CN1506349A - Prepn process of 4-amino diphenylamine - Google Patents
Prepn process of 4-amino diphenylamine Download PDFInfo
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Abstract
The present invention relates to nitrobenzene process to prepare 4-amino diphenylamine, and aims at providing production process superior available technology, which uses noble metal in catalyst, needs alone recovering of the main impurities produced intelligent the technological process or needs pure material. The technological scheme of the present invention includes first condensation of aniline and nitrobenzene under the presence of water and alkali, and the subsequent hydroreduction of the condensated liquid to produce 4-amino diphenylamine under the presence of skeleton nickel, especially modified skeleton nickel catalyst in water and aromatic amine solvent. The hydroreduction realizes the reduction of nitro, nitroso, azo and/or azoxy compound, and may be used in the industrial production of 4-amino diphenylamine.
Description
Technical field
The present invention relates to a kind of method of the 4-of preparation aminodiphenylamine, particularly be equipped with the method for 4-aminodiphenylamine about the oil of mirbane legal system.
Background technology
4-aminodiphenylamine (4-aminodiphenylamine) has another name called mutual-amido two polyaniline, N-diphenyl-para-phenylene diamine or RT training department, is mainly used in to produce Ursol D class rubber antioxidant 4010NA, 4020,4010 and 688 etc.Can be used for synthesizing blue salt VRT in addition, be used for aspects such as dyestuff, weaving, printing and pharmaceutical industry.
Surplus the production method of 4-aminodiphenylamine has ten more than the kind, industrialized at present aniline process, formylaniline method, pentanoic method and the oil of mirbane method of mainly containing.This several method all will synthesize 4 nitrodiphenyl amine or 4-nitrosodiphenylamine earlier, and reduction obtains the 4-aminodiphenylamine then.
Aniline process is to be raw material with p-Nitrophenyl chloride and aniline, and condensation generates 4 nitrodiphenyl amine in the presence of catalyzer, obtains RT training department through reduction.Do not introduce formic acid in this method condensation reaction, etching apparatus not, but temperature of reaction height, reaction conversion ratio is low, and three-waste pollution is serious.
The formylaniline method is a raw material with p-Nitrophenyl chloride and aniline, earlier the aniline formylation is generated more active formylaniline, generates 4 nitrodiphenyl amine with the p-Nitrophenyl chloride condensation then, restores and obtains RT training department.This method is used formic acid in condensation reaction, equipment is had corrosion, and increases production cost, and technical process is long, and three-waste pollution is serious, and especially chlorine-contained wastewater is difficult to administer.
The pentanoic method is to be raw material with the pentanoic, earlier makes its nitrosification with nitrite, makes N nitrosodiphenyl amine, and position rotaring rearrangement becomes the 4-nitrosodiphenylamine then, reduce at last RT training department.The condensation reaction condition of pentanoic method is relatively gentleer, and quality product is better, but the production technique of domestic pentanoic is relatively backward, makes the pentanoic amount lack the valency height, so this method production cost height, and quantity of three wastes is bigger.
Aniline process, formylaniline method, pentanoic method all exist cost height, problems such as serious three wastes.
The oil of mirbane method is the up-to-date production technique (US5608111) of Monsanto Company's invention in 1992, this method is a raw material with oil of mirbane and aniline, generate 4 nitrodiphenyl amine and/or 4-nitrosodiphenylamine under the organic bases effect, gained mixture directly reduction obtains RT training department.This method is compared with aforementioned several method, has that temperature of reaction is low, energy consumption is low, flow process is short, raw material is cheap and easy to get, does not produce advantages such as chlorine-contained wastewater in the production process.The typical technology of this method following (US6140528, Chinese patent application number 99807982.1), concrete processing condition are as follows:
1, condensation: oil of mirbane and aniline in the presence of the tetramethyl-oxyammonia (TMAH) under 20～80 ℃ of oxygen free conditions, through 2～20 hours the reaction coupling;
2, hydrogenating reduction: the coupled reaction mixture is hydrogenating reduction in the presence of noble metal catalysts such as platinum carbon or palladium carbon, can produce major impurity zinin/nitrogen benzide and/or hydrazobenzene, about 1～25% (based on the oil of mirbane) of its content in 1,2 liang of step;
3, hydrogenation catalyst is removed in separation, and demixing obtains two-phase, and water (containing TMAH) is capable of circulation to condensation reaction;
4, organic phase rectification under vacuum separates and removes aniline and impurity nitrogen benzide or hydrazobenzene, can get object;
5, back obtains nitrogen benzide or hydrazobenzene, and hydrogenating reduction becomes aniline in the presence of noble metal catalyst and promotor again, and recovery set is used to condensation reaction.
The main drawback of this method is, the by product zinin/nitrogen benzide that generates in the condensation reaction may partly become nitrogen benzide/hydrazobenzene during catalytic hydrogenation, and unreacted oil of mirbane also may form nitrogen benzide during condensation simultaneously when hydrogenation.Though the acid of high density can promote the catalytic hydrogenation of nitrogen benzide to aniline, acid also promotes the formation of detrimental impurity p-diaminodiphenyl.Therefore under the condition of this method, have a large amount of organic bases (TMAH) in the condensation reaction products, can have more nitrogen benzide or hydrazobenzene in the hydrogenating reduction product, this partial impurities needs individual curing.The hydrogenating reduction product is after removing TMAH, aniline and finished product 4-aminodiphenylamine, and nitrogen benzide/hydrazobenzene is in reactor independently, and hydrogenating reduction becomes aniline in the presence of noble metal catalyst and promotor, and recovery set is used to condensation reaction again.Though this method can reclaim nitrogen benzide, improve yield, therefore to increase equipment and operation steps, increase investment, increase cost.
Introduced a kind of preparation method of 4-aminodiphenylamine among the document Chinese patent CN1209430A, it is in the presence of alkali that contains oxyhydroxide, oxide compound and/or alkoxide and heterogeneous catalyst, in the presence of the inertia non-protonic solvent, under 0 to 200 ℃ of temperature and 0.1～150 bar pressure, prepare 4-aminodiphenylamine compounds with the mixture of hydroxide oil of mirbane or nitrosobenzene and oil of mirbane.The mixture of raw material hydroxide oil of mirbane or nitrosobenzene and oil of mirbane must be purified in the document, can not be impure, especially do not speak of highly basic or strong organic bases for example Tetramethylammonium hydroxide have response situation under the situation.
Summary of the invention
Technical problem to be solved by this invention is that relevant in the past oil of mirbane legal system is equipped with in the document of 4-aminodiphenylamine and exists catalyzer need use precious metal, makes Preparation of Catalyst cost height; Major impurity zinin/nitrogen benzide that produces in the technology and/or hydrazobenzene need to reclaim separately in addition, prolong operation steps, increase production cost, maybe can only use the shortcoming of pure raw material, and a kind of new method for preparing the 4-aminodiphenylamine is provided.It is low that this method has a production cost, and technical process is short, nitrogen benzide/zinin and/or hydrazobenzene can be in hydrogenation step direct hydrogenation become the characteristics of aniline.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing the 4-aminodiphenylamine may further comprise the steps successively:
A) aniline and oil of mirbane are reacted in the presence of water and alkali, control simultaneously water for the amount of alkali so that guaranteeing the water that adds is not less than about 4: 1 and is not less than about 0.6: 1 when coupled reaction finishes with the mol ratio of alkali when coupled reaction begins, thereby acquisition contains the mixture flow of 4 nitrodiphenyl amine, 4-nitrosodiphenylamine and/or their salt reaction product;
B) hydrogenation contains the mixture flow of step a) reaction product in the presence of the water of skeletal nickel catalyst and interpolation and aromatic amine, so that guarantee the reaction product of step a): aromatic amine: the weight ratio of water is 100: 30～80: 10～50, the reaction product of step a): the weight ratio of skeleton nickel is 100: 2～6;
C) from reaction mixture, separate skeletal nickel catalyst; And
D) from reaction mixture, obtain water and organic phase, water after organic phase and the aqueous phase separation is circulated to step a); Be circulated to step a) after organic phase isolated the 4-aminodiphenylamine.
In the technique scheme, the mol ratio of aniline and oil of mirbane is 1～10: 1, and the mol ratio of alkali and oil of mirbane is 0.7～4: 1, and alkali is selected from Tetramethylammonium hydroxide; The coupled reaction temperature is 20～80 ℃, and the coupling time is 2～20 hours.In the required skeletal nickel catalyst also load be selected from promotor in rare earth element, phosphorus, sulphur, boron, tin, aluminium, titanium, bismuth, arsenic, chromium, molybdenum, tungsten, gallium, copper or the halogen, wherein in weight ratio with respect to nickel, the consumption of rare earth element is 0～0.3%, preferable range is 0.005～0.2%, and more preferably scope is 0.01～0.1%; At least a consumption that is selected from phosphorus, sulphur or the boron is 0.005～1%, and preferable range is 0.05～0.5%; At least a consumption that is selected from tin, aluminium, titanium, bismuth, arsenic, chromium, molybdenum, tungsten, gallium, copper or the halogen is 0～0.6%, and preferable range is 0.01～0.3%, and more preferably scope is 0.05～0.2%; The rare earth element preferred version is to be selected from least a in praseodymium, neodymium, samarium, cerium or the lanthanum.The aromatic amine preferred version is an aniline; The reaction product of step a): aromatic amine: the weight ratio preferable range of water is 100: 40～60: 10～30; The reaction product of step a): the weight ratio preferable range of skeleton nickel is 100: 3～5.The temperature of reaction of step b) generation hydrogenation is 30～200 ℃, and preferable range is 30～100 ℃; Reaction pressure is 1.5～10MPa, and preferable range is 2.5～6MPa; Reaction times is 1～6 hour.
Employed method for preparing catalyst is as follows among the present invention:
At first nickel-aluminium alloy is reacted with the sodium hydroxide solution of required reacting weight earlier, water cleans to neutral, and the promotor composition that adds aequum then carries out modification, through wash, washing with alcohol 2～3 times and being kept in the ethanol.
The present invention controls water and alkali mol ratio in the coupled reaction of step a) purpose can produce nitrogen benzide or/and zinin with Chinese patent CN1307556A in the reaction of step a).Contain the alkali tetramethyl-oxyammonia of coupled reaction and nitrogen benzide in the present invention in the mixture of the reaction product of step a) or/and zinin, generally in 1～25% (weight), they are entered in the step b) their amount together.Owing in the hydrogenation of step b), used skeletal nickel catalyst, particularly, compare with using noble metal catalyst on the one hand through the skeletal nickel catalyst of modification, the Preparation of Catalyst cost is reduced greatly; Modified skeletal nickel catalyst has in the presence of organic bases or strong organic bases nitrogen benzide or/and zinin effectively is reduced to the function of raw material aniline on the other hand, skeletal nickel catalyst can not poisoned and inactivation, prolonged the work-ing life of skeletal nickel catalyst, saved simultaneously in the subsequent technique and must shorten operating process greatly and reduce production cost with nitrogen benzide or/and zinin and hydrazobenzene separate separately in addition, the hydrogenant operation steps.Making water and aromatic amine in step b), is as reaction solvent on the one hand wherein, the separation of water in the also guaranteed step d) of water on the other hand, and aromatic amine selects aniline more can save follow-up separating step, and shortened process reduces production costs.Use the present invention to prepare the method for 4-aminodiphenylamine in sum, it is low to have production cost, technical process is short, nitrogen benzide or/zinin and/or hydrazobenzene can be in hydrogenation step direct hydrogenation become the advantage of aniline, obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
The tetramethyl-oxyammonia aqueous solution of 50 grams, 40% (weight) is warmed up to 55 ℃ [under the situation that water is applied mechanically under-0.090MPa, the tetramethyl-oxyammonia aqueous solution 100 grams with 20% (weight), under-0.096MPa, be warmed up under 55 ℃, be condensed into the solution of 40% (weight)], add 135 gram aniline then, under-0.090MPa, be warmed up to 75 ℃, aniline and the dehydration of water component distillation, to water/tetramethyl-oxyammonia mol ratio be 5: 1 o'clock, the oil of mirbane that added 28 grams in 3 hours continues to stir and kept 8 hours, gets condensation product; Wherein the organism weight percent consists of: aniline 48.9%, 4-nitrosodiphenylamine 30.1%, 4 nitrodiphenyl amine 7.0%, azophenlyene 0.35%, nitrogen benzide 7.6%, tetramethyl-oxyammonia 6.5%.
The hydro-reduction reaction takes place in autoclave pressure, adds 4 gram modified skeletal nickel catalysts (butt) in the condensation product, aniline 45 grams, water 20 grams, under agitation, during 70 ℃ of temperature of reaction, hydrogen pressure rises to 2.5MPa, till not inhaling hydrogen, hydrogenation time 2 hours.Comprise boron, tungsten and tin in the modified skeletal nickel catalyst, wherein in the weight ratio with respect to Ni, Ni: P: W: Sn is 100: 0.15: 0.1: 0.05.
Reaction finishes postcooling, elimination catalyzer, static layering, water is applied mechanically to condensation reaction after the water phase separated, reaction solution oil phase efficient liquid phase chromatographic analysis hydrogenation products, and its organism weight percent consists of aniline 76.44%, 4-aminodiphenylamine 22.30%, azophenlyene 0.26%, all the other are water; Hydrogenation conversion is 100%.Go fractionation to handle the reaction solution oil phase, obtain object 4-aminodiphenylamine, purity is 99.6%, and 4-aminodiphenylamine yield is 94.5% (for oil of mirbane), and other composition that fractionates out is applied mechanically to condensation reaction.
Use the catalyzer of above-mentioned filtered and recycled, with above-mentioned same condition, use 20 times repeatedly after, reaction result is: do not have nitrogen benzide, hydrazobenzene and other by product in the product.4 nitrodiphenyl amine and 4-nitrosodiphenylamine transformation efficiency are 100%, and 4-aminodiphenylamine yield is 94.0% (for oil of mirbane).
[embodiment 2～5]
According to each operation steps and the condition of embodiment 1, just change the composition of catalyzer, its reaction result is listed in table 1.
[comparative example 1]
According to each operation steps of embodiment 1, just change the composition of catalyzer, its reaction result is listed in table 1.
Table 1
| Sequence number | Skeletal nickel catalyst is formed (weight ratio meter) | 4 nitrodiphenyl amine and 4-nitrosodiphenylamine transformation efficiency % | 4-aminodiphenylamine yield % (for oil of mirbane) | ||
| Use for the first time | After using 20 times | Use for the first time | After using 20 times | ||
| Embodiment 1 | ?Ni 100P 0.15W 0.1Sn 0.05 | ??100 | ??100 | ??94.5 | ??94.0 |
| Embodiment 2 | ?Ni 100P 0.1Pr 0.01Cr 0.05Sn 0.1B 0.20 | ??100 | ??100 | ??96.5 | ??96.3 |
| Embodiment 3 | ?Ni 100P 0.10S 0.05Ce 0.1W 0.1Sn 0.1 | ??100 | ??100 | ??95.1 | ??94.8 |
| Embodiment 4 | ?Ni 100Sm 0.02La 0.03Bi 0.2B 0.05Cr 0.10 | ??100 | ??100 | ??94.7 | ??94.3 |
| Embodiment 5 | ?Ni 100P 0.2S 0.10La 0.1Mo 0.05W 0.1 | ??100 | ??100 | ??95.0 | ??94.6 |
| Comparative example 1 | Skeleton nickel | ??100 | Use for the second time catalyzer inactivation | ??62.3 | ??/ |
[embodiment 6]
Press each operation steps and the condition of embodiment 2, the condition that just changes the hydro-reduction reaction is: add aniline 60 grams in the autoclave pressure, temperature of reaction is 50 ℃, and hydrogen pressure rises to 6.0MPa, hydrogenation time 5 hours.After reaction finishes, there are not nitrogen benzide, hydrazobenzene and other by product in the product.4 nitrodiphenyl amine and 4-nitrosodiphenylamine transformation efficiency are 100%, and 4-aminodiphenylamine yield is 96.7%, and catalyzer uses 20 afterreaction results to be: do not have nitrogen benzide, hydrazobenzene and other by product in the product.4 nitrodiphenyl amine and 4-nitrosodiphenylamine transformation efficiency are 100%, and 4-aminodiphenylamine yield is 96.6%.
[embodiment 7]
Press each operation steps and the condition of embodiment 2, the condition that just changes the hydro-reduction reaction is: add aniline 50 grams in the autoclave pressure, and water 40 grams, temperature of reaction is 100 ℃, hydrogen pressure rises to 3.0MPa, hydrogenation time 1 hour.After reaction finishes, there are not nitrogen benzide, hydrazobenzene and other by product in the product.4 nitrodiphenyl amine and 4-nitrosodiphenylamine transformation efficiency are 100%, and 4-aminodiphenylamine yield is 96.1%.Catalyzer uses 20 afterreaction results to be: do not have nitrogen benzide, hydrazobenzene and other by product in the product.4 nitrodiphenyl amine and 4-nitrosodiphenylamine transformation efficiency are 100%, and 4-aminodiphenylamine yield is 95.8%.
Claims (10)
1, a kind of method for preparing the 4-aminodiphenylamine may further comprise the steps successively:
A) aniline and oil of mirbane are reacted in the presence of water and alkali, control simultaneously water for the amount of alkali so that guaranteeing the water that adds is not less than about 4: 1 and is not less than about 0.6: 1 when coupled reaction finishes with the mol ratio of alkali when coupled reaction begins, thereby acquisition contains the mixture flow of 4 nitrodiphenyl amine, 4-nitrosodiphenylamine and/or their salt reaction product;
B) hydrogenation contains the mixture flow of step a) reaction product in the presence of the water of skeletal nickel catalyst and interpolation and aromatic amine, so that guarantee the reaction product of step a): aromatic amine: the weight ratio of water is 100: 30～80: 10～50, the reaction product of step a): the weight ratio of skeleton nickel is 100: 2～6;
C) from reaction mixture, separate skeletal nickel catalyst; And
D) from reaction mixture, obtain water and organic phase, water after organic phase and the aqueous phase separation is circulated to step a); Be circulated to step a) after organic phase isolated the 4-aminodiphenylamine.
2, according to the described method for preparing the 4-aminodiphenylamine of claim 1, the mol ratio that it is characterized in that aniline and oil of mirbane is 1～10: 1, and the mol ratio of alkali and oil of mirbane is 0.7～4: 1, and alkali is selected from Tetramethylammonium hydroxide; The coupled reaction temperature is 20～80 ℃, and the coupling time is 2～20 hours.
3, according to the described method for preparing the 4-aminodiphenylamine of claim 1, it is characterized in that going back load in the skeletal nickel catalyst promotor that is selected from rare earth element, phosphorus, sulphur, boron, tin, aluminium, titanium, bismuth, arsenic, chromium, molybdenum, tungsten, gallium, copper or the halogen, wherein in weight ratio with respect to nickel, the consumption of rare earth element is 0～0.3%, at least a consumption that is selected from phosphorus, sulphur or the boron is 0.005～1%, and at least a consumption that is selected from tin, aluminium, titanium, bismuth, arsenic, chromium, molybdenum, tungsten, gallium, copper or the halogen is 0～0.6%.
4, according to the described method for preparing the 4-aminodiphenylamine of claim 3, it is characterized in that in weight ratio with respect to nickel, the consumption of rare earth element is 0.005～0.2%, at least a consumption that is selected from phosphorus, sulphur or the boron is 0.05～0.5%, and at least a consumption that is selected from tin, aluminium, titanium, bismuth, arsenic, chromium, molybdenum, tungsten, gallium, copper or the halogen is 0.01～0.3%.
5, according to the described method for preparing the 4-aminodiphenylamine of claim 4, it is characterized in that in weight ratio with respect to nickel, the consumption of rare earth element is 0.01～0.1%, rare earth element is selected from least a in praseodymium, neodymium, samarium, cerium or the lanthanum, and at least a consumption that is selected from tin, aluminium, titanium, bismuth, arsenic, chromium, molybdenum, tungsten, gallium, copper or the halogen is 0.05～0.2%.
6,, it is characterized in that aromatic amine is an aniline according to the described method for preparing the 4-aminodiphenylamine of claim 1.
7, according to the described method for preparing the 4-aminodiphenylamine of claim 1, it is characterized in that the reaction product of step a): aromatic amine: the weight ratio of water is 100: 40～60: 10～30.
8, according to the described method for preparing the 4-aminodiphenylamine of claim 1, it is characterized in that the reaction product of step a): the weight ratio of skeleton nickel is 100: 3～5.
9, according to the described method for preparing the 4-aminodiphenylamine of claim 1, the temperature of reaction that it is characterized in that step b) generation hydrogenation is 30～200 ℃, and reaction pressure is 1.5～10MPa, and the reaction times is 1～6 hour.
10, according to the described method for preparing the 4-aminodiphenylamine of claim 9, the temperature of reaction that it is characterized in that step b) generation hydrogenation is 30～100 ℃, and reaction pressure is 2.5～6MPa.
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| CN101691332A (en) * | 2009-09-28 | 2010-04-07 | 江苏扬农化工集团有限公司 | Method for preparing 4-amino diphenylamine by catalytic hydrogenation |
| CN102010341A (en) * | 2010-06-25 | 2011-04-13 | 天津市有机化工一厂 | Method for catalytically producing 4-aminodiphenylamine from Ni-B amorphous alloy catalyst |
| CN102010340A (en) * | 2010-06-25 | 2011-04-13 | 天津市有机化工一厂 | Method of catalytic preparation of 4-aminodiphenylamine by Ni-B amorphous alloy-loaded catalyst |
| CN102093231A (en) * | 2010-06-25 | 2011-06-15 | 天津市有机化工一厂 | Method for producing 4-aminodiphenylamine under catalysis of cobalt-boron (Co-B) amorphous alloy catalyst |
| CN103420849A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for continuously synthesizing 4-aminodiphenylamine |
| CN111689866A (en) * | 2019-03-15 | 2020-09-22 | 中石化南京化工研究院有限公司 | Preparation method of tower reaction RT base |
| CN112341338A (en) * | 2019-08-07 | 2021-02-09 | 中石化南京化工研究院有限公司 | Catalytic hydrogenation method of 4-nitrodiphenylamine and 4-nitrosodiphenylamine |
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| CN101691332B (en) * | 2009-09-28 | 2014-06-11 | 江苏扬农化工集团有限公司 | Method for preparing 4-amino diphenylamine by catalytic hydrogenation |
| CN101691332A (en) * | 2009-09-28 | 2010-04-07 | 江苏扬农化工集团有限公司 | Method for preparing 4-amino diphenylamine by catalytic hydrogenation |
| CN102010341A (en) * | 2010-06-25 | 2011-04-13 | 天津市有机化工一厂 | Method for catalytically producing 4-aminodiphenylamine from Ni-B amorphous alloy catalyst |
| CN102010340A (en) * | 2010-06-25 | 2011-04-13 | 天津市有机化工一厂 | Method of catalytic preparation of 4-aminodiphenylamine by Ni-B amorphous alloy-loaded catalyst |
| CN102093231A (en) * | 2010-06-25 | 2011-06-15 | 天津市有机化工一厂 | Method for producing 4-aminodiphenylamine under catalysis of cobalt-boron (Co-B) amorphous alloy catalyst |
| CN103420849B (en) * | 2012-05-16 | 2015-04-08 | 中国石油化工股份有限公司 | Method for continuously synthesizing 4-aminodiphenylamine |
| CN103420849A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for continuously synthesizing 4-aminodiphenylamine |
| CN111689866A (en) * | 2019-03-15 | 2020-09-22 | 中石化南京化工研究院有限公司 | Preparation method of tower reaction RT base |
| CN112341338A (en) * | 2019-08-07 | 2021-02-09 | 中石化南京化工研究院有限公司 | Catalytic hydrogenation method of 4-nitrodiphenylamine and 4-nitrosodiphenylamine |
| CN112341338B (en) * | 2019-08-07 | 2023-09-08 | 中石化南京化工研究院有限公司 | Catalytic hydrogenation method for 4-nitrodiphenylamine and 4-nitrosodiphenylamine |
| CN112441928A (en) * | 2019-09-05 | 2021-03-05 | 中石化南京化工研究院有限公司 | Preparation method of RT base condensation liquid |
| CN112441928B (en) * | 2019-09-05 | 2023-06-20 | 中国石油化工股份有限公司 | Preparation method of RT pessary condensation liquid |
| CN114230470A (en) * | 2021-12-19 | 2022-03-25 | 曼哈格检测技术股份有限公司 | Synthetic method and application of stable isotope labeled benzidine |
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