
- any desired amounts of constituents such as white, coloured or black pigments.
- the high-molecular-weight organic materials and the compounds of formula (1 ) optionally together with additional ingredients, such as fillers, dyes, pigments, siccatives or plasticisers, are finely dispersed or dissolved in a common organic solvent or solvent mixture. That procedure may comprise dispersing or dissolving each individual component on its own or dispersing or dissolving several components together and only then combining all the components. Processing is carried out in accordance with customary methods, for example by spraying, film-spreading or one of the many printing methods, whereupon the paint or printing ink is advantageously cured thermally or by irradiation, optionally after previous drying.
- the high-molecular-weight material to be coloured is a paint
- it may be a conventional paint or a special paint, for example an automobile finish, preferably a metal-effect finish containing, for example, metal or mica particles.
- thermoplastics especially also in the form of fibres, and printing inks.
- Preferred high-molecular-weight organic materials that can be coloured according to the invention are, very generally, polymers having a dielectric constant > 2.5, especially polyesters, polycarbonate (PC), polystyrene (PS), polymethylmethacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or acrylonitrile/butadie- ne/styrene (ABS). More especially preferred are polyesters, polycarbonate, polystyrene and PMMA.
- polyesters especially preferred are polyesters, polycarbonate and PMMA, especially aromatic polyesters that can be obtained by polycondensation of terephthalic acid, such as, for example, polyethylene terephthalate (PET) or polybutylene terephthalate.
- PET polyethylene terephthalate
- PMMA polybutylene terephthalate
- They can be used in the form of their monomers or copolymers or in the polymerised state in dissolved form as film formers or binders for paints that can be used for the decoration of metal or for decorative colour finishes, and for printing inks used, for example, in the ink-jet printing process, or also for wood stains.
- the present invention also relates to mineral oils, lubricating greases and waxes comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
- the present invention also relates to a process for the preparation of mineral oils, lubricating greases and waxes, which comprises mixing high-molecular-weight organic material with a colour-producing amount of the compound of formula (1 ).
- the present invention also relates to non-impact printing material comprising high-molecular- weight organic material and a compound of formula (1 ), in a colour-producing amount.
- the present invention relates, in addition, to a process for the preparation of non-impact printing material, which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
- the present invention further relates to a process for the production of colour filters comprising a transparent substrate and a red, a blue and a green coating applied thereto in any desired sequence, which comprises using for the production of the red, blue and green coatings a correspondingly coloured compound of formula (1 ).
- the different-coloured coatings are preferably arranged in such a pattern that they do not overlap over at least 5 % of their respective surface area and, most preferably, do not overlap at all.
- the colour filters can be coated, for example, using inks, especially printing inks, comprising the compounds according to the invention, or, for example, by mixing a compound according to the invention with a chemically, thermally or photolytically structurable high-molecular- weight material (resist).
- the further production can be carried out, for example, analogously to EP-A-654 711 , by application to a substrate, such as an LCD, subsequent photo-structuring and developing
- the invention further includes a transparent substrate coated with a red, a blue and a green coating each of a correspondingly coloured compound of formula (1 ), comprising pigmented high-molecular-weight organic material.
- the sequence in which coating is carried out is not important as a rule.
- the different-coloured coatings are preferably arranged in such a pattern that they do not overlap over at least 5% of their respective surface area and, most preferably, do not overlap at all.
- the present invention also includes colour filters comprising a transparent substrate and, applied thereto, a red, a blue and a green coating, each obtainable from a correspondingly coloured compound of formula (1 ).
- the present invention also includes the use of the compounds of formula (1 ) for optical infor- mation storage applications (ois).
- the present invention relates, in addition, to toners comprising high-molecular-weight organic material and a compound of formula (1), in a colour-producing amount.
- the present invention also relates to a process for the production of toners, which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
- the present invention also relates to inks or colourants for paints, printing inks, mineral oils, lubricating greases or waxes, or coloured or pigmented plastics, non-impact printing material, colour filters, cosmetics or toners comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
- toners, paints, inks or coloured plastics are produced by processing master batches of toners, paints, inks or coloured plastics in roll mills or mixing or grinding apparatus.
- a colour-producing amount of the compound of formula (1 ) means in the present invention normally from 0.0001 to 99.99 % by weight, preferably from 0.001 to 50 % by weight and especially from 0.01 to 50 % by weight, based on the total weight of the material coloured or pigmented therewith.
- the coloured/pigmented high-molecular-weight materials obtained are distinguished by very high colour intensity, high saturation, good fastness to overspraying, good migration-stability, good fastness to heat, light and weathering and by a high gloss and good IR reflectance behaviour.
- UV absorbers are advantageously mixed into the plastics or polymeric particles to be coloured with the compound of formula (1 ) according to the invention.
- the amount of UV absorber can vary within a wide range; advantageously there is used from 0.01 to 1.0 % by weight, especially from 0.05 to 0.6 % by weight, more especially from 0.1 to 0.4 % by weight, of a UV absorber, based on the weight of the plastics or polymeric particles.
- the following Examples serve to illustrate the invention Unless otherwise indicated, the parts are parts by weight and the percentages are percentages by weight The temperatures are given in degrees Celsius The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres
- Et means -CH 2 CH 3
- Me means -CH 3
- OMe means -OCH 3
- t-But means -C(CH 3 ) 3
- Ph means -Phenyl
- OEt means -OCH 2 CH 3
- n-But means -(CH 2 ) 3 CH 3
- Table 1
- Benzoylacrylic acid (10. Og, 0.056 mol), cuprous chloride (2.0 g, 0.010 mol), ammonium chloride (2.2 g, 0.041 mol) are taken in acetic anhydride (50 ml). It is gradually heated to reflux under stirring for 2 hours. After the reaction is over, it is thoroughly cooled in an ice bath. Settled solids are filtered through Buchner funnel. Solids are washed with acetic anhydride, water and ethanol to give the crude product (5.2 g). The crude solids are purified by soxhlet extraction in toluene to give pure red colored solids (3.8 g, 42%). m. p.315°C, Anal. Gale. For C 20 H 12 O 4 ; C, 75.94; H, 3.82; Found: C, 74.79; H, 3.82. All other compounds given in the Table 2 are obtained following the above same procedure.
- 2,3-Bis-benzoylamino-succinic acid (5.0 g, 0.014 mol) (synthesized as given in Stachei, S. D. et al. Arch. Pharm. 312, 968, 1979) is taken in thionyl chloride (50 ml) and refluxed for 2 hours. Excess thionyl chloride is distilled off. Traces of thionyl chloride are removed by toluene co-distillation. It is cooled to room temperature and water is added to it. The crude mass is then filtered and dried in an oven till constant weight. The red colored pure product obtained, weighted (3.5g, 78%). Anal. Calc.
- Benzamidine free base (6.0 g, 0.049 mol) and dimethyl acetylenedicarboxylate (3.6 g, 0.025 mol) are taken in benzene (ca. 50 ml).
- the deep red colored solution obtained is heated to reflux for 2 hours.
- the cooled mixture is filtered to give (9.0 g) of the crude.
- the crude product is taken in minimum amount of warm DMF and poured on large excess of water under stirring.
- the solids separated (2.1 g) are filtered and soxhlet extracted with methanol for 16 hours.
- the methanol insoluble pure red colored product obtained, weighted (0.8 g, 10%).
- 5-Phenyl-4-carbethoxy-1 ,3-dihydro-pyrrol-2-one (2.3 g, 0.01 mol) is dissolved in acetic acid (50 ml) at 60 to 70° C.
- acetic acid 50 ml
- 2,5-dimethoxy- terephthalaldehyde 1.0 g, 0.005 mol
- temperature is increased to 100° C. Heating is continued for 3 hours and after cooling, solids are filtered through Buchner funnel.
- the crude product is washed with acetic acid, water, DMF and methanol. Finally the crude product is dissolved in cone, sulphuric acid, reprecipitated from water and filtered.
- polyester granules (PET Arnite D04-300, DSM) are pre-dried for 4 hours at
- the resulting greenish yellow-coloured polyester granules have good allround fastness properties, especially good light fastness and high-temperature light fastness properties.
- polyamide-6 granules Ultramid B3K, BASF are pre-dried for 4 hours at 75°C and then mixed homogeneously with
- the homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin,
- the resulting orange-coloured polyamide granules have good allround fastness properties, especially good light fastness and high-temperature light fastness properties.
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Compounds of formula (I) wherein R1 is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, R'1 is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic arnide, alkylthio, arylthio, alkoxy or aryloxy, X is -O-, -S-, -NH- or -N(alkyl)-, X' is -0-, -S-, -NH- or -N(alkyl)-, Y is hydrogen or carboxylic ester, Y' is hydrogen or carboxylic ester, Z is =C- or =N-, Z' is =C- or =N-, x is 0 or 1, when Z is =N-, then x is 0, y is 0 or 1, when Z' is =N-, then y is 0, A is a conjugated linking bridge of the formulae (II), (III), (IV), (V), or (VI), wherein n is 0, 1, 2 or 3, m is 0, 1, 2 or 3, B is a phenyl ring, T is =C(R3)- or =N-, wherein R3 is hydrogen, C1-C12alkyl or CN, W is a heterocyclic, or linear or polycondensed aromatic group which is unsubstituted or substituted by alkyl, halogen, hydroxy, alkoxy, alkylthio or amino, G is -CH= or -N=, and R2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino, their preparation and their use in the production of coloured plastics or polymeric color particles.
Description
NEW HETEROCYCLIC COMPOUNDS, A PROCESS FOR THEIR PREPARATION AND
THEIR USE AS DYES AND PIGMENTS
The present invention relates to new compounds, to their preparation and to their use in the production of coloured plastics or polymeric colour particles
The subject of the present invention are compounds of formula (1)
wherein
R-i is hydrogen, hydroxy, halogen, nitro, cyano, ammo, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, R'ι is hydrogen, hydroxy, halogen, nitro, cyano, ammo, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, X is -0-, -S-, -NH- or -N(alkyl)-, X' is -0-, -S-, -NH- or -N(alkyl)-, Y is hydrogen or carboxylic ester, Y' is hydrogen or carboxylic ester, Z ιs =C- or =N-, Z' ιs =C- or =N-, x is 0 or 1 , when Z is =N-, then x is 0, y is 0 or 1 , when Z' is =N-, then y is 0, A is a conjugated linking bridge of the formula
wherein
n is 0, 1 , 2 or 3, m is 0, 1 , 2 or 3, B is a phenyl ring,
T is =C(R3)- or =N-, wherein R3 is hydrogen, CrC12alkyl or CN,
W is a heterocyclic, or linear or polycondensed aromatic group which is unsubstituted or substituted by alkyl, halogen, hydroxy, alkoxy, alkylthio or amino, G is -CH= or-N=, and R2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino.
According to the invention an alkyl is for example a straight-chain or branched C^alkyl as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl or octyl, preference being given to a C1-4alkyl.
According to the invention an alkylthio is for example methylthio, ethylthio, propylthio, butyl- thio, heptylthio or hexylthio.
According to the invention an alkoxy is for example a straight-chain or branched C1-8alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert. butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1 ,1 ,3,3-tetramethylbutoxy or 2-ethylhexyloxy.
According to the invention an aryloxy is to be understood as being for example a C6.24aryl- oxy, preferably a C6-ι2aryloxy radical, for example phenoxy or 4-methylphenoxy.
According to the invention an arylthio is for example phenylthio or napthylthio.
G is preferred -CH=.
W as aromatic group includes, for example, phenylene, naphthalene, acenaphthylene, anthracene, phenanthrene, naphthacene, chrysene, pyrene or perylene. W is preferably phenylene, naphthalene, anthracene, phenanthrene, perylene or pyrene, and most preferably phenylene or naphthalene.
W as heterocyclic group is, for instance, pyhdine, pyrazine, pyrimidine, pyridazine, indole iso- indole, quinoline, isoquinoline, carbazole, phenothiazine, benzimidazolone, benzothiazole, pyrrolo, imidazole, pyrrolidine, piperidine, piperazine, morpholine or pyrazole. According to the invention an ester is for example methyl-, ethyl-, propyl- or butylester.
If A is a single double bond ^^ , preferred compounds of formula (1 ) are a) compounds of phenyl-butyrolactams of formula
b) compounds of phenyl-butyrolactones of formula
c) compounds of phenyl oxazolones of formula
and
d) compounds of phenyl imidazolones of formula
wherein Ri has the meaning given under the formula (1 ) and Et is -CH2CH3.
If A is a conjugated linking bridge, preferred compounds of formula (1 ) are e) compounds of phenyl-carboethoxy-butyrolactams of formula
f) compounds of phenyl-butyrolactones of formula
§g) compounds of phenyl-butyrolactams of formula
h) compounds of phenyl-oxazolones of formula
and i) compounds of phenyl-imidazolones of formula
n = 0, 1 or 2
wherein Ri and R2 have the meaning given under the formula (1 ), Et is -CH2CH3 and nBut is n-butanole.
Further preferred are compounds of formula (1 ), wherein
is hydrogen, chloro, bromo, methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro is, R'ι is hydrogen, chloro, bromo, methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro, R2 is hydrogen or methoxy, X is -NH-, -N(n-C4H9)-, or -0-, X' is -NH-, -N(n-C4H9)-, or -0-, Y is hydrogen or COOC2H5, Ϋ is hydro¬
gen or COOC2H5, Z is =C- or =N-, Z' is =C- or =N-, A is = or
T is =C(R3)-, R3 is hydrogen and n is 0, 1 or 2.
The most preferred compounds of formula (1) are the compounds of the formulae
The compounds of formula (1 ) according to the invention are prepared, for example, by reacting 2 mol of compound of formula
(50) which possess an active methylene group -CH2
or 1 mol of compound of formula (50) and 1 mol of compound of formula
(51 ), which possess an active methylene group -CH2
with 1 mol of one of the compounds of formula
wherein R1, R ι, X, X , Y, Y , Z, Z, x and y are as defined above for formula (1), n is 0, 1 , 2 or 3, m is 0, 1 , 2 or 3, B is a phenyl ring, R2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino and R3 is hydrogen, C C12alkyl or CN, at elevated temperature or by oxidation 2 mol of compound of formula (50) at elevated temperature or by oxidation 1 mol of compound of formula (50) and 1 mol of compound of formula (51 ) at elevated temperature.
The general synthesis of phenyl-butyrolactams (in this case C-substituted by carboethoxy) derivatives is characterized by the following reaction schema:
5-Phenyl-4-carboethoxy- butyrolactam type wherein Ac means acetic acid residue and Et means ethyl.
The general synthesis of phenyl-butyrolactam and phenyl-butyrolactone (N- and C- unsubstituted) derivatives is characterized by the following reaction schema:
wherein Ac20 means acetic anhydride.
The general synthesis of phenyl-oxazolone derivatives is characterized by the following reaction schema:
Hippuπc acid 2-Phenyl-5-oxazolone* *- Heterocycles, 19(12) 2331 , 1982
Phenyl-Oxazolone type
wherein Ph means phenyl and Ac20 means acetic anhydride
The general synthesis of pheny-imidazolone derivatives is characterized by the following reaction schema:
COOMe
COOMe
phenyl-imidazolone type wherein R^ has the meaning given under the formula (1 ) and Me is methyl.
The general synthesis based on the condensation of a dialdehyde with an active methylene compound is characterized by the following reaction schema:
wherein X, Y and Z have the meaning given under the formula (1 ).
The compound of formula (1 ) can be symmetrical or asymmetrical and can contain one or more water soluble groups (sulfonic, carboxylic or cationic groups).
Water soluble derivatives of compounds of formula (1 ) can be used as dyestuffs for textile application, coloration of cotton, wool, polyamide and polyacrylonitrile using all the well known dyeing processes.
Such dyes are useful for dyeing and printing manufactured natural polymer and especially synthetic hydrophobic fibre materials, especially textile materials. Textile materials composed of blend fabrics comprising such manufactured natural polymer or synthetic hydrophobic textile materials are likewise dyeable or printable with the dyes of the invention.
Useful manufactured natural polymer textile materials are especially cellulose acetate and cellulose triacetate.
Synthetic hydrophobic textile materials are especially linear aromatic polyesters, for example polyesters formed from a terephthalic acid and glycols, particularly ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hydroxymethyl)cyclohexane; polycarbonates, for example those formed from α,α-dimethyl-4,4-dihydroxydiphenylmethane and phosgene; or fibres based on polyvinyl chloride or polyamide.
The above dyes are applied to the textile materials according to known dyeing processes. For example, polyester fibres are exhaust dyed from an aqueous dispersion in the presence of customary anionic or nonionic dispersants with or without customary carriers at temperatures between 80 and 140°C. Cellulose acetate is preferably dyed at between about 65 to 85°C and cellulose triacetate at up to 1 15°C.
The above dyes are also useful for dyeing by the thermosol, exhaust and continuous processes and for printing processes. The exhaust process is preferred. The liquor ratio depends on the apparatus, the substrate and the make-up form. However, the liquor ratio can be chosen to be within a wide range, for example in the range from 4:1 to 100:1 , but it preferably is between 6:1 to 25:1.
The textile material mentioned may be present in the various processing forms, for example as a fibre, yarn or web or as a woven or loop-formingly knitted fabric. It is advantageous to convert the dyes into a dye preparation before use For this, the dyes are ground so that their particle size is on average between 0.1 and 10 microns. The grinding may be effected in the presence of dispersants. For example, the dried dye is ground with a dispersant or kneaded in paste form with a dispersant and then dried under reduced pressure or by spray drying. The preparations thus obtained can be used to prepare print pastes and dyebaths by adding water.
Printing utilizes the customary thickeners, for example modified or nonmodified natural products, for example alginates, British gum, gum arabic, crystal gum, carob bean flour, traga- canth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof or polyvinyl alcohols.
The above dyes confer on the materials mentioned, especially on polyester material, level shades having very good service fastnesses, such as in particular good light fastness, especially a very good hot light fastness, fastness to dry heat setting and pleating, chlorine fastness and wet fastness such as fastness to water, perspiration and washing; the dyeings are further characterized by good rub fastness and heat stability.
Water insoluble derivatives of compounds of formula (1) can be used as disperse dyes for coloration of PET by exhaustion or pigments for mass coloration of plastics or can be used for inks and paints. These products can also be used for coloration of wood and metals and they are also suitable as functional dyes for special applications such as optical information storage, or display devices or printed circuit boards.
The present invention relates also to a process for the production of coloured plastics or polymeric colour particles, which comprises mixing together a high molecular weight organic material and a tincto ally effective amount of at least one compound of formula (1 ).
The present invention further relates to the use of the compounds of formula (1 ) individually as colourants, especially for colouring or pigmenting organic or inorganic, high-molecular- weight or low-molecular-weight material, especially high-molecular-weight organic material. It is also possible, however, for the compositions according to the invention comprising compounds of formula (1 ) to be used in the form of mixtures, solid solutions or mixed crystals. Compounds of formula (1 ) can also be combined with colourants of another chemical class, for example with dyes or pigments, for example those selected from the group of the diketo- pyrrolopyrroles, quinacridones, perylenes, dioxazines, anthraquinones, indanthrones, fla- vanthrones, indigos, thioindigos, quinophthalones, isoindolinones, isoindolines, phthalocyani- nes, metal complexes, azo pigments and azo dyes.
The high-molecular-weight material may be organic or inorganic and may be synthetic and/or natural material. The high-molecular-weight organic material usually has an average molecular weight of 105-107g/m°l. It may be, for example, a natural resin or a drying oil, rubber or casein or a modified natural material, such as chlorinated rubber, oil-modified alkyd resins, viscose, or a cellulose ether or ester, such as ethylcellulose, cellulose acetate, propionate or butyrate, cellulose acetobutyrate or nitrocellulose, but is especially a completely synthetic organic polymer (duroplasts and thermoplasts) as may be obtained by polymerisation, for example by polycondensation or polyaddition. The class of polymers includes, for example,
polyolefins, such as polyethylene, polypropylene, polyisobutylene, and substituted polyole- fins, such as polymerisates of monomers such as vinyl chloride, vinyl acetate, styrene, acry- lonitrile, acrylates, methacrylates, fluoropolymers, such as polyfluoroethylene, polytrifluoro- chloroethylene or tetrafluoroethylene/hexafluoropropylene mixed polymerisate, and copoly- merisates of the mentioned monomers, especially ABS (acrylonitrile/butadiene/styrene) or EVA (ethylene/vinyl acetate). From the group of polyaddition and polycondensation resins it is possible to use, for example, condensation products of formaldehyde with phenols, the so- called phenoplasts, and condensation products of formaldehyde and urea or thiourea, also melamine, the so-called aminoplasts, and the polyesters used as surface coating resins, either saturated, such as alkyd resins, or unsaturated, such as maleic resins, and also linear polyesters, polyamides, polyurethanes, polycarbonates, polyphenylene oxides or silicones, and silicone resins. The mentioned high-molecular-weight compounds may be present individually or in mixtures in the form of kneadable compounds, melts or in the form of spinning solutions. They may also be present in the form of their monomers or in the polymerised state in dissolved form as film-formers or binders for paints or printing inks, such as, for example, boiled linseed oil, nitrocellulose, alkyd resins, melamine resins and urea-formaldehyde resins or acrylic resins.
Low-molecular-weight materials are, for example, mineral oils, waxes or lubricating greases.
The present invention further relates, therefore, to the use of the compounds of formula (1) for the production of inks, for printing inks in printing processes, for flexographic printing, screen printing, the printing of packaging, security colour printing, intaglio printing or offset printing, for preliminary printing stages and for textile printing, for office and home use or for graphics, such as, for example, for paper goods, for ball-point pens, felt-tip pens, fibre-tip pens, paperboard, wood, (wood) stains, metal, stamp pads or inks for impact printing processes (with impact printing ink ribbons), for the production of colourants, for paints, for use in industry or advertising, for textile decoration and industrial labelling, for roll coating or powder coating compositions or for automobile paints, for high-solids (low-solvent), water-containing or metallic paints or for pigmented formulations for aqueous paints, for mineral oils, lubricating greases or waxes, for the production of coloured plastics for coatings, fibres, plates or moulded substrates, for the production of non-impact printing material for digital printing, for the thermal wax-transfer printing process, the ink-jet printing process or for the thermal transfer printing process, and also for the production of colour filters, especially for visible light in
the range of from 400 to 700 nm, for liquid crystal displays (LCDs) or charge-coupled devices (CCDs) or for the production of cosmetics or for the production of polymeric colour particles, toners, dry copy toners, liquid copy toners or electrophotographic toners.
The present invention further relates to inks comprising high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
For example, the inks can be produced by mixing the compounds according to the invention with polymeric dispersants.
The mixing of the compounds according to the invention with the polymeric dispersant is preferably carried out by generally known mixing methods, such as stirring or mixing, and the use of an intensive mixer, such as an Ultraturax, is especially to be recommended.
When mixing the compounds according to the invention with polymeric dispersants, a water- dilutable organic solvent is advantageously used.
The weight ratio of the compounds according to the invention to ink is advantageously selected to be in the range of from 0.0001 to 75 % by weight, preferably from 0.001 to 50 % by weight, based on the total weight of the ink.
The present invention therefore relates also to a process for the production of inks which comprises mixing high-molecular-weight organic material with a colour-producing amount of the compound of formula (1 ).
The present invention further relates to colourants comprising high-molecular-weight organic material and a compound according to the invention of formula (1 ) in a colour-producing amount.
The present invention relates, in addition, to a process for the preparation of colourants which comprises mixing a high-molecular-weight organic material and a colour-producing amount of the compound according to the invention of formula (1 ).
The present invention further relates to coloured or pigmented plastics or polymeric coloured particles comprising high-molecular-weight organic material and compound of formula (1 ) in
a colour-producing amount.
The present invention relates, in addition, to a process for the preparation of coloured or pigmented plastics or polymeric coloured particles which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula
(1 ).
The colouring of high-molecular-weight organic substances with the colourants of formula (1 ) is carried out, for example, by mixing such a colourant, optionally in the form of a master batch, into those substrates using roll mills or mixing or grinding apparatus, whereby the colourant is dissolved or finely distributed in the high-molecular-weight material. The high-molecular-weight organic material with the admixed colourant is then processed according to procedures known per se, such as, for example, calendering, compression moulding, extrusion moulding, coating, spinning, casting or injection-moulding, whereby the coloured material acquires its final form. Admixing of the colourant can also be carried out immediately prior to the actual processing step, for example by continuously metering a powdered colourant according to the invention and a granulated high-molecular-weight organic material, and optionally also additional ingredients, such as additives, directly into the inlet zone of an extruder simultaneously, where mixing takes place just before the processing operation. In general, however, prior mixing of the colourant into the high-molecular-weight organic material is preferred, since more uniform results can be obtained.
It is often desirable for the purpose of producing non-rigid mouldings or reducing the brittle- ness thereof to incorporate so-called plasticisers into the high-molecular-weight compounds before shaping. There may be used as plasticisers, for example, esters of phosphoric acid, phthalic acid or sebacic acid. In the process according to the invention, the plasticisers can be incorporated into the polymers before or after the incorporation of the colourant. In order to obtain different colour shades it is also possible to add to the high-molecular-weight organic substances, in addition to the compounds of formula (1), any desired amounts of constituents such as white, coloured or black pigments.
For the colouring of paints and printing inks, the high-molecular-weight organic materials and the compounds of formula (1 ) optionally together with additional ingredients, such as fillers, dyes, pigments, siccatives or plasticisers, are finely dispersed or dissolved in a common organic solvent or solvent mixture. That procedure may comprise dispersing or dissolving each individual component on its own or dispersing or dissolving several components together and
only then combining all the components. Processing is carried out in accordance with customary methods, for example by spraying, film-spreading or one of the many printing methods, whereupon the paint or printing ink is advantageously cured thermally or by irradiation, optionally after previous drying.
When the high-molecular-weight material to be coloured is a paint, it may be a conventional paint or a special paint, for example an automobile finish, preferably a metal-effect finish containing, for example, metal or mica particles.
Preference is given to the colouring of thermoplastics, especially also in the form of fibres, and printing inks. Preferred high-molecular-weight organic materials that can be coloured according to the invention are, very generally, polymers having a dielectric constant > 2.5, especially polyesters, polycarbonate (PC), polystyrene (PS), polymethylmethacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or acrylonitrile/butadie- ne/styrene (ABS). More especially preferred are polyesters, polycarbonate, polystyrene and PMMA. Most especially preferred are polyesters, polycarbonate and PMMA, especially aromatic polyesters that can be obtained by polycondensation of terephthalic acid, such as, for example, polyethylene terephthalate (PET) or polybutylene terephthalate.
They can be used in the form of their monomers or copolymers or in the polymerised state in dissolved form as film formers or binders for paints that can be used for the decoration of metal or for decorative colour finishes, and for printing inks used, for example, in the ink-jet printing process, or also for wood stains.
Special preference is also given to the colouring of mineral oils, lubricating greases and waxes with the compounds according to the invention.
The present invention also relates to mineral oils, lubricating greases and waxes comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
The present invention also relates to a process for the preparation of mineral oils, lubricating greases and waxes, which comprises mixing high-molecular-weight organic material with a colour-producing amount of the compound of formula (1 ).
The present invention also relates to non-impact printing material comprising high-molecular-
weight organic material and a compound of formula (1 ), in a colour-producing amount.
The present invention relates, in addition, to a process for the preparation of non-impact printing material, which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
The present invention further relates to a process for the production of colour filters comprising a transparent substrate and a red, a blue and a green coating applied thereto in any desired sequence, which comprises using for the production of the red, blue and green coatings a correspondingly coloured compound of formula (1 ).
The different-coloured coatings are preferably arranged in such a pattern that they do not overlap over at least 5 % of their respective surface area and, most preferably, do not overlap at all.
The colour filters can be coated, for example, using inks, especially printing inks, comprising the compounds according to the invention, or, for example, by mixing a compound according to the invention with a chemically, thermally or photolytically structurable high-molecular- weight material (resist). The further production can be carried out, for example, analogously to EP-A-654 711 , by application to a substrate, such as an LCD, subsequent photo-structuring and developing
The invention further includes a transparent substrate coated with a red, a blue and a green coating each of a correspondingly coloured compound of formula (1 ), comprising pigmented high-molecular-weight organic material.
The sequence in which coating is carried out is not important as a rule. The different-coloured coatings are preferably arranged in such a pattern that they do not overlap over at least 5% of their respective surface area and, most preferably, do not overlap at all.
The present invention also includes colour filters comprising a transparent substrate and, applied thereto, a red, a blue and a green coating, each obtainable from a correspondingly coloured compound of formula (1 ).
The present invention also includes the use of the compounds of formula (1 ) for optical infor-
mation storage applications (ois).
The present invention relates, in addition, to toners comprising high-molecular-weight organic material and a compound of formula (1), in a colour-producing amount.
The present invention also relates to a process for the production of toners, which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
The present invention also relates to inks or colourants for paints, printing inks, mineral oils, lubricating greases or waxes, or coloured or pigmented plastics, non-impact printing material, colour filters, cosmetics or toners comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
In a special embodiment of the process according to the invention, toners, paints, inks or coloured plastics are produced by processing master batches of toners, paints, inks or coloured plastics in roll mills or mixing or grinding apparatus.
A colour-producing amount of the compound of formula (1 ) means in the present invention normally from 0.0001 to 99.99 % by weight, preferably from 0.001 to 50 % by weight and especially from 0.01 to 50 % by weight, based on the total weight of the material coloured or pigmented therewith.
The coloured/pigmented high-molecular-weight materials obtained, such as, for example, plastics, fibres, paints and prints, are distinguished by very high colour intensity, high saturation, good fastness to overspraying, good migration-stability, good fastness to heat, light and weathering and by a high gloss and good IR reflectance behaviour.
In order to improve the light fastness properties, UV absorbers are advantageously mixed into the plastics or polymeric particles to be coloured with the compound of formula (1 ) according to the invention. The amount of UV absorber can vary within a wide range; advantageously there is used from 0.01 to 1.0 % by weight, especially from 0.05 to 0.6 % by weight, more especially from 0.1 to 0.4 % by weight, of a UV absorber, based on the weight of the plastics or polymeric particles.
The following Examples serve to illustrate the invention Unless otherwise indicated, the parts are parts by weight and the percentages are percentages by weight The temperatures are given in degrees Celsius The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres
Example 1 (general procedure for oxidative dimeπzation)
A solution of 5-phenyl-4-carbethoxy-1 ,3-dιhydro-pyrrol-2-one (10 0 g, 0 04 mol) is heated at 130° C , under stirring in dry DMF (dimethyl formamide) (100 ml) Slow stream of oxygen gas is bubbled through the solution and progress of the reaction is monitored by TLC (~3 hours) After completion of the reaction, it is poured on water (5-tιmes) Bluish suspension is filtered through Buchner funnel to give dark violet colored crude product (11 0 g) The crude product is purified by selective precipitation from hexane-ethyl acetate solvent mixture to give (2 0 g, 20%) of the pure product 1H NMR (dmso) δ 1 1 (6H, t), 4 1 (4H, q), 7 4-7 7 (10H, m), 11 2 (2H, s) All other compounds given in the Table 1 (entries 1 , 3, 4, 7) are obtained following the same procedure
Example 2 (general procedure for N-butylation)
Dimer obtained from process of Examplel (4 5 g, 0 009 mol) is taken in dry DMF (70 ml) under nitrogen atmosphere and the solution is cooled to 5° C To this sodium hydride 50% (0 94 g, 0 019 mol) is added in portions After some time n-butyl bromide (4 65 g, 0 034 mol) is added in one lot Reaction was monitored by TLC and aftei the completion, it is poured on brine Aqueous part is extracted with ethyl acetate, dried over anhydrous sodium sulfate Evaporation of organic layer gives the crude violet colored product It is purified on silica gel column using hexane-ethyl acetate solvent mixture (10 90) to give (3 3 g, 58%) of the pure product 1H NMR (dmso) δ 0 6(6H, t), 0 8(1 OH, m), 1 2(4H, t), 3 4(4H, t), 3 9(4H, q), 7 7 (10H, s) All other compounds given in the Table 1 (entries 2, 5, 6) are obtained following the same procedure
In the following Tables Et means -CH2CH3, Me means -CH3, OMe means -OCH3, t-But means -C(CH3)3, Ph means -Phenyl, OEt means -OCH2CH3 and n-But means -(CH2)3CH3
Table 1
Example 8:
Benzoylacrylic acid (10. Og, 0.056 mol), cuprous chloride (2.0 g, 0.010 mol), ammonium chloride (2.2 g, 0.041 mol) are taken in acetic anhydride (50 ml). It is gradually heated to reflux under stirring for 2 hours. After the reaction is over, it is thoroughly cooled in an ice bath. Settled solids are filtered through Buchner funnel. Solids are washed with acetic anhydride, water and ethanol to give the crude product (5.2 g). The crude solids are purified by soxhlet extraction in toluene to give pure red colored solids (3.8 g, 42%). m. p.315°C, Anal. Gale. For C20H12O4; C, 75.94; H, 3.82; Found: C, 74.79; H, 3.82. All other compounds given in the Table 2 are obtained following the above same procedure.
Table 2
Example 17:
2.0 g of the above dimmer from Example 8 is taken in acetic acid (50 ml). Ammonia gas is then bubbled through the solution under reflux for 2 hours. Reaction mixture is cooled to 70° C. and filtered. Solids are washed with water, ethanol and ether. The crude product is purified by continuous soxhlet extraction to give (1.4 g, 70%) of violet colored product. Anal. Gale. For C-20H14N2O2; C, 76.42; H, 4.49; N, 8.90; Found: C, 75.84; H, 5.10 ; N, 7.70. All other compounds given in the Table 3 are obtained following the above same procedure.
Table 3
Example 26:
2,3-Bis-benzoylamino-succinic acid (5.0 g, 0.014 mol) (synthesized as given in Stachei, S. D. et al. Arch. Pharm. 312, 968, 1979) is taken in thionyl chloride (50 ml) and refluxed for 2 hours. Excess thionyl chloride is distilled off. Traces of thionyl chloride are removed by toluene co-distillation. It is cooled to room temperature and water is added to it. The crude mass is then filtered and dried in an oven till constant weight. The red colored pure product obtained, weighted (3.5g, 78%). Anal. Calc. For C18Hι0N2O4; C, 67.90; H, 3.17; N, 8.8; Found: C, 67.07; H, 4.95 ; N, 8.81. All other compounds given in the Table 4 are obtained following the above same procedure.
Table 4
Example 30:
Benzamidine free base (6.0 g, 0.049 mol) and dimethyl acetylenedicarboxylate (3.6 g, 0.025 mol) are taken in benzene (ca. 50 ml). The deep red colored solution obtained is heated to reflux for 2 hours. The cooled mixture is filtered to give (9.0 g) of the crude. The crude product is taken in minimum amount of warm DMF and poured on large excess of water under stirring. The solids separated (2.1 g) are filtered and soxhlet extracted with methanol for 16 hours. The methanol insoluble pure red colored product obtained, weighted (0.8 g, 10%). Anal. Calc. For C18H12N402; C, 68.37; H, 3.79; N, 17.72; Found: C, 69.33; H, 3.43 ; N, 17.47. Methoxy derivative from Example 31 (see Table 5) is synthesized using above same method.
Table 5
Example 33:
5-Phenyl-4-carbethoxy-1 ,3-dihydro-pyrrol-2-one (2.3 g, 0.01 mol) is dissolved in acetic acid (50 ml) at 60 to 70° C. To this PTSA (0.7 g) is added, followed by addition of 2,5-dimethoxy- terephthalaldehyde (1.0 g, 0.005 mol) and temperature is increased to 100° C. Heating is continued for 3 hours and after cooling, solids are filtered through Buchner funnel. The crude product is washed with acetic acid, water, DMF and methanol. Finally the crude product is dissolved in cone, sulphuric acid, reprecipitated from water and filtered. It is then dried in an oven to give red colored pure product (1.5 g, 50%). Anal. Calc. For C36H32N2θ8; C, 69.60; H, 5.15; N, 4.52; Found: C, 66.47; H, 4.98 ; N, 4.34. All other compounds given in the Table 6 are obtained following the above same procedure
Table 6
Example 44:
5-(p-Methylphenyl)-4-carbethoxy-1 ,3-dihydro-pyrrol-2-one (5.1 g, 0.0086 mol) is taken in dry DMF (70 ml) under nitrogen atmosphere and the solution is cooled to 5° C. To this sodium hydride 50% (1.0 g, 0.04 mol) is added in portions. After some time n-butyl bromide (6.35 g, 0.046 mol) is added to it at ones. Reaction is monitored by TLC and after the completion, it is poured on brine. Aqueous part is extracted with ethylacetate, dried over anhydrous sodium sulfate. Evaporation of organic layer gives the crude violet colored product. It is purified on silica gel column using hexane-ethyl acetate solvent mixture (10 : 90) to give (3.5 g,58%) of the pure product. 1H NMR (dmso): δ 0.6(6H, t), 0.8(6H, t), 1.2(4H, m), 1.4(4H, m), 2.4(6H, s),3.4(4H, t), 4.0(4H, q), 7.2-8.3(14H, m). All other compounds given in the Table 7 are obtained following the same procedure.
Table 7
Example 54:
Terephthalaldehyde (2.0 g, 0.015 mol), sodium acetate (7.5 g, 0.091 mol) and acetic anhydride (70 ml) are taken in round bottom flask and heated to 90° C under nitrogen atmosphere. To this is added β-Benzoylpropionic acid (16.0 g, 0.09 mol). Temperature of the reaction is maintained for 3 hours and after cooling solids are filtered through Buchner funnel, washed with acetic acid, water and methanol. The crude product is heated in DMF at 80-90° C for 2 hours. After filtration and washing with water, it is dried in an oven till constant weight to give (5.2g, 83%) of the pure product. Anal. Calc. For C28H1804; C, 78.37; H, 4.34; Found: C, 78.87; H, 4.45. The compounds of Examples 55 and 56 (see table 8) are synthesized using above same method.
Table 8
Example 57:
Above prepared lactone of Example 54 (1 1.5 g, 0.027 mol) is taken in acetic acid (200 ml). Ammonia gas is bubbled through it and the solution is refluxed for 2 hours. After completion of the reaction, it is cooled and filtered. The solids are washed with acetic acid, water and methanol. Final purification is done by stirring the solids in DMF at room temperature for 4-5 hours. Filtered solids are then washed with water, methanol and dried in an oven till constant
weight to give (10.2 g, 89%) of the orange colored pure product. Anal. Calc. For C28H20N2O2; C, 80.76; H, 4.80;N, 6.73 Found: C, 80.37; H, 4.14; N, 7.21. Example 58 (see Table 9) is synthesized using above same method.
Example 59:
Above lactam from Example 57 (6.5 g, 0.020 mol) is taken in dry DMF (90 ml) under nitrogen atmosphere and the solution is cooled to 5° C. To this sodium hydride 50% (1.8 g, 0.075 mol) is added in portions. After some time n-butyl bromide (9.90 g, 0.075 mol) is added to it at ones. Reaction is monitored by TLC and after completion, it is poured on brine. Aqueous part is extracted with ethyl acetate, dried over anhydrous sodium sulfate. Evaporation of organic layer gives the crude orange colored product. It is purified on silica gel column using hexane-ethyl acetate solvent mixture (10 : 90) to give orange colored (2.0 g,18%) of the pure product, m. p. 160°C; 1H NMR (cdcl3): δ 0.8(6H, t), 1.2(4H, t), 1.4(4H, m), 3.7(4H, t), 6.2(2H, s), 7.2-7.6(16H, m).
Table 9
Example 60:
Terephthalaldehyde (7.0 g, 0.055 mol), sodium acetate (14 g, 0.017 mol) and acetic anhydride (150 ml) are taken in round bottom flask and heated to 90° C under nitrogen atmosphere. To this is added hippuric acid (30.0 g, 0.167 mol). Temperature of the reaction is maintained for 4 hours and after cooling yellow solids are filtered through Buchner funnel, washed with acetic acid, water and methanol. The crude product is heated in DMF at 80-90° C for 2 hours. After filtration and washing with water, it is dried in an oven till constant weight to give
(14.5g, 66%) of the pure product. Anal. Calc. For C26Hi6N204; C, 74.28; H, 3.84;N, 6.66 Found: C, 73.57; H, 3.67; N, 6.79.
Table 10
Example 63:
Above oxazoline based compound of Example 61 (1.0 g, 0.0023 mole) is taken in acetic acid (30 ml). The reaction mixture is refluxed while ammonia gas is bubbled through the solution for 2 hours. The reaction mixture is filtered after cooling and washed with acetic acid, water and methanol. The crude mass is stirred in DMF at room temperature for 15 hours followed by boiling in water for 3 hours. Final wash is given with methanol and dried in an oven till constant weight. The pure product obtained in this way gives (2.5 g, 22%) yield of the pure product. Anal. Calc. For C2sH18N4θ2; C, 74.64; H, 4.34;N, 13.79 Found: C, 72.75; H, 4.19; N, 13.60.
Table 11
Dyeing Example 1 :
1200.00 g of polyester granules (PET Arnite D04-300, DSM) are pre-dried for 4 hours at
130°C and then mixed homogeneously with
2.6 g of the compound of formula
in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute. The homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin, D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 275°C, cooled with water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) and then dried for 4 hours at 130°C.
The resulting greenish yellow-coloured polyester granules have good allround fastness properties, especially good light fastness and high-temperature light fastness properties.
Dyeing Example 2:
1200.00 g of polyamide-6 granules (Ultramid B3K, BASF) are pre-dried for 4 hours at 75°C and then mixed homogeneously with
3.5 g of the compound of formula
in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute.
The homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin,
D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 220°C, cooled with water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) and then dried for 4 hours at 75°C.
The resulting orange-coloured polyamide granules have good allround fastness properties, especially good light fastness and high-temperature light fastness properties.
Claims
1. Compounds of formula (1)
wherein
Ri is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, R is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, X is -0-, -S-, -NH- or — N(alkyl)-, X' is -0-, -S-, -NH- or -N(alkyl)-, Y is hydrogen or carboxylic ester, Y' is hydrogen or carboxylic ester, Z is =C- or =N-, T is =C- or =N-, x is 0 or 1 , when Z is =N-, then x is 0, y is 0 or 1 , when Z' is =N-, then y is 0, A is a conjugated linking bridge of the formula
wherein n is 0, 1 , 2 or 3, m is 0, 1 , 2 or 3, B is a phenyl ring, T is =C(R3)- or =N-, wherein R3 is hydrogen, CrCι2alkyl or CN, W is a heterocyclic, or linear or polycondensed aromatic group which is unsubstituted or substituted by alkyl, halogen, hydroxy, alkoxy, alkylthio or amino, G is -CH= or -N=, and R2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino.
2. Compounds according to claim 1 , wherein Ri is hydrogen, chloro, bromo, methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro is, R. is hydrogen, chloro, bromo, methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro, R2 is hydrogen or methoxy, X is -NH-, -N(n-C4Hg)-, or -0-, X' is -NH-, -N(n-C4H9)-, or -O-, Y is hydrogen or COOC2H5, Y" is hydrogen or
COOC2H5, Z is =C- or =N-, Z' is =C- or =N-, A is = or T is =C(R3)-, R3 is hydrogen and n is 0, 1 or 2.
3. Compounds according to either claim 1 or claim 2 of formula
4) Process for the preparation of compounds of formula (1 ), which process comprises reacting 2 mol of compound of formula
(50) which possess an active methylene group -CH2
or 1 mol of compound of formula (50) and 1 mol of compound of formula (51), which possess an active methylene group -CH2
with 1 mol of one of the compounds of formula
wherein R1 ( R X, X , Y, Y', Z, Z , x and y are as defined above for formula (1 ), n is 0, 1 , 2 or 3, m is 0, 1 , 2 or 3, B is a phenyl ring, R2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino and R3 is hydrogen, Cι-C12alkyl or CN, at elevated temperature or by oxidation 2 mol of compound of formula (50) at elevated temperature or by oxidation 1 mol of compound of formula (50) and 1 mol of compound of formula (51 ) at elevated temperature.
5) Process for the preparation of coloured or pigmented plastics or polymeric coloured particles, which process comprises mixing together a high-molecular-weight organic material and a colour-producing amount of at least one compound of formula (1 ) according to claim 1.
6) Coloured or pigmented plastics or polymeric coloured particles comprising compound of formula (1) according to claim 1. 7) Use of the compounds of formula (1) according to claim 1 for the production of inks, for printing inks in printing processes, for flexographic printing, screen printing, the printing of packaging, security colour printing, intaglio printing or offset printing, for preliminary printing stages and for textile printing, for office and home use or for graphics, such as, for example, for paper goods, for ball-point pens, felt-tip pens, fibre-tip pens, paperboard, wood, (wood) stains, metal, stamp pads or inks for impact printing processes (with impact printing ink ribbons), for the production of colourants, for paints, for use in industry or advertising, for textile decoration and industrial labelling, for roll coating or powder coating compositions or for automobile paints, for high-solids (low-solvent), water-containing or metallic paints or for pigmented formulations for aqueous paints, for mineral oils, lubricating greases or waxes, for the production of coloured plastics for coatings, fibres, plates or moulded substrates, for the production of non-impact printing material for digital printing, for the thermal wax-transfer printing process, the ink-jet printing process or for the thermal transfer printing process, and also for the production of colour filters, especially for visible light in the range of from 400 to 700 nm, for liquid crystal displays (LCDs) or charge-coupled devices (CCDs) or for the production of cosmetics or for the production of polymeric colour particles, toners, dry copy toners, liquid copy toners or electrophotographic toners, or for optical information storage applications (ois).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IN228CH2003 | 2003-03-19 | ||
INMA02282003 | 2003-03-19 | ||
PCT/EP2004/050276 WO2004089941A1 (en) | 2003-03-19 | 2004-03-10 | New heterocyclic compounds, a process for their preparation and their use as dyes and pigments |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1603902A1 true EP1603902A1 (en) | 2005-12-14 |
Family
ID=33156196
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04741425A Withdrawn EP1603902A1 (en) | 2003-03-19 | 2004-03-10 | New heterocyclic compounds, a process for their preparation and their use as dyes and pigments |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1603902A1 (en) |
CA (1) | CA2519157A1 (en) |
WO (1) | WO2004089941A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008106021A (en) * | 2006-10-27 | 2008-05-08 | Dainippon Ink & Chem Inc | Method for producing pyrrolinone compound, and method for producing bipyrrolinone compound |
CN103664916B (en) * | 2012-09-12 | 2016-08-24 | 中国科学院化学研究所 | Conjugation small molecule material based on sub-two pyrroles of bithiophene and derivant thereof and preparation method and application |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2440405A1 (en) * | 1974-08-23 | 1976-03-04 | Basf Ag | Modifcn. of azlactone dispersion dye - into stable form by heat treatment |
DE2608481C2 (en) * | 1976-03-02 | 1978-03-30 | Hoechst Ag, 6000 Frankfurt | Process for coloring water-insoluble, thermoplastic polymers and polycondensates in bulk |
-
2004
- 2004-03-10 EP EP04741425A patent/EP1603902A1/en not_active Withdrawn
- 2004-03-10 CA CA002519157A patent/CA2519157A1/en not_active Abandoned
- 2004-03-10 WO PCT/EP2004/050276 patent/WO2004089941A1/en active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2004089941A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2519157A1 (en) | 2004-10-21 |
WO2004089941A1 (en) | 2004-10-21 |
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