WO2009017288A1 - Process for preparation of disodium stilbenedisulfonates - Google Patents
Process for preparation of disodium stilbenedisulfonates Download PDFInfo
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- WO2009017288A1 WO2009017288A1 PCT/KR2008/000182 KR2008000182W WO2009017288A1 WO 2009017288 A1 WO2009017288 A1 WO 2009017288A1 KR 2008000182 W KR2008000182 W KR 2008000182W WO 2009017288 A1 WO2009017288 A1 WO 2009017288A1
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- Prior art keywords
- chemical formula
- compound
- mono
- mixture
- preparing sodium
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- -1 disodium stilbenedisulfonates Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title description 11
- 230000008569 process Effects 0.000 title description 11
- 238000002360 preparation method Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 97
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims abstract description 15
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims abstract description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 136
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 24
- 125000003282 alkyl amino group Chemical group 0.000 claims description 16
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims description 11
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- KDKGWGUUUVROTO-UHFFFAOYSA-N 1-hydroxypiperazine Chemical compound ON1CCNCC1 KDKGWGUUUVROTO-UHFFFAOYSA-N 0.000 claims description 5
- OURXRFYZEOUCRM-UHFFFAOYSA-N 4-hydroxymorpholine Chemical compound ON1CCOCC1 OURXRFYZEOUCRM-UHFFFAOYSA-N 0.000 claims description 5
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 5
- 125000006310 cycloalkyl amino group Chemical group 0.000 claims description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 claims description 3
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052717 sulfur Chemical group 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 abstract description 9
- 229940092714 benzenesulfonic acid Drugs 0.000 abstract description 9
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 abstract description 5
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 abstract description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000004811 liquid chromatography Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 101100446506 Mus musculus Fgf3 gene Proteins 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical group 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 5
- 239000012467 final product Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 0 CC(N=C(*)N=*1)=NC1Cl Chemical compound CC(N=C(*)N=*1)=NC1Cl 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
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 101000767160 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) Intracellular protein transport protein USO1 Proteins 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- LSSSYVGXQGICJL-UHFFFAOYSA-N 2,4-dichloro-1h-1,3,5-triazin-4-amine Chemical compound NC1(Cl)N=CNC(Cl)=N1 LSSSYVGXQGICJL-UHFFFAOYSA-N 0.000 description 1
- ZTGKHKPZSMMHNM-UHFFFAOYSA-N 3-(2-phenylethenyl)benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1S(O)(=O)=O ZTGKHKPZSMMHNM-UHFFFAOYSA-N 0.000 description 1
- IHDBZCJYSHDCKF-UHFFFAOYSA-N 4,6-dichlorotriazine Chemical compound ClC1=CC(Cl)=NN=N1 IHDBZCJYSHDCKF-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 101100348848 Mus musculus Notch4 gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical group N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
Definitions
- the present invention relates to a process for preparing sodium stilbenedisulfonate having aminotriazine substituent, as an intermediate for fluorescence brightener.
- the present invention relates to a process for preparing a compound represented by Chemical Formula (1) . More specifically, it relates to a process for preparing sodium benzenesulfonate, which comprises the steps of a) reacting compound represented by Chemical Formula (2) with compound represented by Chemical Formula (3) to produce a mixture of Chemical Formula (1) and Chemical Formula (4); b) adding compound represented by Chemical Formula (5) to the mixture from a) to produce a mixture of Chemical Formula (1) and Chemical Formula (6); c) adding compound represented by Chemical Formula (7) to the mixture from b) to produce a compound represented by Chemical Formula (1); and d) separating and purifying the product to obtain the final compound (Chemical Formula 1). [Chemical Formula 1]
- X represents linear or branched, saturated or unsaturated (Ci-Cio) alkyl, (Ci-C 7 ) alkoxy, (Ci- C 7 ) alkoxy (Ci-C 7 ) alkyl, (Ci-C 7 ) alkoxycarbonyl, (Ci- C 7 ) alkoxycarbonyl (Ci-C 7 ) alkoxy, (Ci-C 7 ) alkoxycarbonyl (Ci- C 7 ) alkylamino, (Ci-C 7 ) alkoxycarbonyl (Ci-C 7 ) alkylaminocarbonyl, (Ci-C 7 ) alkylcarbonyloxy (Ci-C 7 ) alkoxycarbonyl, hydroxyl, cyano, nitro, amino, mono or di (Ci-C 7 ) alkylamino, mono or di (Ci- C 7 ) alkylaminocarbonyl, mono or dibenzylamino, mono
- the compound represented by Chemical Formula (1) is used as an intermediate for a brightener compound for textile goods over broad field of chemical industry, by substituting with an organic substituent such as morpholine, morpholine oxide, piperazine, piperazine oxide and guanidine.
- a conventional method for preparing compound of Chemical Formula (1) includes, as can be seen from Reaction Scheme (1), 1) substituting 4,4'- diamino-2, 2 ' -stilbenedisulfonic acid (hereinafter, referred to as 'DAS') with sodium sulfonate; 2) adding cyanuric chloride
- step 3 (3)) from step 1); and 3) adding aqueous ammonia to the resultant product from step 2) (hereinafter, referred to as 'Int-1') to obtain the benzenesulfonic acid, 2,2'- (1,2- ethenediyl) bis [5- [4-amino-6-chloro-l, 3, 5-triazine-2-yl] amino] - disodium salt (hereinafter, referred to as ' Int-2 ' ) .
- 'Int-1' 2,2'- (1,2- ethenediyl) bis [5- [4-amino-6-chloro-l, 3, 5-triazine-2-yl] amino] - disodium salt
- the byproducts have similar physical properties to those of Int-2 and high boiling temperature, so that separation and purification is difficult, to give the problem of low conversion of overall Int-2 of 70 to 73%.
- the product was used with comprising the byproducts for subsequent step of introducing other substituent such as morpholine, there remains unreacted Int-2 in an amount of 5 to 11%, resulting in decrease of the conversion of the compound substituted with morpholine or the like to 60-70%.
- impurities are produced due to the byproducts of Int-2, purification becomes difficult, and a compound substituted with morpholine or the like having low purity (purity from 82 to 85%) is produced.
- ADT should be added in an excess amount with respect to the equivalent ratio of DAS, or the reaction should be carried out at a high temperature. If ADT is added in an excess amount to the equivalent ratio, separation of ADT in the subsequent process is difficult because melting point of ADT is 230 ° C . Moreover, residual ADT
- the object of the invention is to overcome the problems described above, and to provide a commercially available continuous process wherein dichlorotriazine having a substituent at 2-position is used; both amine groups of compound of Chemical Formula (3) are substituted in order to minimize production of byproduct with only one amine group substituted; and the impurities of Int-2 are minimized to increase the purity and yield of final Int-2.
- the present invention provides a process for preparing sodium benzenesulfonate represented by Chemical Formula (1) , which comprises the steps of a) reacting compound represented by Chemical Formula (2) with compound represented by Chemical Formula (3) to produce a mixture of Chemical Formula (1) and Chemical Formula (4); b) adding compound represented by Chemical Formula (5) to the mixture from a) to produce a mixture of Chemical Formula (1) and Chemical Formula (6); c) adding compound represented by Chemical Formula (7) to the mixture from b) to produce a compound represented by- Chemical Formula (1); and d) separating and purifying the product to obtain the final compound (Chemical Formula 1) .
- X represents linear or branched, saturated or unsaturated (Ci-Cio) alkyl, (Ci-C 7 ) alkoxy, (Ci- C 7 ) alkoxy (Ci-C 7 ) alkyl, (Ci-C 7 ) alkoxycarbonyl, (Ci- C 7 ) alkoxycarbonyl (Ci-C 7 ) alkoxy, (Ci-C 7 ) alkoxycarbonyl (Ci- C 7 ) alkylamino, (Ci-C 7 ) alkoxycarbonyl (Ci-C 7 ) alkylaminocarbonyl, (Ci-C 7 ) alkylcarbonyloxy (Ci-C 7 ) alkoxycarbonyl, hydroxyl, cyano, nitro, amino, mono or di (Ci-C 7 ) alkylamino, mono or di (Ci- C 7 ) alkylaminocarbonyl, mono or dibenzylamino, mono
- compound of Chemical Formula (2) Since compound of Chemical Formula (2) has lower reactivity than that of compound of Chemical Formula (5) , there occurs a problem of difficult separation and purification due to existence of unreacted compound of Chemical Formula (4) . In order to overcome the problem, it is desirable that compound of Chemical Formula (2) is used in an amount of 1 ⁇ 2 equivalent (s) with respect to compound of Chemical Formula (3) to minimize residual compound of Chemical Formula (2) .
- step a) compound of Chemical Formula (4) without compound of Chemical Formula (2) substituted is produced, and compound of Chemical Formula (4) thus produced is contained in the final product to cause the problems including lowered crystallinity and purity.
- compound of Chemical Formula (5) is added to compound of Chemical Formula (4), to produce the substituted compound of Chemical Formula (6) .
- compound of Chemical Formula (5) is more than 1.5 equivalents with respect to compound of Chemical Formula (4), compound of Chemical Formula (5) remains in a too much amount, so that cyanuric acid might be produced by hydrolysis to cause problem of byproducts. On the other hand, if it is less than 1 equivalent, compound of Chemical Formula (4) remains unreacted. Thus, compound of Chemical Formula (5) is preferably added in an amount from 1 to 1.5 equivalent (s) with respect to compound of Chemical Formula (4).
- cyano, nitro, amino, mono- or di (Ci-C 7 ) alky1 amino, (C 3 ⁇ C 7 ) cycloalkylamino, morpholine oxide, piperazine, piperazine oxide, guanidine, urea, and the like can be used instead of morpholine.
- LC liquid chromatography
- Reactor-1 To Reactor-1, incorporated was cooling water (615 mL) , and the reactor was slowly charged with 4, 4 ' -diamino-2 , 2 ' - stilbenedisulfonic acid (DAS) (122.23 g, 0.5 eq., purity (LC Area) : 95%) . Upon stirring, the mixture became an emulsion. While maintaining the stirring rate in Reactor-1 at about 70 rpm, NaOH (28.06 g) was added at ambient temperature. Then, 4, 4 ' -diamino-2, 2 ' -stilbenedisulfonic acid was completely dissolved to be a clear dark brown solution.
- DAS 4, 4 ' -diamino-2 , 2 ' -stilbenedisulfonic acid
- Example 2 4-Amino-4 , 6-dichloro-l, 3, 5-triazine Reactor-1 was charged with methyl ethyl ketone (105.8 ml), and then cyanuric chloride (121.7 g, 1.0 eq., purity: 99%), and the mixture was stirred while maintaining the internal temperature at -5 ° C . The reaction mixture then was in emulsion state. To the reaction mixture in Reactor-1, slowly added was aqueous 28% NH 4 OH solution (88.6 ml, 1.1 eq. ) over 20 minutes.
- reaction mixture becomes acidic as the reaction progresses, aqueous 23% Na 2 CO 3 solution (87 g) was added thereto in order to maintain the pH over 7. The reaction was exothermic, but the internal temperature of the reactor was maintained at 0 ° C . After 1 hour from complete addition of the reactants, the reaction mixture was sampled to analyze with respect to the structure of 4-amino-4,6- dichloro-1, 3, 5-triazine (ADT).
- ADT 4-amino-4,6- dichloro-1, 3, 5-triazine
- Int-3 is a compound with said Int-2-half being substituted with CNC.
- Example 4 The mixture from Example 4 was maintained at a temperature lower than 10 ° Q and aqueous 28% NH 4 OH solution
- both amine groups of compound of Chemical Formula (3) are substituted according to the invention, to minimize the impurities wherein only one amine group is substituted. Accordingly, additional processes for purifying impurities are unnecessary (omitted) , to provide high economic and industrial advantages. Furthermore, the invention gives excellent effect of increase in crystallinity and purity of the final product
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to a process for preparing sodium benzenesulf onate, more specifically, to a process for preparing sodium benzenesulfonate, which comprises the steps of a) reacting 2-X-4, 6-dichloro-l, 3, 5-triazine with a benzenesulf onic acid, 2, 2- (1, 2-ethenediyl) bis [5-amino] - disodium salt to produce a mixture; b) adding cyanuric chloride to the mixture from a); c) adding the compound, XH to the mixture from b) to produce a benzenesulf onic acid, 2,2'- (1, 2-ethenediyl) bis [5- (4-X-β-chloro-l, 3, 5-triazine-2- yl) amino] disodium salt; and d) separating and purifying the product to obtain the final benzenesulf onic acid, 2, 2'- (1,2- ethenediyl) bis [5- (4-X-β-chloro-l, 3, 5-triazin-2-yl) amino] - disodium salt [wherein, X represents an organic substituent].
Description
[DESCRIPTION]
[invention Title]
PROCESS FOR PREPARATION OF DISODIUM STILBENEDISULFONATES
[Technical Field]
The present invention relates to a process for preparing sodium stilbenedisulfonate having aminotriazine substituent, as an intermediate for fluorescence brightener.
[Background Art]
The present invention relates to a process for preparing a compound represented by Chemical Formula (1) . More specifically, it relates to a process for preparing sodium benzenesulfonate, which comprises the steps of a) reacting compound represented by Chemical Formula (2) with compound represented by Chemical Formula (3) to produce a mixture of Chemical Formula (1) and Chemical Formula (4); b) adding compound represented by Chemical Formula (5) to the mixture from a) to produce a mixture of Chemical Formula (1) and Chemical Formula (6); c) adding compound represented by Chemical Formula (7) to the mixture from b) to produce a compound represented by Chemical Formula (1); and d) separating and purifying the product to obtain the final compound (Chemical Formula 1).
[Chemical Formula 1]
[Chemical Formula 2]
[Chemical Formula 3]
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
[Chemical Formula 7] XH
In the Formula, X represents linear or branched, saturated or unsaturated (Ci-Cio) alkyl, (Ci-C7) alkoxy, (Ci- C7) alkoxy (Ci-C7) alkyl, (Ci-C7) alkoxycarbonyl, (Ci- C7) alkoxycarbonyl (Ci-C7) alkoxy, (Ci-C7) alkoxycarbonyl (Ci- C7) alkylamino, (Ci-C7) alkoxycarbonyl (Ci-C7) alkylaminocarbonyl, (Ci-C7) alkylcarbonyloxy (Ci-C7) alkoxycarbonyl, hydroxyl, cyano, nitro, amino, mono or di (Ci-C7) alkylamino, mono or di (Ci- C7) alkylaminocarbonyl, mono or dibenzylamino, mono or di (Ci- C7) alkylamino (Ci-C7) alkoxy, (C3-C7) cycloalkylamino, (Ci- C7) alkylcarbonylamino, aminocarbonyl, 3- to 7-membered saturated or unsaturated heterocycloalkyl containing at least one oxygen, nitrogen or sulfur atom(s) in the heterocyclic ring, (Ci-C7) alkylsulfonamino without mono- or dihalogen substituent (s) , morpholine, morpholine oxide, piperazine, piperazine oxide, guanidine, (Ci-C7) alkylguanidine, urea, (Ci- C7) alkylurea, phenyl, phenoxy, benzyl, benzyloxy, thiobenzyl, carboxylic acid, carboxyl (Ci-Cio) alkylamino, carboxyl (Ci-
Cio) alkylaminocarbonyl, (Ci-C7) alkylketone or benzoyl.
The compound represented by Chemical Formula (1) is used as an intermediate for a brightener compound for textile goods over broad field of chemical industry, by substituting with an organic substituent such as morpholine, morpholine oxide, piperazine, piperazine oxide and guanidine. A conventional method for preparing compound of Chemical Formula (1) includes, as can be seen from Reaction Scheme (1), 1) substituting 4,4'- diamino-2, 2 ' -stilbenedisulfonic acid (hereinafter, referred to as 'DAS') with sodium sulfonate; 2) adding cyanuric chloride
(2, 4 , β-trichloro-1, 3, 5-triazine, compound of Chemical Formula
(5) ) to the resultant product (compound of Chemical Formula
(3)) from step 1); and 3) adding aqueous ammonia to the resultant product from step 2) (hereinafter, referred to as 'Int-1') to obtain the benzenesulfonic acid, 2,2'- (1,2- ethenediyl) bis [5- [4-amino-6-chloro-l, 3, 5-triazine-2-yl] amino] - disodium salt (hereinafter, referred to as ' Int-2 ' ) .
[Reaction Scheme 1]
The byproducts have similar physical properties to those of Int-2 and high boiling temperature, so that separation and purification is difficult, to give the problem of low conversion of overall Int-2 of 70 to 73%. When the product was used with comprising the byproducts for subsequent step of introducing other substituent such as morpholine, there
remains unreacted Int-2 in an amount of 5 to 11%, resulting in decrease of the conversion of the compound substituted with morpholine or the like to 60-70%. Further, since impurities are produced due to the byproducts of Int-2, purification becomes difficult, and a compound substituted with morpholine or the like having low purity (purity from 82 to 85%) is produced.
In USP 4,552,959, a process for substituting compound of Chemical Formula (5) with an amino group, and then substituting DAS was introduced. However, the process produces the byproduct wherein 2-amino-4 , β-dichloro-1, 3, 5-triazine (hereinafter, referred to as 'ADT') has been substituted for only one side of the amino groups, and the byproduct cannot be easily separated and purified since it has similar physical properties to the compound having both amino groups substituted. If the process is subsequently progressed to obtain final product without removing the byproduct, the final product will comprise the byproduct and the byproducts of the byproduct to cause the problems including lowered crystallinity and decreased purity. Eventually, the productivity of the final substance is lowered.
In order to reduce the byproduct, ADT should be added in an excess amount with respect to the equivalent ratio of DAS, or the reaction should be carried out at a high temperature. If ADT is added in an excess amount to the equivalent ratio,
separation of ADT in the subsequent process is difficult because melting point of ADT is 230 °C . Moreover, residual ADT
(from the excess amount) further results in subsequent production of byproducts in the next step, to decrease overall yield and purity.
[Disclosure]
[Technical Problem]
The object of the invention is to overcome the problems described above, and to provide a commercially available continuous process wherein dichlorotriazine having a substituent at 2-position is used; both amine groups of compound of Chemical Formula (3) are substituted in order to minimize production of byproduct with only one amine group substituted; and the impurities of Int-2 are minimized to increase the purity and yield of final Int-2.
[Technical Solution]
In order to achieve the object, the present invention provides a process for preparing sodium benzenesulfonate represented by Chemical Formula (1) , which comprises the steps of a) reacting compound represented by Chemical Formula (2) with compound represented by Chemical Formula (3) to produce a mixture of Chemical Formula (1) and Chemical Formula (4);
b) adding compound represented by Chemical Formula (5) to the mixture from a) to produce a mixture of Chemical Formula (1) and Chemical Formula (6); c) adding compound represented by Chemical Formula (7) to the mixture from b) to produce a compound represented by- Chemical Formula (1); and d) separating and purifying the product to obtain the final compound (Chemical Formula 1) .
[Chemical Formula 1]
[Chemical Formula 2]
[Chemical Formula 3]
[Chemical Formula 4]
[ Chemical Formula 5 ]
[Chemical Formula 6]
[Chemical Formula 7] XH
In the Formula, X represents linear or branched, saturated or unsaturated (Ci-Cio) alkyl, (Ci-C7) alkoxy, (Ci- C7) alkoxy (Ci-C7) alkyl, (Ci-C7) alkoxycarbonyl, (Ci- C7) alkoxycarbonyl (Ci-C7) alkoxy, (Ci-C7) alkoxycarbonyl (Ci- C7) alkylamino, (Ci-C7) alkoxycarbonyl (Ci-C7) alkylaminocarbonyl, (Ci-C7) alkylcarbonyloxy (Ci-C7) alkoxycarbonyl, hydroxyl, cyano, nitro, amino, mono or di (Ci-C7) alkylamino, mono or di (Ci- C7) alkylaminocarbonyl, mono or dibenzylamino, mono or di (Ci-
C7) alkylamino (Ci-C7) alkoxy, (03-C7) cycloalkylamino, (Ci- C7) alkylcarbonylaraino, aminocarbonyl, 3- to 7-membered saturated or unsaturated heterocycloalkyl containing at least one oxygen, nitrogen or sulfur atom(s) in the heterocyclic ring, (Ci-C7) alkylsulfonamino without mono- or dihalogen substituent (s) , morpholine, morpholine oxide, piperazine, piperazine oxide, guanidine, (Ci-C7) alkylguanidine, urea, (Ci- C7) alkylurea, phenyl, phenoxy, benzyl, benzyloxy, thiobenzyl, carboxylic acid, carboxyl (C1-C10) alkylamino, carboxyl (Ci- Cio) alkylaminocarbonyl, (Ci-C7) alkylketone or benzoyl.
As described above, a lot of byproducts are produced in the next step, when compound of Chemical Formula (5) is directly substituted with compound of Chemical Formula (3) . In order to overcome the problem, compound of Chemical Formula (2) is firstly produced and then reacted with compound of Chemical Formula (3) to prepare compound of Chemical Formula (1). During the process, compound of Chemical Formula (5) is additionally added to compound of Chemical Formula (4) which is produced with compound of Chemical Formula (1) to obtain compound of Chemical Formula (6) . Compound of Chemical Formula (7) is incorporated thereto to be substituted with compound of Chemical Formula (1), thereby reducing the production of the byproduct which is generated.
Since compound of Chemical Formula (2) has lower reactivity than that of compound of Chemical Formula (5) ,
there occurs a problem of difficult separation and purification due to existence of unreacted compound of Chemical Formula (4) . In order to overcome the problem, it is desirable that compound of Chemical Formula (2) is used in an amount of 1~2 equivalent (s) with respect to compound of Chemical Formula (3) to minimize residual compound of Chemical Formula (2) .
If the amount of compound of Chemical Formula (2) is more than 2 equivalents with respect to compound of Chemical Formula (3), it is difficult to separate and purify the residual compound of Chemical Formula (2) as described above. On the other hand, if it is less than 1 equivalent, compound of Chemical Formula (3) remains unreacted, which requires excessive amount of compound of Chemical Formula (5) in the next step, and the reaction produces a lot of byproducts as described above.
In step a), compound of Chemical Formula (4) without compound of Chemical Formula (2) substituted is produced, and compound of Chemical Formula (4) thus produced is contained in the final product to cause the problems including lowered crystallinity and purity. Thus, compound of Chemical Formula (5) is added to compound of Chemical Formula (4), to produce the substituted compound of Chemical Formula (6) .
If the amount of compound of Chemical Formula (5) is more than 1.5 equivalents with respect to compound of Chemical
Formula (4), compound of Chemical Formula (5) remains in a too much amount, so that cyanuric acid might be produced by hydrolysis to cause problem of byproducts. On the other hand, if it is less than 1 equivalent, compound of Chemical Formula (4) remains unreacted. Thus, compound of Chemical Formula (5) is preferably added in an amount from 1 to 1.5 equivalent (s) with respect to compound of Chemical Formula (4).
Compound of Chemical Formula (7) is added to compound of Chemical Formula (6) thus produced to obtain compound of Chemical Formula (1), while compounds of Chemical Formula (5) and of Chemical Formula (7), which remain in a trace amount, are separated and purified to obtain objective compound of Chemical Formula (1) .
Individual steps of the process are characterized to be continuously carried out.
Compound of Chemical Formula (1) produced as above can be substituted with morpholine to give compound of Chemical Formula (8) .
[Chemical Formula 8]
In Chemical Formula (8), X is defined as in Chemical
Formula ( 1 ) .
In compound of Chemical Formula (8), cyano, nitro, amino, mono- or di (Ci-C7) alky1 amino, (C3~C7) cycloalkylamino, morpholine oxide, piperazine, piperazine oxide, guanidine, urea, and the like can be used instead of morpholine.
[Best Mode]
Now the present invention is illustrated in more detail by referring to specific examples. However, the present invention is not restricted by those examples, and it is apparent to a person having ordinary skill in the art that various alterations and modifications can be made within the spirit and scope of the invention.
In the Examples, for liquid chromatography (LC), used were 1100 Series from Agilent, a column of Luna C18, and a mixture of distilled water and acetonitrile as eluent, and measurement was carried out under UV 254 nm. For NMR, used was DRX500 model (500 MHz) from Bruker, and for IR, used was Nicolet 380 from Scinco.
Since the Examples were continuous processes, NMR and IR data for only the product from Example 2 and the final product are reported.
[Example 1] Benzenesulfonic acid, 2, 2 '-(1,2-
ethenediyl) bis [5-amino] -disodium salt
To Reactor-1, incorporated was cooling water (615 mL) , and the reactor was slowly charged with 4, 4 ' -diamino-2 , 2 ' - stilbenedisulfonic acid (DAS) (122.23 g, 0.5 eq., purity (LC Area) : 95%) . Upon stirring, the mixture became an emulsion. While maintaining the stirring rate in Reactor-1 at about 70 rpm, NaOH (28.06 g) was added at ambient temperature. Then, 4, 4 ' -diamino-2, 2 ' -stilbenedisulfonic acid was completely dissolved to be a clear dark brown solution. The benzenesulfonic acid thus prepared, 2,2 '-(1,2- ethenediyl) bis [5-amino] -disodium salt reaction mixture was transferred to a clean Reactor-2. Inner side of Reactor-1 was washed with pure water. The washing was poured into Reactor-2. The next stage was progressed without purification.
[Example 2] 4-Amino-4 , 6-dichloro-l, 3, 5-triazine Reactor-1 was charged with methyl ethyl ketone (105.8 ml), and then cyanuric chloride (121.7 g, 1.0 eq., purity: 99%), and the mixture was stirred while maintaining the internal temperature at -5°C . The reaction mixture then was in emulsion state. To the reaction mixture in Reactor-1, slowly added was aqueous 28% NH4OH solution (88.6 ml, 1.1 eq. ) over 20 minutes. Since the reaction mixture becomes acidic as the reaction progresses, aqueous 23% Na2CO3 solution (87 g) was added thereto in order to maintain the pH over 7. The
reaction was exothermic, but the internal temperature of the reactor was maintained at 0 °C . After 1 hour from complete addition of the reactants, the reaction mixture was sampled to analyze with respect to the structure of 4-amino-4,6- dichloro-1, 3, 5-triazine (ADT).
1H NMR (500MHz, DMSO/TMS): δ 8.56 (s, 2H) 13C NMR (500MHz, DMSO/TMS): δ 167.32, 169.55 IR (KBr/Film, cm"1) : 3393, 3210, 2895, 2748, 1734, 1684, 1653, 1541, 1507, 1419, 1344, 1319, 1256, 1214, 1077, 1014, 898, 850, 799, 747, 686, 584, 531
[Example 3] Benzenesulfonic acid, 2, 2 '-(1,2- ethenediyl) bis [5- (4-amino-6-chloro-l, 3, 5-triazin-2-yl) amino] - disodium salt The reaction mixture of Reactor-2 was slowly incorporated to Reactor-1 over 2 hours, while simultaneously adding aqueous 23% Na2CO3 solution (158 g) thereto to maintain the pH over 7. The reaction was exothermic, but the internal temperature was maintained at ambient temperature. After complete addition of the reaction mixture of Reactor-2, the internal temperature was raised to 45°C , and the content of Compound of Chemical Formula (1) was analyzed via LC at 30- minute intervals. The results are shown in Table 1. In the Table, Int-2-half represents a compound wherein only one side of compound of Chemical Formula (3) was substituted with ADT.
[Table 1] LC analysis over time (Example 31
[Example 4] Benzene sulfonic acid, 2,2 '-(1,2- ethenediyl ) bis [5- (4 , β-dichloro-1, 3, 5-triazin-2-yl) amino] - disodium salt mixture
The mixture from Example 3 was maintained at a temperature lower than 10 °C , and cyanuric chloride (CNC)
(1.10 g) was slowly added thereto. Then, aqueous 23% Na2CO3 solution (1.34 g) was added to maintain the pH of the mixture over 7. The reaction was exothermic, but the internal temperature was maintained at a temperature lower than 10°C .
Then the internal temperature was raised to 45 °C , and the reaction mixture was analyzed via LC at 30-minute intervals. The results are shown in Table 2. In the Table, Int-3 is a compound with said Int-2-half being substituted with CNC.
[Table 2]
LC analysis over time (Example 41
[Example 5] Benzenesulfonic acid, 2,2'- (1,2- ethenediyl)bis [5- (4-amino-β-chloro-l, 3, 5-triazin-2-yl ) amino] - disodium salt
The mixture from Example 4 was maintained at a temperature lower than 10 °Q and aqueous 28% NH4OH solution
(0.55 g) was added thereto. Then, aqueous 23% Na2CO3 solution
(1.34 g) was added to maintain the pH of the mixture over 7.
The reaction was exothermic, but the internal temperature was maintained at a temperature lower than 10 °C . Then the internal temperature was raised to 45 °C , and the reaction mixture was analyzed via LC at 30-minute intervals. The results are shown in Table 3.
[Table 3]
LC analysis over time (Example 5)
(90 torr) . During distillation, methyl ethyl ketone and a small amount of water are distilled together. Then, morpholine (60.8 g) was added for 10 minutes while maintaining the temperature at 45 °C , and aqueous 23% Na2CO3 solution (346 g) was added at the same time to maintain the pH in the range from 8.8 to 9.2. The reaction temperature was raised to 70 °C, and the reaction was carried out for 2 hours while maintaining the same temperature. The content of the final compound was analyzed via LC at 30-minute intervals.
Then, the internal temperature of Reactor-1 was cooled to about 5 °C , and the reaction mixture was filtered by using a
Nutsche filter. The filtered substance was dried at 80°Cin vacuo to obtain the final compound (252.03 g) . The purity and yield of the final compound were analyzed.
Purity of the morpholine substituent: 97.2% Yield of the morpholine substituent: 99.4% 1H NMR (500MHz, D2O/TMS) : δ7.23(s.lH), 7.45(d.lH), 7.61(s. IH), 8.18(s. IH) IR (KBr/Film, cm"1): 3363, 2862, 1615, 1539, 1506, 1448,
1407, 1306, 1284, 1223, 1183, 1108, 1081, 1022, 888, 834, 806, 700, 631, 541
[industrial Applicability] As described above, both amine groups of compound of Chemical Formula (3) are substituted according to the invention, to minimize the impurities wherein only one amine group is substituted. Accordingly, additional processes for purifying impurities are unnecessary (omitted) , to provide high economic and industrial advantages. Furthermore, the invention gives excellent effect of increase in crystallinity and purity of the final product
Claims
[ Chemical Formula 1 ]
[Chemical Formula 2]
[Chemical Formula 3]
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6\
[Chemical Formula 7]
XH
In the Formula, X represents linear or branched, saturated or unsaturated (Ci-Cio) alkyl, (C1-C7) alkoxy, (Ci- C7) alkoxy (Ci-C7) alkyl, (Ci-C7) alkoxycarbonyl, (Ci- C7) alkoxycarbonyl (Ci-C7) alkoxy, (Ci-C7) alkoxycarbonyl (Ci- C7) alkylamino, (Ci-C7) alkoxycarbonyl (Ci-C7) alkylaminocarbonyl, (Ci-C7) alkylcarbonyloxy (Ci-C7) alkoxycarbonyl, hydroxyl, cyano, nitro, amino, mono or di (Ci-C7) alkylamino, mono or di(Ci- C7) alkylaminocarbonyl, mono or dibenzylamino, mono or di (Ci- C7) alkylamino (Ci-C7) alkoxy, (C3~C7) cycloalkylamino, (Ci- C7) alkylcarbonylamino, aminocarbonyl, 3- to 7-membered saturated or unsaturated heterocycloalkyl containing at least one oxygen, nitrogen or sulfur atom(s) in the heterocyclic ring, (Ci-C7) alkylsulfonamino without mono- or dihalogen substituent (s) , morpholine, morpholine oxide, piperazine, piperazine oxide, guanidine, (Ci-C7) alkylguanidine, urea, (Ci- C7) alkylurea, phenyl, phenoxy, benzyl, benzyloxy, thiobenzyl, carboxylic acid, carboxyl (Ci-Cio) alkylamino, carboxyl(Ci~ Cio) alkylaminocarbonyl, (Ci-C7) alkylketone or benzoyl.
[Claim 2]
A process for preparing sodium benzenesulfonate according to claim 1, wherein X represents nitro, amino, mono or di (Ci- C7) alkylamino, mono or di (Ci-C7) alkylaminocarbonyl, mono or
dibenzylamino, mono or di (Ci-C7) alkylamino (Ci-C7) alkoxy, (C3- C7) cycloalkylamino, (Ci-C7) alkylcarbonylamino, and (Ci- C7) alkylsulfonamino without mono- or dihalogen substituent (s) .
[Claim 3]
A process for preparing sodium benzenesulfonate according to claim 1, wherein X represents amino.
[Claim 4] A process for preparing sodium benzenesulfonate according to claim 1, wherein compound of Chemical Formula (2) is reacted in an amount of from 1 to 2 equivalents with respect to compound of Chemical Formula (3) , in step a) .
[Claim 5]
A process for preparing sodium benzenesulfonate according to claim 1, wherein compound of Chemical Formula (5) is reacted in an amount of from 1 to 1.5 equivalents with respect to compound of Chemical Formula (4) of step a), in step b) .
[Claim β]
A process for preparing sodium benzenesulfonate, which comprises the steps of a) reacting compound represented by Chemical Formula (2) with compound represented by Chemical Formula (3) to produce a
mixture of Chemical Formula (1) and Chemical Formula (4); b) adding compound represented by Chemical Formula (5) to the mixture from a) to produce a mixture of Chemical Formula (1) and Chemical Formula
(6); c) adding the compound represented by Chemical Formula
(7) to the mixture from b) to produce compound represented by Chemical Formula (1); d) separating and purifying the product to obtain compound of Chemical Formula (1); and e) adding morpholine to compound of Chemical Formula (1) obtained from step d) to produce compound of Chemical Formula
(8) :
[Chemical Formula 8]
wherein, X is defined as in Chemical Formula (I)-
[Claim 7]
A process for preparing sodium benzenesulfonate according to claim β, wherein X represents nitro, amino, mono or di(Cχ-
C7) alkylamino, mono or di (Ci-C7) alkylaminocarbonyl, mono or dibenzylamino, mono or di (Ci-C7) alkylamino (Ci-C7) alkoxy, (C3-
C7) eyeloalkylamino, (Ci-C7) alkylcarbonylami.no, and (Ci- C7) alkylsulfonamino without mono- or dihalogen substituent (s) .
[Claim 8] A process for preparing sodium benzenesulfonate according to claim 7, wherein X represents amino.
[Claim 9]
A process for preparing sodium benzenesulfonate according to claim 6, wherein compound of Chemical Formula (2) is reacted in an amount of from 1 to 2 equivalents with respect to compound of Chemical Formula (3) , in step a) .
[Claim 10] A process for preparing sodium benzenesulfonate according to claim 6, wherein compound of Chemical Formula (5) is reacted in an amount of from 1 to 1.5 equivalents with respect to compound of Chemical Formula (4) from step a), in step b) .
[Claim ll]
A process for preparing sodium benzenesulfonate according to any one of claims 1 to 10, wherein individual steps are continuously carried out.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2007-0076592 | 2007-07-30 | ||
| KR1020070076592A KR100907903B1 (en) | 2007-07-30 | 2007-07-30 | Method for preparing stilbenesulfonic acid sodium salt substituted with amino triazine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2009017288A1 true WO2009017288A1 (en) | 2009-02-05 |
Family
ID=40304499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2008/000182 WO2009017288A1 (en) | 2007-07-30 | 2008-01-11 | Process for preparation of disodium stilbenedisulfonates |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100907903B1 (en) |
| WO (1) | WO2009017288A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014105689A1 (en) * | 2012-12-26 | 2014-07-03 | Kimberly-Clark Worldwide, Inc. | Modified cellulosic fibers having reduced hydrogen bonding |
| US9410292B2 (en) | 2012-12-26 | 2016-08-09 | Kimberly-Clark Worldwide, Inc. | Multilayered tissue having reduced hydrogen bonding |
| US9416494B2 (en) | 2012-12-26 | 2016-08-16 | Kimberly-Clark Worldwide, Inc. | Modified cellulosic fibers having reduced hydrogen bonding |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5656760A (en) * | 1994-09-21 | 1997-08-12 | Ciba-Geigy Corporation | Fluorescent whitening agents |
| WO1998005653A1 (en) * | 1995-01-13 | 1998-02-12 | Bayer Aktiengesellschaft | Process for preparing substituted 4,4'-diaminostilbene-2,2'-disulphonic acid salts |
| US6365737B1 (en) * | 1998-02-20 | 2002-04-02 | Ciba Specialty Chemical Corporation | Process for the preparation of stilbene compounds |
| WO2004069790A2 (en) * | 2003-02-10 | 2004-08-19 | Ciba Specialty Chemicals Holding Inc. | Crystalline modifications of triazinylaminostilbenes |
-
2007
- 2007-07-30 KR KR1020070076592A patent/KR100907903B1/en not_active IP Right Cessation
-
2008
- 2008-01-11 WO PCT/KR2008/000182 patent/WO2009017288A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5656760A (en) * | 1994-09-21 | 1997-08-12 | Ciba-Geigy Corporation | Fluorescent whitening agents |
| WO1998005653A1 (en) * | 1995-01-13 | 1998-02-12 | Bayer Aktiengesellschaft | Process for preparing substituted 4,4'-diaminostilbene-2,2'-disulphonic acid salts |
| US6365737B1 (en) * | 1998-02-20 | 2002-04-02 | Ciba Specialty Chemical Corporation | Process for the preparation of stilbene compounds |
| WO2004069790A2 (en) * | 2003-02-10 | 2004-08-19 | Ciba Specialty Chemicals Holding Inc. | Crystalline modifications of triazinylaminostilbenes |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014105689A1 (en) * | 2012-12-26 | 2014-07-03 | Kimberly-Clark Worldwide, Inc. | Modified cellulosic fibers having reduced hydrogen bonding |
| US8980054B2 (en) | 2012-12-26 | 2015-03-17 | Kimberly-Clark Worldwide, Inc. | Soft tissue having reduced hydrogen bonding |
| US9410292B2 (en) | 2012-12-26 | 2016-08-09 | Kimberly-Clark Worldwide, Inc. | Multilayered tissue having reduced hydrogen bonding |
| US9416494B2 (en) | 2012-12-26 | 2016-08-16 | Kimberly-Clark Worldwide, Inc. | Modified cellulosic fibers having reduced hydrogen bonding |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20090012625A (en) | 2009-02-04 |
| KR100907903B1 (en) | 2009-07-15 |
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