PL206169B1 - Production method of 4,4-diamindiphenylourea-3,3-disulphone acid - Google Patents
Production method of 4,4-diamindiphenylourea-3,3-disulphone acidInfo
- Publication number
- PL206169B1 PL206169B1 PL384486A PL38448608A PL206169B1 PL 206169 B1 PL206169 B1 PL 206169B1 PL 384486 A PL384486 A PL 384486A PL 38448608 A PL38448608 A PL 38448608A PL 206169 B1 PL206169 B1 PL 206169B1
- Authority
- PL
- Poland
- Prior art keywords
- acid
- sodium
- diaminobenzenesulfonic acid
- diaminodiphenylurea
- urea
- Prior art date
Links
- 239000002253 acid Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 238000000034 method Methods 0.000 claims description 15
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims 1
- 229940001584 sodium metabisulfite Drugs 0.000 claims 1
- 235000010262 sodium metabisulphite Nutrition 0.000 claims 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YQCKQDZVUQEQFT-UHFFFAOYSA-N 5-amino-2-nitrobenzenesulfonic acid Chemical compound NC1=CC=C([N+]([O-])=O)C(S(O)(=O)=O)=C1 YQCKQDZVUQEQFT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004816 paper chromatography Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000006100 radiation absorber Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Opis wynalazkuDescription of the invention
Przedmiotem wynalazku jest sposób wytwarzania kwasu 4,4'-diaminodifenylomoczniko-3,3'-disulfonowego, który jest stosowany jako produkt pośredni do syntezy barwników, środków optycznie rozjaśniających, absorberów promieniowania UV, preparatów biochemicznych.The subject of the invention is a process for the production of 4,4'-diaminodiphenylurea-3,3'-disulfonic acid, which is used as an intermediate for the synthesis of dyes, optically brightening agents, UV radiation absorbers, biochemical preparations.
W dotychczasowych metodach syntezy kwasu 4,4'-diaminodifenylomoczniko-3,3'-disulfonowego stosuje się toksyczny fosgen (COCI2).To date, the methods of synthesizing 4,4'-diaminodiphenylurea-3,3'-disulfonic acid use toxic phosgene (COCl2).
Jeden ze sposobów wytwarzania kwasu 4,4'-diaminodifenylomoczniko-3,3'-disulfonowego przy użyciu fosgenu, opisany w opisie patentowym DE 140613, polega na kondensacji fosgenu z solą sodową kwasu 5-amino-2-nitrobenzenosulfonowego w środowisku wodnym w obecności węglanu sodowego, a następnie na redukcji produktu kondensacji za pomocą żelaza w środowisku wodnym w obecnoś ci kwasu mineralnego.One of the methods of producing 4,4'-diaminodiphenylurea-3,3'-disulfonic acid using phosgene, described in DE 140 613, is the condensation of phosgene with the sodium salt of 5-amino-2-nitrobenzenesulfonic acid in an aqueous medium in the presence of carbonate sodium and then reduction of the condensation product with iron in an aqueous medium in the presence of a mineral acid.
Inny sposób wytwarzania kwasu 4,4'-diaminodifenylomoczniko-3,3'-disulfonowego przy użyciu fosgenu, opisany także w opisie patentowym DE 140613, polega na bezpośredniej reakcji fosgenu z kwasem 2,5-diaminobenzenosulfonowym w środowisku wodnym.Another method of producing 4,4'-diaminodiphenylurea-3,3'-disulfonic acid using phosgene, also described in DE 140 613, consists in the direct reaction of phosgene with 2,5-diaminobenzenesulfonic acid in an aqueous medium.
Sposób wytwarzania kwasu 4,4'-diaminodifenylomoczniko-3,3'-disulfonowego, z kwasu 2,5-diaminobenzenosulfonowego, według wynalazku polega na tym, że wodny roztwór kwasu 2,5-diaminobenzenosulfonowego ogrzewa się z mocznikiem w temperaturze wrzenia w obecności środka redukującego jak wodorosiarczan(IV) sodowy, siarczan(IV) sodowy, pirosiarczan(IV) sodowy, ditionit sodowy, ditionian sodowy, aż do momentu zaprzestania wydzielania się gazowego amoniaku, po czym produkt reakcji w znany sposób wydziela się ze środowiska reakcji i suszy. Stosuje się 1 mol mocznika na 2,2 mola kwasu 2,5-diaminobenzenosulfonowego, zaś środek redukujący stosuje się w ilości 0,05 mola na 1 mol kwasu 2,5-diaminobenzenosulfonowego. Ś rodek redukują cy wprowadza się do ś rodowiska reakcji porcjami.The method of producing 4,4'-diaminodiphenylurea-3,3'-disulfonic acid from 2,5-diaminobenzenesulfonic acid according to the invention consists in heating an aqueous solution of 2,5-diaminobenzenesulfonic acid with urea at the boiling point in the presence of the agent reducing agents such as sodium bisulfate, sodium sulfate, sodium metabisulfate, sodium dithionite, sodium dithionite until the evolution of ammonia gas ceases, and then the reaction product is separated from the reaction medium in a known manner and dried. 1 mole of urea is used for 2.2 moles of 2,5-diaminobenzenesulfonic acid and the reducing agent is used in an amount of 0.05 moles per mole of 2,5-diaminobenzenesulfonic acid. The reducing agent is introduced into the reaction environment in portions.
W sposobie wedł ug wynalazku unika się stosowania szkodliwego fosgenu, a nadto sposób według wynalazku jest procesem jednoetapowym, ekologicznym. Sposób według wynalazku ilustruje poniższy przykład.The method according to the invention avoids the use of harmful phosgene and, moreover, the method according to the invention is a one-step, ecological process. The method according to the invention is illustrated by the following example.
P r z y k ł a d g (0.75 mola) mocznika i 310 g (1.65 mola) kwasu 2,5-diaminobenzenosulfonowego ogrzewano w 1.5 dm3 wody w temperaturze wrzenia do momentu zaprzestania wydzielania się gazowego amoniaku. W trakcie ogrzewania dodawano porcjami 0,0825 mola wodorosiarczanu(IV) sodowego. Po zakończeniu reakcji wydzielono produkt przez wysolenie chlorkiem sodowym dodanym w ilości 20% w stosunku do obję toś ci mieszaniny reakcyjnej, w temperaturze 80°C i po obniż eniu temperatury do temperatury otoczenia produkt odsączono i oczyszczono w drodze przemycia na sączku 0.5 dm3 20% solanki aż do bezbarwnego odcieku. Produkt wysuszono w temperaturze 60°C. Otrzymano 226 g soli sodowej kwasu 4,4'-diaminodifenylomoczniko-3,3'-disulfonowego, co stanowiło 65% wydajności teoretycznej.Example (0.75 mol) of urea and 310 g (1.65 mol) of 2,5-diaminobenzenesulfonic acid was heated in 1.5 dm 3 of water at reflux until the evolution of ammonia gas ceased. While heating, 0.0825 mol of sodium bisulfate was added in portions. After completion of the reaction, the product was isolated by salting out with sodium chloride added in the amount of 20% in relation to the volume of the reaction mixture at 80 ° C and after lowering the temperature to ambient temperature, the product was filtered and purified by washing on a filter 0.5 dm 3 20% brine to a colorless drain. The product was dried at 60 ° C. 226 g of the sodium salt of 4,4'-diaminodiphenylurea-3,3'-disulfonic acid were obtained, which was 65% of theoretical yield.
Czystość i jednorodność otrzymanego produktu potwierdzono za pomocą chromatografii bibułowej stosując bibułę Whatman 1 oraz jako eluent n-propanol i 5% wodny roztwór NaHCO3 w stosunku 2:1 - współczynnik chromatograficzny produktu Rf = 0,21, chromatogram obserwowany w świetle UV przy długości fali λ = 365 nm wykazywał pojedynczą plamę.The purity and homogeneity of the obtained product was confirmed by paper chromatography using Whatman 1 paper and as eluent n-propanol and 5% aqueous NaHCO3 solution in the ratio 2: 1 - product chromatographic coefficient Rf = 0.21, chromatogram observed in UV light at wavelength λ = 365 nm showed a single spot.
Zawartość procentową kwasu 4,4'-diaminodifenylomoczniko-3,3'-disulfonowego w produkcie oznaczono w drodze miareczkowania próbki 0,1 N wodnym roztworem NaNO2 w środowisku wodnego roztworu kwasu mineralnego. Analiza elementarna próbki produktu wykazała praktycznie zgodność zawartości węgla, azotu i wodoru (C-34,58%, H-3,01%, N-12,47%) z wyliczeniami teoretycznymi (C-34,82%, H-3,15%, N-12,49%).The percentage of 4,4'-diaminodiphenylurea-3,3'-disulfonic acid in the product was determined by titrating the sample with 0.1 N aqueous NaNO2 in an aqueous mineral acid solution. Elemental analysis of the product sample showed that the content of carbon, nitrogen and hydrogen (C-34.58%, H-3.01%, N-12.47%) was practically in line with the theoretical calculations (C-34.82%, H-3, 15%, N, 12.49%).
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL384486A PL206169B1 (en) | 2008-02-18 | 2008-02-18 | Production method of 4,4-diamindiphenylourea-3,3-disulphone acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL384486A PL206169B1 (en) | 2008-02-18 | 2008-02-18 | Production method of 4,4-diamindiphenylourea-3,3-disulphone acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL384486A1 PL384486A1 (en) | 2009-08-31 |
| PL206169B1 true PL206169B1 (en) | 2010-07-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL384486A PL206169B1 (en) | 2008-02-18 | 2008-02-18 | Production method of 4,4-diamindiphenylourea-3,3-disulphone acid |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL206169B1 (en) |
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2008
- 2008-02-18 PL PL384486A patent/PL206169B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| PL384486A1 (en) | 2009-08-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Decisions on the lapse of the protection rights |
Effective date: 20120218 |