PL144803B1 - Process for preparing 4,4'-diaminostilben-2,2'-disulfonic acid - Google Patents
Process for preparing 4,4'-diaminostilben-2,2'-disulfonic acid Download PDFInfo
- Publication number
- PL144803B1 PL144803B1 PL25820886A PL25820886A PL144803B1 PL 144803 B1 PL144803 B1 PL 144803B1 PL 25820886 A PL25820886 A PL 25820886A PL 25820886 A PL25820886 A PL 25820886A PL 144803 B1 PL144803 B1 PL 144803B1
- Authority
- PL
- Poland
- Prior art keywords
- disulfonic acid
- catalyst
- diaminostilbene
- dinitrostilbene
- diaminostilben
- Prior art date
Links
- REJHVSOVQBJEBF-UHFFFAOYSA-N 5-azaniumyl-2-[2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-UHFFFAOYSA-N 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 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 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 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 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 4,4'-dinitrostilbene-2,2'-disulfonic acid hydrogen Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical class [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012000 urushibara nickel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest sposób otrzymywania kwasu 4,4'-diaminostilbeno-2,2'-disulfo- nowego, który stanowi wazny pólprodukt w syntezie barwników i wybielaczy fluoroscencyjnych.Znany jest, z opisu patentowego Wielkiej Brytanii nr 1447354, sposób otrzymywania soli disodowej kwasu 4,4'-diaminostilbeno-2,2'-disulfonowego na drodze redukcji soli disodowej kwasu 4,4'-dinitrostilbeno-2,2'-disulfonowego wodorem przy cisnieniu co najmniej 98kPa, w obecnosci katalizatora niklowego, korzystnie niklu Raney'a lub Urushibara, w temperaturze 20-200°C, w srodowisku alkoholowym zawierajacym przed rozpoczeciem redukcji mniej niz 3% wagowych wody, wzglednie w srodowisku wodnym o pH = 5-10, ustalonym w wyniku dodania buforu.Znany jest takze, z opisu patentowego RFN nr 2 362 781, sposób otrzymywania kwasu 4,4'- diaminostilbeno-2,2'-disulfonowego polegajacy na redukcji kwasu 4,4'-dinitrostilbeno-2,2'-disulfo- nowego wodorem przy cisnieniu 4000-8000 kPa,w obecnosci kobaltu Raney'a lub kobaltu osadzo¬ nego na zelu krzemionkowym jako katalizatora, w temperaturze 120°C, przy pH srodowiska reakcji 6-7.Niedogodnoscia sposobów wedlug patentów Wielkiej Brytanii i RFN jest stosowanie pirofo¬ rycznych katalizatorów takich, jak nikiel lub kobalt Raney'a, a takze koniecznosc stosowania buforów utrzymujacych wlasciwe pH srodowiska reakcji.Zjaponskich opisów patentowych nr nr 7 593 952 i 74127 955jest znany sposób otrzymywania kwasu 4,4'-diaminostilbeno-2,2/-disulfonowego na drodze redukcji kwasu 4,4'-dinitrostilbeno-2,2'- disulfonowego wodorem, przy czym redukcje prowadzi sie przy cisnieniu 101-102 kPa, w obec¬ nosci platyny lub palladu osadzonych na nosniku weglowym jako katalizatora, w temperaturze 50°C, w srodowisku wodnym lub metanolu, z dodatkiem jodków lub bromków potasu.Niedogodnoscia tych sposobówjest koniecznosc poddawania stosowanych w tych sposobach katalizatorów wstepnej obróbce parami J2 lub Br2- Sposób otrzymywania kwasu 4,4/-diaminostilbeno-2,2/-disulfonowego na drodze redukcji kwasu 4,4'-dinitrostilbeno-2,2'-disulfonowego wodorem, w obecnosci katalizatora metalicznego, w srodowisku alkoholowym, korzystnie metanolu, wedlug wynalazku polega na tym, ze jako2 144 m katalizator metaliczny stosuje sie pallad osadzony na nosniku krzemionkowym zawierajacym 5% wagowych fazy metalicznej, przy czym redukcje prowadzi sie pod cisnieniem 566,5-618 kPa, w temperaturze 80°C, przy stosunku wagowym substratu do katalizatora od 5:1 do 10:1.Sposób wedlug wynalazku zapewnia otrzymanie kwasu 4,4'-diaminostilbeno-2,2'-disulfo- nowego o wysokiej czystosci i z dobra wydajnoscia. Nadto w sposobie wedlug wynalazku wyelimi¬ nowano stosowanie piroforycznych katalizatorów, a takze koniecznosc wprowadzania do srodo¬ wiska reakcji dodatkowych substancji takich, jak bufory, jodki, bromki.Sposób wedlug wynalazku ilustruje blizej nizej podany przyklad.Przyklad. Reaktor zawierajacy roztwór 5 g kwasu 4,4'-dinitrostilbeno-2,2'-disulfonowego w 120 cm3 metanolu oraz 1 g katalizatora palladowego osadzonego na nosniku krzemionkowym, zawierajacego 0,05 g fazy metalicznej napelniono wodorem do cisnienia 566,5 kPa, po czym pro¬ wadzono reakcje redukcji w temperaturze 80°C w ciagu 4 godzin mieszajac intensywnie zawartosc reaktora. Po zakonczeniu redukcji odfiltrowano katalizator, a kwas 4,4'-diaminostilbeno-2,2'- disulfonowego wytracono w znany sposób przez zakwaszenie 2n kwasem solnym. Otrzymano 4,18 g kwasu 4,4'-diaminostilbeno-2,2'-disulfonowego, co stanowilo 97,38% wydajnosci teore¬ tycznej.Zastrzezenie patentowe Sposób otrzymywania kwasu 4,4'-diaminostilbeno-2,2'-disulfonowego na drodze redukcji kwasu 4,4'-dinitrostilbeno-2,2'-disulfonowego wodorem, w obecnosci katalizatora metalicznego, w srodowisku alkoholowym, korzystnie metanolu, znamienny tym, ze jako katalizator metaliczny stosuje sie pallad osadzony na nosniku krzemionkowym zawierajacym 5% wagowych fazy metali¬ cznej, przy czym redukcje prowadzi sie pod cisnieniem 566,5-618 kPa, w temperaturze 80°C, przy stosunku wagowym substratu do katalizatora od 5:1 do 10:1.Pracownia Poligraficzna UP PRL. Naklad 100 egz.Cena 400 zl PLThe subject of the invention is a method for the preparation of 4,4'-diaminostilbene-2,2'-disulfonic acid, which is an important intermediate in the synthesis of fluorescent dyes and bleaches. It is known from the British Patent No. 1,447,354 to obtain the disodium salt of 4 , 4'-diaminostilbene-2,2'-disulfonic acid by reduction of the disodium salt of 4,4'-dinitrostilbene-2,2'-disulfonic acid with hydrogen at a pressure of at least 98kPa, in the presence of a nickel catalyst, preferably Raney or Urushibara nickel , at a temperature of 20-200 ° C, in an alcoholic environment containing less than 3% by weight of water before the start of the reduction, or in an aqueous environment with a pH = 5-10, determined by adding a buffer. It is also known from German patent specification No. 2 362 781, method of obtaining 4,4'-diaminostilbene-2,2'-disulfonic acid by reducing 4,4'-dinitrostilbene-2,2'-disulfonic acid with hydrogen at a pressure of 4000-8000 kPa, in the presence of Raney cobalt or deposited cobalt on silica gel as a catalyst, at a temperature of 120 ° C, at a pH of the reaction environment of 6-7. The disadvantage of the methods according to the British and German patents is the use of pyrophoric catalysts such as nickel or Raney cobalt, as well as the necessity to use proper pH of the reaction environment. Japanese patents No. 7 593 952 and 74 127 955 is a known method of obtaining 4,4'-diaminostilbene-2,2) -disulfonic acid by reducing 4,4'-dinitrostilbene-2,2'-disulfonic acid hydrogen, the reductions being carried out at a pressure of 101-102 kPa, in the presence of platinum or palladium supported on a carbon carrier as a catalyst, at a temperature of 50 ° C., in an aqueous environment or methanol, with the addition of potassium iodides or bromides. necessity of subjecting the catalysts used in these methods to pre-treatment with J2 or Br2 steam - Method for obtaining 4,4 H-diaminostilbene-2,2 H -disulfonic acid by reducing the acid in 4,4'-dinitrostilbene-2,2'-disulfonic acid with hydrogen, in the presence of a metal catalyst, in an alcoholic environment, preferably methanol, according to the invention, according to the invention, palladium is used as a metal catalyst, deposited on a silica support containing 5% by weight of the metallic phase, the reductions being carried out at a pressure of 566.5-618 kPa, at a temperature of 80 ° C, with a substrate to catalyst weight ratio of 5: 1 to 10: 1. The method according to the invention provides the acid 4.4'- diaminostilbene-2,2'-disulfonic acid with high purity and good performance. In addition, the process according to the invention eliminates the use of pyrophoric catalysts, as well as the need to introduce additional substances into the reaction medium, such as buffers, iodides, bromides. The method according to the invention is illustrated by the following example. The reactor containing a solution of 5 g of 4,4'-dinitrostilbene-2,2'-disulfonic acid in 120 cm3 of methanol and 1 g of a palladium catalyst supported on a silica support, containing 0.05 g of a metallic phase, was filled with hydrogen to a pressure of 566.5 kPa, then The reduction reactions were carried out at a temperature of 80 ° C. for 4 hours while the contents of the reactor were thoroughly stirred. After the reduction was completed, the catalyst was filtered off and the 4,4'-diaminostilbene-2,2'-disulfonic acid was precipitated in a known manner by acidification with 2N hydrochloric acid. 4.18 g of 4,4'-diaminostilbene-2,2'-disulfonic acid were obtained, which was 97.38% of theoretical yield. Patent claim The method of obtaining 4,4'-diaminostilbene-2,2'-disulfonic acid on by reduction of 4,4'-dinitrostilbene-2,2'-disulfonic acid with hydrogen, in the presence of a metal catalyst, in an alcoholic environment, preferably methanol, characterized in that palladium is used as the metal catalyst on a silica support containing 5% by weight of metal phases The reduction is carried out at a pressure of 566.5-618 kPa, at a temperature of 80 ° C, with a substrate / catalyst weight ratio from 5: 1 to 10: 1. Mintage 100 copies Price PLN 400 PL
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL25820886A PL144803B1 (en) | 1986-03-03 | 1986-03-03 | Process for preparing 4,4'-diaminostilben-2,2'-disulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL25820886A PL144803B1 (en) | 1986-03-03 | 1986-03-03 | Process for preparing 4,4'-diaminostilben-2,2'-disulfonic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| PL144803B1 true PL144803B1 (en) | 1988-07-30 |
Family
ID=20030661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL25820886A PL144803B1 (en) | 1986-03-03 | 1986-03-03 | Process for preparing 4,4'-diaminostilben-2,2'-disulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL144803B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206175A (en) * | 2011-04-18 | 2011-10-05 | 河北华戈染料化学股份有限公司 | Method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature |
| CN102417471A (en) * | 2011-10-31 | 2012-04-18 | 天津大学 | Preparation method of 4-amino-2-sulfobenzoic acid |
| CN102675161A (en) * | 2011-03-10 | 2012-09-19 | 中国中化股份有限公司 | Method for preparing DSD acid |
-
1986
- 1986-03-03 PL PL25820886A patent/PL144803B1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675161A (en) * | 2011-03-10 | 2012-09-19 | 中国中化股份有限公司 | Method for preparing DSD acid |
| CN102206175A (en) * | 2011-04-18 | 2011-10-05 | 河北华戈染料化学股份有限公司 | Method for preparing DSD (4,4'-Diamino 2,2'-Stilbene Disulphonic) acid by hydrogenating and reducing disodium dinitrosalicylate (DNS) at high temperature |
| CN102417471A (en) * | 2011-10-31 | 2012-04-18 | 天津大学 | Preparation method of 4-amino-2-sulfobenzoic acid |
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