CA1120472A - Process for the production of vat dyes and use thereof - Google Patents
Process for the production of vat dyes and use thereofInfo
- Publication number
- CA1120472A CA1120472A CA000307288A CA307288A CA1120472A CA 1120472 A CA1120472 A CA 1120472A CA 000307288 A CA000307288 A CA 000307288A CA 307288 A CA307288 A CA 307288A CA 1120472 A CA1120472 A CA 1120472A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- formula
- radical
- dimethyl
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000984 vat dye Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims abstract description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims abstract description 4
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000203 mixture Substances 0.000 description 19
- HKKLVMURVKXUTR-UHFFFAOYSA-N dihydroxyviolanthrone Chemical compound C1=CC(=C23)C(O)=C4C=CC=CC4=C2C=CC2=C3C1=C(C=C1)C3=C2C(=O)C(=O)C2=C3C1=C(O)C1=CC=CC=C12 HKKLVMURVKXUTR-UHFFFAOYSA-N 0.000 description 15
- 229940093956 potassium carbonate Drugs 0.000 description 13
- 235000011181 potassium carbonates Nutrition 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 6
- -1 alkylene radical Chemical group 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 150000002367 halogens Chemical group 0.000 description 4
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229940083608 sodium hydroxide Drugs 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 description 2
- XFNJYAKDBJUJAJ-UHFFFAOYSA-N 1,2-dibromopropane Chemical compound CC(Br)CBr XFNJYAKDBJUJAJ-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- UOORRWUZONOOLO-UHFFFAOYSA-N 1,3-dichloropropene Chemical compound ClCC=CCl UOORRWUZONOOLO-UHFFFAOYSA-N 0.000 description 2
- GJGVSVOBAALCJW-UHFFFAOYSA-N 2-chlorobutane Chemical compound C[CH]C(C)Cl GJGVSVOBAALCJW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 2
- 238000012505 colouration Methods 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- OPTDDWCXQQYKGU-UHFFFAOYSA-N diphenyldichloromethane Chemical compound C=1C=CC=CC=1C(Cl)(Cl)C1=CC=CC=C1 OPTDDWCXQQYKGU-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- FJEFRYPSCFFXEX-UHFFFAOYSA-N (1,2-dichloro-2-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(Cl)C(Cl)C1=CC=CC=C1 FJEFRYPSCFFXEX-UHFFFAOYSA-N 0.000 description 1
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- IYJYRKYSUOTLAE-UHFFFAOYSA-N 1,2-dibromoethanol Chemical compound OC(Br)CBr IYJYRKYSUOTLAE-UHFFFAOYSA-N 0.000 description 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- XGWWAEZPFMBRMQ-UHFFFAOYSA-N 1,3-dibromobutan-2-ol Chemical compound BrCC(C(C)Br)O XGWWAEZPFMBRMQ-UHFFFAOYSA-N 0.000 description 1
- KIHQZLPHVZKELA-UHFFFAOYSA-N 1,3-dibromopropan-2-ol Chemical compound BrCC(O)CBr KIHQZLPHVZKELA-UHFFFAOYSA-N 0.000 description 1
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- FEWDXGMBVQULLN-UHFFFAOYSA-N 1-hydroxy-2-phenyl-1,5,6,7-tetrahydro-4H-benzimidazol-4-one Chemical compound ON1C=2CCCC(=O)C=2N=C1C1=CC=CC=C1 FEWDXGMBVQULLN-UHFFFAOYSA-N 0.000 description 1
- OGZJULUCZAZKHP-UHFFFAOYSA-N 2,2-dibromoethanol Chemical compound OCC(Br)Br OGZJULUCZAZKHP-UHFFFAOYSA-N 0.000 description 1
- IDJOCJAIQSKSOP-UHFFFAOYSA-N 2,2-dichloroethanol Chemical compound OCC(Cl)Cl IDJOCJAIQSKSOP-UHFFFAOYSA-N 0.000 description 1
- ZEOVXNVKXIPWMS-UHFFFAOYSA-N 2,2-dichloropropane Chemical compound CC(C)(Cl)Cl ZEOVXNVKXIPWMS-UHFFFAOYSA-N 0.000 description 1
- RZUXIYDMQGCCDD-UHFFFAOYSA-N 2,3-dibromobutan-1-ol Chemical compound CC(Br)C(Br)CO RZUXIYDMQGCCDD-UHFFFAOYSA-N 0.000 description 1
- BXXWFOGWXLJPPA-UHFFFAOYSA-N 2,3-dibromobutane Chemical compound CC(Br)C(C)Br BXXWFOGWXLJPPA-UHFFFAOYSA-N 0.000 description 1
- QWVCIORZLNBIIC-UHFFFAOYSA-N 2,3-dibromopropan-1-ol Chemical compound OCC(Br)CBr QWVCIORZLNBIIC-UHFFFAOYSA-N 0.000 description 1
- RMISVOPUIFJTEO-UHFFFAOYSA-N 2,3-dichlorobutane Chemical compound CC(Cl)C(C)Cl RMISVOPUIFJTEO-UHFFFAOYSA-N 0.000 description 1
- FALCMQXTWHPRIH-UHFFFAOYSA-N 2,3-dichloroprop-1-ene Chemical compound ClCC(Cl)=C FALCMQXTWHPRIH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- UPSXAPQYNGXVBF-UHFFFAOYSA-N 2-bromobutane Chemical compound CCC(C)Br UPSXAPQYNGXVBF-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- IMFLCARKJQRLKB-UHFFFAOYSA-N 3,4-dibromobutan-1-ol Chemical compound OCCC(Br)CBr IMFLCARKJQRLKB-UHFFFAOYSA-N 0.000 description 1
- XVEASTGLHPVZNA-UHFFFAOYSA-N 3,4-dichlorobut-1-ene Chemical compound ClCC(Cl)C=C XVEASTGLHPVZNA-UHFFFAOYSA-N 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- CLBQZVYRGNGAMS-UHFFFAOYSA-N C1([ClH][ClH]C=C1)CCCO Chemical compound C1([ClH][ClH]C=C1)CCCO CLBQZVYRGNGAMS-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GQWNECFJGBQMBO-UHFFFAOYSA-N Molindone hydrochloride Chemical compound Cl.O=C1C=2C(CC)=C(C)NC=2CCC1CN1CCOCC1 GQWNECFJGBQMBO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- MEXUFEQDCXZEON-UHFFFAOYSA-N bromochlorodifluoromethane Chemical compound FC(F)(Cl)Br MEXUFEQDCXZEON-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- IHUREIPXVFKEDT-UHFFFAOYSA-N dibromo(dichloro)methane Chemical compound ClC(Cl)(Br)Br IHUREIPXVFKEDT-UHFFFAOYSA-N 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229960004109 potassium acetate Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
- C09B3/22—Dibenzanthrones; Isodibenzanthrones
- C09B3/30—Preparation from starting materials already containing the dibenzanthrone or isodibenzanthrone nucleus
- C09B3/36—Preparation from starting materials already containing the dibenzanthrone or isodibenzanthrone nucleus by etherification of hydroxy compounds
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for which the production of vat dyes of the formula (1) , wherein R is an alkylene radical of 1 to 6 carbon atoms which can be substituted by halogen, hydroxy or phenyl, an alkenylene radical of 1 to 6 carbon atoms or a phenly-lene radical, and the radical R can form 1 to 3 ring members between the two oxygen atoms, which process com-prises reacting the compound of the formula
A process for which the production of vat dyes of the formula (1) , wherein R is an alkylene radical of 1 to 6 carbon atoms which can be substituted by halogen, hydroxy or phenyl, an alkenylene radical of 1 to 6 carbon atoms or a phenly-lene radical, and the radical R can form 1 to 3 ring members between the two oxygen atoms, which process com-prises reacting the compound of the formula
Description
The present i.nvention relates to a process for the production of vat dyes of the formula ~: "' '`', ' t)~3 ' 1~~
wherein R is an alkylene radical o~ 1 to 6 carbon atoms which can be substituted by halogen, hydroxy or phenyl~ an alkenylene radical of 1 to 6 carbon atoms or a phenylene radical, and the radical R can form l to 3 ring members~
between the two oxygen atoms, which process comprises reacting the compound of the formula . ., . , , . . , . . .. , .. , . . .. ...... , .. . .. . , , . , . .. . , ., . , .. , ., ,. .:, , .. , .. ,.,.. ,., ., ., ., ,. ,. ._, .... .. . .............
' ` ' ' '' 7~
' 1~o~l, ~ ', o~3 in aprotic dipolar solvellts selected from the group con-sisting of sulfolane, N-methyl-2-pyrrolidone, hexamethyl-phosphoric triamide, dimethyl sulphoxide, dimethyl forma-mide, dimethyl acetamide, diethyl acetamide, acetonitrile and tetramethyl urea, with compounds o~ the formula X - R - X (3), wherein X is halogen and R is as defined in formula (I), in the presence of bases, at elevated temperature.
The alkylene radicals R can be straight~chain or bran~hed. If R is substituted by halogen, possible halogen substituents are fluorine, chlorine and bromine atoms. Preferably R is the ethylene radical.
. - As examples of R there may be cited:
-CH2-~ -CF2-, CC12-, -CBr~-, -CH~CH2-,-CH2-CH-, -CH - CH-, ~H~ CH3 CH3 -~=C-, -CH2-C-CH2~ -CH2-cH2-c~2 , ~H2 CH 2 ~ H
-CH~-CH2-CH~
¢~ .
()4~'~
Halogen atoms in the compo-mds of the formula (3) can be fluorine, chlorine and bromine atoms.
The starting compound of the formula (2), dihy-droxyviolanthrone, is known . Compounds of the form~lla (3), wherein R has the above meanings, are also known. Examples of such compounds are: dichloromethane, tr:ichloromethane, tetrachloromethane, 1,1 dichloroethane, 1,2-dichloro-ethane~ 1,1,2-trichloroethane, 1,2-dichloroethylene, 1,1-, 1;2-, 1,3- and 2,2-dichloropropane a 1,2,3-trichloropropane, 1,3-dichloro-1 propene, 2,3-dichloro-1-propene, 1,1-, 1,2-, 1,3-, 2,2- and 2,3-dichlorobutane, 3,4 dichloro-l-butene,
wherein R is an alkylene radical o~ 1 to 6 carbon atoms which can be substituted by halogen, hydroxy or phenyl~ an alkenylene radical of 1 to 6 carbon atoms or a phenylene radical, and the radical R can form l to 3 ring members~
between the two oxygen atoms, which process comprises reacting the compound of the formula . ., . , , . . , . . .. , .. , . . .. ...... , .. . .. . , , . , . .. . , ., . , .. , ., ,. .:, , .. , .. ,.,.. ,., ., ., ., ,. ,. ._, .... .. . .............
' ` ' ' '' 7~
' 1~o~l, ~ ', o~3 in aprotic dipolar solvellts selected from the group con-sisting of sulfolane, N-methyl-2-pyrrolidone, hexamethyl-phosphoric triamide, dimethyl sulphoxide, dimethyl forma-mide, dimethyl acetamide, diethyl acetamide, acetonitrile and tetramethyl urea, with compounds o~ the formula X - R - X (3), wherein X is halogen and R is as defined in formula (I), in the presence of bases, at elevated temperature.
The alkylene radicals R can be straight~chain or bran~hed. If R is substituted by halogen, possible halogen substituents are fluorine, chlorine and bromine atoms. Preferably R is the ethylene radical.
. - As examples of R there may be cited:
-CH2-~ -CF2-, CC12-, -CBr~-, -CH~CH2-,-CH2-CH-, -CH - CH-, ~H~ CH3 CH3 -~=C-, -CH2-C-CH2~ -CH2-cH2-c~2 , ~H2 CH 2 ~ H
-CH~-CH2-CH~
¢~ .
()4~'~
Halogen atoms in the compo-mds of the formula (3) can be fluorine, chlorine and bromine atoms.
The starting compound of the formula (2), dihy-droxyviolanthrone, is known . Compounds of the form~lla (3), wherein R has the above meanings, are also known. Examples of such compounds are: dichloromethane, tr:ichloromethane, tetrachloromethane, 1,1 dichloroethane, 1,2-dichloro-ethane~ 1,1,2-trichloroethane, 1,2-dichloroethylene, 1,1-, 1;2-, 1,3- and 2,2-dichloropropane a 1,2,3-trichloropropane, 1,3-dichloro-1 propene, 2,3-dichloro-1-propene, 1,1-, 1,2-, 1,3-, 2,2- and 2,3-dichlorobutane, 3,4 dichloro-l-butene,
2,2-dichloroethanol, 2,3-dichloro l-propanol, 1,3-dichloro-2-propanol, dibromomethane, chlorobromomethane, tribromo-methane, te~rabromomethane~ dichlorodibromomethane, tri-chlorobromomethane, l,l-dibromoethane, 1,2-dibromoethane, l,l-, 1,2- and 1,3-dibromopropane, 1,1-, 1,2-, 1,3-~ 2,2-and 2,3-dibromobutane, 1,2-dibromoethanol, 2,2-dibromo-ethanol, 1,3-dibromo-2-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-2-butanol, 2,3-dibromo-l-butanol, 3,4-dibromo-l-butanol, difluoromethane, tri1uoromethane, tetrafluor-methane, trifluorochlormethane, dichlorodifluoromethanc, chlorotrifluoromethane, dichlorofluoromethane, chloro-difluoromethane, trifluorobromomethane, difluorochloro-bromomethane, l,l-difluoroethane, penta1uoroethane, hexa-fluoroethane, tetrachloro-1,2-difluoroe~hane, 1,2~dichloro-l,l-di-fluoroethane, tetrafluoroethylen, a,a-dichlorodi-phenylmethane, 1,2-dichloro-1,2-diphenylethane, 1,2-dibro-mo-1,2-diphenylethane, benzal chloride, benzal bromide, 1~2-dichlorobenzene, 1,3-dichlorobenzene, 1,2-dibromo-benzene and 1,3-dibromobenzene.
Sulpholane, N-methyl-2-pyrrolidone or hexa-methylphosphoric triamide are preferably used as ap.rotic dipolar solvents.
. . .
:
9L7~:
.
As bases there may be mentioned: sodium hydro-xide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, potassium hydrogen carbonate, potassium formiate, sodium propionate, potassium phosphate etc. Pre-ferred bases are sodium carbonate, potassium carbonate or sodium acetate.
To shorten the reaction times, the reaction of the present invention is carried out at elevated te~peratu-re, i.e. above room temperature. Preferably the reaction is carried out in the temperatu~ range between 100 and The reaction is carried out in a manner which is in itself known in closed reaction vessel and under re-1ux etc., if necessary~ under pressure in an autoclave.
The working up of the reaction mixture also is effected in a manner which is in itsel known.
Ethylene chloride is preferably used as compound of the formula (3).
The vat dyes of the formula (1) give blue (navy blue) shades; but if R is a methylene or substituted methy-lene group, the shades are red, and if R has 3 ring members (e.g. propylene, methylpropylene), greenish shades are obtained The dyes have a very good build-up and exhaustion capacity and the dyeings obtained with them are distin-guished by good fastness properties.
The preferred vat dye of the formula (1), wherein R is ethylene, gives a clear unitary navy blue shade. It is also distinguished by a good build-up and exhaustion capaci-ty and, in particular, by the very good fastness to water-spotting of the dyeings obtained with it.
Compared with the prior art (~IOS 987, 70, US
patent specifications 1,531,261, 1,761,624, 1,950~366, 2,218,663, 2~318,663, 2,318,266, 2,662,892 and 3,036,095~, ,, , . ,~. , . ,.. . . ,.. .......... ,.. ,.. - ....
.
the process of the present inventlon is distinguished by the fact that it makes possible shorter reaction times, the use of simpler apparatus, and lower reaction temperatures.
The process of the present invention, which is carried out with dihydroxyviolanthrone and ethylene chlo-ride as starting materials, constitutes the simplest and cheapest method of obtaining the preferred vat dye of the formula (1~ (C.I. Vat Blue 16).
The invention is illustrated by the following Examples, in which the parts are by weigbt, .. ... . .
; ~...,., ..~.... ..
,:
Example 1 ~
1~1 o~ CH2 ~0~ 2 (4) o~
A mixture of 20 parts of dihydroxyviolanthrone and 20 parts of potassium carbonate is suspended in 150 parts of sulpho-lane. To the suspension are added 20 parts of ethylene chloride and the resulting reaction mixture is heated. The temperature is kept for 1 hour at 130 C, then raised to 150-155C, and the mixture is stirred for 5 hours. I'hen the reaction mixture is allowed to cool to room temperature and filtered. The product is washed with sulpholane, then suspended in water, washed neutral, and dried at 100C.
Yield: 20 parts (94.9 % of theory).
Analysis: Cl~ 0.3%.
A vat dye which is virtually identical with the product of this Example is obtained by using ethylene bromide as starting material instead of ethylene chloride.
The same vat dye is also obtained in good,,yield by using the corresponding amount of dimethyl sulphoxide, dimethyl formamide, dimethyl acetamide~ diethyl acetamide, acetonitrile or tetramethyl urea instead of sulpholane as solvent, and carrying out the reaction in a manner analogous to that described in this Example or, if necessary, under pressure in an autoclave.
. _ . _ .. . . . ... .. .... . .. . .. . . . . . . .
.
.~ ' . ' z 20 parts of dihydroxyviolanthrone and 20 parts of potas-sium carbonate are suspended in 150 parts of N-methyl-2-pyrrolidone. To the suspension are added 20 parts of ethylene chloride, then the mixture is heated and the temperature is kept for 1 hour at 130C. The temperature is then raised to 145-150C and the mixture is stirred for S hours at this temperature. The reaction mixture is then allowed to cool to room temperature, filtered, and the residue is washed with N-methyl-2-pyrrolidone. The resulting product is suspended in water, washed neutral and dried at 100C.
Yield: 19.8 parts (94.5% of theory).
Analysis: Cl~ 0.3%.
The resulting vat dye is identical with that of Example L.
Example 3 '. 0~
~L
- - ~ C~:~ (5) '. o~3 15 parts of dihydroxyviolanthrone and 15 parts of potassium carbonate are suspended in 100 parts of N-methyl-2-pyrro-.
.. , . , .. . . , . . ... . . . . . . . .. , .. . ... .... ., .. , . " .. . . ... ., ,,.. ~"_ . . .... ~ .
..
0~7Z
lidone. Then 15 parts of methylene bromide are added to thesuspension. The reactivn mixture is heated and stirred for 6 hours at 140-145C, ~hen cooled to room ~emperature and poured into water. The precipitated product is collected by filtration 9 washed neutral with water and dried at 100C.
Yield: 15.5 parts ~100% of theory).
Analysis: Br~ 0.3%.
Example 4 15 parts of dihydroxyviolanthrone and 15 parts of sodium carbonate are suspended in 100 parts o N-methyl-2 pyrro-lidone. Then 15 parts of ethylene bromide are added to the suspension. The reaction mixture is heated and stirred for 6 hours at 140-145C, then cooled to room temperature and poured into water. The precipitated product is collected by filtration, washed neutral with water aIId dried at 100C.
Yield: 15 parts.
Analysis: Br ~ 0.3%.
The resulting vat dye is identical with that of Example 1.
Instead of using 15 parts of sodium carbonate, it is also possible to use 15 parts of a mixture of sodium carbonate and potassium carbonate in the ratio 1:1.
20 parts of dihydroxyviolanthrone and 20 parts of potas-sium carbonate are suspended in 150 parts of hexamethyl-phosphoric triamide. To the suspension are added 20 parts of ethylene chloride and the mixture is then heated and kept for 1 hour at 130C. The temperature is subsequently raised to 145-150C and the reaction mixture is stirred for 5 hours at this temperature, then cooled to room temperature and filtered. The residue is washed with hexa-methylphosphoric triamide and the resulting product is :
suspended in water, washed neutral and dried at 100 C.
Yield: 19.8 parts (94.5% of theory).
Analysis ClS 0.3%.
The resulting vat dye is identical with that of Example 1.
Example 6 lS parts of dihydroxyviolanthrone and lS parts of potas-sium carbonate are suspended in 100 parts of sulpholane.
To the suspension are then added 15 parts of methylene bromide and the mixture is heated and stirred for 6 hours at 140-145C. The react:ion mixture is then cooled to room temperature and poured into water. The precipitated product is collected by filtration~ washed neutral with water and dried at 100C.
Yield: 15 parts.
Analysis: Br ~0.3%.
The resulting vat dye is identical with that of Example 3.
15 parts of dihydroxyviolanthrone and 15 parts of sodium carbonate are suspended in 100 parts of N~methyl-2-pyrro-lidone. Then 15 parts of methylene bromide are addecl to the suspension. The mixture is heated and stirred for 6 hours at 140-145C. The reaction mixture is subsequently cooled to room tem~erature and poured into water. The precipitated product is collected by filtration, washed neutral with water and dried at 100C.
Yield: 15.2 parts.
Analysis: Br~ 0.3~/0.
The resulting vat dye is identical with that of Example 3.
Example 8 20 parts of dihydroxyviolanthrone and 20 parts of a mixtu-re of 10 parts of sodium carbonate and 10 parts of potas-sium carbonate are suspended in lS0 parts of N-methyl-2-pyrrolidone. Then 20 parts of methylene bromide are added to the suspension and the mixture is heated and stirred for 6 hours at 140-145C. The reaction mixture is subse-quently cooled to room temperature and poured into water.
The precipitated product is collected by filtration, washed neutral with water and dried at 100C.
Yield: 20.7 parts Analysis: Br~ 0.3%.
The resulting vat dye is identical with that of Example 3.
E mple 9 o~
(~Lo~
~ 0/C ~ (6) 0~
30 parts of dihydroxyviolanthrone and 30 parts o~ potas-siwm carbonate are suspended in 200 parts of N-methyl-2-pyrroLidone. Then 20 parts of dichlorodiphenylmethane arP
added to the suspension and the mixture is heated and stir-red for 6 hours at 140-145C. The reaction mixture is subsequently cooled to room temperature and poured into water. The precipitated product is collected by filtration, washed neutral with water and dried at 100C.
The resulting vat dye colours cotton in navy blue shades.
Yield: 36.7 parts (92% of theory).
.
, 47;~
Analysis: Cl~ 0.3%.
Example 10 ~', ' ' .
~--O--CH2 ~ ~ C 3 0~
15 parts of dihydroxyviolanthrone and 15 parts of potas-sium carbonate are suspended in 100 parts of N-~lethyl-2-pyrrolidone. Then 15 parts of 1,2-dibromopropane are added to the suspension and the mixture is heated and stirred for 6 hours at 140-145C. The reaction mixture is subsequently cooled to room temperature and poured into water. The preci-pitated product is collected by filtration, washed neutral with water and dried at L00C. The resulting vat dye co-lours cotton in navy blue shades.
, Yield: 15.8 parts (98% of theory).
Analysis: Br G 0~.3%.
: :
Exampl-e 11 15 parts of dihydroxyviolanthrone and lS parts of potas-sium carbonate are suspended in 100 parts of sulpholane~
Then 15 parts of 1,2-dibromopropane are added to the suspen-sion and the mixture is heated and stirred for ~ hours at 140-145C. The reaction mixture is subsequently cooled to room temperature and poured into water. The precipitated product is collected by filtration, washed neutral with ` ' , .
4~
water and dried at 100C.
Yield: 15.6 parts ~97% of theory)~
Analysis: Br~ 0.37/0.
The resulting vat dye is identi.cal with that of Example 10.
Example 12 0~
~L O-CH2 _ O_~H2/ 2 t8) 0~
20 parts of dihydroxyviolanthrone and 20 parts of potas-sium carbonate are suspended in lS0 parts of N-methyl-2-pyrrolidone. Then 20 parts of 1,3-dibromopropane are added to the suspension and the mixture is heated and stirred for 10 hours in an autoclave at 140-145C and under a pres-sure of 5 to 9 bar. The reaction mixture is then cooled to room temperature and poured into water. The precipita~ed product is collected by filtration, washed neutral with water and dried at 100C. The resulting vat dye colours cotton in bluish-green shades.
Yield: 22 parts (~J100% of theory).
Analysis: Br ~ 0.3%, l~Z~g~7Z
Example 13 ~3 ' o-CH2~1 (9 ) O~CH
~ ~ CH3 :: 0 ~
~: :
20 parts of dihydroxyviolanthrone~ and 20 parts of potas-sium carbonate are suspended in 150 parts of N-methy'L-2-pyrrolidone. The 20 parts of 1,3-dibromopropane are added to the suspension and the mixture is heated and stirred ~or 6 hours at 140-145C. The reaction mixture is then cooled to room temperature and poured into water. The pre-cipitated product is collected by filtration, washed neu-~ral with water and dried at 100C. The resulting vat dye colours cotton in bluish-green~shades.
Yield: 22 parts (99% of theory) - Analysis: Br~ 0.3%.
DyeLn~ Procedure .
1 part of dye is stirred at 50-70C with 10 parts by vo-lume of sodium hydroxide having a specific gravity of 36 Bé and 5 parts of sodium hydrosulphite in 200 parts of water. The above stock vat is aflded to a dyebath which con-tains, in 2000 parts of water, 5 parts by volume of sodium hydroxide solution with a specific gravity of 36 Bé and
Sulpholane, N-methyl-2-pyrrolidone or hexa-methylphosphoric triamide are preferably used as ap.rotic dipolar solvents.
. . .
:
9L7~:
.
As bases there may be mentioned: sodium hydro-xide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, potassium hydrogen carbonate, potassium formiate, sodium propionate, potassium phosphate etc. Pre-ferred bases are sodium carbonate, potassium carbonate or sodium acetate.
To shorten the reaction times, the reaction of the present invention is carried out at elevated te~peratu-re, i.e. above room temperature. Preferably the reaction is carried out in the temperatu~ range between 100 and The reaction is carried out in a manner which is in itself known in closed reaction vessel and under re-1ux etc., if necessary~ under pressure in an autoclave.
The working up of the reaction mixture also is effected in a manner which is in itsel known.
Ethylene chloride is preferably used as compound of the formula (3).
The vat dyes of the formula (1) give blue (navy blue) shades; but if R is a methylene or substituted methy-lene group, the shades are red, and if R has 3 ring members (e.g. propylene, methylpropylene), greenish shades are obtained The dyes have a very good build-up and exhaustion capacity and the dyeings obtained with them are distin-guished by good fastness properties.
The preferred vat dye of the formula (1), wherein R is ethylene, gives a clear unitary navy blue shade. It is also distinguished by a good build-up and exhaustion capaci-ty and, in particular, by the very good fastness to water-spotting of the dyeings obtained with it.
Compared with the prior art (~IOS 987, 70, US
patent specifications 1,531,261, 1,761,624, 1,950~366, 2,218,663, 2~318,663, 2,318,266, 2,662,892 and 3,036,095~, ,, , . ,~. , . ,.. . . ,.. .......... ,.. ,.. - ....
.
the process of the present inventlon is distinguished by the fact that it makes possible shorter reaction times, the use of simpler apparatus, and lower reaction temperatures.
The process of the present invention, which is carried out with dihydroxyviolanthrone and ethylene chlo-ride as starting materials, constitutes the simplest and cheapest method of obtaining the preferred vat dye of the formula (1~ (C.I. Vat Blue 16).
The invention is illustrated by the following Examples, in which the parts are by weigbt, .. ... . .
; ~...,., ..~.... ..
,:
Example 1 ~
1~1 o~ CH2 ~0~ 2 (4) o~
A mixture of 20 parts of dihydroxyviolanthrone and 20 parts of potassium carbonate is suspended in 150 parts of sulpho-lane. To the suspension are added 20 parts of ethylene chloride and the resulting reaction mixture is heated. The temperature is kept for 1 hour at 130 C, then raised to 150-155C, and the mixture is stirred for 5 hours. I'hen the reaction mixture is allowed to cool to room temperature and filtered. The product is washed with sulpholane, then suspended in water, washed neutral, and dried at 100C.
Yield: 20 parts (94.9 % of theory).
Analysis: Cl~ 0.3%.
A vat dye which is virtually identical with the product of this Example is obtained by using ethylene bromide as starting material instead of ethylene chloride.
The same vat dye is also obtained in good,,yield by using the corresponding amount of dimethyl sulphoxide, dimethyl formamide, dimethyl acetamide~ diethyl acetamide, acetonitrile or tetramethyl urea instead of sulpholane as solvent, and carrying out the reaction in a manner analogous to that described in this Example or, if necessary, under pressure in an autoclave.
. _ . _ .. . . . ... .. .... . .. . .. . . . . . . .
.
.~ ' . ' z 20 parts of dihydroxyviolanthrone and 20 parts of potas-sium carbonate are suspended in 150 parts of N-methyl-2-pyrrolidone. To the suspension are added 20 parts of ethylene chloride, then the mixture is heated and the temperature is kept for 1 hour at 130C. The temperature is then raised to 145-150C and the mixture is stirred for S hours at this temperature. The reaction mixture is then allowed to cool to room temperature, filtered, and the residue is washed with N-methyl-2-pyrrolidone. The resulting product is suspended in water, washed neutral and dried at 100C.
Yield: 19.8 parts (94.5% of theory).
Analysis: Cl~ 0.3%.
The resulting vat dye is identical with that of Example L.
Example 3 '. 0~
~L
- - ~ C~:~ (5) '. o~3 15 parts of dihydroxyviolanthrone and 15 parts of potassium carbonate are suspended in 100 parts of N-methyl-2-pyrro-.
.. , . , .. . . , . . ... . . . . . . . .. , .. . ... .... ., .. , . " .. . . ... ., ,,.. ~"_ . . .... ~ .
..
0~7Z
lidone. Then 15 parts of methylene bromide are added to thesuspension. The reactivn mixture is heated and stirred for 6 hours at 140-145C, ~hen cooled to room ~emperature and poured into water. The precipitated product is collected by filtration 9 washed neutral with water and dried at 100C.
Yield: 15.5 parts ~100% of theory).
Analysis: Br~ 0.3%.
Example 4 15 parts of dihydroxyviolanthrone and 15 parts of sodium carbonate are suspended in 100 parts o N-methyl-2 pyrro-lidone. Then 15 parts of ethylene bromide are added to the suspension. The reaction mixture is heated and stirred for 6 hours at 140-145C, then cooled to room temperature and poured into water. The precipitated product is collected by filtration, washed neutral with water aIId dried at 100C.
Yield: 15 parts.
Analysis: Br ~ 0.3%.
The resulting vat dye is identical with that of Example 1.
Instead of using 15 parts of sodium carbonate, it is also possible to use 15 parts of a mixture of sodium carbonate and potassium carbonate in the ratio 1:1.
20 parts of dihydroxyviolanthrone and 20 parts of potas-sium carbonate are suspended in 150 parts of hexamethyl-phosphoric triamide. To the suspension are added 20 parts of ethylene chloride and the mixture is then heated and kept for 1 hour at 130C. The temperature is subsequently raised to 145-150C and the reaction mixture is stirred for 5 hours at this temperature, then cooled to room temperature and filtered. The residue is washed with hexa-methylphosphoric triamide and the resulting product is :
suspended in water, washed neutral and dried at 100 C.
Yield: 19.8 parts (94.5% of theory).
Analysis ClS 0.3%.
The resulting vat dye is identical with that of Example 1.
Example 6 lS parts of dihydroxyviolanthrone and lS parts of potas-sium carbonate are suspended in 100 parts of sulpholane.
To the suspension are then added 15 parts of methylene bromide and the mixture is heated and stirred for 6 hours at 140-145C. The react:ion mixture is then cooled to room temperature and poured into water. The precipitated product is collected by filtration~ washed neutral with water and dried at 100C.
Yield: 15 parts.
Analysis: Br ~0.3%.
The resulting vat dye is identical with that of Example 3.
15 parts of dihydroxyviolanthrone and 15 parts of sodium carbonate are suspended in 100 parts of N~methyl-2-pyrro-lidone. Then 15 parts of methylene bromide are addecl to the suspension. The mixture is heated and stirred for 6 hours at 140-145C. The reaction mixture is subsequently cooled to room tem~erature and poured into water. The precipitated product is collected by filtration, washed neutral with water and dried at 100C.
Yield: 15.2 parts.
Analysis: Br~ 0.3~/0.
The resulting vat dye is identical with that of Example 3.
Example 8 20 parts of dihydroxyviolanthrone and 20 parts of a mixtu-re of 10 parts of sodium carbonate and 10 parts of potas-sium carbonate are suspended in lS0 parts of N-methyl-2-pyrrolidone. Then 20 parts of methylene bromide are added to the suspension and the mixture is heated and stirred for 6 hours at 140-145C. The reaction mixture is subse-quently cooled to room temperature and poured into water.
The precipitated product is collected by filtration, washed neutral with water and dried at 100C.
Yield: 20.7 parts Analysis: Br~ 0.3%.
The resulting vat dye is identical with that of Example 3.
E mple 9 o~
(~Lo~
~ 0/C ~ (6) 0~
30 parts of dihydroxyviolanthrone and 30 parts o~ potas-siwm carbonate are suspended in 200 parts of N-methyl-2-pyrroLidone. Then 20 parts of dichlorodiphenylmethane arP
added to the suspension and the mixture is heated and stir-red for 6 hours at 140-145C. The reaction mixture is subsequently cooled to room temperature and poured into water. The precipitated product is collected by filtration, washed neutral with water and dried at 100C.
The resulting vat dye colours cotton in navy blue shades.
Yield: 36.7 parts (92% of theory).
.
, 47;~
Analysis: Cl~ 0.3%.
Example 10 ~', ' ' .
~--O--CH2 ~ ~ C 3 0~
15 parts of dihydroxyviolanthrone and 15 parts of potas-sium carbonate are suspended in 100 parts of N-~lethyl-2-pyrrolidone. Then 15 parts of 1,2-dibromopropane are added to the suspension and the mixture is heated and stirred for 6 hours at 140-145C. The reaction mixture is subsequently cooled to room temperature and poured into water. The preci-pitated product is collected by filtration, washed neutral with water and dried at L00C. The resulting vat dye co-lours cotton in navy blue shades.
, Yield: 15.8 parts (98% of theory).
Analysis: Br G 0~.3%.
: :
Exampl-e 11 15 parts of dihydroxyviolanthrone and lS parts of potas-sium carbonate are suspended in 100 parts of sulpholane~
Then 15 parts of 1,2-dibromopropane are added to the suspen-sion and the mixture is heated and stirred for ~ hours at 140-145C. The reaction mixture is subsequently cooled to room temperature and poured into water. The precipitated product is collected by filtration, washed neutral with ` ' , .
4~
water and dried at 100C.
Yield: 15.6 parts ~97% of theory)~
Analysis: Br~ 0.37/0.
The resulting vat dye is identi.cal with that of Example 10.
Example 12 0~
~L O-CH2 _ O_~H2/ 2 t8) 0~
20 parts of dihydroxyviolanthrone and 20 parts of potas-sium carbonate are suspended in lS0 parts of N-methyl-2-pyrrolidone. Then 20 parts of 1,3-dibromopropane are added to the suspension and the mixture is heated and stirred for 10 hours in an autoclave at 140-145C and under a pres-sure of 5 to 9 bar. The reaction mixture is then cooled to room temperature and poured into water. The precipita~ed product is collected by filtration, washed neutral with water and dried at 100C. The resulting vat dye colours cotton in bluish-green shades.
Yield: 22 parts (~J100% of theory).
Analysis: Br ~ 0.3%, l~Z~g~7Z
Example 13 ~3 ' o-CH2~1 (9 ) O~CH
~ ~ CH3 :: 0 ~
~: :
20 parts of dihydroxyviolanthrone~ and 20 parts of potas-sium carbonate are suspended in 150 parts of N-methy'L-2-pyrrolidone. The 20 parts of 1,3-dibromopropane are added to the suspension and the mixture is heated and stirred ~or 6 hours at 140-145C. The reaction mixture is then cooled to room temperature and poured into water. The pre-cipitated product is collected by filtration, washed neu-~ral with water and dried at 100C. The resulting vat dye colours cotton in bluish-green~shades.
Yield: 22 parts (99% of theory) - Analysis: Br~ 0.3%.
DyeLn~ Procedure .
1 part of dye is stirred at 50-70C with 10 parts by vo-lume of sodium hydroxide having a specific gravity of 36 Bé and 5 parts of sodium hydrosulphite in 200 parts of water. The above stock vat is aflded to a dyebath which con-tains, in 2000 parts of water, 5 parts by volume of sodium hydroxide solution with a specific gravity of 36 Bé and
3.7 parts of sodium hydrosulphite. 100 parts of cotton are put into thls batb at 40C. After L0 m~nutes, 15 parts of ~ , , ' ' :
' ' ' sodium chloride are added and after 20 minutes a further 15 parts are added and dyeing is performed for ~5 m.inutes at 40 C~ The cotton is squeezed out, oxidised, and finished in the usual manner.
Pigment Colouration 5 parts of dye are mixed with 95 parts o~ dioctyl phthalate and the mixture is ground in a ball mill until the dye particles are smaller than 3 ~I
0~8 part of this dioctyl phthalate paste are mixed with 13 parts of polyvinyl chloride, 7 parts of dioctyl phthalate and 0 1 part of càdmium stearate and this mixture is rol-led for 5 minutes on a two roll mill at 140C to a colou-red sheet having good migration properties and good light-fastness.
Lacquer Colouration 10 g of titanium dioxide and 2 g o dye are ground for 48 hours in a ball mill with a mixture of 26.4 g of coconut alkyd resin, 24 g of melamine/formaldehyde resin (50% so-lids content), 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene. The resulting lacquer is sprayed onto an aluminium sheet, predried for 30 minutes at room tempe-rature and then stoved for 30 minutes at 120C, to give a finish which has very good colour strength and is dis-tinguished by good fastness to overstripe bleeding, out-standing lightfastness and good resistance to atmospheric influences.
~;
: .
' ' ' sodium chloride are added and after 20 minutes a further 15 parts are added and dyeing is performed for ~5 m.inutes at 40 C~ The cotton is squeezed out, oxidised, and finished in the usual manner.
Pigment Colouration 5 parts of dye are mixed with 95 parts o~ dioctyl phthalate and the mixture is ground in a ball mill until the dye particles are smaller than 3 ~I
0~8 part of this dioctyl phthalate paste are mixed with 13 parts of polyvinyl chloride, 7 parts of dioctyl phthalate and 0 1 part of càdmium stearate and this mixture is rol-led for 5 minutes on a two roll mill at 140C to a colou-red sheet having good migration properties and good light-fastness.
Lacquer Colouration 10 g of titanium dioxide and 2 g o dye are ground for 48 hours in a ball mill with a mixture of 26.4 g of coconut alkyd resin, 24 g of melamine/formaldehyde resin (50% so-lids content), 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene. The resulting lacquer is sprayed onto an aluminium sheet, predried for 30 minutes at room tempe-rature and then stoved for 30 minutes at 120C, to give a finish which has very good colour strength and is dis-tinguished by good fastness to overstripe bleeding, out-standing lightfastness and good resistance to atmospheric influences.
~;
: .
Claims (5)
1. A process for the production of vat dyes of the formula (l), wherein R is an alkylene radical of 1 to 6 carbon atoms which can be substituted by halogen, hydroxy or phenyl, an alkenylene radical of 1 to 6 carbon atoms or a pheny-lane radical, and the radical R can form 1 to 3 ring members between the two oxygen atoms, which process com-prises reacting the compound of the formula (2), in aprotic dipolar solvents selected from the group con-sisting of sulpholane, N-methyl-2-pyrrolidone, hexamethyl-phosphoric triamide, dimethyl sulphoxide, dimethyl forma-mide, dimethyl acetamide, diethyl acetamide, acetonitrile and tetramethyl urea, with compounds of the formula X - R - X (3), wherein X is halogen and R is as defined in formula (1), in the presence of bases, at elevated temperature.
2. A process according to claim 1, wherein sulpho-lane, N methyl-2-pyrrolidone or hexamethylphosphoric triami-de are used as aprotic dipolar solvents.
3. A process according to claim 1, wherein sodium carbonate, potassium carbonate or sodium acetate are used as bases.
4. A process according to claim 1, wherein the reaction is carried out in the temperature range between 100° and 200°C
5. A process according to claim 1, wherein ethy-lene chloride is used as compound of the formula (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
LU77773 | 1977-07-15 | ||
LU77773A LU77773A1 (en) | 1977-07-15 | 1977-07-15 | COIL COLORS, THEIR PRODUCTION AND USE |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1120472A true CA1120472A (en) | 1982-03-23 |
Family
ID=19728640
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000307288A Expired CA1120472A (en) | 1977-07-15 | 1978-07-13 | Process for the production of vat dyes and use thereof |
Country Status (11)
Country | Link |
---|---|
JP (1) | JPS5420040A (en) |
BE (1) | BE868990A (en) |
BR (1) | BR7804544A (en) |
CA (1) | CA1120472A (en) |
CH (1) | CH637413A5 (en) |
DE (1) | DE2830881A1 (en) |
ES (1) | ES471713A1 (en) |
FR (1) | FR2397441A1 (en) |
GB (1) | GB2001093B (en) |
IT (1) | IT7850258A0 (en) |
LU (1) | LU77773A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4463174A (en) * | 1981-09-28 | 1984-07-31 | Ciba-Geigy Corporation | Process for producing dibenzanthrone containing vat dyes |
JPS59125222A (en) * | 1982-12-29 | 1984-07-19 | Matsushita Giken Kk | Positioning device of top plate for drum can |
DE3631072A1 (en) * | 1986-09-12 | 1988-03-24 | Basf Ag | METHOD FOR PRODUCING C.I. VAT BLUE 16 |
JPH0787952B2 (en) * | 1989-12-25 | 1995-09-27 | ナショナル住宅産業株式会社 | Press device with loading / unloading function |
CN106243769B (en) * | 2016-07-26 | 2017-08-25 | 安徽凯奇化工科技股份有限公司 | A kind of preparation method of Vat Brilliant Green FFB |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR972498A (en) * | 1947-10-01 | 1951-01-30 | Gen Aniline Et Film Corp | Further training in the manufacture of coloring materials |
US2888463A (en) * | 1957-07-01 | 1959-05-26 | Du Pont | Process for preparing dibenzanthrone vat dyes |
-
1977
- 1977-07-15 LU LU77773A patent/LU77773A1/en unknown
-
1978
- 1978-06-30 CH CH716678A patent/CH637413A5/en not_active IP Right Cessation
- 1978-07-12 FR FR7820894A patent/FR2397441A1/en active Granted
- 1978-07-12 IT IT7850258A patent/IT7850258A0/en unknown
- 1978-07-13 DE DE19782830881 patent/DE2830881A1/en not_active Withdrawn
- 1978-07-13 CA CA000307288A patent/CA1120472A/en not_active Expired
- 1978-07-14 BR BR7804544A patent/BR7804544A/en unknown
- 1978-07-14 GB GB7829838A patent/GB2001093B/en not_active Expired
- 1978-07-14 BE BE189276A patent/BE868990A/en unknown
- 1978-07-14 ES ES471713A patent/ES471713A1/en not_active Expired
- 1978-07-15 JP JP8666778A patent/JPS5420040A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
FR2397441A1 (en) | 1979-02-09 |
GB2001093B (en) | 1982-03-03 |
BR7804544A (en) | 1979-04-10 |
LU77773A1 (en) | 1979-03-26 |
ES471713A1 (en) | 1979-10-01 |
JPS5420040A (en) | 1979-02-15 |
FR2397441B1 (en) | 1980-07-11 |
DE2830881A1 (en) | 1979-02-01 |
BE868990A (en) | 1979-01-15 |
GB2001093A (en) | 1979-01-24 |
IT7850258A0 (en) | 1978-07-12 |
CH637413A5 (en) | 1983-07-29 |
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