CN1111158C - Process for preparing crystal violet lactone - Google Patents
Process for preparing crystal violet lactone Download PDFInfo
- Publication number
- CN1111158C CN1111158C CN 00113433 CN00113433A CN1111158C CN 1111158 C CN1111158 C CN 1111158C CN 00113433 CN00113433 CN 00113433 CN 00113433 A CN00113433 A CN 00113433A CN 1111158 C CN1111158 C CN 1111158C
- Authority
- CN
- China
- Prior art keywords
- crystal violet
- violet lactone
- preparation
- hydrocarbon solvent
- oxidation
- 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 - Fee Related
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- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 24
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- -1 heptane Alkanes Chemical class 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- NEGFNJRAUMCZMY-UHFFFAOYSA-N 3-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC(C(O)=O)=C1 NEGFNJRAUMCZMY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 150000003623 transition metal compounds Chemical class 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 3
- DVVXXHVHGGWWPE-UHFFFAOYSA-N 2-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC=C1C(O)=O DVVXXHVHGGWWPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229960003540 oxyquinoline Drugs 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 2
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 230000004907 flux Effects 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 239000012452 mother liquor Substances 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000243 solution Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- XZXCWRSZJMLMQQ-UHFFFAOYSA-N chembl3144663 Chemical compound O=C1C(N=NC=2C3=CC=CC=C3C(=CC=2O)S(O)(=O)=O)=C(C)NN1C1=CC=CC=C1 XZXCWRSZJMLMQQ-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BXWLVQXAFBWKSR-UHFFFAOYSA-N 2-methoxy-5-methylsulfonylbenzoic acid Chemical compound COC1=CC=C(S(C)(=O)=O)C=C1C(O)=O BXWLVQXAFBWKSR-UHFFFAOYSA-N 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
- C09B11/14—Preparation from aromatic aldehydes, aromatic carboxylic acids or derivatives thereof and aromatic amines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种结晶紫内酯的制备方法，为了克服目前生产结晶紫内酯成本高，质量低的缺点，采用本发明1)不需要萃取装置，只需用烃类溶剂处理一下就可以除去白结晶紫内能中的杂质；2)通过共沸蒸馏除去残留在白结晶紫内酯中溶剂，既回收了溶剂，又省除了干燥过程；3)采用催化空气氧化或氧气氧化，既降低了成本，又提高了质量；4)本发明氧化催化剂及催化剂配体都是常见的化合物，廉价易得；5)将含有催化剂和碱液母液回收循环使用，既充分节省了成本又减少了环境污染。The invention discloses a preparation method of crystal violet lactone. In order to overcome the disadvantages of high cost and low quality in the current production of crystal violet lactone, the invention 1) does not require an extraction device, and only needs to be treated with a hydrocarbon solvent. Remove the impurities in the internal energy of white crystal violet; 2) remove the solvent remaining in white crystal violet lactone by azeotropic distillation, which not only reclaims the solvent, but also saves the drying process; 3) adopts catalytic air oxidation or oxygen oxidation, which not only reduces 4) the oxidation catalyst and the catalyst ligand of the present invention are all common compounds, cheap and easy to get; 5) the mother liquor containing catalyst and lye is reclaimed and recycled, which not only fully saves the cost but also reduces the environment pollute.
Description
所属技术领域Technical field
本发明属于结晶紫内酯的制备生产方法。The invention belongs to the preparation production method of crystal violet lactone.
背景技术Background technique
结晶紫内酯的学名为：3，3-双(4-二甲氨基苯基)-6-二甲氨基苯酞，结构式为：
结晶紫内酯(简称CVL)Crystal Violet Lactone (CVL for short)
结晶紫内酯既是一种压敏染料，又是一种热敏染料，主要用作压敏复写纸和热敏记录纸。Crystal violet lactone is both a pressure-sensitive dye and a heat-sensitive dye, and is mainly used for pressure-sensitive copying paper and heat-sensitive recording paper.
关于结晶紫内酯的制备方法国外曾有多种报道。1984的美国专利4455435报道先将对二甲氨基苯甲醛、间二甲氨基苯甲酸和N，N-二甲基苯胺在强酸性溶液中缩合，再在碱性溶液中用甲苯萃取以除去三(对二甲氨基苯基)甲烷，得到无色结晶紫内酯： There have been many reports abroad about the preparation method of crystal violet lactone. U.S. Patent No. 4455435 of 1984 reported that p-dimethylaminobenzaldehyde, m-dimethylaminobenzoic acid and N, N-dimethylaniline were condensed in a strongly acidic solution, and extracted with toluene in an alkaline solution to remove three ( p-Dimethylaminophenyl) methane to obtain colorless crystal violet lactone:
无色结晶紫内酯(简称LCVL)Colorless crystal violet lactone (abbreviated as LCVL)
然后用过硫酸钾将无色结晶紫内酯氧化，得到结晶紫内酯，结晶紫内酯的总产率为31.8％。这种方法有两个缺点：Then, the colorless crystal violet lactone was oxidized with potassium persulfate to obtain crystal violet lactone, and the total yield of crystal violet lactone was 31.8%. This approach has two disadvantages:
1)用甲苯在55℃萃取三(对二甲氨基苯基)甲烷时，由于甲苯、无色结晶紫内酯及三(对二甲氨基苯基)甲烷的相互增溶作用，使得萃取时一部分无色结晶紫内酯进入有机相而损失掉，同时由于无色结晶紫内酯钠盐的表面活性溶有杂质三(对二甲氨基苯基)甲烷的甲苯溶液又乳化在水相中从而使得无色结晶紫内酯钠盐中又混有杂质三(对二甲氨基苯基)甲烷和甲苯。这样的最后结果是无色结晶紫内酯的产率低，质量差。1) When tris(p-dimethylaminophenyl)methane is extracted with toluene at 55°C, due to the mutual solubilization of toluene, colorless crystal violet lactone and tris(p-dimethylaminophenyl)methane, part of the The colorless crystal violet lactone enters the organic phase and is lost, and at the same time, the toluene solution that is dissolved with impurity tris (p-dimethylaminophenyl) methane due to the surface activity of the colorless crystal violet lactone sodium salt is emulsified in the water phase so that Colorless crystal violet lactone sodium salt is mixed with impurities three (p-dimethylaminophenyl) methane and toluene. The net result of this is a low yield of colorless crystal violet lactone and poor quality.
2)由于采用化学试剂氧化，氧化的选择性差，反应不容易停止在结晶紫内酯阶段，容易产生过度氧化，不仅使产率降低，而且产品质量下降，使产品的外观呈褐色，熔点下降。2) Due to the use of chemical reagents to oxidize, the selectivity of oxidation is poor, and the reaction is not easy to stop at the stage of crystal violet lactone, which is prone to excessive oxidation, which not only reduces the yield, but also reduces the quality of the product, making the appearance of the product brown and the melting point lowered.
1981年美国专利4271075报道了用钴络合物作催化剂用过氧化氢氧化无色结晶紫内酯，合成结晶紫内酯，但这些钴络合物的配体1-[(2-羟基萘基)偶氮]-2-羟基-5-苯磺酸、1-[(2-羟基萘基-5-硝基苯基)偶氮]-2-羟基-3，6-萘二磺酸、1-[(1-苯基-3-甲基-5-吡唑啉酮-4-基)偶氮]-2-羟基-4-萘磺酸、1-[(1-苯基-3-甲基-5-吡唑啉酮-4-基)偶氮]-2-羟基-4-萘甲酸等不易得到的复杂分子。In 1981, U.S. Patent No. 4,271,075 reported using cobalt complexes as catalysts to oxidize colorless crystal violet lactone with hydrogen peroxide to synthesize crystal violet lactones, but the ligands of these cobalt complexes 1-[(2-hydroxynaphthyl ) azo] -2-hydroxy-5-benzenesulfonic acid, 1-[(2-hydroxynaphthyl-5-nitrophenyl) azo]-2-hydroxy-3,6-naphthalene disulfonic acid, 1 -[(1-phenyl-3-methyl-5-pyrazolone-4-yl)azo]-2-hydroxyl-4-naphthalenesulfonic acid, 1-[(1-phenyl-3-methyl Base-5-pyrazolone-4-yl)azo]-2-hydroxy-4-naphthoic acid and other complex molecules that are not easily available.
1980年美国专利4233223报道了在铁氰化合物存在下用过氧化氢氧化无色结晶紫内酯合成结晶紫内酯，但由于过度氧化问题，即使在无色结晶紫内酯纯度达到99.1％的情况下，氧化产物仍然不纯，需要在乙二醇单丁醚重结晶才能得到熔点为179～180℃的产物。这样既增加了操作成本，又增加了原料成本。In 1980, U.S. Patent 4233223 reported the synthesis of crystal violet lactone by oxidizing colorless crystal violet lactone with hydrogen peroxide in the presence of ferricyanide, but due to excessive oxidation, even when the purity of colorless crystal violet lactone reached 99.1%. However, the oxidation product is still impure and requires recrystallization in ethylene glycol monobutyl ether to obtain a product with a melting point of 179-180°C. This not only increases the operating cost, but also increases the raw material cost.
发明内容Contents of the invention
本发明的目的是提供一种总产率高，成本低，设备合操作都简单，产品质量好的制备结晶紫内酯的方法。The purpose of the present invention is to provide a method for preparing crystal violet lactone with high overall yield, low cost, simple equipment and operation, and good product quality.
本发明的目的是通过如下方式实现的：一种结晶紫内酯的制备方法，将1～1.5摩尔份的间二甲氨基苯甲酸、1～2摩尔份的对二甲氨基苯甲醛和1～2.5摩尔份的N，N-二甲基苯胺在0.4～1.5摩尔份的脲和1～6摩尔份的强酸存在下在50～100℃的温度下进行缩合4～20小时；将缩合液冷却，用碱性水溶液中和弱酸性，沉淀结晶，过滤得无色结晶紫内酯粗品；将无色结晶紫内酯粗品放入到烃类溶剂中，回流，滤出烃类溶剂，以除去杂质三(对二甲氨基苯基)甲烷，回收精制的无色结晶紫内酯；将精制的无色结晶紫内酯放入水中，调节pH值为碱性，共沸蒸馏除去残留的烃类熔剂；加入过渡金属化合物和配体，或由配体阴离子与过渡金属离子组成的盐作催化剂，在加热条件下通入空气或氧气数小时，过滤，收集滤饼得产品结晶紫内酯，回收滤液直接作为下一次氧化的催化剂和氧化介质。The object of the present invention is achieved in the following manner: a preparation method of crystal violet lactone, comprising 1-1.5 molar parts of m-dimethylaminobenzoic acid, 1-2 molar parts of p-dimethylaminobenzaldehyde and 1-2 molar parts 2.5 molar parts of N, N-dimethylaniline are condensed for 4 to 20 hours at a temperature of 50 to 100° C. in the presence of 0.4 to 1.5 molar parts of urea and 1 to 6 molar parts of strong acid; the condensation liquid is cooled, Neutralize the weak acidity with alkaline aqueous solution, precipitate and crystallize, and filter to obtain the crude product of colorless crystal violet lactone; put the crude product of colorless crystal violet lactone into a hydrocarbon solvent, reflux, and filter out the hydrocarbon solvent to remove the impurity III (p-dimethylaminophenyl) methane, reclaim refined colorless crystal violet lactone; put refined colorless crystal violet lactone into water, adjust the pH value to be alkaline, remove residual hydrocarbon solvent by azeotropic distillation; Add a transition metal compound and a ligand, or a salt composed of a ligand anion and a transition metal ion as a catalyst, feed air or oxygen for several hours under heating conditions, filter, collect the filter cake to obtain the product crystal violet lactone, and recover the filtrate directly As a catalyst and oxidation medium for the next oxidation.
本发明是将从二甲氨基苯甲酸、对二甲氨基苯甲醛和N，N-二甲基苯胺缩合而得的无色结晶紫内酯粗产物通过将无色结晶紫内酯粗产物放入烃类溶剂中回流、过滤除去溶有杂质滤液的方法来进行精制；回流时间为0.5小时以上；烃类溶剂的用量为相当无色结晶紫内酯重量3～9倍。The present invention is that the crude product of colorless crystal violet lactone obtained by condensation of dimethylaminobenzoic acid, p-dimethylaminobenzaldehyde and N,N-dimethylaniline is put into the crude product of colorless crystal violet lactone Reflux in a hydrocarbon solvent and filter to remove the impurity-dissolved filtrate for refining; the reflux time is more than 0.5 hours; the amount of hydrocarbon solvent is 3 to 9 times the weight of the colorless crystal violet lactone.
本发明所使用的烃类溶剂是汽油、煤油、柴油、正戊烷、正己烷、环己烷、环庚烷、庚烷、石油醚、石油英、苯、甲苯、对二甲苯、邻二甲苯、间二甲苯、联苯，联苯衍生物、氯苯，或是由上述溶剂的两种或三种所组成的混合溶剂。The hydrocarbon solvent used in the present invention is gasoline, kerosene, diesel oil, n-pentane, n-hexane, cyclohexane, cycloheptane, heptane, sherwood oil, petrolatum, benzene, toluene, p-xylene, o-xylene , m-xylene, biphenyl, biphenyl derivatives, chlorobenzene, or a mixed solvent composed of two or three of the above solvents.
本发明放入烃类溶剂中的无色结晶紫内酯粗产物可以是经过干燥的；也可以是将湿的无色结晶紫内酯粗产物直接放入烃类溶剂中，通过装有分水器的蒸馏或回流装置进行共沸蒸馏进行脱水。The crude product of the colorless crystal violet lactone that the present invention puts into the hydrocarbon solvent can be through drying; It is also possible to directly put the wet colorless crystal violet lactone crude product into the hydrocarbon solvent, and the The distillation or reflux device of the device is used for azeotropic distillation for dehydration.
本发明将精制出来的含有烃类溶剂无色结晶紫内酯滤饼直接放入装有分水器的氧化反应釜中，加入碱水溶液，用共沸蒸馏的方法除去和回收残留在无色结晶紫内酯中的的烃类熔剂。In the present invention, the refined colorless crystal violet lactone filter cake containing hydrocarbon solvents is directly put into an oxidation reaction kettle equipped with a water separator, and an aqueous alkali solution is added to remove and recover the colorless crystals remaining in them by means of azeotropic distillation. Hydrocarbon solvent in purple lactone.
本发明共沸蒸馏除去烃类溶剂和催化空气氧化或氧气氧化时介质的pH为8～14。The pH of the medium is 8-14 when the azeotropic distillation of the present invention removes hydrocarbon solvents and catalyzes air oxidation or oxygen oxidation.
本发明空气氧化或氧气氧化所用的催化剂中过渡金属化合物主要是含钴化合物、含铜化合物或含铁化合物。The transition metal compound in the catalyst used for air oxidation or oxygen oxidation in the present invention is mainly cobalt-containing compound, copper-containing compound or iron-containing compound.
本发明含钴化合物为卤化钴、硝酸钴、醋酸钴、氢氧化钴。The cobalt-containing compound of the present invention is cobalt halide, cobalt nitrate, cobalt acetate and cobalt hydroxide.
本发明含铜化合物为卤化亚铜、卤化铜、醋酸铜、醋酸亚铜，硝酸铜、氢氧化铜。The copper-containing compound of the present invention is cuprous halide, copper halide, copper acetate, cuprous acetate, copper nitrate, copper hydroxide.
本发明含铁化合物是卤化亚铁、卤化铁、醋酸铁、醋酸亚铁，硝酸铁、铁氰化钠、铁氰化钾、亚铁氰化钾、亚铁氰化钠、氢氧化铁、氢氧化亚铁。The iron-containing compound of the present invention is ferrous halide, ferric halide, ferric acetate, ferrous acetate, ferric nitrate, sodium ferricyanide, potassium ferricyanide, potassium ferrocyanide, sodium ferrocyanide, ferric hydroxide, hydrogen Ferrous oxide.
本发明所用的组成催化剂的配体是羟基酸阴离子、氨基酸阴离子、氨羧络合剂阴离子、氰根阴离子(CN-)、含氮杂环化合物等，配体试剂是酒石酸及其钠盐、钾盐和铵盐，乙二胺四乙酸及其钠盐和钾盐，水杨酸及其钠盐、钾盐和铵盐，氰化钾，氰化钠，二甲基甲酰铵，8-羟基喹啉。The ligands used in the present invention to form the catalyst are hydroxyl acid anions, amino acid anions, ammonia carboxyl complexing agent anions, cyanide anions (CN - ), nitrogen-containing heterocyclic compounds, etc., and the ligand reagents are tartaric acid and its sodium salt, potassium salt and ammonium salts, ethylenediaminetetraacetic acid and its sodium and potassium salts, salicylic acid and its sodium, potassium and ammonium salts, potassium cyanide, sodium cyanide, dimethylformamide, 8-hydroxy quinoline.
本发明催化空气氧化或氧气氧化温度为40～100℃，最好为60～80℃。The catalytic air oxidation or oxygen oxidation temperature of the present invention is 40-100°C, preferably 60-80°C.
本发明显然优于现有技术。该技术有如下优点：1)不需要萃取装置，只需用烃类溶剂处理一下就可以除去无色结晶紫内酯中的杂质。2)通过共沸蒸馏除去残留在无色结晶紫内酯中溶剂，既回收了溶剂，又省除了干燥过程。3)采用催化空气氧化或氧气氧化，比起采用化学试剂氧化法来既降低了成本，有防止了过度氧化，从而提高了产率和产品质量。氧化一步的产率达95％，总产率可达到45％～50％，产品熔点达181～183℃。4)本发明氧化催化剂及催化剂配体都是非常常见的化合物，都是廉价易得的。尤其是催化剂配体，本发明使用的配体比起美国专利427 1075的诸如1-[(2-羟基萘基)偶氮]-2-羟基-5-苯磺酸、1-[(2-羟基萘基-5-硝基苯基)偶氮]-2-羟基-3，6-萘二磺酸、1-[(1-苯基-3-甲基-5-吡唑啉酮-4-基)偶氮]-2-羟基-4-萘磺酸、1-[(1-苯基-3-甲基-5-吡唑啉酮-4-基)偶氮]-2-羟基-4-萘甲酸等钴络合物配体来要廉价易得得多。5)将含有催化剂和碱液氧母液回收循环使用，既充分节省了成本，又减少了环境污染。The present invention is clearly superior to the prior art. This technology has the following advantages: 1) No extraction device is needed, and the impurity in the colorless crystal violet lactone can be removed only by treatment with a hydrocarbon solvent. 2) Removing the solvent remaining in the colorless crystal violet lactone by azeotropic distillation, which not only reclaims the solvent, but also saves the drying process. 3) The use of catalytic air oxidation or oxygen oxidation not only reduces the cost, but also prevents excessive oxidation compared with the chemical reagent oxidation method, thereby improving the yield and product quality. The yield of the oxidation step can reach 95%, the total yield can reach 45%-50%, and the melting point of the product can reach 181-183°C. 4) The oxidation catalyst and the catalyst ligand of the present invention are very common compounds, which are cheap and easy to obtain. Especially the catalyst ligand, the ligand used in the present invention is compared with U.S. Patent 427 1075 such as 1-[(2-hydroxynaphthyl) azo]-2-hydroxyl-5-benzenesulfonic acid, 1-[(2- Hydroxynaphthyl-5-nitrophenyl)azo]-2-hydroxy-3,6-naphthalene disulfonic acid, 1-[(1-phenyl-3-methyl-5-pyrazolone-4 -yl)azo]-2-hydroxyl-4-naphthalenesulfonic acid, 1-[(1-phenyl-3-methyl-5-pyrazolone-4-yl)azo]-2-hydroxyl- Cobalt complex ligands such as 4-naphthoic acid are much cheaper and easier to obtain. 5) Recycling and recycling the mother liquor containing catalyst and alkali liquid oxygen, which not only fully saves the cost, but also reduces environmental pollution.
具体实施方式Detailed ways
下面结合实施例对本发明做进一步说明：The present invention will be further described below in conjunction with embodiment:
本发明实施例1Embodiment 1 of the present invention
往装有搅拌器，温度计的500升反应釜中加入135公斤浓度为22～25％盐酸(814～925摩尔)，12公斤脲(200摩尔)，33公斤间二甲氨基苯甲酸(200摩尔)，31公斤对二甲氨基苯甲醛(200摩尔)，26公斤N，N-二甲基苯胺(215摩尔)，在氮气保护下于94℃搅拌反应6.5～7.5小时。冷却，用20％的氢氧化钠水溶液中和至pH5.0以沉淀出无色结晶紫内酯，过滤，干燥得无色结晶紫内酯粗产品。Stirrer is housed, in the 500 liters of reactors of thermometer, add 135 kilograms of concentrations and be 22～25% hydrochloric acid (814～925 moles), 12 kilograms of urea (200 moles), 33 kilograms of m-dimethylaminobenzoic acids (200 moles) , 31 kilograms of p-dimethylaminobenzaldehyde (200 moles), 26 kilograms of N, N-dimethylaniline (215 moles), stirred and reacted at 94 ° C for 6.5 to 7.5 hours under nitrogen protection. Cool, neutralize to pH 5.0 with 20% aqueous sodium hydroxide solution to precipitate colorless crystal violet lactone, filter and dry to obtain a crude product of colorless crystal violet lactone.
将无色结晶紫内酯粗产品放入500升反应釜中，加入300公斤苯和石油醚(2∶1)混合物，回流0.5小时，过滤。将滤饼放入到1000升装有水份分离器的蒸馏釜中，加入500公斤水(28千摩尔)，用氢氧化钠调节至pH8.5～9，通过水份分离器共沸蒸馏除去残留的有机溶剂，加入2.4公斤三氯化铁，5.7公斤氰化钾，在70～80℃吹入0.12MPa压力的空气7小时，冷却，过滤，回收滤液以备重复使用。滤饼用0.5％的氢氧化钠水溶液洗涤，再用水洗涤，干燥即得37.6公斤结晶紫内酯，熔点181～183℃。Put the crude product of colorless crystal violet lactone into a 500-liter reactor, add 300 kg of benzene and petroleum ether (2:1) mixture, reflux for 0.5 hours, and filter. Put the filter cake into a 1,000-liter distillation still equipped with a water separator, add 500 kg of water (28 kilomoles), adjust the pH to 8.5-9 with sodium hydroxide, and remove it by azeotropic distillation through the water separator. For the residual organic solvent, add 2.4 kg of ferric chloride and 5.7 kg of potassium cyanide, blow in air with a pressure of 0.12 MPa at 70-80°C for 7 hours, cool, filter, and recover the filtrate for reuse. The filter cake was washed with 0.5% aqueous sodium hydroxide solution, then washed with water, and dried to obtain 37.6 kg of crystal violet lactone with a melting point of 181-183°C.
本发明实施例2Embodiment 2 of the present invention
将180毫升水，53克浓硫酸，30克间二甲氨基苯甲酸，34克N，N二甲基苯胺和35克对二甲氨基苯甲醛在反应瓶中搅拌混合均匀，在氮气保护下于95℃搅拌8小时，冷却，氢氧化钠溶液中和到pH5.0，过滤收集固体无色结晶紫内酯粗产品。180 milliliters of water, 53 grams of concentrated sulfuric acid, 30 grams of m-dimethylaminobenzoic acid, 34 grams of N, N dimethylaniline and 35 grams of p-dimethylaminobenzaldehyde were stirred and mixed uniformly in a reaction flask, and were placed under nitrogen protection in Stir at 95°C for 8 hours, cool, neutralize with sodium hydroxide solution to pH 5.0, and collect solid colorless crystal violet lactone crude product by filtration.
将无色结晶紫内酯粗产品放入带有分水器的反应瓶中，加入500毫升甲苯和石油醚(2∶1)混合溶剂，共沸蒸馏通过分水器除去水后，回流15分钟，过滤。将滤饼放入到蒸馏瓶中，加入900毫升水，用氢氧化钠调节至pH8.5～9，共沸蒸馏除去残留的的有机溶剂，加入0.02摩尔二氯化钴，0.02摩尔酒石酸钾钠，在70～80℃吹入0.1MPa压力的氧气10小时，冷却，过滤，用0.5％的氢氧化钠水溶液洗涤滤饼，再用水洗涤滤饼，干燥即得43克结晶紫内酯，熔点181～183℃。Put the crude product of colorless crystal violet lactone into a reaction bottle with a water separator, add 500 ml of toluene and petroleum ether (2:1) mixed solvent, azeotropic distillation removes water through the water separator, and then reflux for 15 minutes ,filter. Put the filter cake into a distillation bottle, add 900 ml of water, adjust the pH to 8.5-9 with sodium hydroxide, remove the residual organic solvent by azeotropic distillation, add 0.02 mole of cobalt dichloride, 0.02 mole of potassium sodium tartrate , blowing oxygen at 0.1MPa pressure at 70-80°C for 10 hours, cooling, filtering, washing the filter cake with 0.5% aqueous sodium hydroxide solution, then washing the filter cake with water, and drying to obtain 43 grams of crystal violet lactone with a melting point of 181 ~183°C.
本发明实施例3Embodiment 3 of the present invention
按实施例1所讲方法合成无色结晶紫内酯粗产品和用苯和石油醚混合物处理无色结晶紫内酯粗产品。过滤。将滤饼放入到1000升蒸馏釜中，加入实施例1回收的氧化母液，用氢氧化钠调节至pH8.5～9，共沸蒸馏除去残留的溶剂，在70～80℃吹入0.12MPa压力的空气7小时，冷却，过滤，回收滤液以备重复使用。滤饼用0.5％的氢氧化钠水溶液洗涤，再用水洗涤，干燥即得37公斤份结晶紫内酯，熔点181～183℃。Synthesize the crude product of colorless crystal violet lactone according to the method described in Example 1 and treat the crude product of colorless crystal violet lactone with a mixture of benzene and petroleum ether. filter. Put the filter cake into a 1000-liter still, add the oxidation mother liquor recovered in Example 1, adjust the pH to 8.5-9 with sodium hydroxide, remove the residual solvent by azeotropic distillation, and blow in 0.12MPa at 70-80°C Pressed air for 7 hours, cool, filter, and recover the filtrate for reuse. The filter cake was washed with 0.5% aqueous sodium hydroxide solution, then washed with water, and dried to obtain 37 kg of crystal violet lactone with a melting point of 181-183°C.
本发明实施例4Embodiment 4 of the present invention
将按照实施例1所述方法得到湿的无色结晶紫内酯粗产品不经干燥，直接投入到500升装有水份分离器的反应釜中，加入300公斤苯和石油醚(2∶1)混合物，通过水份分离器共沸蒸馏除去水份，回流0.5小时，过滤。将滤饼放入到1000升装有水份分离器的蒸馏釜中，加入500公斤水，用氢氧化钠调节至pH8.5～9，通过水份分离器共沸蒸馏除去残留的有机溶剂，加入6.5公斤铁氰化钾，在70～80℃吹入0.12MPa压力的空气6小时，冷却，过滤，回收滤液以备重复使用。滤饼用0.5％的氢氧化钠水溶液洗涤，再用水洗涤，干燥即得31公斤结晶紫内酯，熔点181～183℃。The wet colorless crystal violet lactone crude product obtained by the method described in Example 1 is directly dropped into a 500-liter reactor equipped with a water separator without drying, and 300 kilograms of benzene and sherwood oil (2: 1) are added. ) mixture, removed water by azeotropic distillation of water separator, refluxed for 0.5 hour, and filtered. Put the filter cake into a 1000 liter distillation still equipped with a water separator, add 500 kg of water, adjust the pH to 8.5 to 9 with sodium hydroxide, and remove the residual organic solvent through the azeotropic distillation of the water separator. Add 6.5kg of potassium ferricyanide, blow in 0.12MPa pressure air at 70-80°C for 6 hours, cool, filter, and recover the filtrate for reuse. The filter cake was washed with 0.5% aqueous sodium hydroxide solution, then washed with water, and dried to obtain 31 kg of crystal violet lactone with a melting point of 181-183°C.
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