• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    Preparation of a nitrodiarylamine from a nitrohaloarene and alkali metal salt of the formyl derivative of a primary aromatic amine is disclosed.
    公开号:SU886734A3
    申请号:SU782688154
    申请日:1978-11-22
    公开日:1981-11-30
    发明作者:Лудвиг Мертен Хельмут；Рай Вайлдер Джин
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING 4-NITRODIFEN1-1-1LAHS
    I
    The invention relates to an improved process for the preparation of 4-nitrodiphenylamine, which is a valuable intermediate product for the preparation of antioxidants. g
    A method of producing 4-nitrodiarylamine by reacting formanilide with p-nitrohalobenzene in the presence of a copper catalyst and potassium carbonate is known, and the target product is contaminated with 1 T impurities.
    There is also known a method for producing nitrodiphenylamines by reacting 4-nitrochlorobenzene with aniline in dimethylformamide in the presence of potassium carbonate and copper iodide.
    Closest to the present invention is a method for preparing 4-nitrodifferase, which consists in the reaction of 4-nitro. 20 chlorobenzene with formanilide sodium in dimethylformamide in the presence of an excess of formanilide. The process is carried out at reflux. Next, from the reaction mixture 25
    when heated under vacuum. the solvent is removed. Excess formanilide is hydrolyzed with alkali. The mixture is distilled and then slowly cooled to 80 ° C until the product solidifies as small granules, after which the solution is rapidly cooled to 25 ° C. The precipitate is separated and washed with water until neutral. The yield of the target product is 87-91%. Reaction time 3 h.
    However, the process of separating the desired product of this method is long and laborious.
    The purpose of the invention is to simplify the process.
    This goal is achieved by the fact that in the process of reacting an alkali metal formanilide with 4-nitrohalobenzene under reflux in the presence of formanilide, potassium formanilide (i) or cesium is used as the formanilide alkali.
    At the same time, the process of isolation of the final product is greatly improved.
    Typically, the process is carried out by heating a mixture of formanilide K (Cs) with 4-nitrochlorobenzene in formanilide, which is used as a process accelerator and solvent, at 110-180 ° C, preferably at I55t. 165C, followed by cooling the reaction mixture to. Upon settling, the solid product crystallizes out, upon dilution of the reaction mixture with water and stirring, the desired product precipitates. Its yield is 87-97%. The degree of conversion is 95-100%. In this case, it is possible to reduce the number of stages in the isolation of the target product, the latter being of good quality. Example 1. Dry potassium formanilide is prepared and recovered as follows: out of 122 parts by weight. (1.3 mol) of 45% potassium hydroxide, 300 parts by weight of butanol and 100 parts by weight of xylene are obtained by distilling (distilling water into a trap) 1.3 mol of potassium butoxide, which is then added to a suspension of 156 parts by weight . formanilide 250 weight.h. xylene at room temperature. The butanol-xylene suspension is distilled in vacuum (100 mm Hg) until a total index is reached, a refraction equal to 1.497 with the addition of xyloid for pulling off and volume. The suspension is then cooled to room temperature; the vacuum is discharged to atmospheres. After that, the suspension is filtered, the xylene is replaced by benzene, constantly having a cotton layer over the powder. Benzene is replaced with hexane in the same way, the hexane mass is passed through, and the cake is quickly withdrawn into the appropriate container and dried. A white crystalline product is obtained which is dissolved in dimethylformamide, methanol and butanol. Potassium formad-schlide melts at 184-186 ° C. The by-product (formanilide-K-formanilide) melts at 140-145 ° C. Some samples of potassium formanilide with differential. Noise scanning colorimetry shows both exothermic characteristics. . . Examples 2-5. 4-rhodiphenylamine is obtained by using (without isolating) potassium formanilide in formanilide prepared from methylate to
    li, as well as intermediate formanilide and potassium methoxide. The molar ratio is 0.7 mol of formanilide.
    8867344
    and 1.3 mol of potassium formanilide per mole of p-nitrochlorobenzene. Formanilide.
    Gradually to 113.0 weight.h. aniline 5 add 58.8 ppm by weight. formic acid (97%), holds the temperature in the range. Upon completion of the addition, the yellow solid crystallizes as it rises. Then 300 parts by weight are added. water, and after stirring the reflux distillation of the order of 25 ± 5 C to a temperature in the vessel 170t5C. The distillate collected consists of 27.0 parts by weight of water and a very small amount of formic acid ((maximum 0.3 weight. By product in a container, including 142.7 parts by weight of formanilide and 2.2 and 0.3 weight. of aniline, 75.0 parts by weight of xylene are added. Potassium methoxide. 153.1 parts by weight of methanol and 66.0 parts by weight of 50% potassium hydroxide are charged to the solution, heating the mixture to a boil. discharged into a column suitable for purifying aqueous methanol. Non-water-containing methanol is recycled back to the reactor. The reaction is complete when the test sample selected from the tank shows water less than O, 1 wt.%. The resulting product is a 25% solution of potassium methylate in methanol. Potassium aniline. After stirring 184 parts by weight of 25% potassium methylate in methanol (0.65 mol) about 180 parts by weight of xylene and 121 parts by weight (1.0 mol) of formanilide are obtained the reaction mixture. It is heated in vacuum at 75-85 ° C, distilled methanol to obtain the xylene refractive index. The resulting hot mixture contains about 0.65 MOL.h. potassium formanilide and 0.35 mol.h. formanilide. 4-nitrodiphenylMin. Into the above described hot reaction mixture of formanilide potassium and formanilide in xylene, 79.0 parts by weight are added. (0.5 mol) p-nitro-6-chlorobenzene. The solution is heated under reflux (temperature in the tank is about 142143 s). The reaction first takes place at a temperature in the tank of about 110115 ° C, which is due to a color change followed by gas evolution. The reaction mixture is then cooled with stirring to 40 ° C. When the suspension is allowed to stand, the solid product is filtered for half an hour and washed with xylene. The mother liquor is concentrated, the second portion is added. The yield of 4-nitrodiphenylamine is about 87%, the degree of conversion of p-nitrochlorobenzene is approximately 85%. The duration of the reaction can be reduced by reducing the amount of xSylol. Formanilide. K 51,2 weight.h. aniline and 71.6 wt. isolated xylene of the following composition, parts by weight; xylene 30; aniline 16.3; formanipid is appropriate. 34.1 parts by weight are added to the reaction vessel. formic acid (97%) is added gradually, at a maximum temperature of 95 ° C. The mixture is heated at 90-95 0 for about 1 hour until 3 minutes later. After that, it is gradually heated to 156-170 C. The distillate collected consists of 13.8 parts by weight. vodts 0.1 weight.h. xylene and 2.2 parts by weight aniline formate. The product in the reactor contains 109 weight.h. formanilide, 29.9 weight parts. xylene and 1.8 wt.h. aniline .. Vutoxide potassium. In nitrogen atmosphere, 80.5 parts by weight 45% KOH ,. 154 weight.h. 1-butanol and 175 weight.h. xylene is introduced into a device for the preparation of butox: ida. This device is a reactor equipped with a stirrer, a column with two or three plates and a condenser. The distillate is sent from the column to the phase separator. The reaction is heated to a temperature of the content of 105Pc, and vaporization begins. The initial boiling point of steam at the top of the column is about 80 ° C. Distillation is carried out so quickly as to achieve maximum water removal. During the distillation process, the temperature rises to 136 ± 3 ° C, and the temperature of the vapor rises to C. The lower layer of water is continuously removed, the higher-lying organic layer is returned to the cycle at the top of the column. Distillation is continued until the water content in the reaction mass is below 0.5%, as determined by Karl Fischer titration; The mixture is cooled to 50-60 ° C, after which it can be used at the next stage of the process. 4 Foremanlyde potassium. The device for obtaining potassium formanilide is equipped with a stirrer, a 5-plate column and a vacuum nozzle. The above written product consists of 109.0 parts by weight. formanilide and 1.8 weight.h. aniline in xylene, mixed with xylene 3 a device to obtain potassium formanilide and a total weight of 247.2 parts by weight. Then the full portion of potassium butoxide is added at maximum speed. At the same time, you expel some heat, or it does not at all. The reactor is closed, a vacuum is created, the absolute pressure is adjusted to 100 ± 5 mmHg. In order to carry out the distillation, the reactor is heated. The initial distillation starts at a temperature of about 74 ° C, at a vapor temperature. -The latter quickly rises to 6870 ° C and remains relatively constant until a low concentration of butanol in capacitance is reached. Initially, all reagents are in a dissolved state. Approximately half of the distillation process begins to drop potassium formanilide. In the final stages and stages, the mixture is a thick mass. With the depletion of butanol, the temperature of the steam rises to about 78-80 ° C (10), the temperature of the reactor to about 85 ° C; As soon as an increase in temperature is observed, they proceed to the determination of the refractive indices of the distillate samples. The removal of butanol ceases when the refractive index is reached, 496. Suspension contains 103 weight.h. formanilide potassium, 2.1 wt.h. aniline (0.3 parts by weight of potassium formate and 272.0 parts by weight of xylene), 4-nitrodiphenylamine. In the above suspension containing 103,0 weight.h. formanilide potassium, 302 weight.h. formanil.ida 2.1 weight.h. aniline and 0.3 weight.h. potassium formate at 272.0 wt.h. xylene, 73.5 parts by weight is added. p-nitrochlorobenzene at 754 C. The solution is heated under reflux under a 5-tray column, equipped with a sample opening between the reactor and the column. The temperature of the tank is 1451 C during the delegation. The reaction first proceeds at the temperature of mixture C, which is expressed in the release of CO, which is accompanied by a change in the color of the mixture.
    s nz yellow to dark red. As soon as the heating is stopped and the deflgmation is established, the overheating of the overhead begins at a rate sufficient to remove 200 parts by weight. xylene. Upon completion of the removal of xylene, the temperature of the mixture is 162 ± 3 ° C, and the degree of conversion of p-nitrochlorobenzene is more than 90%. The end of the reaction is reached when the p-nitrochlorobenzene content is less than 0.01%. If appropriate, the mixture is held for some time at the upper temperature to reach the end point. The required time is approximately 3 ± 0.5 hours. At the end of the reaction, the reaction mass is withdrawn into the wash tank and washed twice with hot water over 270 bps. The washed oily layer contains 100.0 parts by weight. (yield about 94%) of 4-nitrodiphieylamine, 10.4 wt.h. by-products, 16.3 weight.h. aniline, 25.3 weight formanilide and 72.0 wee.h. xylene, 225.0 parts by weight about 90% by weight of the 4-nitrodifbiyl amine was isolated from the washed oil by crystallization, and the difference was usually isolated after the separation of xylene, aniline and formanilide, which were introduced back into the cycle.
    Foremanlide.
    The original formanilide mixture was prepared as follows. Aniline and formic acid are reacted to obtain formanilide and water. The reaction is carried out by loading aniline and xylene into a reaction vessel equipped with a dehumidifier, followed by heating to 455 (HS. Then formic acid is slowly added. The exothermic reaction to form aniline formate results in an increase in temperature to about 80-90 °. The mixture is kept at this temperature for 1 h. Then it is slowly picked up by collecting water by azeotropic distillation. With the complete completion of the removal of water, the temperature of the mixture reaches about 165 C. Heating is continued with careful refluxing Ilola in vlatootdelitel. Collect an additional amount of water and formic acid, directing them into the separator until the end point is not determined conductivity Zamora or elementary whether an ohm. The final tei348
    The temperature of CMCfii is equal to | bli: then 165-170 ° C. The obtained pkk-tkor formanilide in xylene in a tank is ready for transformation into potassium formanilide and condensation of the latter with p-nitrochlorobenzene.
    Formanilide potassium.
    The transformations of formanilide potassium and the condensation of the latter are carried out in a stainless steel reactor equipped with a mechanical stirrer and a distillation system to condense the overhead (vapors) and the possibility of separating water, with the xylene being fed back to the reactor. In such a reactor load 162.21 43 weight.h. the above formanilide solution containing 122,7i: tljO weight.h. formanilide. 79.5 + 0.5 pbw is also added. p-nitrochlorobenzene and xylene to a total weight of 134.8i: 3 parts by weight. The system is closed, the pressure in the reactor is reduced to 65i2 mm Hg. Heating regulate with the calculation of the heating content of 5 C per min. When the temperature of the mass in the reactor reaches 60 ° C, but prior to its increase, a constant controlled flow of 85.9drO, 5 parts by weight, is introduced. 50% KOH at a rate of 2.8 ± 0.3 weight per minute. This means a KOH loading time of 33 minutes. The temperature does not go beyond 75s during KOH input. Then the heating is again regulated with the calculation of the heating rate of the reactor 4s / min. The boiling of water and xylene begins with the start of the KOH intake and continues until the KOH stream stops flowing until the controlled heat input boils down to 56.3 parts by weight. water and 900.8 weight.h. xylene. The water is separated, discharged from the condenser through the outlet, xylene is recycled back to the cycle. The temperature of the reaction mass during this dehydration process does not exceed.
    4-nitrodiphenylamine.
    The pressure in the reactor rises to atmospheric, above the specified heating volume. The reaction mass (potassium formanilide) is heated to reflux temperature, which approaches 150 ° C at atm. pressure. Upon reaching forward reflux distillation, distillate was distilled in a volume sufficient to raise the temperature of the reaction 9 wt.% To 16i-165 ° C, and 83.7 parts by weight were removed. distillate containing 80.8 parts by weight xylene. The above temperature is kept for 75 minutes, after which the reaction mass is cooled, followed by rapid cooling with water in a quantity of 105.6 parts by weight. After washing the reaction mass with hot water at 90-95 ° C, the A-nitrodiphenylamine is isolated by recrystallization. The process gives a yield in the amount of 90-95% with a conversion degree of 98-100%. 4-nitrodiphenylamine. 63 parts by weight are added to the resulting cesium formanilide slurry. (0.4 mol of p-nitrochlorobenzene, 7.9 parts by weight (.0.065 mol) of formanilide and 200 parts by weight of xylene. The reaction mixture is heated to approximately for about 1 hour, continuing heating at 140-146 ° C to about 3 The addition of gas increases rapidly at a temperature of about 12 without interruption during most of the heating process. During heating, a larger amount of hydrocarbon solvent is removed as distillate. The reaction mixture is washed with water, then added with xylene. dried from the organic layer 54.6 parts by weight (0.255 mol) of 4-nitrodiphenyl-Nine are recrystallized. 0.041 MU more is obtained from the brown mother liquor, the yield is 74.1%, the conversion is 80.3%. Example 6. 2-methyl-4-nitrodiphenylamine, 321% by weight, (3.0 mol) of o-toluidine, is heated to 90 ° C, to which, under reflux conditions, 147 parts by weight, (3.1 mol) of 97% - Noah Mousa Vinic Acid at 90-97 ° C for about 40 minutes, Then set up a water trap, continuing to heat up. For about 5 minutes at 104-118 with collecting water. After about 1 hour, 185 parts by weight are added. After cooling, the mass is cooled, the crystallization process is induced, and heptane is slowly added by cooling. The resulting violet solid is isolated by filtration and dried to give 2-methyl forms. 111 111 Lead in 97% yield. 4 Into the reactor load 29.7 nes.ch. (0.22 mol) of 2-methyl-formanilide obtained above, 69.9 parts by weight (0.2 mol} of 20% potassium methylate in methanol and about 170 weight, including xylene. The mixture is heated for about 2 hours at about 50-78 ° C under reduced pressure, collecting distillate. In order to maintain the liquid volume of the reaction toluene is added to the mixtures. The resulting xylene suspension of potassium 2-methyl-formanilide, mostly 1 not containing methanol, is cooled to 50 ° C and mixed with 24.2 wt. parts (0.154 mol) p-nitrochlorobenzene and 10.4 wt. , hours (0.077 mol) of 2-methylformanilide. The resulting mixture is heated and stirred at atm, with a pressure of about one and a half hours at 130149 ° C. Isolation of hectares starts at about 124 C. The hot reaction mixture is quenched with 85 wt. parts of xylene and 100 parts of water (90 sec.), gradually added with stirring. The organic layer is pressed and washed a second time with 100 wt. h, hot water. 2-methyl-4-nitrodiphenylamine is isolated from xylene in a yield of 97.5%. The degree of conversion of p-nitrochlorobenzene is 100%. EXAMPLE 7 4. 4-methoxy-4-nitrodiphenylamine. The intermediate product 4-methoxyformanilide is obtained by heating 369.6 weight, h, (3.0 mol) p-aniside to 90 ° C with the addition of 147 weight parts. (3.1 mol) of 97% formic acid for 80 minutes at 95-105 C under reflux. Then a water trap is installed and heating is continued at 91-111 ° C for about 5 minutes while collecting water. Dp remove water to add toluene. The reaction mixture is cooled, crystallization is initiated by scratching, heptane is added. The crystalline mass is cooled to 5 ° C and filtered to obtain 447.6 weight after drying in air .. h. 4-methoxyformanilide as a purple solid. 33.2 parts by weight are charged to the reactor. (0.22 mol) 4-methoxyformanilide ,. obtained above, 69.9 weight.h. (0.2 mol) of 20% potassium methylate in methanol and 85 parts by weight of xylene. The mixture is heated and stirred under reduced pressure for 52 minutes at 54 ° C. collecting a small amount of distillate. Then add emc 85 and "s.ch. xylene, which causes some precipitation of a white solid. Heating is continued for 1 hour at 70-78 ° C (SOO mm Hg) collecting the distillate. Then, 22.4 parts by weight are added to the methane-free residue of 4-mitoxyformate potassium in xylene. (0.154 mol) p-nitrochlorobenzene and 11.6 parts by weight (0.077 mol) of 4-methoxyformanilide. The reactgdaone mixture is heated and stirred at atmospheric pressure for about an hour and a half at 130-149 ° C. The product is introduced from the reaction mixture in the same way as Example 7, yielding 4-methoxy-4-nitrodiphenyl amine in 84% yield. The degree of conversion of AND-nitrochlorobenzene is 100%. PRI me R 8. 2-chloro-4-nitrodiphenylamine. 3 corresponding reactor load-34, 2 weight.h. (0.22 mol) 2-chloro, formanilide, 69.9 wt. (0.2 mol) of 20% potassium methylate in methanol and 85 parts by weight, of xylene. To form the potassium salt, the mixture is heated and stirred under reduced pressure for about 2 hours at 54-78 ° C, collecting distillate, xylene is added during the reaction to maintain the amount of liquid in the mixture. The vacuum is then discarded by adding 24.2 ppm by weight in one portion. (0.154 mol) 1-nitrochlor of benzene and 12.0 parts by weight (0.077 mol) of 2-chlorfbrmanilide. The mixture is heated with stirring at atmospheric pressure for 3 min at 130-185 ° C. From the special mixture, pe is processed by treatment as in Example 7 and recrystallization from hot xylene gives 24.4 parts by weight of 2-chloro-4-nitrodiphenylamine. Example 9 4-chloro-4-nitrodiphenylamine. Load the reactor 34,2 jBec, 4. (O, 22 mol) of 4-chloroformanilide, 69.9 parts by weight (0.2 mol) of 20% potassium methylate in methanol and 85 parts by weight of xylene. The mixture is stirred under reduced pressure and heated for about 1 hour, then distilled distillate. A fraction of the liquid in the reaction mixture is maintained by the addition of xylene. The vacuum is then removed by adding 24.2 parts by weight in one portion. (0.154 mol): At -nitrochlorobenzene and 12.0 parts by weight (0.077 mol of 4-chloroformiolide. The mixture is heated and stirred at 70-80 ° C at 412-100 mm Hg to remove xylene, and thereafter heated and stirred at 135-158 ° C at atmospheric pressure for about 2 hours. The reaction mixture is then cooled by 85 parts by weight of xylene and washed with 100 parts by weight of hot water. After the first washing with water, a solid from xylene crystallized out at 90 ° C. The mass was filtered without isolation of water, 31.8 parts by weight xpor-4-nitrodiphenylamine in the brown solid, i.e., a second porous is removed from the filtrate) 14.0 weight . h. PRIREY 10-11. 4,4-dinitrodiphenylamine. Potassium 4-nitroformedilide is obtained by weighing the reaction flask 83 in its e.ch, (0.5 mol) of 4-nitroforming in a dimethylformamide with 62.2 parts by weight of the suspension. (0.5 mol of 45% KOH, then stirring for half an hour at room temperature. The solid was filtered, washed with acetone and dehydrated into 130 parts by weight of benzene, to obtain 46 parts by weight of 4-potassium nitroformanilide as an yellow solid product To 40.8 parts by weight of 4-nitroformanilide, potassium (0.20 mol), obtained above, was added 21.7 parts by weight (O, 154 mol) to nitrofluorobenzene, 12.8, by weight. part (0.077 mol) of 4-ishtropformans and 25 parts by weight of dimethylformamide. A mixture of g-j at this temperature, the reaction becomes exothermic. The temperature is then raised to about 1 hour and Then heated with stirring at 130-170 ° C for 85 minutes While cooling, the reaction mixture hardens to form a bright orange cake, hot water is added to the pet flask, and the solid product is washed with stirring for 30 minutes with reverse the solid is filtered, dissolved in DMF and cooled in an ice bath. 10 parts by weight of 4,4-dinitrodiphenylamine are obtained, melting point 214-216 is 0. Formanilide sodium. K.41.6 g (0.35 mol) of formanilide, dissolved in 200 ml of xylene, is added dropwise with stirring at 80 ° C at approximately 100 mm RT. 70.2 g of 2–5% isecy sodium methoxide in methanol (0.325 mol). Methanol is distilled off, followed by distilling off the higher-boiling solvent in vacuo in a reactor with a temperature below 8 ° G to match the xylene refractive index (1.497 K. The solid sodium salt is filtered and protected from moisture to exploration. For the preparation of formanilide, it is protected by oxidation. use without admixture of sodium formanilide follow the above method, lowering the filtration stage, using the desired formanilide current and replacing methanol with xylene or other appropriate solvent for Holding the suspension in a liquid state. Then AND-nitrochlrrbeneol is added, distilled off, until the desired temperature is reached. 4-nitrophenylamine. , 93.8 parts by weight (0.65 mol of sodium formanilide and 96 parts by weight (0.8 mol) of formanilide. The mixture is gradually heated and agitated, and approximately at the start of separation of CO. Heating is continued to 180 ° C, at which the reaction mixture becomes self heating. The stirring is continued at 180 ° C, after about two and a half hours, 18 weight parts are recovered. Soo The reaction is stopped, xylene is added, the xylene solution is washed with 250 parts by weight. water, the water is separated and cooled to ICP. The resulting 4-nitrodiphenylamine crystals are isolated by filtration and washed with a small amount of xylene. From the mother liquor, the second position of 4-nitrodiphenylamine is obtained, which is obtained in a yield of 86% with a 4J4 conversion of V -nitrochlorobenzene equal to 96%. Due to the presence of formanilide, the amount of byproduct of tr 4-amine formed is reduced, which becomes excessive in the case of a reaction, for example, in dimethylformamide. PRI me R I2. 39.6 g (0.5 mol) of formanilide are used as an aid, generally providing a ratio of 1.3 mol of sodium formanilide and 0.62 mol of formanilide per I mol of V) -nitrochlorrbe ash. y -nitrochlorobenzene and formanilide are heated with stirring to 90 ° C by adding formanipid sodium in one portion. In Comparative Example 12A, formanilide is not used. And 10 ml of xylene is added as an aid. In comparative example 12B, formanilide is not used, and 50 ml of DIP is added as an aid. The reaction mass is heated and stirred. vay in accordance with table. 1. After heating, 150200 ml of xylene is added in order to quench the reaction mixtures, the resulting reaction mixtures are washed twice with water, 200 ml each (90 s). The xylene layers were isolated and cooled in an ice bath. Solid 4-nitrodiphenylamine is isolated by filtration and washed with 50 ml of cold xylene and dried. The amount of 4-nitrodifensch1amine in the mother liquor is determined by gas-liquid chromatography. Molar quantities of the 4,4-dinitrophenshamine (DNTFA) obtained are also recorded. Table 1
    Formanilide Xylene Dimethylformamide
    90
    89
    159-171 162-183
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of producing 4-nitrodiphenylamine by reacting an alkali metal formanilide with 4-nitrohalogenbenzene in the presence of formanilide under reflux, characterized in that, in order to simplify the process, potassium or cesium formanilide is used as alkali formanilide.
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    同族专利:
    公开号 | 公开日
    BR7807673A|1979-07-31|
    BE872210A|1979-05-22|
    FR2409979A1|1979-06-22|
    DE2850680C2|1988-06-09|
    ES475261A1|1979-12-01|
    DE2850680A1|1979-05-31|
    AU519515B2|1981-12-10|
    FR2409979B1|1983-11-25|
    GB2008592B|1982-03-17|
    IT1101294B|1985-09-28|
    US4187248A|1980-02-05|
    JPS5481230A|1979-06-28|
    AU4181178A|1979-06-28|
    GB2008592A|1979-06-06|
    IT7830073D0|1978-11-22|
    JPS6223741B2|1987-05-25|
    IN150612B|1982-11-13|
    CA1102352A|1981-06-02|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/854,109|US4187248A|1977-11-23|1977-11-23|Making a nitrodiarylamine by reacting an alkali metal salt of a formamide with a nitrohaloarene|
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