GB2136430A - Production of 4,4'-Dinitrostilbene-2,2'-disulfonic Acid or a Salt Thereof - Google Patents
Production of 4,4'-Dinitrostilbene-2,2'-disulfonic Acid or a Salt Thereof Download PDFInfo
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- GB2136430A GB2136430A GB08406552A GB8406552A GB2136430A GB 2136430 A GB2136430 A GB 2136430A GB 08406552 A GB08406552 A GB 08406552A GB 8406552 A GB8406552 A GB 8406552A GB 2136430 A GB2136430 A GB 2136430A
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- GB
- United Kingdom
- Prior art keywords
- lithium
- dinitrostilbene
- salt
- reaction
- disulfonic acid
- 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.)
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- 150000003839 salts Chemical class 0.000 title claims abstract description 18
- UETHPMGVZHBAFB-OWOJBTEDSA-N 4,4'-dinitro-trans-stilbene-2,2'-disulfonic acid Chemical compound OS(=O)(=O)C1=CC([N+]([O-])=O)=CC=C1\C=C\C1=CC=C([N+]([O-])=O)C=C1S(O)(=O)=O UETHPMGVZHBAFB-OWOJBTEDSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- -1 hydroxyl ions Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 33
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 150000002697 manganese compounds Chemical group 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 5
- 239000000543 intermediate Substances 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- ZDTXQHVBLWYPHS-UHFFFAOYSA-N 4-nitrotoluene-2-sulfonic acid Chemical compound CC1=CC=C([N+]([O-])=O)C=C1S(O)(=O)=O ZDTXQHVBLWYPHS-UHFFFAOYSA-N 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 150000002642 lithium compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- CPXWJGQVGBSGDW-TYYBGVCCSA-M sodium;5-nitro-2-[(e)-2-(4-nitro-2-sulfophenyl)ethenyl]benzenesulfonate Chemical compound [Na+].OS(=O)(=O)C1=CC([N+]([O-])=O)=CC=C1\C=C\C1=CC=C([N+]([O-])=O)C=C1S([O-])(=O)=O CPXWJGQVGBSGDW-TYYBGVCCSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 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
- 235000010842 Sarcandra glabra Nutrition 0.000 description 2
- 240000004274 Sarcandra glabra Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- YAKFHPREDNNSFX-SEPHDYHBSA-L disodium;5-amino-2-[(e)-2-(4-amino-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S([O-])(=O)=O YAKFHPREDNNSFX-SEPHDYHBSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- REJHVSOVQBJEBF-UHFFFAOYSA-N DSD-acid Natural products OS(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052791 calcium Chemical class 0.000 description 1
- 239000011575 calcium Chemical class 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
4,4,-Dinitrostilbene-2,2'-disulfonic acid and salts thereof, useful as intermediates in the preparation of dyes and pigments, are prepared by oxidizing a compound of formula: <IMAGE> or a salt thereof in the presence of lithium and hydroxyl ions and, if desired, a catalyst.
Description
SPECIFICATION
Production of 4,4'-Dinitrostilbene-2,2'-Disulfonic Acid or a Salt Thereof
The present invention relates to a process for producing 4,4'-dinitrostilbene-2,2'-disulfonic acid or a salt thereof.
4,4'-diaminostilbene-2,2'-disulfonic acid, obtained by reducing 4,4'-dinitrostilbene-2,2'-disulfonic acid or its salt (hereinafter referred to as 4,4'-dinitrostilbene-2,2'-disulfonic acid compounds), has been produced on a large scale and used as an intermediate for dyes and pigments such as fluorescent whitening agents.
Conventional processes for producing 4,4'-dinitrostilbene-2,2'-disulfonic acid compounds, such as the process mentioned on page 511 of Yutaka Hosoda "Senryo Kagaku" published by Gihodo Co.,
Ltd. or in the Specification of Japanese Patent Laid-Open No. 38764/1 982, have defects in that the yield of product per unit volume of the reactor is very poor and a long reaction time is required.
According to the process mentioned in "Senryo Kagaku" or the Specification of Japanese Patent
Laid-Open No. 38764/1982, the 4,4'-dinitrostilbene-2,2'-disulfonic acid compounds are obtained in a yield of as low as about 6 wt. % based on the quantity of the reaction solution.
Further, a reaction time of 1 8 to 20 h is required in both processes. According to a process disclosed in the Specification of Japanese Patent Laid-Open No. 29561/1981, the intended product can be obtained in a yield of about 15% based on the reaction solution and the reaction time can be reduced to about 6 h. Though this process has improved to some extent the yield per unit volume of a reaction solution and the reaction time, it is costly since use of an organic solvent such as dimethylformamide or methanol is necessitated. Other industrial demerits of this process are that it includes the dangerous step of mixing the oxidizing agent with the organic solvent and that special care is necessary to avoid the presence of water when carrying out the reaction.
The present inventors have made intensive investigations for the purpose of developing an industrially advantageous process for producing the 4,4'-dinitrostilbene-2,2'-disulfonic acid compounds in improved yield per unit volume of a reaction solution and in a reduced reaction time. A reason why the yield of the 4,4'-dinitrostilbene-2,2'-disulfonic acid compound per unit volume of reaction solution is poor when oxidation of 4-nitrotoluene-2-sulfonic acid is effected in an alkaline aqueous medium is that the solubilities of 4-nitrotoluene-2-sulfonic acid (starting material), 4,4' dinitrodibenzyl-2,2'-disulfonic acid (intermediate product) a nd and 4,4'-dinitrostilbene-2,2'-disulfonic acid (product) in water are low.The inventors have now found that when a lithium compound is incorporated in the oxidation reaction system, the amount of the starting material charged per unit volume of the reaction solution can be increased noticeably and the oxidation reaction rate can be increased sharply. According to the inventors knowledge, the process wherein 4-nitrotoluene-2sulfonic acid is oxidized in the presence of a lithium compound has not been known. Accordingly, the present invention provides a process for producing 4,4'-dinitrostilbene-2,2'-disulfonic acid or a salt thereof, which process comprises oxidising a compound of formula (I):
or a salt thereof in the presence of lithium and hydroxyl ions.
In carrying out the process of the present invention, 4-nitrotoluene-2-sulfonic acid or its alkali metal or alkaline earth metal salt, such as K, Na, Mg or Ca salt, is used as the starting material and water is used as a solvent. Water may be used in the form of a mixture with an organic solvent. The quantity of water used is about 0.8 to 20 parts by weight, preferably 1 to 10 parts by weight, per part by weight of 4-nitrotoluene-2-sulfonic acid.
Examples of the lithium compounds releasing lithium ion are lithium oxide, lithium hydroxide, salts such as lithium carbonate and lithium acetate, lithium hypohalites and halides such as lithium chloride and lithium bromide. These lithium compounds form lithium salts of 4-nitrotoluene-2-sulfonic acid. The above mentioned lithium compounds are used in an amount of 1-5 moles per 1 mole of 4nitrotoluene-2-sulfonic acid.
The presence of hydroxyl ion (OH-) is indispensable in carrying out the oxidation reaction of the present invention. If, among the above-mentioned lithium compounds, lithium oxide and/or lithium hydroxide are used, since these compounds release hydroxyl group in water, the addition of another compound releasing a hydroxyl group, if desired, may be omitted. If lithium salts such as lithium carbonate and lithium acetate, lithium hypohalites and lithium halides such as lithium chloride and lithium bromide are used as lithium compounds, hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide or compounds capable of forming a hydroxide in water such as magnesium oxide and calcium oxide have to be added. In this case, the amount of a hydroxide or a compound capable of forming a hydroxide in water is about 0.3 to 5 mol/l.
Though the oxidation reaction of the present invention proceeds even in the absence of any catalyst, the reaction can be carried out more efficiently when a catalyst is used. The most suitable catalysts are manganese compounds. Further, compounds of transition metals such as Co, Fe, Ni, Pd,
Pt, Cr, Ce, Ru, Rh, Ti, V, Zr, Pb, Th, Cu, Ag, Mo and W may also be used either alone or in the form of a mixture of them. The catalyst is used in an amount of about 1 x10-4 to 1 xl 0-1 mol/l. In addition, active carbon silica gel, alumina, urea, phase transfer catalysts and ion exchange resins are also usable as the effective catalysts.
The examples of oxidizing agents to be used are gases containing molecular oxygen, hypohalites, ozone and peroxides. From the economical viewpoint, gases containing molecular oxygen, particularly oxygen gas and air, are preferred.
The reaction temperature is 20 to 1000C, preferably 40 to 85cm.
The reaction may be carried out by a continuous process or a batch process under atmospheric pressure or elevated pressure. The reaction time is 4 to 10 h which is far shorter than those required in the conventional processes.
After-treatments of the reaction mixture are carried out according to an ordinary method. The following method is an example.
After completion of the oxidation reaction, water is added to the reaction mixture to dissolve the 4,4'-dinitrostilbene-2,2'-disulfonic acid compounds. Then, carbon dioxide, an alkali carbonate or an alkali bicarbonate is added to the reaction mixture to precipitate the lithium ion in the form of a iess soluble salt thereof. After filtration, the intended 4,4'-dinitrostilbene-2,2'-disulfonic acid compounds are obtained by an ordinary method such as deposition by acidification or salting out.
For easy understanding of the present invention, the process will now be elaborated in more detail.
Water, 4-nitrotoluene-2-sulfornic acid or its salt and, if necessary, a catalyst are charged in an alkali-resistant reactor. A lithium compound and an oxidizing agent are added thereto. After thorough stirring, a hydroxide or a compound releasing hydroxyl group is added thereto. (When lithium hydroxide is used, the addition of a hydroxide may be omitted). The hydroxide may be used in the form of solid or aqueous solution thereof.
Then, the stirring is continued at the reaction temperature mentioned above to effect the reaction. When the reaction temperature is elevated slowly, better result can be obtained compared with that obtained in a rapid temperature elevation. The reaction time is 4 to 10 h.
According to the pursuit of the reaction progress by a liquid chromatography analysis, it has been found that the amount of 4,4'-dinitrodibenzyl-2,2'-disulfonic acid (intermediate product) formed is far smaller than that formed in the conventional processes. This fact suggests that the mechanism of the process of the invention is different from that of the conventional processes. After completion of the reaction, 4,4'-dinitrostilbene-2,2'-disulfonic acid compounds is filtered after cooling, and the filtrate which still contains the intended product can be recycled for the next reaction. But the reaction mixture, usually, is treated as follows. The reaction mixture is diluted with water until the intended 4,4'-dinitrostilbene-2,2'-disulfonic acid compounds have been dissolved completely.Then, carbon dioxide, an alkali carbonate or an alkali bicarbonate is added thereto in an oxidation atmosphere.
Carbon dioxide is used in the form of dry ice and carbon dioxide kept in a cylinder. The alkali carbonates include sodium carbonate, potassium carbonate and ammonium carbonate. The alkali bicarbonates include sodium hydrogencarbonate and ammonium hydrogencarbonate. They are used in an amount sufficient for the lithium ion in the reaction mixture to form a salt thereof perfectly. After stirring for about 30 min, the insolubie lithium salt is filtered off. Generally, the higher the temperature is, the higher the efficiency of lithium salt separation is. According to this process, a lithium recovery of at least about 75% can be attained. The filtrate from which the lithium salt has been separated is made acidic and the intended 4,4'-dinitrostilbene-2,2'-disuífonic acid compounds are separated by, for example, salting out.
The effects of the present invention will be shown in comparison with those of the conventional processes:
Conventional Process Present (Example 1 of Japanese Invention Pat. Laid-Open (Example 3) No. 38764/1982) Conc. of the intended product after completion 32.4% 6.6% of the oxidation reaction Reaction time 6.5 h 18h Yield L 86.5% 81% The following examples will further illustrate the present invention, which by no means limit the invention.
EXAMPLE 1
1 50 g of 4-nitrotoluene-2-sulfonic acid, 0.2 g of manganese acetate tetrahydrate and 640 g of water were charged in a four-necked glass flask and stirred while air was introduced therein at a rate of 1.6 1/min. 95.5 g of lithium hydroxide monohydrate was added slowly to the mixture. After completion of the addition, the temperature was elevated to 500C. The reaction was carried out at 50 to 550C for 2 h and then the temperature was elevated slowly to 700C in 4 h while air was introduced therein to effect the reaction.
Thereafter, the reaction mixture was transferred to a beaker. Hot water was added to the liquid and the resulting solution was stirred at 65 to 70 C while air was introduced therein. 121 g of anhydrous sodium carbonate was added to the solution and the resulting mixture was stirred for 30 min. Lithium carbonate thus precipitated was filtered off. The crystal was washed with 200 mi of hot water. The filtrates were gathered together and adjusted to pH 3 with conc. hydrochloric acid. 1 90 g of sodium chloride was added thereto. After cooling, sodium 4,4'-dinitrostilbene-2,2'-disulfonate was separated by filtration. After washing with about 400 ml of a 1 5% aqueous sodium chloride solution followed by drying, 1 52 g of a crystalline product was obtained.The purity of the product was 99% according to a liquid chromatography analysis and 92.3% according to a reduction analysis using TiCI3.
The yield of sodium 4,4'-dinitrostilbene-2,2'-disulfonate calculated from the latter purity was 85.5%.
It was confirmed that sodium 4,4'-diaminostilbene-2,2'-disulfonate obtained by reducing this product was sufficiently usable as an intermediate for a fluorescent dye.
The recovery of lithium in the form of lithium carbonate was 82.5%. According to an atomic absorption analysis, it had a sodium content of 0.23%.
EXAMPLE 2
The same procedure as in Example 1 was repeated except that the amount of lithium hydroxide monohydrate was altered to 103.7 g and that 264 g of anhydrous sodium carbonate was used for recovering lithium after completion of the reaction.
1 46 g of sodium 4,4'-dinitrostilbene-2,2'-disulfonate was obtained. This product had a purity of 99% according to a liquid chromatography analysis and 90.9% according to a reduction analysis with
TiCI3. The yield of the intended product calculated from the latter purity was 80.9%. The recovery of lithium was 82.8%.
EXAMPLE 3
200 g of 4-nitrotoluene-2-sulfonic acid and 600 g of water were charged in a four-necked flask.
0.2 g of manganese acetate tetrahydrate was charged therein under stirring to obtain a solution. 98.3 g of lithium hydroxide monohydrate was added thereto slowly at 30 C while air was introduced therein at a rate of 4.8 1/min. After completion of the addition. the temperature was elevated to 460C. Then, the reaction was carried out by elevating the temperature slowly from 460C to 640C for 6.5 h.
After completion of the reaction, the mixture was cooled to 550C and transferred to a beaker. 1.3
I of water was added thereto to control the total quantity to about 2.11. 1 57 g of sodium carbonate was added thereto at 50 to 550C and the mixture was stirred at 50 to 550C for about 30 min while air was introduced therein. A precipitate thus formed was filtered off at 550C. (It was found that the precipitate was lithium carbonate containing 0.18% of sodium compounds according to an atomic absorption analysis effected after drying. The recovery of lithium was 74.9%). Sulfuric acid was added to the filtrate to control its pH to 3 to 4. The total quantity was adjusted to 2.5 1.250 g of sodium chloride was added thereto and a crystalline product precipitated was filtered and washed with a 13% aqueous sodium chloride solution.After drying, 225 g of sodium .4,4'-dinitrostilbene-2,2'-disulfonate was obtained in the form of yellow crystal. The purity of the compound was 83.95% according to the nitro group-reduction analysis and the yield based on the purity was 86.5%. According to a liquid chromatographic analysis, the product had 100% purity.
Sodium 4,4'-diaminostilbene-2,2'-disulfonate obtained by reducing the above product had a purity sufficient for use as an intermediate for a fluorescent dye.
EXAMPLE 4
75 g of 4-nitrotoluene-2-sulfonic acid, 0.1 g of manganese acetate and 400 g of water were charged in a four-necked flask to obtain a solution. 14.5 g of lithium hydroxide monohydrate was added thereto and the mixture was stirred for a while with introduction of 4 1/min of air. Then, 18 g of sodium hydroxide was added slowly thereto. The reaction was carried out with introduction of air at 600C for 3 h and then at 680C for 4.5 h. After completion of the reaction, the same after-treatment as in Example 3 was effected to recover lithium carbonate. 74 g of sodium 4,4'-dinitrostilbene-2,2'disulfonate was obtained in the form of yellow crystals.
The yield of the product based on the purity was 80.7% according to the purity based on the nitro group-reduction analysis. According to a liquid chromatography analysis, the product had a 99% purity.
EXAMPLE 5
4-Nitrotoluene-2-sulfonic acid was oxidized in the same manner as in Example 3. After completion of the reaction, the reaction mixture was cooled to 600 C. Air and carbon dioxide were introduced therein each at a rate of 2 1/min for 1 h. Crystal thus formed was filtered at 600C and washed with about 200 ml hot water. 100 g of sodium carbonate was added to the filtrate while air was introduced therein at 60 C and the solution was stirred for 30 min. Crystal thus precipitated was filtered off. (The recovery of lithium carbonate was 87.0% in total). The filtrate was controlled to pH 3 with sulfuric acid and 1 25 g of sodium chloride was added thereto. After filtration, the crystal was dried, to obtain 221 g of sodium 4,4'-dinitrostilbene-2,2'-disulfonate in the form of yellow crystal. The purity of the product was 88.8% according to the nitro group-reduction analysis and the yield of the product based on the purity was 89.8%.
According to a liquid chromatography analysis, the product had 100% purity. Thus, the product had a quality to be sufficient for use as a starting material for a fluorescent dye.
Claims (6)
1. A process for producing 4,4'-dinitrostilbene-2,2'-disulfonic acid or a salt thereof, which process comprises oxidising a compound of formula (I):
or a salt thereof in the presence of lithium and hydroxyl ions.
2. A process according to claim 1, in which the compound of formula (I) or salt thereof is oxidised in the presence of a catalyst.
3. A process according to claim 2, in which the catalyst is a manganese compound or a transition metal compound.
4. A process according to claim 3, in which the catalyst is manganese acetate.
5. A process according to any one of the preceding claims, in which the compound of formula (I) or salt thereof is oxidised in the presence of lithium hydroxide and sodium hydroxide.
6. A process for producing 4,4'-dinitrostilbene-2,2'-disulfonic acid or a salt thereof, said process being substantially as hereinbefore described in any one of Examples 1 to 5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58040803A JPS59167560A (en) | 1983-03-14 | 1983-03-14 | Preparation of 4,4'-dinitrostilbene-2,2'-disulfonic acid or its salt |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8406552D0 GB8406552D0 (en) | 1984-04-18 |
| GB2136430A true GB2136430A (en) | 1984-09-19 |
| GB2136430B GB2136430B (en) | 1986-10-01 |
Family
ID=12590789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08406552A Expired GB2136430B (en) | 1983-03-14 | 1984-03-13 | Production of 4,4'-dinitrostilbene-2,2'-disulfonic acid or a salt thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS59167560A (en) |
| CH (1) | CH659065A5 (en) |
| DE (1) | DE3409171A1 (en) |
| GB (1) | GB2136430B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0203506A1 (en) * | 1985-05-31 | 1986-12-03 | Bayer Ag | Process for the preparation of 4,4'-dinitrostilbene-disulfonic acid |
| US4952725A (en) * | 1988-03-08 | 1990-08-28 | Ciba-Geigy Corporation | Process for the preparation of 4,4'dinitrostilbene-2,2'-disulfonic acid and its salts |
| US5021132A (en) * | 1990-08-07 | 1991-06-04 | Sandoz Ltd. | Electrochemical process for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and the salts thereof |
| US5041632A (en) * | 1987-08-12 | 1991-08-20 | Ciba-Geigy Corporation | Process for the preparation of 4,4'-dinitrostilbene-2,2-disulfonic acid |
| US5583252A (en) * | 1994-05-26 | 1996-12-10 | Bayer Aktiengesellschaft | Process for preparing 4,4'-dinitrostilbene-2,2'-disulphonic acid and its salts |
| US5808141A (en) * | 1993-09-08 | 1998-09-15 | Bayer Aktiengesellschaft | Process for preparing 4,4'-dinitrostilbene-2,2'-disulphonic acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351748B (en) * | 2011-08-22 | 2013-08-21 | 山西阳煤丰喜肥业(集团)有限责任公司 | Preparation method for DNS (4,4'-dinitrostilbene-2,2'-disulphonic acid) sodium salt in DSD (4,4'-diaminodiphenylethylene-2,2'-disulfonic acid) acid production process |
-
1983
- 1983-03-14 JP JP58040803A patent/JPS59167560A/en active Granted
-
1984
- 1984-03-09 CH CH119584A patent/CH659065A5/en not_active IP Right Cessation
- 1984-03-13 DE DE19843409171 patent/DE3409171A1/en not_active Withdrawn
- 1984-03-13 GB GB08406552A patent/GB2136430B/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0203506A1 (en) * | 1985-05-31 | 1986-12-03 | Bayer Ag | Process for the preparation of 4,4'-dinitrostilbene-disulfonic acid |
| US4680146A (en) * | 1985-05-31 | 1987-07-14 | Bayer Aktiengesellschaft | Process for the preparation of 4,4'-dinitrostilbene-2,2'-disulphonic acid salts |
| US5041632A (en) * | 1987-08-12 | 1991-08-20 | Ciba-Geigy Corporation | Process for the preparation of 4,4'-dinitrostilbene-2,2-disulfonic acid |
| US4952725A (en) * | 1988-03-08 | 1990-08-28 | Ciba-Geigy Corporation | Process for the preparation of 4,4'dinitrostilbene-2,2'-disulfonic acid and its salts |
| US5021132A (en) * | 1990-08-07 | 1991-06-04 | Sandoz Ltd. | Electrochemical process for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and the salts thereof |
| GB2246792A (en) * | 1990-08-07 | 1992-02-12 | Sandoz Ltd | Electrochemical production of 4,4` dinitrostilbene -2,2` disulphonic acid |
| FR2665715A1 (en) * | 1990-08-07 | 1992-02-14 | Sandoz Sa | ELECTROCHEMICAL PROCESS FOR THE PREPARATION OF 4,4'-DINITROSTILBENE-2,2'-DISULFONIC ACID AND ITS SALTS. |
| GB2246792B (en) * | 1990-08-07 | 1994-10-05 | Sandoz Ltd | Electrochemical process for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and the salts thereof |
| US5808141A (en) * | 1993-09-08 | 1998-09-15 | Bayer Aktiengesellschaft | Process for preparing 4,4'-dinitrostilbene-2,2'-disulphonic acid |
| US5583252A (en) * | 1994-05-26 | 1996-12-10 | Bayer Aktiengesellschaft | Process for preparing 4,4'-dinitrostilbene-2,2'-disulphonic acid and its salts |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8406552D0 (en) | 1984-04-18 |
| GB2136430B (en) | 1986-10-01 |
| CH659065A5 (en) | 1986-12-31 |
| JPH0149260B2 (en) | 1989-10-24 |
| DE3409171A1 (en) | 1984-09-20 |
| JPS59167560A (en) | 1984-09-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19950313 |