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    • 专利摘要:

    公开号:SU927112A3
    申请号:SU802930005
    申请日:1980-06-06
    公开日:1982-05-07
    发明作者:Гуглильметти Леонардо
    申请人:Циба-Гейги Аг(Фирма)；
    IPC主号:
    专利说明:

    39
    The disadvantage of this method is the relatively low yield of the target product.
    The aim of the invention is to increase the yield of the target product.
    The methods of the half-A, -diiitrostilben-2, 2-disulfonic acid by oxidation of 4-nitrotoluene-2-sulfonic acid in organic solvents are not described in the literature.
    The goal is achieved by the fact that according to the method of producing alkaline salts A, α-dinitrostilben-2 2-disulfonic acid, consisting in oxidizing 4-nitrotoluene-2-sulfonic acid with an air-gas mixture in the presence of a base, the process is carried out in an organic solvent at 0-25 ° C .
    The yield of the target product is up to 98.5%. Preferably, aprotic dipolar solvents, such as dimethylformamide, hexamethylphosphoric acid trisamide, diethylformamide, dimethylacetamide or diethylacetamide or their mixture with methanol are used as the organic solvent. As the base, sodium or potassium hydroxide or alcoholate is used.
    Advantageously, the process is carried out in the presence of a salt, oxide or hydroxide of heavy metals and / or organic compounds of heavy metals as a catalyst.
    It is also preferable to carry out the process at 55-760 mm Hg.
    Solvents can be used alone or as mixtures of solvents. .
    Especially beneficial is the use of a mixture of one or more solvents with methanol.
    The solvents used may be anhydrous, but not necessary. The small amount of water that appears in technical solvents does not interfere with oxidation.
    These strong bases are used predominantly in the anhydrous state, either alone or as a mixture. The small amounts of water that appear in technical strong bases do not interfere with oxidation.
    The number of bases used varies widely. Although the base is not consumed during
    24
    reactions and therefore by itself
    a catalytic amount would be sufficient, but it is used predominantly in an equivalent amount, but also in a multiple equivalent amount, the latter especially when working at temperatures at which a part of the base is consumed by reaction with a solvent.
    However, the optimally added amount of base can easily be established by preliminary experiments and is very often limited by the solubility of the base in the applied reaction solvent.
    Salts, oxides or hydroxides of compounds of heavy metals and / or organic compounds of heavy metals, such as, for example, are used as catalysts. Co, No, Cr, Ce, Fe, Ni, Cu, Ru, Pd, or Pt. Ir. However, salts, oxides or hydroxides of manganese and / or organic manganese compounds, such as manganese sulfate and / or manganese acetate, are of particular importance as catalysts.
    Inorganic or organic compounds of bromine and / or iodine, such as NaJ, KJ, KBr and ammonium bromide, can also be successfully used.
    SRI.
    The amount of catalyst introduced may vary widely. In many cases, it is sufficient if the catalyst is used predominantly in an amount of about 0.115% by weight, in terms of 4-nitrotoluene-2-sulfonic acid.
    Pure oxygen or its mixtures with inert gases, for example nitrogen, especially air, are used as oxidizers, and oxidation can be carried out at atmospheric pressure or under pressure.
    The oxidation of the invention is very slightly exothermic and proceeds fairly quickly also at low temperatures and without the formation of colored by-products.
    In the following examples, the percentages are by weight, unless otherwise indicated.
    Example 1  50 ml of dimethylformamide are cooled to 0 ° C. and at this temperature, 108 g of methanol 30% sodium methoxide solution is mixed with stirring and cooling.  The resulting solution is mixed with 1 g of margan sulphate monohydrate and at 0 ° C for 15 minutes, saturated with air by passing a dry air stream at 5 l / h through a frit immersed in a solution.  Under stirring for 1 h, this solution is instilled into this solution from a kB g sodium salt of nitrotoluene-2-sulfonic acid in 150 ml of dimethylformamide, while a dry air flow of 5 l / h is introduced through a submerged frit.  The dark green suspension, which had become dark green suspension during the addition of the C-nitrotoluene-2-sulfonic acid sodium salt, was then stirred for an additional 5 hours with the passage of 5 l / h of dry air.  Already after about 3 hours, the green color disappears, and the reaction mixture is partially precipitated by forming the reaction product formed into a yellow suspension, which after 2 hours is neutralized with 108 ml of concentrated c. lactic acid-water (1: 1) at, is freed from solvents in vacuo and absorbed by 200 ml of water.  The reaction product is salted out with 200 ml of brine, the precipitated product is filtered under suction, washed with 100 ml of brine - water (2: 1) and dried to constant weight. 55 g of disodium salt are obtained, C-dinitrostilben-2,2-disulfonic acid in the form of a yellow crystalline powder with t. square  above 300 ° C, which has a NaCl content of 16.2% and an active content (determined by ultraviolet spectrophotometric analysis) of 9.8%.  The yield of the disodium salt of 4,4-dinitrostilbene -2,2-disulfonic acid is 92.15 per theory.   Similar results are obtained by using trisamide hexamethylphosphoric acid, diethylformamide, di ethyl acetamide or dimethylacetamide instead of dimethylformamide.  .  Example 2  Example 1 is repeated with the difference that the reaction mixture, after adding the sodium salt of k-nitrotoluene-2-sulfonic acid to the dimethylformamide solution, is then stirred only for 3 hours instead of 5 hours with and with a passage of 5 liters / h of dry air.  53.2 g of disodium salt, 4-dinitrostilben-2, 2-disulfonic acid in the form of a yellow crystalline powder with m are obtained. square  above, which has a NaCl 16 content, "and an active content (determined by ultraviolet spectrophotometric analysis). The yield of disodium salt i, β-dinitrostilbene-2, 2 -disulfonic acid is 38.2% of theory.  Example 3  Example 1 is repeated with the following differences: instead of 108 g of methanol 30% methylate solution. 72 g of this solution are used in sodium; instead of a dry air flow of 5 l / h, a dry air flow of 8 l / h is used, the reaction mixture after adding A-nitro sodium salt to the dimethylformamide solution.  the toluene-2-sulfonic acid is then stirred only for k hours instead of 5 hours at 0-5 ° C while passing 8 l / h of dry air.  51.5 g of disodium salt are obtained, V-dinitrostilbene-2,2-disulfonic acid is obtained in the form of a yellow crystalline powder with m. square  above, which has a NaCl content of 12.1 and an active content (determined by ultraviolet spectral-photomanalysis) of 86.6.  The yield of disodium salt C, -dinitrostilbene-2, 2-disulfonic acid is 82.7 from the theory.  Example if.  Example 1 is repeated with the following differences: instead of 50 ml, 100 ml of dimethylformamide are cooled to, instead of 108 g of methanol / 30% sodium methoxide solution, 72 g of this solution is used, instead of dry air stream 5, dry air stream 8 l / h is used After the addition of dimethyl forms and t-nitrotoluene-2-sulfonic acid sodium salt to the solution in the solution, the reaction mixture is stirred only for C h instead of 5 h with and with the passage of 8 l / h of dry air.  Get g disodium salt, -dinitrostilbene-2,2-disulfonic in the form of a yellow crystalline powder with t. square  above, which has a NaCl content of 11.1 and an active content (determined by ultraviolet spectrophotometry) of 98.2.  The yield of disodium salt, α-dinitrostilben-2,2-disulfonic acid is. 8A, 7t from theory.  7 Example 5.  Example 1 is repeated with the following differences: instead, 50 ml are cooled with 100 ml of dimethylformamide, instead of 108 g of methanol solution of 30% methyl sodium solution, 3 g of h / h are used instead of dry air flow The dry air flow is 8 l / h, the reaction mixture, after adding dimethyl forms to the solution and the sodium salt of nitrotoluene-2-sulfonic acid, is stirred for 6 h instead of 5 h with and with the passage of 8 l / h of dry air.  35 g of disodium salt 4, -dinitrostilben-2,2-disulfonic acid are obtained in the form of a yellow crystalline powder with m. square  above 3 0 0 ° C, which has a NaCl content and an active content (determined by UV spectrophotometry) -96.7%.  The yield of disodium salt, t-dinitrostilbene-2,2-disulfonic acid, is 61.6 times the theory.  Example 6 , 27.8 g of powdered sodium methylate (97% dissolved in 190 ml of dimethylformamide.  The resulting suspension is mixed in 1 g of manganese sulphate monohydrate and in 7 g of benzyl-tri-p-butyl-ammonium bromide and cooled to.  With stirring for 2 hours, a solution of sodium hydrochloride-nitrotoluene-2-sulfonic acid in 100 ml of dimethylformamide is instilled into this suspension, while a dry air flow of 10 l / h under pressure (in the reaction flask) 50 mmHg. Art.  The dark green-suspension suspension of sodium salt of 4-nitroluene-2-sulfonic acid during the addition of the reaction mixture is then stirred for another 6 hours at 0-5 ° C while passing 10 l / h of dry air at a pressure (in the reaction flask) of 55 mmHg. The dark brown reaction mixture is neutralized with a solution of 5 < 1 > L of concentrated hydrochloric acid in 30 ml of water, released in vacuo from dimethylformamide and absorbed in 150 ml of water.  The reaction product is suctioned out at room temperature, washed with 50 ml of 7% NaCl solution and dried to constant weight.  28 Grams of disodium salt 4, A-dinitrostilben-2,2-disulfonic acid are obtained in the form of a yellow crystalline powder with m. square  above, which has a content of NaCl of 1.8, the content of HjO, 6% and the active content (determined by UV spectrophotometry).  The yield of disodium salt, 4-dinitrostilben-2, 2-disulfonic acid, is k3.7% of theory.  Example 7  37.5 g of powdered potassium hydroxide () is dissolved in 100 ml of hot methanol.  The resulting clear solution is cooled to 10 ° C, mixed with 1 g of manganese sulphate monohydrate and 100 ml of dimethylformamide, with potassium hydroxide partially precipitated as a thin suspension.  The reaction mixture is cooled to, and it is simultaneously saturated with air for 15 minutes by passing a dry air stream of 8 liters per hour through a frit immersed in the solution.  This air flow of 8 l / h is kept constant throughout the entire oxidation.  With the stirring, a solution of 8 g of the latin salt of nitro toluene-2-sulfonic acid in 100 ml of dimethylformamide is instilled into the formed thick porridge with stirring for 2 hours, and the reaction mixture immediately turns dark green.  The reaction mixture is then stirred for another 6 hours at 0-5 ° C, and the reaction product, with the slow disappearance of the dark green color — the dark green color completely disappears after about an hour — forms an increasingly thick precipitate.  The air flow is interrupted and the formed dark yellow, the crystalline reaction mixture is neutralized at 0-5 with a solution of 52 ml of concentrated hydrochloric acid in 90 ml of water.  The light yellow crystalline suspension is freed from solvents in a vacuum, absorbed 200 ml of water; precipitated with 200 ml of a saturated solution of potassium chloride, the precipitated product is suctioned off under suction, washed with 100 ml of a solution of saturated potassium chloride — water (2: 1) and dried to constant weight; Get 50.01.  g of dipotassium salt, “-dinitrostilben-2,2-disulfonic acid in the form of a yellow cristapletic powder with t. square  higher, which has the content of KC1, and the active content (determined by the method of ultraviolet spectrophotometry of the metry) 69,%.  The yield of 4,4-dinitrostilben-2,2-disulfonic acid dipotassium salt is 67% of theory.  Similar results are obviated by the use of diethylformamide, diethyl acetamide, or hexamethylphosphoric acid trisamide instead of dimethylpipermamide.  Example 8  24.5 g of powdered sodium hydroxide () is dissolved in 90 ml of methanol in a hot state.  The resulting almost clear solution is cooled to, mixed with 1 g of manganese sulphate monohydrate and 100 ml of dimethyl formamide, with sodium hydroxide partially precipitating as a thin suspension.  The reaction mixture is cooled to 0-5 ° C, and at the same time for 15 minutes it is saturated with air by passing a dry air stream of 8 l / h through a Frit immersed in the solution.  This air flow (8 l / h) is then kept constant during the entire oxidation. In the formed thick porridge with stirring, a solution is dropped from 48 g of 4-nitrotoluene-2-sulfonic acid sodium salt in 100 ml of dimethylformamide for 2 hours, and the reaction mixture instantly turns a dark green color.  The reaction mixture is then stirred for another 6 hours at.  moreover, the reaction product at the slow disappearance of dark green color — dark green color disappears completely after approximately 3 hours — an increasingly thick precipitate forms, the air flow is interrupted, and the formed dark green crystalline reaction porridge is neutralized at 0-5 ° C with 104 ml of concentrated salt (1: 1), - The resulting light yellow crystalline suspension is freed from solvents in vacuo, and the residue is absorbed by 200 ml of water.  The reaction product is salted out with 200 ml of brine, sucked off with suction, washed with 200 ml of brine-water (2: 1) and dried to constant weight.  50.2 g of disodium salt of 4,4-dinitrostilben-2,2-disulfonic acid are obtained in the form of a light yellow crystalline powder with m. square  above, which has a NaCl content of 9.3 and an active content (determined by ultraviolet spectrophotometry) of 99.2%. The yield of disodium salt 4,4-dinitrostilbene -2, 2-disulfonic acid is 95, 21 from the theory.  The infrared spectrum of this product coincides with the infrared spectrum of an analytically pure sample of the disodium salt of 4,4-dinitrostilben-2, 2-disulfonic acid.  Similar results are obtained by using trisamide hexamethylphosphoric acid, diethylformamide, or diethyl acetamide instead of dimethylformamide. .  Example 9- Example B is repeated with the following differences: powdered sodium hydroxide is dissolved in 100 ml of methanol instead of 90 ml of methanol in a hot state, the reaction mixture after adding 4-nitrotoluene-2-sulfonic acid sodium salt to a solution of dimethylformamide, is stirred only 4 h instead of 6 h at 0-5С and by passing 8 l / h of dry air.  50.1 g of 4,4-disodium salt of 4,4-dinitrostilben-2,2-disulfonic acid are obtained in the form of a light yellow crystalline powder with m. square  above 320 ° C, which has a NaCl content of 11.1% and an active content (determined by ultraviolet spectrophotometry) of 99.0%.  The yield of disodium salt 4,4-dinitrostilben-2, 2-disulfonic acid is 92.9% of theory.  Example 10  Repeat with.  measures 8 with the following differences: instead of 24.5 g of powdered sodium hydroxide, 32 g of powdered sodium hydroxide are used, the oxidation is carried out not at 0-5 ° C, but at 20-25 °.  48.4 g of disodium salt of 4,4-dinitrostilben-2,2-disulfonic acid are obtained in the form of a dark yellow crystalline powder with m. square  above 340 C, which has a NaCl content of 20.9% and an active content (determined by ultraviolet spectrophotometry) 89-, 4%.  The yield of the disodium salt of 4,4-dinitrostil 11 ben-2,2-disulfonic acid is 71.6 per theory.  Example 11  Example 8 is repeated with the following differences: instead of 2.5 g of powdered sodium hydroxide, 16 g of powdered sodium hydroxide are used, the powder image of sodium hydroxide dissolves not in 90 ml, but only in 50 ml of methanol in a hot state, The sodium salt of t-nitrotoluene-2-sulfonic acid is dissolved in 150 ml instead of 100 ml of dimgtilformamide.  48.0 g of disodium salt, α-dinitrostilbene-2,2-disulfonic acid are obtained in the form of a light yellow crystalline powder with t. square  above 320 C, which has a NaCl content of 9.3 and an active content (determined by ultraviolet spectrophotometry) of 98.0%.  The yield of the disodium salt, dinitrostilben-2, 2-disulfonic acid is 90.1 from the theory.  PRI me R 12.  Example 8 is repeated with the following differences: instead of 2.5 g of powdered sodium hydroxide, 12.2 g of powdered sodium hydroxide are used, powdered sodium hydroxide dissolves not in 90 ml, but only in 50 ml of methanol in a hot state , the reaction mixture is not diluted with 200 ml, but with ml of dimethylformamide, the dimethylformamide solution of the sodium salt of 4-nitrotoluene-2-sulfonic acid is instilled in not 2 hours, but 1 hour, and the reaction mixture then. stirred for 7 hours instead of 6 hours  Get + ,. 5 With disodium salt k, k -dinitrostilben-2,2-disulfonic in the form of a yellow crystalline powder with t. square  above 320 ° C, which has a NaCl content of 0.6 and an active content (determined by ultraviolet spectrophotometry) of 99.7.  The yield of k, k -dinitrostilbene-2,2-disulfonic acid disodium salt is 83.6 per theory.  Example 13  Example 8 is repeated with the following differences: powdered sodium hydroxide.  it is not dissolved in 90 ml, but in 100 ml of methanol in a hot state, the oxidation is carried out without a catalyst.  Obtain +2.0 g of the disodium salt of 4,4-dinitrostilben-2,2-disulfide 2 phonic acids in the form of a yellow crystalline powder with t. square  which has a NaCl content of 10.2% and an active content (determined by UV spectrophotometry) of 98.5.  The yield of disodium salt, " - dinitrostilben-2, 2-disulfonic acid, is 78.5 per theory.  I Example C, Example 8 is repeated with the difference that instead of 1 g of manganese sulfate monohydrate, 0.5 g of catalyst is used.  50.63 g of disodium salt k, C-dinitrostilben-2,2-disulfonic acid in the form of a yellow crystalline powder with m are obtained. square  higher, which has a NaCl content of 11.7 and an active content (determined by ultraviolet spectrophotometry) 9b, 9%.  The yield of disodium salt, α-dinitrostilbene-2,2-disulfonic acid is 91, from theory.  Example 15- Example 8 is repeated with the following differences: instead.  2.5 g of powdered sodium hydroxide is used 8.2 g of powdered sodium hydroxide, powdered sodium hydroxide is not dissolved in 90 ml, but only in 50 ml of methanol in a hot state, not only 1 g of monohydrate is used as a catalyst manganese sulfate, but 1 g of monohydrate. manganese sulfate and 1 g of lead (II) acetate acetate hydrate.  48.28 g of disodium salt k, C-dinitrostilben-2,2-disulfonic acid are obtained in the form of a yellow crystalline powder with t. square  above 320 °, which has a NaCl content of 12.3% and an active content (determined by UV spectrophotometry) of 99.3%.  The yield of 4, 4-dinitrostilbene-2,2-disulfonic acid disodium salt is 88.7% of theory.  Example 1b.  Example 8 is repeated with the difference that instead of 1 g of manganese sulfate monohydrate, 1 g of manganese (II) sodium tetrahydrate is used as a catalyst.  47.75 g of disodium salt of 4,4-dinitrostilben-2,2-disulfonic acid are obtained in the form of a yellow crystalline powder with 7.3 and the active content (determined by UV ultraviolet spectrophotometry method 13) 97. %  The yield of disodium salt, 4-dinitrostilben-2, 2-disulfonic acid, is from theory.  Similar results are obtained when Example 8 is repeated, with the difference that instead of monohydrate. manganese sulfate is used as a catalyst manganese dioxide, manganese (II) perchlorate hexahydrate, manganese (III) acetate monohydrate, manganese (II) acetylacetonate, manganese (II) carbonate, manganese (II) bromide, manganese tetrahydrate, manganese tetrahydrate (P), nickel sulfate hexahydrate, nickel (II) acetate tetrahydrate, nickel (II) bromide trihydrate, nickel phthalocyanine, cobalt sulfate heptahydrate (11) cobalt (II) acetate tetrahydrate. .  Example 17  20 g of sodium hydroxide cereal (98%) is dissolved in 90 ml of methanol in a hot state.  The resulting almost transparent, 4 L o / h solution is cooled to 10 ° C, mixed with 1 g of sodium sulfate monohydrate and with to ml of dimethylformamide, with sodium hydroxide partially precipitating as a thin suspension.  The reaction mixture is cooled to 0-5 ° C, and it is. at the same time, for 15 minutes, the air stream is filled with an air stream of 10 l / h at a surplus pressure (in the reaction flask) of 55 mm Hg. Art.  through the frit immersed in the solution.  This air flow is 10 l / h and the excess air pressure in the reaction flask is 55 mm Hg. Art.  The formed thick porridge is kept constant during all the oxides. At a temperature of about 5 ° C with stirring, a solution of 4 g of rotuol-2-sulfonic acid sodium salt of k8 g in 100 ml of dimethylformamide for 1 h is mixed, and the reaction mixture immediately turns to dark green color.  The reaction mixture is stirred for another 2 h 5 min at 0-5 ° C, and the reaction product disappears dark green when slowly disappears — dark green completely disappears with vigorous stirring after approximately 2 h and 15 min — gives an ever thicker precipitate.  The air flow is interrupted, and the formed dark green 2U crystalline reaction porridge is formed at normal pressure with a solution of 5 ml of concentrated hydrochloric acid in 90 ml of water.  The resulting light yellow crystalline suspension in vacuo on a rotary evaporator is concentrated to dryness.  The dry reaction mixture is absorbed in 150 ml of water and then stirred on a rotary evaporator without vacuum at 90 ° C for 15 minutes.  The hot crystalline suspension is always cooled to room temperature, then it is sucked off under suction and washed with 50 ml of 7.5 wt. a solution of sodium chloride and dried at 100 ° C in vacuo to constant weight.  Obtain 8, B5 g of the disodium salt of 4,4-dinitrostilben-2,2-disulfonic acids in the form of a light yellow crystalline powder with t. square  above, which has a NaCl content of 2, a water retention of 1.3, and an active content (determined by ultraviolet spectrophotometry) 98.7.  The yield of disodium salt 4, -dinitrostilbene-2,2-disulfonic acid is 95.6 per theory.  The infrared spectrum of this product coincides with the infrared spectrum of an analytically pure sample of disodium salt, k-dinitrostilben-2, 2 -disulfonic acid.  Example 18  Example 17 is repeated, with the difference that the oxidation is carried out, instead of being carried out at an overpressure of 55 mm Hg. Art. , in a glass autoclave with an overpressure of air T atm.  Receive g disodium salt C, -dinitrostilben-2,2-disulfonic acids in the form of a light yellow crystalline powder with t. square  above 320C, which has a NaCl content of 12.9%, a water content of 1.3%, and an active content (determined by UV spectrophotometry) of 100%.  The yield of disodium salt C, -dinitrostilben-2,2-disulfonic acid is 90.3% of theory.  Example 19-. Example 17 is repeated with the following differences: oxidation is carried out not with air, but with oxygen, oxidation is carried out not at an overpressure, but at atmospheric pressure, after the addition
    权利要求:
    Claims (5)
    [1]
    Claim
    1. The method of producing alkaline salts of 4,4-dinitrostilben-2,2 * -sul-. acids by oxidation of 4-nitrotoluene-2-sulfonic acids with a gas-air mixture in the presence of a base, characterized in that, in order to increase the yield of the target product, the process is carried out in an organic solvent at 0-25 ° C.
    [2]
    2. The method of Pop. 1, characterized in that the solvent used is aprotic dipolar solvents such as dimethylformamide, hexamethylphosphoric trisamide, diethylformamide, dimethylacetamide or diethylacetamide, or a mixture thereof with methanol, g.
    [3]
    3 · Method popp. 1 and 2, which is characterized in that sodium or potassium hydroxides or alkoxides are used as the base.
    [4]
    4. The way popp. 1 ~ 3, characterized in that the process is carried out in the presence as a catalyst of a salt, oxide or hydroxide of heavy metals and / or organic compounds of heavy metals.
    [5]
    5. The method according to PP. 1-4., With the fact that the process is carried out at 55-760 mm Hg.
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    同族专利:
    公开号 | 公开日
    DE3063958D1|1983-08-04|
    ES492243A0|1981-04-01|
    AR226180A1|1982-06-15|
    US4719051A|1988-01-12|
    CA1159082A|1983-12-20|
    PL224776A1|1981-03-27|
    DD152545A5|1981-12-02|
    AU5910380A|1980-12-11|
    PL125844B1|1983-06-30|
    EP0026154B1|1983-06-29|
    AT3974T|1983-07-15|
    JPS5629561A|1981-03-24|
    MX153817A|1987-01-19|
    ZA803393B|1981-05-27|
    ES8104213A1|1981-04-01|
    BR8003536A|1981-01-05|
    AU538454B2|1984-08-16|
    YU148580A|1983-02-28|
    EP0026154A1|1981-04-01|
    JPH025741B2|1990-02-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2212084A|1940-08-20|Nucleak alkylated diaminostilbene |
    US2821550A|1956-12-27|1958-01-28|Gen Aniline & Film Corp|Process of preparing 4-nitro-2-stilbene sulfonic acid salts|
    BE792103A|1971-12-01|1973-05-30|Clayton Aniline Co Ltd|NEW MANUFACTURING PROCESS FOR DINITROSTILBENE DISULPHONIC ACID ON AN INDUSTRIAL SCALE|EP0083555B1|1981-12-31|1985-05-29|Ciba-Geigy Ag|Process for the preparation of p-nitrotoluene sulfonic acid|
    DE3519552A1|1985-05-31|1986-12-04|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 4,4'-DINITROSTILBEN-2,2'-DISULPHONIC ACID SALTS|
    AT51398T|1987-08-12|1990-04-15|Ciba Geigy Ag|METHOD FOR PRODUCING 4,4'-DINITROSTILBEN-2,2'-DISULPHONIC ACID.|
    US4952725A|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|1990-08-07|1991-06-04|Sandoz Ltd.|Electrochemical process for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and the salts thereof|
    DE4330377A1|1993-09-08|1995-03-09|Bayer Ag|Process for the preparation of 4,4'-dinitrostilbene-2,2'-disulfonic acid|
    DE4418305A1|1994-05-26|1995-11-30|Bayer Ag|Process for the preparation of 4,4'-dinitrostilbene-2,2'-disulfonic acid and its salts|
    CN103626681B|2012-08-20|2015-09-09|中国中化股份有限公司|One prepares 4, the method for 4 '-dinitrostilbene-2,2 '-disulfonic acid|
    TWI567051B|2015-11-06|2017-01-21|財團法人工業技術研究院|Process for preparing stilbene-based compound|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH536979|1979-06-08|
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