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    • 专利摘要:
    A process for the oxidation of 4-nitrotoluene-2-sulphonic acid to 4,4'-dinitrostilbene-2,2'-disulphonic acid, characterised in that a solution or dispersion of a catalytic amount of an alkali metal hydroxide or alkoxide is slowly added to a solution of an alkali metal salt of 4-nitrotoluene-2-sulphonic acid in dimethyl sulphoxide as the solvent, in the presence of a catalytic amount of an organic or inorganic transition metal salt, oxide or hydroxide, said solution being saturated with oxygen until the oxidation is virtually complete.
    公开号:SU1736336A3
    申请号:SU894613777
    申请日:1989-03-07
    公开日:1992-05-23
    发明作者:Бордман Ланд Ричард；Вейн Макконнел Уэсли；Гэллард Лэдд Сэм
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of salts of 4,4-dinitrostilbene-2,2-disulfonic acid.
    The compound 4,4-dinitrostilben-2,2-disulfonic acid (DNS) is an industrial intermediate for many optical brighteners.
    A known method for producing 4,4-dinitrostilben-2, 2-disulfonic acid and its salts by the oxidative condensation of 2 mol of 4-nitrotoluene-2-sulfonic acid under aqueous alkaline conditions. Ordinary
    the oxidizing agents are oxygen (air) in the presence of a catalyst or sodium hydrochloride.
    The disadvantage of this method is the realization at a large dilution, about 5% of a solid, due to the heat of reaction and the poor solubility in water of forming the intermediate dinitrobenzyl intermediate. In addition, a large amount of by-products is produced. All this makes the known method uneconomical.

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    The aim of the invention is to develop a method of obtaining salts of 4,4-dinitrostilben-2, 2-disulfonic acids with high yield and purity without the use of harmful solvent, which makes it necessary to control the air at the workplace and to obtain which requires high costs, as well as improved performance process. Due to this, it is possible to achieve an increase in the concentration of reagents and / or a shortened reaction time.
    The aim of the invention is also to develop a process in which the recovery of the solvent can be carried out in a simple and economical manner.
    The objective of the invention is to reduce the cost of wastewater treatment, which is associated with the production of 4,4-dinitrostilben-2,2-disulfonic acid, which can be achieved by reducing the amount of heavy metal used, painted products and / or oxidative by-products 4,4-dinitrostilbene-2,2-disulfonic acids contained therein.
    The goal is achieved in that the oxidation of 4-nitrotoluene-2-sulfonic acid or its alkali metal salts is carried out with pure oxygen or air in the presence of a catalytic amount of hydroxide or alkoxide. Alkali metal metals and hydroxide, oxide or transition metal salt in dimethyl sulfoxide (DMSO), which is used as a solvent. Preferably, the oxidation of 4-nitro-toluene-2-sulfonic acid and its conversion to 4.4 (α-dinitrostilben-2,2-disulfonic acid) is carried out by slowly adding a solution or dispersion of a catalytic amount of an alkali metal hydroxide or alkoxide 4 -nitrotoluene-2-sulfonic acid in dimethyl sulfoxide, which is used as a solvent, in the presence of a catalytic amount of an organic or inorganic salt, oxide or transition metal hydroxide, simultaneously indicated solution n oxygenated until almost complete oxidation.
    Alkali hydroxide or alkoxide used as base
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    tal in the amount of 0.05-0.9 mol eq per 1 mol eq of 4-nitrotoluene-2-sulfonic acid salt, dissolved in water, alcohol or their mixtures, in the presence of a catalyst, is added to a solution of 4-nitrotoluene-2- salt sulfonic acid in dimethyl sulfoxide, and the oxidation is carried out at 10-25 C.
    The solvent used (dimethyl sulfoxide) does not necessarily have to be anhydrous, however, it is preferable if the water content is initially about 1.5% by weight. The amount of water can be up to 40% if anhydrous alcohol is used to dissolve the base. Due to the high viscosity of the reaction solution, a higher water content is undesirable; it prevents the reaction from being carried out in the preferred range of nitrotoluenesulfonic acid concentration. Preferred is an initial water content in the reaction mixture below 0.5 ", in particular, if an aqueous solution of an alkali metal hydroxide is used.
    Before oxidation, a base, lithium hydroxide and sodium hydroxide, is required to neutralize nitrotoluene sulphonic acid. Sodium hydroxide is preferred because it is inexpensive, and optical brighteners, which are obtained from 4, 4-dinitrostilben-2, 2 -disulfonic acid, are sold in the form of its sodium salts. Thus, it is advantageous to use only sodium compounds during all synthesis operations.
    The method uses catalytic amounts, i.e. 0.05-0.9 mol eq, strong base per 1 mol eq nitro toluenesulfonic acid salt. An excessive amount of base may slow down the reaction, as it reduces the solubility of the intermediate product dibenzyl and complicates subsequent processing, requires additional acid to neutralize and pollutes waste water in vain. It is preferable to use 0.08-0.2 mol eq of the base dissolved in the C-C alcohol.
    Strong bases are alkali metal hydroxides and alcohol, in particular sodium. The use of an anhydrous base, (finely divided solid sodium hydroxide or an alcoholic, for example sodium methylate), is not necessary. Methylate
    sodium is expensive and with the help of a residual amount of water in the reaction mixture is converted mostly or completely into sodium hydroxide. Therefore, the strictest (in the case of dimethyl sulfoxide, nonzero) precautions should be taken to remove “traces of water from the reaction mixture.
    To facilitate handling and costs, the reaction mixture is dried in dimethyl sulfoxide by vacuum distillation so that it contains about 0.3% water and then the required catalytic amount of sodium hydroxide in the form of solid sodium hydroxide dissolved in C ( -C.-alcohol, which may contain a small amount of water, thus preventing difficulties in handling and with the addition of a small amount of solid sodium hydroxide.
    Another type of base addition is the dissolution of 20-50% aqueous sodium hydroxide in a C-C alcohol, which is preferably anhydrous. In any case, there is a base in the form of a simple to handle and commensurate alcohol solution.
    Methanols, ethanol and isopropanol and mixtures thereof are the alcohols, the choice of alcohol depending on which processing method is used. If alcohol recovery is undesirable, then methanol is chosen as the alcohol, because it is cheaper and sodium hydroxide is especially soluble in it. In the case of recovery and recycling of alcohol after crystallization of 4,4-nitrosylben-2,2-disulfonic acid from the reaction mixture, ethanol is preferably used (including mixtures with methanol and / or propanol, for example SDA-3 or 94% alcohol) or isopropanol .
    The ratio in a mixture of dimethylsulfoxide and alcohol reaches 50: 1 for methanol and about 4: 1 for isopropanol. Although wet alcohols can be used with the oxidative combination (up to 10% of water in alcohol), the yield decreases and the amount of azostilbenes and other by-products increases with increasing water content. The total content of soda in the initial reaction mass may amount to 1.5% by weight of fimer, without significantly affecting the yield of 4,4-dimethyl
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    stilbene-2,21-disulfonic acids or do not form a large number of by-products.
    Since alcohols, such as methanol, alleviate the solubility in dimethyl sulfoxide salt, nitrotoluene sulfonic acid and, in particular, the dibenzyl intermediate, their minimum amount should be used.
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    necessary for dissolving the base.
    Another type of addition of the required amount of base is to dry the mixture with dimethyl sulfoxide by distillation in vacuo to a water content below about 0.3% and then slowly adding to it a 10-15% aqueous solution of sodium hydroxide. Since the alcohol is not used at the same time, the subsequent recovery of the solvent is simpler. If the alcohol is not used, vigorous stirring is necessary to obtain a fine dispersion of sodium hydroxide in the reaction mixture in dimethyl sulfoxide. Preferably, a maximum of 30% sodium hydroxide solution (15-20% solution) is added to ensure a good dispersion. If no alcohol is added, 0.2-0.7 mol-eq of base is used.
    Oxidants are pure oxygen or its mixtures with inert gases, for example nitrogen, preferably
    5 use dry air. A sufficient flow of oxygen (air) and vigorous stirring are a prerequisite for obtaining high yields over a short reaction time.
    0 N Oxidation proceeds satisfactorily at normal pressure, however, in order to increase the solubility of oxygen in the reaction medium, it is possible to work at elevated pressures. So
    5, as the cessation of the air supply quickly stops the oxidation, this is a sign that the dissolution of oxygen in the reaction mixture determines the rate. In terms of safety, this is an advantage.
    The use of other oxidizing agents (hydrogen recurrence, anhydrous hypochlorites or quinones) cannot be recommended due to the further dangerous oxidation of 4,4-dinitrostilben-2,2-disulfonic acid and / or dimethyl sulfoxide solvent.
    To oxidatively convert with the aid of air or gaseous
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    oxygen was occurring at an acceptable rate; a transition metal catalyst — inorganic salts, oxides and hydroxides of transition metals, and / or organic compounds — is required. Important catalysts are organic and inorganic salts of copper and iron, for example SHjO and Fe04-7H20. However, the use of copper compounds should be avoided for environmental reasons where the use of iron compounds under basic reaction conditions can lead to filtration problems.
    Preferred catalysts are anhydrous or hydrated salts, oxides or hydroxides of manganese and / or organic manganese compounds, for example manganese sulfate, manganese hydroxide or acetate, in particular Iln (OAc) 2 4I20.
    The amount of catalyst may vary widely. Traces of up to an amount of 0.1-10 wt.% Based on 4-nitro-toluene-2-sulphonic acid (preferably 0.3-1 wt.%) Can be used.
    The starting compound, 4-nitrotoluene-2-sulfonic acid (HPNTSA), is obtained in a known manner by sulfonating 4-nitrotoluene with fuming sulfuric acid, for example 25%. The reaction is terminated by diluting the sulfonated reaction mixture with water or preferably an aqueous solution. The initial HPNTSA solution is stable from the storage point of view (usually 32 - 36% HPNTSA contains a small amount of various auxiliary products and 3-6% sulfuric acid, but there is no need for further purification for preparation of NaPHTSA.
    The conversion of HPNTSA to its sodium salt (Na PNTSA) consists mainly in the neutralization of the sulphonic acid groups. However, this must be done very carefully to avoid conditions that lead to the formation of intensely colored polyazostilbenes.
    Preferred neutralizing agents are NaOH. The use prevents the formation of polyazo compounds, however, due to foaming during neutralization, due to the formation of CO2 and / or crystallization of reagents
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    from solution, it takes a very long time to carry out the reaction. The use of concentrated solutions of NaOH at high temperatures often leads to the formation of polyazostilbene intermediate products.
    Aqueous solutions containing up to 50% NaOH can be used to neutralize aqueous solutions of the initial IIPNTSA / H SO mixture without polyazostilbene formation, provided that the pH is kept below 7 and the addition of NaOH is made slowly with vigorous stirring in order to avoid local high hydroxide concentration. The temperature is maintained above 60 ° C to avoid excessive crystallization during neutralization.
    Upon cooling, most of the neutralized sodium salt is separated from p-nitrotoluene sulphonic acid (Na PNTSA) due to crystallization of the by-product. Contents. after neutralization, the solubility of Na PNTSA decreases. The solubility of Na PNT.SA in pure water at 26 ° C is approximately 13 wt.%. . Three contents in water of 12 or 20% of the solubility of Na PNTSA at 2 ° C decreases to 1.0 or 0.3 wt.%. Due to the age of a portion of the filtrate, a concentration of 20% by weight can be maintained in subsequent neutralization operations. after neutralization and isolation. The return of this filtrate is further reduced, since it contains little dissolved Na PNTSA, and the loss of Na PNTSA is reduced.
    Extraction of crystallized Na PNTSA by filtration removes most of the water. After filtering
    The pellet is dried under vacuum at about 60 ° C to remove residual water, or added to fresh or treated dimethyl sulfoxide and is distilled under reduced pressure to remove residual water. Removal of large amounts of water by vacuum distillation of dimethyl sulfoxide is expensive. However, the costs associated with drying by vacuum distillation are drastically reduced due to the fact that, at first, most of the unwanted water is removed from Na PNTSA by simple filtration.
    The main amount. in a wet precipitate, Na PNTSA is removed by subsequent filtration of the dried solution of methyl sulfate. Since the solubility of Na PNTSA in methyl sulfide at about 26 ° C is about 41 wt.%, Solubility problems appear during the drying operation.
    Oxidation of 4-nitrotoluene-2-sulfonic acid salt.
    If the dried, filtered solution in dimethyl sulfoxide, Na PNTSA is slowly added to the reaction mixture consisting of dimethyl sulfoxide, a transition metal catalyst, a base and, if necessary, a small amount of a C-C alcohol, and at the same time air is passed through the mixture (sequence of adding reagents such as , as with the known method), the output is 90-95%. However, if the base is taken up in reverse order and a base or a small amount of a C-alcohol is added to the reaction mixture (the mixture consists of dimethyl sulfoxide, Na PNTSA and a transitional metal containing catalyst), the output is increased by 3-5% and is 96-98%.
    A solution of an alkali metal hydroxide in water or in C-Cr-alcohol is added over a period of 5-45 minutes (preferably within about 15 minutes) to the cooled, intensively mixed, oxygen-saturated reaction mixture. Further stirring for 50-80 minutes (preferably 60-70 minutes), while oxygen (air) is passed through the mixture in sufficient quantity, sufficient to complete the reaction. Thereafter, the reaction ends in that the excess base is neutralized, for example, with concentrated sulfuric acid or 20-25% sulfuric acid smoke.
    Isolation of 4,4-dinitrostilben-0 2,2-disulfonic acids.
    4,4-Dinitrostilben-2,2-sulfonic acid can be isolated as disodium salt in a variety of ways from the reaction mixture. With very high purity and high output, all dimethyl sulfoxide, water (and alcohol) can be removed, for example, in a vacuum rotary evaporator
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    at a rate of 4,41-dinitrostilben-2,2-disulfonic acid of high quality.
    Another possibility is to crystallize 4,4-dinitrostilben-2,2-disulfonic acid from dimethyl sulfoxide solution by adding an aqueous solution of common salt. In a preferred embodiment, water, if necessary, alcohol and 50-85% dimethyl sulfoxide is removed by distillation. 4,4-Dinitrostilben-2,2 / - disulfonic acid is then precipitated from the concentrated solution by adding water and / or sodium chloride solution.
    In addition, 4,4-dinitrostilben-2,2-disulfonic acid can be reduced from dimethylsulfoxide from the reaction mixture by adding a large amount of organic matter, in which 4,4-dinitrostilbene-2,2-sulfonic acid is practically insoluble. Aromatic substances are suitable, for example toluene, preferred are alcohols especially used to dissolve the base, for example ethanol, including mixtures with methanol and / or isopropanol. Usually, two to three times the amount of the second substance relative to dimethyl sulfoxide ensures a high yield of 4.4 - dinitrostilben-2,2-disulfonic acid. Solids are separated from liquids by a known method of coins, for example, by filtration or centrifugation.
    When using manganese salt as a transition metal catalyst, in particular, Mn (OAc) 2-4H20 in combination with ethanol, approximately 90% of the manganese compound as a precipitant remains in solution and can be used for the subsequent reaction.
    Thus, 4,4-dinitrostilben-2, 2-disulfonic acid is precipitated from the reaction mixture after neutralization by the addition of ethanol and separated by filtration. The filtrate, which still contains some 4,4-dinitrostilben-2, 2-disulfonic acid and by-products, is then used to dissolve the wet compacted sludge NaPNTSA. Thereafter, an aqueous azeotrope of ethanol is removed by distillation in vacuo and subsequent oxidation is carried out only
    111736336
    when using 10% of the normal amount of Mn (OAc) 2-4H20.
    Due to the high yield and the ability to restore the solvents, the treatment of wastewater is required to be less significant than with known methods.
    Example 1. Getting NaPNTSA using.
    In the Erlemeyer flask, with a capacity of 1 l, 480 g of water and 48 g are placed. The mixture is heated to 70 ° C and an initial solution of HPHTSA is added, the temperature is maintained above 70 ° C to avoid strong foaming. The addition of the stock HPNTSA solution (approximately 34% HPNTSA) is continued until the pH of the reaction mixture is 8. The stirred reaction mixture is cooled to room temperature and then filtered under vacuum. The filtrate is again filtered. The compacted compacted sludge is dried for 48 hours at 60 ° C and a pressure of 250 Torr under vacuum. The output of 86% white NaPNTSA (the content of dried HPNTSA 80-82%). Further product can be obtained from the filtrate.
    Instead of drying raw compacted 12
    an ice bath is used to reduce the mass to 20-27 ° C. After vanishing the reaction mass at 2 for 30 min, it is filtered with the help of a Büchner funnel and man-made filter paper (K 541). After removal of the tee for 1 h, it is drawn in
    JQ Output relative to HPNTSA 99,
    The solution of NaPNTSA in dimethylsulium used in the following is obtained because compacted NaPNTS precipitate is entrained in dimethyl sulfoxide and the water content is removed under vacuum at a pressure of 36 torr and the water content is less than 0.3%. O wet compacted sludge is sucked in the same way as in example. Example Z. In a cylindrical reaction vessel with a capacity of 1 t the deflectors are mounted.
    , e puppy casing, lower release
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    With a version and a p-lid cover, 672.56 g of the dried mixture of NaPNTSA in dimethyl sulfoxide (Example 2, respectively, 0.544 mol of NaPNTSA) are used. To this
    The precipitate can be dissolved in DMSO. 30 Bavl 0.392 g (0.0016 mol)
    Example 2. Getting NaPNTSA using NaOH.
    In a 1-liter p-necked flask with built-in baffles, a heating jacket, a thermometer, a Clazen refrigerator, and an adjustable stirrer motor, 516.7 g of NaPNTSA filtrate or 21% NagSO solution are placed. The mixture is heated to 90 ° C and 33.7 g NagSO j is added to it. After it has dissolved and the reaction mixture is heated to 95 ° C, 250 g of the original is added with a dropping funnel to equalize the pressure with a capacity of 250 ml. HPNTSA solution (approximately 24% HPNTSA), while the temperature is maintained above 95 ° C during the addition. After adding the HPNTSA solution, 25% NaOH (about 120 g) to 3.6-6.0 is added (50% NaOH can also be used if the ratio is given accordingly). The heating jacket is removed, the reaction mass is cooled with stirring. Crystallization of NaPNTSA starts at 85-90 ° C. After the reaction mass is cooled to 40-45 ° С, 1
    Mp (OAc). Stir the mixture using a mechanical stirrer (750 rpm) until the thief is solid. R
    The 35th mixture is saturated with the help of dry powder below the mixer (flow rate of 900-1000 ml / using a cooling bath (model Haak A81)
    40 TO 15 ° С. At 15–18 ° C and a hearth flow of 900–1000 ml / m are 47.8 ml (0.068 mol, 0.1 eq in terms of NaPNTSA) 5 NaOH in an aqueous-alcoholic solution
    45 ethanol, 4.4% methanol, 4.9% nola, 6.9% water) through 13.5 m using an automatic titration device (model 655 meter in meters). After 70 min pea
    JQ mass is neutralized with 98%. Full use is also equivalent to the amount of smoked sulfuric acid. High pressure liquid graphy (NHPD 4,4-dinitrostilben-2,21-dis 96.9% acid).
    Example 4. Conduct a but example 3 with the following count
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    an ice bath is used to cool the mass to 20-27 ° C. After keeping the reaction mass at 20-27 for 30 min, it is filtered using a Büchner funnel (15 cm) and filter paper from the company Vatman (K 541) . After the liquid has been removed, the vacuum is drawn for 1 hour.
    Yield relative to HPNTSA is 99.8%.
    The solution of NaPNTSA in dimethyl sulfoxide used in the following examples is obtained by dissolving the wet precipitated NaPNTSA in dimethyl sulfoxide and distilling under vacuum at a pressure of 36 Torr to remove water. If the temperature remains constant, the water content is less than 0.3%. However, the wet compacted sludge can be dried in the same way as in Example 1. Example Z. In a 1-liter cylindrical reaction vessel in which the deflectors are mounted, equipped with a casing, with a bottom outlet
    With a version and a p-cap with a lid, 672.56 g of the dried mixture of NaPNTSA in dimethyl sulfoxide (according to example 2 respectively 0.544 mol of NaPNTSA) are placed. 0.392 g (0.0016 mol) is added to this mixture.
    Mp (OAc). The mixture is stirred with a mechanical stirrer (700-750 rpm) until solids are dissolved. Reaction- /
    The 5th mixture is saturated with the help of dry air blown under the stirrer (flow rate 900-1000 ml / min). With the help of a bath of cooling mixture (model Haak A81) the mixture is cooled
    0 to 15 ° С. At 15-18 ° C and an air flow rate of 900-1000 ml / min, 47.8 ml (0.068 mol, 0.125 mol eq in terms of NaPNTSA) of 5.7% NaOH in an aqueous-alcoholic solution (83, 7%
    5 ethanol, 4.4% methanol, 4.9% 2-propanol, 6.9% water) after 13.5 minutes using an automatic titration device (model 655 meter of dosage). After 70 min, the reaction
    Q mass is neutralized using 2.8 g of 98%. Also use the equivalent amount of 20% sulfuric acid smoke. The yield of 4,4-dinitrostilben-2,21-disulfonic acid, 96.9%, determined by high pressure liquid chromatography (HHDD).
    Example 4. Carried out analogously to example 3 with the following number
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    Your reagents: 653.2 g of a mixture of NaPNTSA and dimethyl sulfoxide (respectively 0.465 mol of NaPNTSA), 2.7 g (0.011 mol) of Mn (OAc). An air flow rate of 900 ml / min and a stirring speed of 753 rpm. After the reaction mass was cooled to 10 ° C, 52.5 g (0.074 mol, 0.158 mol eq in terms of NaPNTSA) of a 5.6% solution of NaOH in aqueous alcohol was added to the mixture after 45 minutes both air flow and temperature are kept constant. After 65 min of reaction, the determination with the help of (CVP yield of 4,4-dinitrostilben-2,2-sulfonic acid 98.0%.
    Examples 5-8. The effect of varying amounts of manganese acetate on the yield.
    Example 3 is repeated with 653; 0 g of a mixture of NaPNTSA and dimethyl sulfoxide (containing 0.431 mol of NaPNTSA) and listed in table. 1 amounts of catalyst Mn (OAc) 2 "4HgO. The air flow rate is kept constant at 800-840 ml / min.
    In all examples, the reaction mass is cooled to 10-12 ° C before 52.5 ml (0.063 mol, 0.145 mol eq in terms of NaPNTSA) of 5.6% NaOH solution in aqueous alcohol is added after 15 minutes. The amount of catalyst, reaction time and yields were determined by QCD and are given in table. one.
    Example 9. In the same reaction vessel as in example 3, placed 66.5 g (0,253 mol) NaPNTSA, 1.6 g (0,0065 mol) MP (OAc) 2. 4H20 (catalyst) and 300.0 g of dry dimethyl sulfoxide. The mixture is stirred at a rotation speed of 720 rpm until the solids dissolve. substances. The solution is saturated with air (flow rate 550 ml / min). After the reaction mass is cooled to 11 ° C, after 30 min, 99 ml (0.036 mol, 0.137 mol eq in terms of NaPNTSA) of 1.8% NaOH solution in anhydrous 2-propanol is added. After 20 min yield 4,4f-dinitrostilben-2,2-disulfonic acid 95.6% (according to HPLC).
    Example 10. As in Example 3, 651.8 g of a mixture of NaPNTSA and dimethyl sulfoxide, which contains 0.444 mol of NaPNTSA, is placed in a reaction vessel together with 1.8 g (0.0072 mol) of ground CuS04 X
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    uSHjjiP as a catalyst. Air flow rate 930 ml / min. After the mixture was cooled to 10 ° C, 52.5 ml (0.059 mol, 0113 mol eq in terms of NaPNTSA) of a 5.3% aqueous solution of NaOH in an alkaline solution were added over 32 minutes. After 70 minutes, the yield of 4.4 / -dinite- .Q rostilben-2, 2 / -disulfonic acid is 95.4% (in accordance with the data of NKVD).
    Example 11. Example 3 is repeated; however, 623.4 g of a mixture of NaPNTSA and methyl sulfide (containing NaPNTSA) together with 2.7 g (0.0108 mol) of CuS04 5H20 are placed in the reaction t vessel. The air flow rate is 900 ml / min, the reaction mass is stirred at 750 rpm,
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    while the reaction mass is cooled to 12 ° C. Within 30 minutes, 173.4 ml (0.061 mol, 0.139 mol eq in terms of NaPNTSA) of a 1.8% solution of NaOH in anhydrous 2-propanol was added to the reaction mass. After 50 min, the yield is 4,4-dinitrostilben-2,2-disulfonic acid, 91.08% (according to HPLC). Examples 12-17 show that the proposed method can be implemented using more than katExample 12. A 1-liter cylindrical reaction vessel equipped with a lower outlet and
    5 pt of the capillary cap, 60.1 g (0.227 mol) of NaPNTSA, 320.0 g of dimethylsufoxide and 1.5 g (0.006 mol) of CuSO SHgO are placed. The reaction mixture is agitated by mechanical mixing at a rotation speed of 1 ..
    715 rpm, the flow rate of air blown below the agitator is 550 ml / min. Using an ice bath, the solution is cooled to 14 ° C. Within 30 min
    5, 10 g (0.25 mol, 1.10 mol-eq equivalent to NaPNTSA) NaOH was added via a dropping funnel to equalize the pressure with a capacity of 125 ml, NaOH dissolved in 70.0 g of methanol. During the reaction, the temperature of the reaction mass is maintained below 15 ° C. After 60 minutes, the yield is 4.4-dinitrostilben-2,2-disulfonic acid, 95.6% (according to HPLC data).
    Example 13.-Carried out analogously to example 12 with the following amounts of reagents: 65.0 g ((0.246 ml) NaPNTSA, 319.6 g of methyl sulfide and 1.1 g (0.0065 mol)
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    MnSO HjjO. After the mixture was cooled to 14 ° C, 11 g (0.275 mol, 1.12 mol eq in terms of NaPNTSA) NaOH dissolved in 70.0 g of methanol was added to the mixture over 30 minutes. After 90 min at 14 C, the yield of 4,4-dinitrostilbene-2,2; -disulfonic acid is 85.8% (according to the KHVD data).
    Example 14. Carried out analogously to example 12 with the following amounts of reagents: 65 g (0.246 mol) of NaPNTSA, 319.7 g of dimethyl sulfoxide and 1.7 g (0.0061 mol) of FeS04-7H20. After the mixture is cooled to 16 ° C, 11 g (0.275 mol, 1.12 mol-eq in terms of NaPNTSA) NaOH, dissolved in 71.1 g of methanol, is added to it over 30 minutes. After 60 minutes, the yield of 4,4-dinitrostilbene-2,21-disulfonic acid is 90.9% (according to the HPLC data).
    Example 15. Carried out analogously to example t2 with the following amounts of reagents: 69.4 g Јf (0.262 mol) NaPNTSA, 320.0, g dimethyl sulfoxide 1.5 g (0.0061 mol) Mp (OAc) 2. After the well-stirred mixture was cooled to 13 ° C, P, 0 g (0.275 mol, 1.05 mol-eq based on NaPNTSA) NaOH dissolved in 70 g of methanol was added to the mixture for 45 minutes. After 75 minutes, the yield of 4,4-dinitro-lben-2,2-disulfonic acid is 95.4% (according to the KHVD data)
    Example 16. In a 1 L vessel, as in Example 3, 153.8 g (0.25 mol, 1.40 mol eq in terms of NaPNTSA) NaOH, 1.5 g (0.0060 mol) CuS04 are placed. 5H20, 5.5 g% 0 and 2.5 g ammonium tributyl chloride. Air flow rate 70-80 ml / min. After the reaction mass was heated to 60 ° C, 244.4 g of a solution of NaPNTSA and dimethyl sulfoxide (containing 0.179 mol of NaPNTSA) was added to it over 15 minutes using a 50 ml equalizing dropping funnel with a capacity of 50 ml. After 65 minutes, the yield of 4,4-dinitrostilben-2,2-disulfonic acids is 74% (according to the HPLC data).
    Example 17. This example shows that the reaction in the absence of a certain amount of water and / or C4-64-alcohol does not proceed so well.
    Example 3 is repeated with the following amounts of reagents: 619.4 g of blend
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    si NaPNTSA and dimethyl sulfoxide (co-derceril, 0.528 mol of NaPNTSA), 0.38 g (0.0016 mol) Mp (OAc) 2.4 NgO. The air flow rate is 900-920 ml / min. To this solution, 57.1 g (0.129 mol, 0.26 mol-eq in terms of NaPNTSA) of a mixture of NaOH (15.0 g) and dimethyl sulfoxide (140.0 g) are added over 5 minutes. After 90 minutes, the yield of 4.4,4-diitrosylben-2,2-sulfonic acid is 84.9% (according to LHVL data).
    Example 18. Carried out analogously to example 3 with the following amounts of reagents: 550.5 g of a mixture of NaPNTSA and DMSO (containing 0.469 mol of NaPNTSA) and 0.33 g (0.0013 mol) of Mp (OAc) 2 4NHO. Air flow rate 1000 ml / min. The mixture is stirred at a stirring speed of 1000 rpm and, after dissolving the solids, is cooled to 20 ° C. Then, at a temperature below 20 ° C, 3.32 ml (5.05 g, 0.063 mol, 0.135 mol eq in terms of NaPNTSA) of 50% NaOH solution are added over 30 minutes. Due to the poor distribution of the base in the reaction mixture, after 90 min, the yield of 4,4-dinitrostil-2,2-disulfonic acid is 88.2% (according to HPLC data).
    Example 19. Carried out analogously to example 18 with the following amounts of reagents: 672.2 g of a mixture of NaPNTSA and DPSO (containing 0.553 mol of NaPNTSA), 0.38 g (0.0016 mol) of Iln (OAc) 24. Air flow rate 99 ml / min. The mixture is stirred at a stirring speed of 1000-1040 rpm and cooled to 17 ° C. 3.78 ml (5.75 g, 0.072 mol, 0.13 mol eq in terms of NaPNTSA) of 50% NaOH dissolved in 5.0 g of methanol are added to this mixture over 25 minutes. After 70 minutes, the yield of 4,4-dinitrostilbene-2,2-sulfonic acid is 94.1% (according to the HPLC data).
    PRI me R s 20-24. It is carried out analogously to Example 3 with the following amounts of reagents: 655.0 g of a solution of NaPNTSA and DMSO (containing 0.478 mol of NaPNTSA), 1.0 i .v (0.0041 mol) Mp (OAc) g. 4H20, 28.5 g of water. An air flow rate of 1000 ml / min., The mixture is stirred at a rotation speed of 800 rpm. After the reaction mass is cooled to 13 ° C for 20 minutes at
    17
    A solution of 11.4 g (0.143 mol, 0.298 mol eq in terms of NaPNTSA) of 50% aqueous NaOH dissolved in varying amounts of methanol is added to maintain the air flow and stirring and at 15-18 ° C. The reaction is monitored by HPLC, and thus the time until the maximum yield in the reactor is determined.
    In tab. 2 shows the reaction time, the amount of methanol and the yield of 4,4f-dinitrostilben-2,2-di-sulfonic acid.
    Examples 25 and 26. Carried out analogously to example 3 with the following amounts of reagents: 657.0 g of a solution of NaPNTSA and DMSO (containing 0.478 mol of NaPNTSA), 1.0 g of Mn (OAc) gH and a different amount of water. An air flow rate of 1000 ml / min., The mixture is stirred at a rotation speed of 800 rpm. After the reaction mass was cooled to 13 ° C, a solution of 5.7 g (0.143 mol, 0.3 in terms of NaPNTSA) NaOH was added at 20 ° C to 18 ° C with constant air flow and stirring dissolved in 40 g of anhydrous alcohol. The reaction is monitored by HPLC, and thus the necessary time is determined for maximum yield in the reactor.
    The results are shown in Table. 3
    Example 27. Carried out analogously to examples 25-26 with the following i quantities of reagents: 655.7 g of a solution of NaPNTSA and DMSO (containing 0.477 mol of NaPNTSA) and 135 g of water. After 265 minutes, a maximum yield of 89.5% is obtained (according to HPLC).
    Example 28. Oxidation in the absence of C — C. Alcohol.
    Example 3 is repeated with the following amounts of reagents: 688.9 g of a mixture of NaPHTSA and DMSO (containing 0.549 mol of NaPNTSA) and 0.84 g (0.0041 mol) of Mn (OAc) g-. An air flow rate of 1000 ml / min., The mixture is stirred at a stirring speed of 800 rpm. After the reaction mass was cooled to 12 ° C, 43.6 g were added over a period of 20 minutes; (0.218 mol, 0.4 mol-eq in terms of NaPNTSA) of 20% aqueous NaOH, the temperature is maintained at 15–19 ° C. After time




    73633618
    reaction (120 min) yield 4,4-dinitro stilbene-2,2-sulfonic acid 94.5% (in accordance with KHVD).
    Example 29. The procedure is carried out analogously to Example 3 with the following amounts of reagents: 611.7 g of a mixture of NaPHTSA and DMSO (containing NaPNTSA About Ommol1). DMSO was used in mecf
    Q. These previous reactions and recovered by removing excess alcohol and j water by distillation in vacuo. Restored in this way DMSO: soderkit 2.3% 4,4-dinitrostilben-2,2-disulfonic acids, soluble impurities and Mn (OAc) 2 4H20 (90% of the required amount) from previous reactions. To this mixture, 0.038 g of fresh Mp reagent (OAc), air flow rate of 900 ml / min, is added. Pos15
    In addition, as the strongly stirred reaction mass is cooled to 12 ° C, 45.5 g (0.064 mol), 0.146 mol eq in switch over to NaPNTSA) of 5.6% NaOH (in aqueous alcohol ). After 60 minutes, the amount of 4,4-dinitrostilben-2,2-disulfonic acid, corrected for the initially contained in solution in DMSO, is 95% (according to
    3D HPLC). Isolated yield 95.6%.
    Example 30. The reaction mass (723.7 g) from Example 3 is transferred to a ring mold with six nets of 2 liters capacity, which is /.
    35 has a bottom outlet, an fc thermometer, a pH electrode and a mechanical stirrer with four sheet impellers. At temperatures below 25 ° C, the reaction mass for 10 minutes
    40 is neutralized by the addition of 2.8 g of 98% sulfuric acid (or an equivalent amount of 23% sulfuric acid smoke) to the droplets. The pH of the solution, which is determined by combining 4.3 grams of distilled water and 2.0 grams of neutralized reaction mass, is about 6.5. Thereafter, within 2-4 minutes, 507.9 g are added to this vessel
    50 94% alcohol. After
    the mixture was stirred at room temperature for 60 minutes, it was cooled to 5 ° C with a cooling bath and stirred for another 20 minutes. With the aid of a Buchner glass filter apparatus, the reaction mass is filtered under vacuum. 956.0 g of filtrate are obtained. The wet, compacted filter cake is then washed with 300.0 g of 94% alcohol (at 5 ° C), 320.5 g of filtrate being obtained, and 225.0 g of precipitate remaining, which contains about 95% 4.4. - dinitrostilbene-2,2-disulfonic acid, yield 4,4-dinitrostilbene-2,2-disulfonic acid S3 /. The filtrates contain approximately 12% of 4,4-dinitroxen-2,2-disulfonic acids and, due to the return of the solvent, the entire amount can be recovered.
    Example 31. The reaction mass (461.7 g) is neutralized as in Example 30. After neutralization, 732 g of toluene is added to the reaction vessel over 5 minutes to precipitate 4,4-dinitrostilben-2,2-di- sulfonic acid. The wet cake is obtained by filtration under vacuum using a Buchner filter (filter paper G 1 from Whatman) and dried under vacuum (250 mm Hg) at 75 ° C for 7 hours. Isolated dry yield 83% 4,4-tin-strobe. - 2,2-disulfonic acid from the reaction mixture, which, according to the LHVD data, contains 88.5% 4,4-dinitrostilben-2, 2-disulfonic acid.
    Example 32. In the reaction vessel with a capacity of 1 l, as in Example 12, 69.4 g (0.262 mol) of NaPNTSA, 320.0 g of DMSO, 20.6 g of 1.5 g (0.0061 mol) of Mp (OAc ) 2-4H20. The reaction mixture is stirred at a stirring speed of 700 rpm and at 14 ° C is saturated with air at a flow rate of 550 ml / min. After that, over 40 minutes, 11.0 g (0.275 mol, 1.05 mol-eq in terms of NaPNTSA) NaOH dissolved in 70 g of methanol is added. After 80 minutes at 14 ° C., the reaction mass is neutralized with 16.2 g of 23% sulfuric acid smoke. After neutralizing the reaction mass, 539.08 g of SD3A aqueous alcohol was added to the reaction vessel over 2-4 minutes. After the reaction mass was stirred for 10 minutes at room temperature, the reaction mass (5.05.5 g) was cooled Using it, they are placed in a 1 L round flask, which is equipped with a mechanical stirrer, a reflux condenser and a thermometer. Stirred reactionary
    lalde vakna to 5 ° C and stirred for a further 15 minutes. The mixture is filtered under vacuum using a glass filter apparatus.
    the mixture is heated to 45 ° C. After this, by Buchner, 1043.2 g of filtrate are obtained.
    To the mixture is added an aqueous solution of 40.6 g of NaCl in 300 g of water. Within 10 minutes the temperature rises to 75-80 ° C. Then the stirred mixture is cooled for 50 minutes by means of an ice bath to 10 ° C. Using a Buchner filter (Whatman filter paper 1 2), the mass is filtered under vacuum. Isolated
    55
    Then the wet sediment (117.9 50.24% 4,4-dinitrostilben-2.21-disulfonic acid) is stirred up with 444.75 g of aqueous alcohol SD3A and heated under reflux for 30 minutes. After cooling to room temperature, the mixture is cooled to 5 ° C using a cooling bath with a mixture of ice and salt. After filter0
    five
    0
    yield 77.7%, determined by LHVD yield 86.7%.
    Example 33. The reaction mass (471.9 g) from example 14 is not neutralized as it is in example 32, and the boil is dried in a vacuum oven (74 mm Hg) at 200 ° C for 24 hours. Time from time the reaction mass is ground outside the furnace to release the 4,4-dinitrostilben-2, 2-disulfonic acid incorporated into the solvent. The dried raw product contains 88.5% of 4,4-dinitro. stilbene-2,2-disulfonic acid; there is no indication for decomposition. The main impurity is. (its hydrated water).
    Example 34. The procedure was carried out analogously to Example 3 with the following amounts of reagents: 672.2 g of a mixture of NaPNTSA and DMSO (containing 0.55 mol of NaPNTSA) and 0.394 g (0.0016 mol) Mp (OAc) 2. Air speed
    From a flow of 900-950 ml / min, the mixture is stirred at a stirring speed of 710-740 rpm. After the reaction mass was cooled to 10-2 ° C, 51.32 g A (0.076 mol, 0.138 mol-eq in terms of NaPNTSA) of 5.9 were added at a constant air supply and constant temperature. % NaOH solution in aqueous SD3A alcohol. After 65-75 minutes, the yield of 4,4-dinitroben-2.2-disulfonic acid is 95.38% (according to LHVD). The reaction mass (722.68 g) is treated in a manner not similar to Example 30, except that after neutralizing the reaction mass, 539.08 g of SD3A aqueous alcohol is added to the reaction vessel over a period of 2-4 minutes. stirring the reaction mass for 10 min at room temperature
    In the meantime, it is cooled with the aid of protection; it is cooled with the help of cooling water to 5 ° C and stirred for a further 15 minutes. The mixture is filtered under vacuum using a glass filter apparatus.
    Buchner, 1043.2 g of filtrate are obtained.
    five
    Then the wet sediment (117.9 50.24% 4,4-dinitrostilben-2.21-disulfonic acid) is stirred up with 444.75 g of aqueous alcohol SD3A and heated under reflux for 30 minutes. After cooling to room temperature, the mixture is cooled to 5 ° C using a cooling bath with a mixture of ice and salt. After filter21
    radios under vacuum using the specified (filter, 186.2 g of wet sediment is obtained with a content of 50.79% by weight of 4.4-dinitrostilben-2.2-disulfonic acid (isolated yield 79.78%) and 405.5 g filtrate.
    The filtrate contains approximately 16% 4,4-dinitrostilben-2,2-disulfonic acid. Due to the processing of the solution, as described in the following example, this 4,4-dinitrostilben-2,2-disulfonic acid can practically be quantitatively restored.
    Examples 35-40. Example 3 is repeated, however, six consecutive reactions are carried out, and the reduced sulfur dioxide of the previous reaction is used together with fresh DMSO, which replaces a small portion lost due to the removal of water and alcohol. For each reaction, a total of 540 g of fresh and reconstituted DMSO is used.
    DMSO is reduced in the same manner as described in Example 30, and contains L of 4,4-dinitroben-2,2-disulfonic acid, dissolved impurities and MpSOAc) 4HgO. At each reaction, approximately 0.04 g of Mn (OAc) 2 4HgO is additionally added. The reaction mixture is stirred at a stirring speed of 710-750 rpm and cooled to 12 ° C. The air flow rate is 900-950 ml / min. Within 23-27 minutes, SD3A NaOH dissolved in 48-56 g of aqueous alcohol is added. After the reaction is complete, the reaction mass is neutralized with 2.8-3.7 g of 98% sulfuric acid. 4.4-Dinitrosgilben-2,2-disulfonic acid is isolated as in Example 34.
    Quantities and yields for six reactions using reduced DMSO are given in gab. 4. Data on the number of MP (OAc) Ј include both the amount that is contained in the reduced DMSO (approximately 90%, determined using atomic absorption spectroscopy), and the additional amount, approximately 10%, that is required to compensate for the losses .
    Example 41. The same reaction mass as in Example 3 is subjected to vacuum distillation in a rotary evaporator at 100 ° C and pressure

    73633622
    6 mm Hg to remove water, alcohol, and about 80Ј of methyl sulfide. The mass thus obtained contains about 50% DMSO and 50% 4,4-din-trostilben-2,2f-disulphonic acid. To reduce DMSO and isolate 4,4-dinitrostilben-2,2-disulfonic acid, this suspension. Q recrystallizes twice. The yield loss of 4,4-dinitrostilben-2,2-dnsulphonic acid is kept at a low theoretical level of about 1% due to the fact that the filtering fluid, the washing liquid and the second crystallization washing liquid are returned.
    A suspension (214.4 g) is placed in a 1 l round vessel with five necks, which is equipped with a bottom 20 outlet and an agitator with
    Teflon imggeller. The suspension is diluted by adding 351.9 g of the filtrate of the second crystallization of the previous experiment and then, with slow stirring, is heated by external heating to 95 ° C. As soon as the 4.4-dinitrostilben-2,2-di-sulfonic acid is dissolved, 30.0 g of NaCl is added. to cause crystallization. After soaking for 30–5 min at 95 ° C, the mixed crystallization mass is cooled with an ice bath to 5 ° C. Before filtration, the mass is kept for 5 min at 5 ° C. After this, the mass 35 is filtered under vacuum for about 5 min with polypropylene filter cloth.
    The filtrate (354.0 g) of the first crystallization is distilled to recover the remaining 20% of methyl sulfate. 239.7 g of the wet sediment is placed in a 1 l round vessel and dissolved by adding 360.6 g of washing liquid (from the additional washing of the second crystallization of WC2 from the previous experiment) with water of the wet precipitate. By heating to 85 ° C with the aid of external heating and with slow stirring, the moist precipitate dissolves. The stirred mass is cooled with an ice bath to 5 ° C and filtered under vacuum using polypropylene filter cloth. After about 2 minutes, filtering is over. The filtrate ML2 (351.9 g) can be used for further crystallization of 50% crude 4,4-dinitrostilben-2.2 g disulfonic acid. Thereafter, the wet precipitate of the second crystallization is washed with 295 g of cold (5 ° C) water. After adding the wash water, the precipitate is filtered under vacuum and is completely removed in dry form for about 5 minutes. Wash liquid (360.6 g) is used for the second crystallization of the subsequent experiment. In a long series of experiments on recovery, the wet residue has a final mass of about 161 g with a content of 61.7% of 4.4-dinitro-2.2-disulfonate. This corresponds to an isolated yield 94 of the reaction mixture, the content of which is 95% (in cooi
    with KHVD).
    Oormula invention
     The method of obtaining salts of 4,4-dinit-rostilben-2,2-disulfonic acids of the formula G / h
    oh iz-pc pc „: legs
    five
    where M is an alkali metal, by oxidation of 4-nitrotoluene-2-sulphonic acid or its alkali salt in dimethyl sulfoxide as a solvent and in the presence of as a base hydroxide or alkali metal alkoxide in water, .alcohol or mixtures thereof, as a catalyst, an organic or inorganic salt, oxide or hydroxide of a transition metal, oxygen in the air or pure oxygen in a mixture with an inert gas, followed by neutralization, characterized in that, in order to increase the efficiency of the process, the base is used in As 0.05-0.9 mol eq, which in water, alcohol or in their mixtures and in the presence of a catalyst, is poured into a solution of the salt of 4-nitrotoluene-2-sulfonic acid in dimethyl sulfide, and the oxidation is carried out at 10-25 C saturation oxygen solution until it is complete.
    table 2
    Example (Amount of Reaction Time-1Exit% 0, g | min, JDNS min,%
    Table A
    权利要求:
    Claims (1)
    [1]
    The claims: A method for producing salts of 4,4-dinitrostilben-2, 2 -disulfonic acids of the formula
    1736336 * where M. is an alkali metal, by oxidation of 4-nitrotoluene-2-sulfonic acid or its alkaline salt in dimethyl sulfoxide as a solvent and in the presence of alkali metal hydroxide or alkoxide in water, a C ^ -C ^ alcohol, or mixtures thereof and as a catalyst - organic or inorganic salt, transitional methoxide oxide or hydroxide, atmospheric oxygen or pure oxygen mixed with inert gas and subsequent neutralization, characterized in that, in order to increase the efficiency of the process, the base is used in 0 , 05-0.9 mol-eq, which 4-pitrotoluene-2-sulfonic acid salts are poured into dimethyl sulfoxide in alcohol, or in mixtures thereof and in the catalyst, and oxidation is carried out at 10-25 ° C. by saturation of the solution with oxygen until until it is fully completed.
    amount in water, in the presence of blitz solution 1
    Example Catalyst, ------ .—Reaction time, min [Exit,'2I G (mole). 5 0.68 (0,0028) 51 95.9 6 0.32 (0,0013) 54 97.5 7 0.17 (0,0007) 53 95.5 8 0.08 (0,0003) 60 87.9
    table 2
    Example numberNEON, g Reaction time, min ExitIDNS, 2 20 40 60 96.1 21 thirty 60 94.9 22 20 80 93.2 23 10 90 91.7 24 0 90 90.1
    25 '1736 336 26
    Table 3
    Example numberg. I Reaction time, min DNS output,% 25 28.8 60-90 96.2 26 61.3 90-120 97.4
    Table 4
    Example NaPNTSA,mole Jaon,mole MP (0HP) 2 . 4H e 0, g (mol) The output of HPLC,% Output (isolated),% Min time 35 0.535 0,072 0.3936 (0.0016) 98.2 92.1 5 60 36 0.558 0,085 0.4080 (0.0017) 95.0 95.5 83 37 0.581 0.103 '0.3421 (0.0014) 95.0 95.8 100 - 38 0.540 0,094 0.4051 (0.0017) 95.2 101.8 125 39 0.529 0,088 About 0.4 (about 0.0017) 93.6 102.1 154 40 0.489 0,088 0.3691 (0.0015) 95.4 97.9 145
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE4311373A1|1993-04-06|1994-10-13|Oekologische Sanierungs Und En|Process for the preparation of 4-nitrotoluene-2-sulphonic acid|AT3974T|1979-06-08|1983-07-15|Ciba-Geigy Ag|METHOD FOR PRODUCING 4,4'-DINITROSTILBEN-2,2'-DISULPHONIC ACID AND THEIR SALTS AND THE USE THEREOF.|
    JPH0149260B2|1983-03-14|1989-10-24|Nippon Kayaku Kk|
    DE3519552A1|1985-05-31|1986-12-04|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 4,4'-DINITROSTILBEN-2,2'-DISULPHONIC ACID SALTS|
    DE3523204A1|1985-06-28|1987-01-02|Bayer Ag|METHOD FOR PRODUCING 4,4'-DINITRODIBENZYLENE|
    DD240201A1|1985-08-12|1986-10-22|Bitterfeld Chemie|PROCESS FOR PREPARING 4,4'-DINITROSTILENE-2,2'-DISULPHONIC ACID II|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|
    US5780358A|1996-04-08|1998-07-14|Chartered Semiconductor Manufacturing Ltd.|Method for chemical-mechanical polishplanarizing of cooper containing conductor layers|
    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
    US07/165,648|US4952725A|1988-03-08|1988-03-08|Process for the preparation of 4,4'dinitrostilbene-2,2'-disulfonic acid and its salts|
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