MXPA00009070A - Preparation of alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrroles - Google Patents
Preparation of alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrolesInfo
- Publication number
- MXPA00009070A MXPA00009070A MXPA/A/2000/009070A MXPA00009070A MXPA00009070A MX PA00009070 A MXPA00009070 A MX PA00009070A MX PA00009070 A MXPA00009070 A MX PA00009070A MX PA00009070 A MXPA00009070 A MX PA00009070A
- Authority
- MX
- Mexico
- Prior art keywords
- formula
- dpp
- carbon atoms
- substituted
- alkyl
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 150000003573 thiols Chemical class 0.000 claims abstract description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 27
- 150000007944 thiolates Chemical class 0.000 claims abstract description 26
- 239000000460 chlorine Substances 0.000 claims abstract description 24
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004662 dithiols Chemical class 0.000 claims abstract description 17
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 150000002367 halogens Chemical class 0.000 claims abstract description 16
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011630 iodine Substances 0.000 claims abstract description 13
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 13
- DKAXSGWOJGVZGP-UHFFFAOYSA-M 3H-dithiole-3-carboxylate Chemical compound [O-]C(=O)C1SSC=C1 DKAXSGWOJGVZGP-UHFFFAOYSA-M 0.000 claims abstract description 12
- 125000002837 carbocyclic group Chemical group 0.000 claims abstract description 11
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 9
- 125000003106 haloaryl group Chemical group 0.000 claims abstract description 9
- 125000005110 aryl thio group Chemical group 0.000 claims abstract description 4
- -1 heterocyclic radical Chemical class 0.000 claims description 95
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 77
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000000049 pigment Substances 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 239000011368 organic material Substances 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 14
- 150000002431 hydrogen Chemical group 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 claims description 8
- 238000000518 rheometry Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 239000003966 growth inhibitor Substances 0.000 claims description 6
- 125000005842 heteroatoms Chemical group 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000004040 coloring Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 3
- 230000000485 pigmenting Effects 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 239000003623 enhancer Substances 0.000 description 5
- 230000002708 enhancing Effects 0.000 description 5
- 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 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 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 5
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 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 4
- 239000004014 plasticizer Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 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 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- 229920000180 Alkyd Polymers 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N Octadecene Chemical group CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000004979 cyclopentylene group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N ethyl amine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinone Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-Octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 description 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- WVPKVHRHRWCSLR-UHFFFAOYSA-N 4-chloro-2,3-diphenyl-1H-pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=2N(Cl)C(=O)C(=O)C=2NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 WVPKVHRHRWCSLR-UHFFFAOYSA-N 0.000 description 1
- HJJVRROPUFSPAT-UHFFFAOYSA-N 5-(4-chlorophenyl)pyrrolo[3,2-b]pyrrole Chemical compound C1=CC(Cl)=CC=C1C1=NC2=CC=NC2=C1 HJJVRROPUFSPAT-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920002301 Cellulose acetate Polymers 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N DMPU Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N Hexamethylphosphoramide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N Isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- TWBLHMKDILPLIB-UHFFFAOYSA-N O=C1C(C(=CC=C1)C=1C(=C2C(=CC(=N2)C2=CC=CC=C2)N=1)Br)=O Chemical compound O=C1C(C(=CC=C1)C=1C(=C2C(=CC(=N2)C2=CC=CC=C2)N=1)Br)=O TWBLHMKDILPLIB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010062080 Pigmentation disease Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N Propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000005092 Ruthenium Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N Sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 125000002465 nonacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000004193 piperazinyl group Chemical group 0.000 description 1
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- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
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- REYJJPSVUYRZGE-UHFFFAOYSA-N stearylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Preparation of alkylthio and/or arylthio-substituted diketo-diaryl-pyrrolopyrroles (DPPs) of formula (Ia) and dithio-bridged bis-diketo-diaryl-pyrrolopyrroles (bis-DPPs) of formula (Ib), in which in formula (Ia) G is phenyl substituted by at least one arylthio or alkylthio group, and G1 is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate, and in formula (Ib) G5 is a phenylene, G6 is G1 but not G, and G7 is alkylene, cycloalkylene or phenylene, by reacting two haloaryls with a dithiol or dithiolate, which comprises reacting a thiol or thiolate with a halo-diketo-diaryl-pyrrolopyrrole ("halo-DPP") of formula (IIa) in which G2 is a halogenated phenyl group and G3 is G2 or G1, or reacting a dithiol or dithiolate with two halo-diketo-diaryl-pyrrolopyrroles ("halo-DPPs") of formula (IIb) in which Hal is halogen such as fluorine, chlorine, bromine or iodine, and G6 is G1, and also novel DPPs and also bis-DPPs, compositions comprising DPPs of formula (Ia) prepared in accordance with the invention, and their uses.
Description
PREPARATION OF DICETO-DIARIL-PIRROLOPIRROLES ALKYLTHY- AND / OR ARILTIUM-SUBSTITUTE The present invention relates to an improved process for preparing alkylthio and / or arylthio-substituted diketo-diaryl pyrrolopyrroles (DPPs) of the formula la and bis-dike- diaryl-pyrrolopyrroles dithio-bridged (bis-DPPs) of the formula Ib
wherein in the formula G is phenyl substituted by at least one arylthio or alkylthio group, and G_ is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate and in formula
Ib G5 is a phenylene, G6 is G_ but not G, and G7 is alkylene or phenylene, by reacting two haloaryls with a dithiol or dithiolate. The invention additionally relates to novel arylthio- or alkylthio-substituted DPPs, their use and compositions comprising the DPPs of the invention.
The Patents of the U.S.A. Nos. 4,579,949 and 4,490,542 describe the preparation of DPPs substituted by at least one thioether group by reacting arylthio- or alkylthio-substituted benzonitriles with succinic esters. The disadvantages are the low yields in the case of long chain alkylthio-DPPs and the impossibility to obtain water-soluble compounds. The reaction of DPP pigments with thiols to give alkylthio- or arylthio-substituted DPPs, gives incomplete conversions due to the poor solubility of these pigments. Chemistry Letters 1978, 13-14 discloses that the inactivated haloaryls can be substituted only in the presence of catalysts. It is therefore an object of the invention to provide an improved process for preparing alkylthio- and / or arylthio-substituted DPPs, which allows in particular the preparation of water-soluble compounds and long chain alkylthio DPPs. In particular, the process should be operable without high pressures and the use of catalysts. In addition, the economy of the process must be guaranteed by high yields. Still further, the invention aims to provide novel thioether-substituted diketo-diaryl pyrrolopyrroles and also bis-DPPs bridged with dithioether, which can be used in compositions with organic material of high molecular weight, in particular as dyes. In addition, DPPs substituted with thioether should be capable of being used in particular, as crystal growth inhibitors or rheology enhancers. Accordingly, the procedure defined at the beginning, which involves reacting a thiol or thiolate with a halo-dike-diaryl-pyrrolopyrrole ("halo-DPP") of the formula
wherein G2 is a halogenated phenyl group unsubstituted or substituted, and G3 is G2 or G1; or reacting a dithiol or dithiolate with two halo-diketo-diaryl-pyrrolopyrroles ("halo-DPPs") of the formula Ilb
wherein Hal is halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine and with particular preference chlorine, Hal in particular, is in the para position of phenylene. Usually, the reaction is initiated by bringing the thio and / or thiolate or the dithiol and / or the dithiolate into contact with the halo-DPP ly or IIb by conventional methods, for example when mixing the starting materials or by dropwise addition. one starting material to the other. To prepare the compounds of the formula la, the molar ratio of thiol to halo-DPP of the formula is generally chosen to be in the range from 0.1: 1 to 20: 1, preferably in the range of 2: 1 to 5: 1 and with particular preference in the range of 2.1: 1 to 2.7: 1, and to prepare the compounds of the formula Ib, the molar ratio of dithiol to halo-DPP of the formula Ilb, is generally chosen to be in the range from 0.5: 1 to 20: 1, preferably in the range of 0.5: 1 to 5: 1 and as a particular preference in the range of 1: 1 to 2.7: 1. Preferably, the reaction temperature is chosen to be within the range of 323 to 453 K, preferably in the range of 333 to 433 K, with particular preference in the range of 343 to 423 K and with very particular preference in the range of range of 343 to 413 K.
The reaction pressure is chosen to be generally in the range of 70 kPa to 10 MPa, preferably 90 kPa to 5 MPa; particularly preferably at atmospheric pressure. The reaction time generally depends on the reactivity of the starting materials, the selected reaction temperature and the desired conversion. The reaction time is usually chosen to be in the range from 15 minutes to 2 days. In a preferred embodiment, the reaction is conducted under an inert gas atmosphere using for this purpose preferably nitrogen or noble gases such as helium or argon. Particular preference is given to reaction in a nitrogen atmosphere. In addition, the reaction can be carried out with or without a solvent, with preference given to reaction in a solvent. Preferred solvents are organic solvents or mixtures of solvents such as aprotic solvents, especially non-aqueous aprotic solvents. Aprotic solvents can be apolar such as benzene, chlorobenzene and chlorinated hydrocarbons, or polar. The latter are particularly preferred. Examples of polar aprotic solvents which may be employed are amides such as hexamethylphosphoramide, carboxamides such as N, N'-dimethylformamide and N, N'-dimethylacetamide or lactams such as N-methylpyrrolidone, N-methyl-2-piperidone, 1,3- dimethyl-3, 4, 5, 6-tetrahydro-3 (1H) pyrimidinone or N-methyl-4-piperidone, or urea bases such as N, N'-dimethylethyleneurea, N, N'-dimethylpropyleneurea and also acetonitrile, sulfolane , dimethyl sulfoxide or aromatic solvents such as nitrobenzene. Preference is given to N, N '-dimethylformamide, N, N'-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-3,4,5,6-tetrahydro-3 (1H) pyrimidinone or N-methylpyrrolidone. The weight ratio of halo-DPP lia or halo-DPP
IIb to the solvent, is generally in the range of 0.5 to 10% by weight, with particular preference in the range of 1 to 5% by weight and with very particular preference in the range of 2 to 3% by weight. In another preferred embodiment, the reaction is conducted in the presence of a base. Examples of suitable bases are alkali metal carbonate, for example Na 2 CO 3 or K 2 CO 3, alkali metal hydrogen carbonates, for example NaHCO 3 or KHCO 3, alkali metal hydroxides, for example NaOH or KOH, alkali metals, such as sodium or potassium and also aromatic bases such as pyridine, N, N'-dimethylamino-pyridine or quinoline. Preference is given to non-aqueous alkali metal bases and aromatic bases, particularly preference to non-aqueous alkali metal carbonates or alkali metal hydrogen carbonates, and very particular preference to anhydrous K2CO3. The molar ratio of the base to the thiol or thiolate is usually in the range of 0.5: 1 to 5: 1, preferably in the range of 1: 1 to 4: 1 and with particular preference in the range of 1: 1 to 3: 1, and the molar ratio of base to dithiol or dithiolate, is usually in the range of 1: 1 to 10: 1, preferably in the range of 1: 1 to 5: 1 and with particular preference in the range from 1: 1 to 4: 1. In a preferred embodiment, of the process of the invention, the reaction is conducted in the presence of a solvent or mixture of solvents and a base. If desired, the reaction can also be conducted in the presence of catalysts, especially transition metal catalysts, examples being tetrakis (triphenylphosphine) palladium (0), -nickel (0) and -platinum (0) chloride, and-ruthenium (II). Preferably, the reaction is conducted without a catalyst. If a catalyst is used, it is generally used in a proportion in the range of 0.001 to 10% by weight, based on halo-DPP of the formula lia or Ilb, and preferably 0.5 to 7% by weight and preferably in particular from 2 to 5% by weight based on the total amount of reagents. The reaction mixture can be processed by conventional methods, for example by filtration and subsequent washing of the filter residue and subsequent optional drying. The product can be an individual compound or a mixture of differently substituted compounds of the formula, or a mixture consisting of halo-DPPlia and a compound of the formula la, or otherwise a mixture consisting of halo-DPP Ilb and a compound of the formula Ib and / or la. According to observations made to date, the thiol or thiolate used can comprise any known thiols or thiolates, are examples aryl or alkyl thiolates substituted or unsubstituted, it being possible that the latter are branched or straight chain, without interrupting or interrupted one or more times by hetero-atoms. In a preferred embodiment, a thiol or thiolate of the formula Illa or a dithiol or dithiolate of the formula Illb is employed. R! -SR2 Illa, R2S-G7-SR2 Illb wherein Rx may be alkyl with 1 to 30 carbon atoms, which may be uninterrupted or interrupted one or more times by hetero-atoms, such as -O- or -S -, or by -NH-, -C (0) 0-, -OC (O) - or -C (0) -NH-, and can be substituted or unsubstituted, or can be cycloalkyl with 5 to 12 carbon atoms carbon or phenyl, each of which may be substituted or unsubstituted, and R2 is hydrogen, a cation ("M") of an alkali metal, or an organic nitrogen base, and G? it may be alkylene having 1 to 30 carbon atoms which may be uninterrupted or interrupted one or more times by hetero-atoms, such as -O- or -S-, or by -NH-, -C (0) 0-, -OC (O) - or -C (0) -NH-, and may be unsubstituted or substituted, or it may be cycloalkylene with 5 to 12 carbon atoms or phenylene, each of which may be substituted or unsubstituted, alkyl with 1 to 30 carbon atoms is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertbutyl, n-pentyl, sec-amyl, tert-amyl, hexyl, 2,2-dimethylbutyl, heptyl , octyl, 2-ethylhexyl, 1,1 ', 3,3'-tetramethylbutyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl or nonacosyl, are gives preference to alkyl having 1 to 18 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl, ter-amyl, hexyl, , 2-dimethylbutyl, heptyl, octyl, 2-ethylhexyl, 1,1 ', 3, 3'-tetramethylbutyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl and in particular, preferably alkyl with 8 to 18 carbon atoms such as octyl, -ethylhexyl, 1, 1 ', 3, 3' -tetramethylbutyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl and especially alkyl with 12 to 18 carbon atoms such as dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl; Particular preference is also given to alkyl having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tertbutyl, n-pentyl, sec-amyl, ter-amyl, hexyl, 2,2'-dimethylbutyl, heptyl, octyl, 2-ethylhexyl and 1,1 ', 3,3'-tetramethylbutyl. C 1 -C 30 -alkylene is methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, sec-amylene, ter-amylene, hexylene, 2, 2 '- dimethylbutylene, heptylene, octylene, 2-ethylhexylene, 1,1 ', 3,3'-tetramethylbutylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, eicosylene, heneicosylene, docosylene, tetracosylene, pentacosylene, hexacosylene, heptacosylene, octacosylene or nonacosylene, preference is given to alkylene with 1 to 18 carbon atoms such as methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, sec-amylene, ter-amylene, hexylene, 2, 2'-dimethylbutylene, heptylene, octylene, 2-ethylhexylene,
1, 1 ', 3, 3' -tetramethylbutylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene or octadecylene, and particular preference is given to alkylene with 8 a
18 carbon atoms such as octylene, 2-ethylhexylene, 1, 1 ', 3, 3' -tetramethylbutylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene or octadecylene; furthermore, preference is given particularly to alkylene with 1 to 8 carbon atoms such as methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, sec-amylene, ter-amylene , hexylene, 2,2 '-dimethylbutylene, heptylene, octylene, 2-ethylhexylene or 1, 1', 3, 3'-tetramethylbutylene. Cycloalkyl with 5 to 12 carbon atoms is for example cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably cycloalkyl with 5 to 6 carbon atoms such as cyclopentyl or cyclohexyl. Cycloalkylene with 5 to 12 carbon atoms is for example cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene, preferably cycloalkylene with 5 to 6 carbon atoms such as cyclopentylene or cyclohexylene.
Alkyl radicals or alkylene radicals of at least two carbon atoms, represented by R_ or G7, can be interrupted one or more times for example by -O-, -NH-, -C (0) 0-, -0-C (0 ) -, -C (0) -NH-; preference is given to -C (0) 0- or -O- and in particular preference to the alkyl radical interrupted with -C (0) 0-, -CH2-C (O) 0 -CH2CH3, or the interrupted alkyl radical - O- in simple form such as -CH2-CH2-0-CH2-CH3, or the double-interrupted alkyl radical -O- such as -CH2-CH2-0-CH2-CH2-0-CH2-CH3. In addition, the alkyl or cycloalkyl radicals of the phenyl radical of Rx can be substituted, for example, by the following radicals: alkyl having 1 to 18 carbon atoms, OR3, S-R3, C (0) R3, COOR3, -OCORj7 S03R3, S02R3 , P03R3, Si (OR) 3, a salt radical such as SM, OM, COOM, S03M, P03M, P (R3) 3A ", P ((R3) 2R4) 3 + X", N02, N (R3) 3 + X ", N ((R3) 2R4) 3 + X" or a nitrogen-containing radical, wherein R3 and R4 independently of one another are hydrogen, alkyl having 1 to 18 carbon atoms, especially methyl, ethyl, propyl, isopropyl , n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl, tert-amyl, hexyl or 2,2-dimethylbutyl, or a cycloalkyl with 5 to 6 carbon atoms or phenyl unsubstituted or substituted with R7, M is a cation of an alkali metal, preferably sodium or potassium, X "is a halide, such as fluoride, chloride, bromide or iodide, and R7 is hydrogen, halogen such as F, Cl, Br, I or is alkyl with 1 to 8 carbon atoms or cycloalkyl with to 6 carbon atoms substituted with NR3R4 or unsubstituted. Preferred OR3 is OH, and preferred S-R3 is SH. Preferred radicals COOR3 are COOH, COOCH3,
COOC2H5, COOC4H9, COOC5Hn, and -OCOR3 preferred is -O-CO-C (CH2) -CH3. Preferred radicals S03R3 are S03H, S03 (C5H4) R7, S03 (C5H5), S03CH3, S03C2H5, and S02R3 preferred is S02 (C5H5) R7, S02 (C5H4) or S02CH3. Preferred radicals P03R3 are P03H, P03 (C5H4) R7 or P03CH3. Radicals containing nitrogens are selected from the group consisting of NR3R4, especially NH2, NHR3 or N (R3R4), with particular preference to substituted alkyl radicals such as (R3R4) N- (alkyl having 1 to 30 carbon atoms) - , especially (CH3) 2N-C2H5-, additionally preferred nitrogen-containing radicals are chosen from the group consisting of CONHNH2, CONHR3, NHCOR3, NCO and a heterocyclic radical and a compound selected from the group of formulas IV to IX
-N [(CH2) r-NR3R4] IV V VI VII
VIII IX selected in particular from the group of compounds of formulas IV and V, wherein R5 independently of R7 has the same definition as
R7, and R6 is a direct bond, -CH2-, -CH (CH3) -, -C (CH3) 2-, -CH = N-,
-N = N-, -O-, -S-, -SO-, -S02- or -NR3-, and r is zero or an integer from 1 to 17. In addition, the alkylene, cycloalkylene or phenylene radical of G, f it can be substituted, for example, by the following radicals: halogens such as fluorine, chlorine, bromine or iodine, preferably chlorine, bromine and, with particular preference, chlorine; -E-alkyl having 1 to 18 carbon atoms, wherein E is -O-, -S-, -NH-, -C (0) 0-, -0C (0) -, -NHC (O) -, -C (0) NH-; CN, N02 / CF3 or alkyl with 1 to 18 carbon atoms, which may be uninterrupted or interrupted one or more times by hetero-atoms, such as -O- or -S-, or by -NH-, -C ( 0) 0-, -OC (O) - or -C (0) -NH-. If E is -O-, then -0-alkyl having 1 to 18 carbon atoms can be methoxy, ethoxy, n-propoxy, isopropoxy, hexadecyloxy or octadecyloxy, preferably methoxy or ethoxy and particularly preferably methoxy. If E is -S-, then -S-alkyl having 1 to 18 carbon atoms can be methylmercapto, ethylmercapto, n-propylmercapto, isopropylmercapto, hexadecylmercapto or octadecylmercapto preferably methylmercapto or ethylmercapto and with particular preference methylmercapto. If E is -NH-, then -NH-alkyl having 1 to 18 carbon atoms can be methylamine, ethylamine, n-propylamine, isopropylamine, hexadecylamine or octadecylamine, preferably methylamine or ethylamine and particularly preferably methylamine.
If E is -C (0) 0- then -C (O) O-alkyl having 1 to 18 carbon atoms can be methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, hexadecoxycarbonyl or octadekoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl and with particular methoxycarbonyl preference. If E is -0C (0) - then -OC (0) -alkyl with 1 a
18 carbon atoms can be a methyl, ethyl, n-propyl, isopropyl, hexadecyl or octadecyl ester radical, preferably a methyl or ethyl ester radical and with particular preference a methyl ester radical. If E is -C (0) NH- then -C (0) NH-alkyl having 1 to 18 carbon atoms can be a methyl-, ethyl-, n-propyl-, isopropyl-, hexadecyl- or octa-decylaminocarbonyl radical , preferably a methyl- or ethylaminocarbonyl radical and with particular preference a methylaminocarbonyl radical. If E is -NHC (O) - then -NHC (O) -alkyl having 1 to 18 carbon atoms can be a methyl-, ethyl-, n-propyl-, isopropyl-, hexadecyl- or octadecylcarbonylamino radical, preferably a methyl- or ethylcarbonylamino radical, and with particular preference a methylcarbonylamino radical. Preferred substituted alkylene radicals for G7 are symmetrically substituted radicals such as - (CH2) m-CH (alkyl having 1 to 30 carbon atoms) - (CH2) m or
- (CH2) mC (alkyl with 1 to 30 carbon atoms) 2- (CH2) m, wherein m is an integer in the range of 1 to 14, with particular preference an integer in the range of 3 to 8. Radical Preferred substituted phenylene G7 possesses one or two substituents such as halogen, alkyl with 1 to 18 carbon atoms, -O-alkyl with 1 to 18 carbon atoms, -S-alkyl with 1 to 18 carbon atoms, -NH-alkyl with 1 to 18 carbon atoms, CN, N02 or CF3, wherein the substituents may be identical or different. Heterocyclic radical 7 for example is a heterocyclic radical containing five-membered nitrogen such as imidazolyl, pyrazolyl, triazolyl, pyrrolyl, pyrrolidinyl, oxazolyl or thiazolyl, a heterocyclic radical containing six-membered nitrogen such as piperazinyl, piperidinyl, pyridinyl or morpholinyl or a bicyclic radical having a five-membered nitrogen containing heterocycle and a fused six-membered aromatic ring such as benzoxazolyl, indolyl, benzothiazolyl, benz imidazolyl or benzotriazolyl. Examples of organic nitrogen bases suitable for R2 are pyridine, morpholine, N, N'-dimethylaminopyridine and quinoline.
Particular preference is given to thiols such as alkyl with 1 to 18 carbon atoms-SH, especially in
HS- (CH2) n -CH3, wherein n is an integer from 8 to 17, HS-CH2COOC2H5, HS-CH2CH2COOC2H5, HS- (para-methylphenyl), HS- (para-hydroxyphenyl) and also HS- (CH2) nl-NR3R4 wherein ni is an integer from 8 to 18, HS- (CH2) 2N (CH3) 2 and also thiolates such as sodium salts or potassium salts of -S- (alkyl with 1 to 18 carbon atoms) , -S- (CH2) 2-0H, -S-CH2COOC2H5,
-S- (para-methylphenyl), -S- (para-hydroxyphenyl) or -S- (CH 2) 2N (CH 3) 2. Particularly preferred dithiols are -S- (1- to 18 -alkylene) -S-, especially
-S- (C3-C8alkylene) -S-, such as -S- (CH2) 3-S-, -S- (CH2) 4-S-, -S- (CH2) 5-S -, -S- (CH2) 6-S-, -S- (CH2) 7-S- or -S- (CH2) 8-S-, and very particularly preferred dithiols are -S- (CH2) 3-S -, -S- (CH2) 5-S- or -S- (CH2) 6-S-. The thiols, dithiols or thiolates, dithiolates of the formula Illa or Illb are obtained commercially or by known methods for preparing thiols, dithiols or thiolates, dithiolates (Houben-Weyl, Methoden der organischen Chemie, (Methods of Inorganic Chemistry) Volume E 11, pp. 32-63, Georg Thieme Verlag, Stuttgart, New York, 1985, and JL Wardell, "Preparation of Tiols", in S. PATAI (ed.), The chemistry of the tiol group from the thiol group), pp. 163-269, John Wiley &Sons, London, New York, 1974). In the process of the invention a halo-DPP of the formula lia is used wherein G 2 is a halogenated phenyl group and G 3 is G 2 or Gl t and G 3 is preferably G 2 or a carbocyclic or heterocyclic radical and with particular preference is G 2; in other words, the halo-DPP of the formula lia in this case is symmetrically substituted halo-DPP. If G3 or G6 is G1; then the radical involved may also be a heterocyclic radical corresponding to the above definition of heterocyclic radicals and additionally is pyrimidine, thiophene or furan, or otherwise the radical involved may be a carbocyclic group of the formula XI, XII or XIII
wherein R8, R9, R10 and Rn independently of each other are hydrogen, halogen such as fluorine, chlorine, bromine or iodine or alkyl having 1 to 18 carbon atoms, -E-alkyl having 1 to 18 carbon atoms, -CN, -N02, trifluoromethyl, cycloalkyl with 5 to 6 carbon atoms
and in particular hydrogen, alkyl having 1 to 5 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl or ter-amyl, or halogen such as Cl or Br, and R12 is a single bond -CH2-, -CH (CH3) -, -C (CH3) 2-, -CH = N-, -N = N-, -O-, -S -, -SO-, -S02- or -NR3-. With particular preference, halo-DPP of formula IIb together with G6 is an organic radical such as
wherein R40 and R41 independently of each other are hydrogen, halogen such as fluorine, chlorine, bromine or iodine or alkyl having 1 to 18 carbon atoms, -E-alkyl having 1 to 18 carbon atoms, -CN, -N02 or trifluoromethyl . With particular preference, G6 is an organic radical such as
wherein R42 and R43 independently of each other are hydrogen, chloro, methyl, tert-butyl or -CN. In a preferred embodiment, the halogenated phenyl group G2 employed is a compound of the formula XIV
wherein Hal is halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine. With particular preference, halogen is in the para position. If desired, the halogenated phenyl group G2 can be a compound of the formula XV
XV
and can carry further substituents, R13 or R14, wherein R13 and R14 independently of each other are, for example, hydrogen, CN, CF3, alkyl with 1 to 5 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, -E- alkyl with 1 to 18 carbon atoms, phenyl, SR ^ amides such as -CONR3R4 or amides of formula XVI to XIX
XVI XVII
XVIII XIX or nitrogen-containing heterocyclic amides such as 1-carbonyl-imidazoles, -pyrazole, -triazole, -pyrrole, -pyrrolidine, -benzimidazole or -benzotriazole, or halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine. Preferably R13 and R14 are in the meta positions.
In a further preference, R14 is hydrogen and R13 is one of the above substituents other than hydrogen, preferably in the meta position. In another preferred embodiment, the halogenated phenyl group G2 is of the formula XX
wherein Hal is preferably fluorine, chlorine, bromine or iodine and with particular preference chlorine or bromine. Halo-DPPs II with correspondingly substituted groups are known, for example from U.S. Pat. Nos. 5,484,943, 5,616,725 or 5,200,528 or obtained in accordance with US Pat. No. 4,579,949. An additional embodiment of the present invention relates to new DPPs of formulas XXI and XXX
XXI XXX and the novel bis-DPPs of the formula Ib
wherein R15 / R16, R20 and R2_ independently of one another are hydrogen or R_3 or R14, and G4 is a carbocyclic or heterocyclic radical with the proviso that (a) Rx in formula XXI is not phenyl if Ri5 and Rib are hydrogen and G4 is phenyl and (b) Rx in the formula XXX is not phenylene (alkyl having 1 to 4 carbon atoms) or alkyl having 1 to 12 carbon atoms if R15, R16, R20 and 2? they are hydrogen and G5 is a phenylene, G6 is a carbocyclic or heterocyclic radical and G7 is alkylene, cycloalkylene or phenylene. Preferred DPPs of formula XXI or XXX are those where R? is alkyl with 1 to 30 carbon atoms mono- or poly-substituted or unsubstituted or a phenyl radical. Particularly preferably R15, R16, R20 and R21 are hydrogen and Rx is alkyl having 1 to 18 carbon atoms, such as C4 alkyl, C6 alkyl, C13 alkyl, C12 alkyl, carbon atoms or alkyl with 18 carbon atoms, and also such as - (para-phenylene) -OH, -CH2CH2OH, -CH2C (0) 0-CH2CH3, - (CH2): C (O) 0-CH2CH3 - ( alkylene with 1 to 30 carbon atoms) -N (R3, R4) such as - (C2H5) -N (CH3) 2. Particular preference is given to compounds of the formula Ib wherein G5 is 1,4-phenylene and G7 is n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene or n-octylene, or substituted or unsubstituted phenylene and G6 is unsubstituted or substituted phenyl. Particular preference is given to compounds of the formula Ib wherein G5 is 1,4-phenylene and G7 is n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene or n-octylene and G6 is phenyl without replacing. Particular preference is given to compounds of the formulas XXXI or XXXII
XXXI or XXXII wherein R30 is alkyl having 1 to 30 carbon atoms, particularly particular alkyl having 1 to 18 carbon atoms and most preferably particular alkyl having 5 to 18 carbon atoms. A further embodiment of the present invention relates to compositions comprising a DPP of the formula la and a halo-DPP of the formula Ia, which are obtained by the process of the invention using a sub-stoichiometric amount of thiol or thiolate of the Illa formula. Preferably, the thiol or thiolate of the formula Illa is used in a molar ratio that is within the range of 0.1 to 49%, based on the total amount of thiol or thiolate of the formula Illa and halo-DPP of the formula . A further embodiment of the process of the invention relates to compositions comprising at least two DPPs substituted differently from the formula la. These compositions are obtained either by reacting at least two halo-DPPs differently substituted from the formula lia, with a thiol or thiolate of the formula Illa, or conversely, by reacting at least two thiols or thiolates substituted differently of the formula Illa with a halo-DPP of the formula lia.
The molar proportion of thiol or thiolate of the formula Illa to halo-DPPs substituted differently from the formula lal, or of thiols or thiolates differently substituted from the formula Illa to halo-DPP of the formula lal, is generally chosen for to be within the range of 20: 0.1 to 1: 1, preferably in the range of 10: 1 to 5: 1 and with very particular preference in the range of 5: 1 to 5: 2. The molar ratio of the halo-DPPs substituted differently from the formula lia to each other, is generally chosen within the range of 0.1 to 99.9 mol%, based on the total amount of halo-DPPs substituted differently from the formula and, preferably - in the range of 20 to 80% by mol and with particular preference in the range of 40 to 60% by mol. The molar ratio of thiols or thiolates differently substituted from the formula Illa to each other is generally chosen within the range of 0.1 to 99.9 mol%, based on the total amount of thiols or thiolates substituted differently from the Illa formula , preferably in the range of 20 to 80% in mol and with particular preference in the range of 40 to 60% in mol. The invention further relates to compositions comprising a DPP of formula XXI and / or XXX and / or DPP la and / or Ib and diketo-diaryl pyrrolopyrrole (DPP) or a latent pigment DPP, wherein DPPs of formula XXI "and the, or XXX and Ib are different latent pigments of DPP that are described for example in U.S. Patent No. 5,616,725 In a preferred embodiment, the molar ratio of DPP of formula XXI and / or XXX to DPP, DPP of formula la or Ib, or latent pigment DPP is chosen in the range of 0.1 to 99.9 mol%, based on the total amount of DPP of formula XXI or XXX, DPP or latent pigment DPP, more preferably 20 to 80% by mol and with particular preference from 40 to 60% by mol These compositions of the invention can be prepared by customary methods, for example by mixing the individual components with each other according to methods customary in analogy for example to the method described in US Patent No. 5,200,528.The DPPs can pre stop by usual methods as described in US Pat. No. 5,200,528.
Similarly, the DPP latent pigments can be prepared in analogy to the method described in US Pat. No. 5,561,232. In addition, the invention relates to the use of DPP of the formula la and / or Ib as rheology enhancers or as crystal growth inhibitors. A further embodiment of the present invention relates to the use of DPPs of formula XXI or XXX as rheology enhancers or as crystal growth inhibitors. In addition, the invention relates to a rheology enhancer or crystal growth inhibitor comprising DPP of the formula la and / or Ib. In common practice, rheology enhancers or crystal growth inhibitors are used in compositions comprising DPP of the formula la and / or Ib and DPP or latent pigment DPP. A further embodiment of the present invention relates to compositions comprising DPP of the formula la and / or Ib and DPP or latent pigment DPP. The present invention further relates to a method for improving rheology or inhibiting crystal growth, which comprises incorporating an effective amount of DPP of the formula la and / or Ib into DPP or a latent pigment.
DPP. The molar ratio of DPP of the formula la and / or Ib is usually in the range of 0.1 to 20% mol based on DPP of the formula la and / or Ib and DPP or latent pigment DPP. In addition, the present invention relates to the use of DPP of formula XXI or XXX or bis-DPP Ib, or of a composition comprising a DPP of formula XXI and / or XXX and / or DPP la and / or Ib and diceto -diaryl-pyrrolopyrrole (DPP) or a latent pigment DPP, wherein DPPs of formula XXI and la, or XXX and Ib are different, to color / pigment organic material of high molecular mass. The invention additionally relates to a method for coloring / pigmenting organic material of high molecular mass, which comprises incorporating a coloristically effective amount of DPP of formula XXI or XXX or of bis-DPP Ib, or of a composition comprising a DPP of formula XXI and / or XXX and / or DPP la and / or Ib and diketo-diaryl-pyrrolopyrrole (DPP) or a latent pigment DPP, where DPPs of formula XXI and la, or XXX and Ib are different, by methods conventional, as described for example in the US patent No. 5,200,528. In addition, the invention relates to compositions comprising organic material of high molecular weight and DPP of the formula XXI or XXX or bis-DPP of the formula Ib. In general, the weight ratio of DPP of formula XXI or XXX or bis-DPP of formula Ib or compositions of the invention is from 0.01 to 30% by weight, preferably from 0.1 to 10% by weight, based on in the organic material of high molecular mass. Another preferred embodiment of the present invention relates to compositions consisting of organic material of high molecular mass and DPP of formula XXI or XXX or bis-DPP of formula Ib and also to compositions consisting of DPP of formula XXI or XXX or bis-DPP of the formula Ib and / or organic material of high molecular mass material and / or DPP of the formula la and also to compositions consisting of DPP of the formula XXI or XXX and / or organic material of high molecular mass and / or DPPs and also to compositions consisting of DPP of formula XXI or XXX and / or organic material of high molecular mass and / or DPP latent pigment and also to compositions consisting of DPP of formula XXI or XXX and / or organic material of high molecular mass and / or halo-DPP of the formula lia and also compositions consisting of DPP of the formula Ib and / or organic material of high molecular mass and / or halo-DPP of the formula IIb. Organic materials of high molecular mass can be of natural or synthetic origin. For example they may comprise natural resins or drying oils, rubber or casein or modified natural substances such as cellulose ethers or esters, cellulose acetate, cellulose propionate, cellulose acetobutyrate or nitrocellulose and especially fully synthetic organic polymers (thermosetting and thermoplastics) as obtained by addition polymerization, polycondensation, or polyaddition. Of the class of addition polymerization resins, mention must be made in particular of polyolefins, such as polyethylene, polypropylene or polyisobutylene, and also substituted polyolefins, such as addition polymers of vinyl chloride, vinyl acetate, styrene, acrylonitrile, acrylates and / or methacrylates or butadiene, and also addition copolymers of the aforementioned monomers, especially acrylonitrile-butadiene-styrene (ABS) or ethylene vinyl acetate (EVA). Of the series of polyaddition resins and polycondensation resins mention may be made of the condensation products of formaldehyde with phenols, known as phenolic resins, and condensation products of formaldehyde with urea, thiourea and melamine, known as amino resins, polyesters employed as film-forming resins, both saturated, such as alkyd resins, and unsaturated resins such as maleate resins, and also linear polyesters and polyamides and silicones. The aforementioned high molecular weight organic materials can be present individually or in mixtures, with plastic masses or fusions that can, if desired, be centrifuged into fibers. They can also be present in the form of their monomers or in the polymerized state in dissolved form as film formers or binders for coating materials or printing inks, such as linseed oil varnish, nitrocellulose, alkyd resins, melamine resins and resins urea-formaldehyde, or acrylic resins. The coloration / pigmentation of organic substances of high molecular mass with the DPPs of the formula XXI or XXX or bis-DPP of the formula Ib or compositions of the invention containing them, is generally carried out with the crude product resulting from the process of the invention, or following appropriate conditioning and treatment, for example in such a way that DPP of formula XXI or XXX or bis-DPP of formula Ib or compositions of the invention containing them, as such or in the form of Master batches are mixed with these substrates using roller mills or mixing or milling apparatus. The colored / pigmented material is generally brought to the desired final shape by techniques known per se, such as calendering, compression molding, extrusion, dispersion, casting or injection molding. It is often convenient, in order to produce non-rigid molded parts or to reduce their fragility, to add plasticizers to the high molecular weight compounds before their formation. Examples of these plasticizers are esters of phosphoric, phthalic or sebasic acid. The plasticizers can be incorporated into the polymers before or after the incorporation of the colorant. It is also possible, in order to obtain different shades, to add fillers or fillers and / or other coloring constituents such as white, colored or black pigments, in the desired amount to the organic substances of high molecular mass in addition to the DPPs of the formula XXI or XXX or bis-DPPs of the formula Ib. For pigmenting coating materials and printing inks, organic materials of high molecular mass and DPPs of formula XXI or XXX or bis-DPP of formula Ib or compositions of the invention comprising them alone or together with additives such as fillers or Fillers, other pigments, driers or plasticizers, are dissolved or finely dispersed in a customary manner in a common organic solvent or solvent mixture. In this context, it is possible to follow a procedure whereby individual components are dispersed or dissolved, individually or otherwise two or more are dissolved or dispersed together and only then all the components are combined. The resulting high molecular weight / bright pigmented molecular materials, examples are plastics, fibers, printing coatings, are remarkable for very high color strength, high saturation, good dispersibility, high strength to overcoating, heat, light, and bad weather and high luster. The process of the invention allows the preparation of a wide range of thio-substituted DPPs of the formula la, and even of long chain alkylthio-DPPs and water-soluble DPPs and also bis-DPPs with dithio bridges of the formula Ib. The DPPs of the formula la, the bis-DPPs of the formula Ib and the compositions of the invention comprising a DPP of the formula XXI or XXX, are dyes of high luster and transparency. The DPPs of the formula la and also the compositions of the invention comprising a DPP of the formula XXI or XXX, are particularly suitable for inhibiting crystal growth and improving rheology. The novel compounds or compositions and the compounds prepared by the process of this invention have good firmness properties when buckling, in high molecular weight material, in particular the material that is processed by injection molding using the novel compounds or compositions. Preferred high molecular weight materials for example are polyolefins. The high yields obtained with the process of the invention and its simplicity, which allows operation without high pressure and without catalysts even more, they are a guarantee of good economy. And emplos:
Example 1: Reaction of 1-octadecantiol with diketobis (4-chlorophenyl) pyrrolopyrrole (DPP of formula XXII, = halo-DPP of formula lia with G2 = G3 = para-phenyl with 1 carbon atom). 17.19 g (60 mmoles) of 1-octadecantiol, dissolved in 60 ml of dimethylacetamide, DMA, are added dropwise under nitrogen to a red suspension of 10.72 g (30 mmoles) of DPP XXII and 9.95 g (72 mmoles) of carbonate potassium in 260 ml of DMA. The resulting mixture is then heated to 393 K for 24 hours, during which time it turns violet. Process and isolation: The reaction mixture is cooled to room temperature and then emptied into 60 ml of ice-water. The aqueous reaction mixture is filtered. The filter residue is washed with methanol and then with water and subsequently dried under vacuum at 353 K. This gives 24.37 g (94.7% theory by weight) of a red pigment. E plos 2-10: see Tables 1, 2, 3 and 4 below. Examples 11-21: The reactions are carried out in analogy to those of Example 1 but, as opposed to Example 1, using instead of the DPP of formula XXII in Example 11: diketo-4,4'-dibromo (diphenyl) pyrrolopyrrole (DPP of the formula lia with G2 = G3 = para-Br-phenyl);
in Examples 12 and 13: diketo-4, 4 ', 3, 3' -tetrachloro- (diphenyl) pyrrolopyrrole (DPP of the formula lia with G2 = G3 = para, meta-dichlorophenyl); in Example 14: diketo-4-chloro (diphenyl) pyrrolopyrrole, (DPP of the formula lia with G2 (G_; G2 = para-chlorophenyl and
G? = phenyl); in Example 15: diketo-4-chloro-4-methyl- (diphenyl) -pyrrolopyrrole (DPP of the formula lia with G2 (G_; G2 = para-chlorophenyl and G1 = para-methylphenyl); in Example 16: diceto -4-chloro-4-tert-butyl (diphenyl) -pyrrolopyrrole (DPP of the formula lane with G2 (G_; G2 = para-chlorophenyl and Gx = para-tert-butylphenyl), -in Example 17: diceto-4 -chloro-4-phenyl (diphenyl) -pyrrolopyrrole (DPP of the formula lia with G2 (Gx; G2 = para-chlorophenyl and G_ = para-phenylphenyl); in Example 18: diketo-3-bromo (diphenyl) pyrrolopyrrole (DPP of the formula lia with G2 (G_; G2 = meta-bromophenyl and Gx = phenyl); in Examples 19-21 (bis-DPP preparation) diketo-4-chloro-4-phenyl (diphenyl) pyrrolopyrrole (DPP of formula 11b with G2 = para-chlorophenyl and G6 = phenyl) is used and in the
Examples 22-28 the reaction is carried out in analogy to
Example 1 but in composition to Example 1, using instead of DPP of formula XXII in Example 22 (composition comprising a halo-DPP XXII and a DPP lia with G, = G ^ = para-phenyl with 1 carbon atoms ) thiol in a stoichiometric amount with respect to halo-DPP XXII, and in Example 23 using in this case 1,3-dimethyl-3,4,5,6-tetrahydro-3 (1H) pyrimidinone in place of the DMA solvent , and in Examples 24-28: varying the bases. Table 1: Examples 1-28, whose reaction is carried out in analogy to that of Example 1, altered starting materials, experimental parameters and yields are indicated in the table.
** DMSO is dimethyl sulfoxide 1,3-dimethyl-3, 4,5,6-tetrahydro-3 (1H) pyrimidinone
Table Examples 1-28, whose processing and isolation are carried out in analogy to those of Example 1:
"+" means: component is used in the reaction. "-" means: component is not used in the reaction.
* Example 2: The residue described is recovered in 300 ml of methanol and stirred at room temperature, T 295 K, for 12 hours. The methanolic reaction mixture is filtered. The filter residue is washed with water. *** Example 4: The reaction mixture is poured into 600 ml of ice-water and neutralized with concentrated hydrochloric acid until the pH reaches 7. The aqueous reaction mixture is filtered. The filter residue is washed with methanol and water.
**** Example 11: After the filter residue has been washed with methanol and then with water, it is mixed with ethyl acetate, heated to boiling temperature and stirred at this temperature for 2 hours. The reaction mixture is subsequently filtered and the filter residue is dried under vacuum at 343 K. ***** Examples 12 and 13: After the filter residue has been washed with water, it is mixed with ethyl acetate, heated to boiling temperature and stirred at this temperature for 6 hours. The reaction mixture is subsequently filtered and the filter residue is dried under vacuum at 343 K. ****** Examples 19-21: As in ***** but using DMA in this case in place of ethyl acetate. ******** Example 22: After the filter residue has been washed with water, it is mixed with 300 ml of methanol / water (1: 1) and stirred at room temperature. The reaction mixture is subsequently filtered and the filter residue is washed with 300 ml of methanol and then with 300 ml of water and subsequently dried under vacuum at 343 K. Table 3: Elemental Analysis of Examples 1-21
Table 4: List of compounds of Examples 1 to 28
Claims (13)
1. A process for preparing an alkylthio- and / or arylthio-substituted diketo-diaryl pyrrolopyrrole (DPP) of the formula or a bis-dithio-diaryl pyrrolopyrrole dithio-bridged bis-DPP of the formula Ib wherein in the formula la, G is phenyl substituted by at least one arylthio or alkylthio group, and Gx is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate and in formula Ib, G5 is a phenylene, G6 is G_ but not G, and G7 is alkylene, cycloalkylene or phenylene, by reacting two haloaryls with a dithiol or dithiolate, which comprises reacting a thiol or thiolate with a halo-dike-diaryl-pyrrolopyrrole ("halo-DPP") of the formula lia wherein G2 is an unsubstituted or substituted halogen phenyl group, and G3 is G2 or G1 # or reacting a dithiol or dithiolate with two halo-diketo-diaryl-pyrrolopyrroles ("halo-DPPs") of the formula Ilb wherein Hal is halogen such as fluorine, chlorine, bromine or iodine. 2. A process according to claim 1, characterized in that the thiol or thiolate used is a compound of the formula Illa or a dithiol or dithiolate of the formula Ill
^ -SR Illa, R.2 ^ ~ ^ 7 - SR-2 Illb wherein Rx may be alkyl having 1 to 30 carbon atoms, which may be uninterrupted or interrupted one or more times by hetero-atoms, such as -O- or -S-, or by -NH-, -C (0 ) 0-, -0-C (0) - or -C (0) -NH-, and can be substituted or unsubstituted, or it can be cycloalkyl with 5 to 12 carbon atoms or phenyl, each of which can be substituted or unsubstituted, and R2 is hydrogen, a cation ("M") of an alkali metal, or an organic nitrogen base, and G7 can be alkylene with 1 to 30 carbon atoms which may be uninterrupted or interrupted or more times by hetero-atoms, such as -0- or -S-, or by -NH-, -C (0) 0-, -0-C (0) - or -C (0) -NH-, and it may be substituted or unsubstituted, or it may be cycloalkylene with 5 to 12 carbon atoms or phenylene, each of which may be substituted or unsubstituted.
3. A process according to claim 2, characterized in that the substituents of the alkyl radical, the cycloalkyl radical or the phenyl radical is alkyl with 1 to 18 carbon atoms, 0R3, S-R3, C (0) R3, C00R3, -OCOR3, S03R3, S02R3, P03R3, Si (OR) 3, a salt radical such as SM, OM, COOM, S03M, P03M, P (R3) Ax_, P ((R3) 2R4) 3 + X ", N02 , N (R3) 3 + X ", N ((R3) 2R4) 3A ~ or a nitrogen-containing radical, wherein R3 and R4 independently of each other are hydrogen, alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 6 carbon atoms or a phenyl unsubstituted or substituted by R7, M is a cation of an alkali metal, preferably sodium or potassium, X "is a halide, such as fluorine, chlorine, bromine or iodine and R7 is hydrogen, halogen such as F, Cl, Br, I or alkyl with 1 to 8 carbon atoms or cycloalkyl with 5 to 6 carbon atoms unsubstituted or substituted by NR3R4.
4. A process according to claim 2, characterized in that G2 in halo-DPP of the formula lia is a halogenated phenyl group unsubstituted or substituted, and G3 is G2 or Gx, or G6 in halo-DPP of the formula IIb is Gl, wherein G1 is a heterocyclic radical or a carbocyclic group of the formulas XI, XII, XIII wherein R ^, R, R10 and R1X independently are hydrogen, halogen such as F, Cl, Br or I or alkyl having 1 to 18 carbon atoms, -E-alkyl having 1 to 18 carbon atoms, -CN , -N02, trifluoromethyl, cycloalkyl with 5 to 6 carbon atoms, or where E is -O-, -S-, -NH-, -C (0) 0-, -0C (0) -, - (CO) NH-, -NHC (O) -, and R12 is a single bond -CH2-, -CH (CH3) -, -C (CH3) 2-, -CH = N-, -N = N-, -O-, -S-, -SO-, -S02- or -NR3 -.
5. A process according to claim 1 or 4, characterized in that G2 is a compound of the formula XV wherein Hal is fluorine, chlorine, bromine or iodine and R13 and R14 independently of each other are, for example, hydrogen, CN, CF3, alkyl with 1 to 5 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, -E-alkyl with 1 to 18 carbon atoms, phenyl, S-Rx, amides, such as -CONR3R4 or amides of the formulas XVI to XIX XVI XVII XVIII XIX or nitrogen-containing heterocyclic amides such as 1-carbonyl-imidazole, -pyrazole, -triazole, -pyrrole, -pyridinidine, -benzimidazole or -benzotriazole, or halogen such as fluorine, chlorine, bromine or iodine.
6. A process according to claim 1 to 5, characterized in that the reaction is conducted in the presence of a base. 7. A process according to claim 1 to 6, characterized in that the reaction is conducted in the presence of a solvent. 8. A diketo-diaryl-pyrrolpyrrole alkylthio and / or arylthio-substituted (DPP) of the formula XXI or XXX
XXI XXX or a bis-DPP of the formula Ib
Ib, wherein R15, R16 / R20 and R2_ independently of each other are hydrogen or R13 or R14, and G4 is a carbocyclic or heterocyclic radical, with the proviso that (a) R? in the formula XXI is not phenyl if R15 and R16 are hydrogen and G4 is phenyl, and (b) Rx in the formula XXX is not phenylene (alkyl with 1 to 3 carbon atoms) or alkyl with 1 to 12 carbon atoms if R15, R16, R2C, and R21 are hydrogen and G5 is a phenylene, G5 is a carbocyclic or heterocyclic radical and G7 is alkylene, cycloalkylene or phenylene.
9. A composition comprising DPP of formula XXI and / or XXX according to claim 8 and DPP la and / or Ib and diketo-diaryl-pyrrolopyrrole (DPP) or a latent pigment DPP, wherein DPPs of formula XXI and the, 0 XXX and Ib, are different.
10. A composition comprising DPP of formula XXI or XXX or bis-DPP of formula Ib according to claim 8 and an organic material of high molecular weight.
11. The use of a DPP of the formula or bis-DPP of the formula Ib prepared in accordance with the claim 1 as a rheology improver.
12. The use of a DPP of the formula or bis-DPP of the formula Ib prepared according to claim 1, as a crystal growth inhibitor.
13. The use of a DPP of formula XXI or XXX or bis-DPP of formula Ib according to claim 8, or of a composition according to claim 9, for coloring / pigmenting organic material of high molecular mass. SUMMARY OF THE INVENTION Preparation of alkylthio and / or arylthio-substituted diketo-diaryl-pyrrrolopyrroles (DPPs) of the formula la and bridged bis-dithio-diaryl-pyrrolopyrroles dithio (bis-DPPs) of the formula Ib wherein in the formula G is phenyl substituted by at least one arylthio or alkylthio group and Gx is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate and in the formula Ib G5 is phenylene, G6 is Gx but not G, and G7 is alkylene, cycloalkylene or phenylene, by reacting two haloaryls with a dithiol or dithiolate, which comprises reacting a thiol or thiolate with a halo-dithio-diaryl-pyrrolopyrrole ("halo-DPP") of the formula Ha He has, wherein G2 is a halogenated phenyl group and G3 is G2 or Gl, or reacting a dithiol or dithiolate with two halo-diketo-diaryl pyrrolopyrroles ("halo-DPPs") of the formula Hb wherein Hal is halogen such as fluorine, chlorine, bromine or iodine and G6 is G_, and also novel DPPs and also bis-DPPs, compositions comprising the DPPs of the formula prepared according to the invention, and their uses.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH915/98 | 1998-04-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA00009070A true MXPA00009070A (en) | 2001-07-09 |
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