• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for the preparation of p-amino-diphenylamine which comprises catalytically hydrogenating p- nitroso-diphenyl hydroxylamine in the presence of an organic solvent, which is aniline or the amine of a benzene homologue containing from 7 to 12 carbon atoms of mono- or di-alkylamino derivatives thereof containing from 1 to 6 carbon atoms in the N-alkyl group(s), and one or more of the metals ruthenium, rhodium, palladium osmium, iridium and platinum or the sulphidic compounds thereof as a catalyst at a temperature of from 20 to 200 DEG C, is disclosed. Inter alia, the present invention is distinguished by the choice of solvent which results in, in particular, good selectivity, high conversion and short reaction times.
    公开号:SU828961A3
    申请号:SU792738051
    申请日:1979-03-09
    公开日:1981-05-07
    发明作者:Ценгель Ханс-Георг；Бергфельд Манфред
    申请人:Акцо Нв (Фирма)；
    IPC主号:
    专利说明:

    one
    This invention relates to an improvement in the method for producing p-aminodiphenylamine used in the manufacture of coloring agents.
    The patent and technical literature describes various methods for preparing pamino diphenylamine, for example, by hydrogenating -nitrosodiphenylhydroxylamine in hydroxyl-containing solvents in the presence of heavy metal catalysts. The yield of crude crude target product 74-90%.
    The closest in technical essence to the proposed method is the method of producing α-aminodiphenylamine, which consists in hydrogenating p-nitrosodiphenylhydroxylamine in a mixture of an organic solvent (alcohol or hydrocarbon) and water at 120 ° C in the presence of catalysts based on metals of group VIII — nickel, cobalt, ruthenium , palladium or platinum 2.
    The disadvantage of this method is the low yield of the obtained crude target product-40-88%.
    The aim of the invention is to eliminate this drawback and increase the yield of the target product.
    This goal is achieved by using aniline or its homolog with 7-12 carbon atoms, their monoalkylamino or dialkylamino derivatives with 1-6 carbon atoms of aqueous or several N-alkyl groups, preferably o-toluidine or l -toluidine.
    Palladium or platinum is preferably used as the catalyst.
    activated carbon or ilatin sulfide
    on activated carbon, preferably
    in the amount of 0.001-0.5 weight. % metal by
    relative to the hydroxylamine used.
    The hydrogenation is carried out at 30-125 ° C, preferably at a hydrogen pressure of from 1 to 30 atm.
    The preferred concentration of l-nitrosodiphenylhydroxylamine is 10-25 wt. %, reaction time 15- 45 min. The method can be carried out continuously or intermittently.
    The method according to the invention is as follows.
    In a reaction vessel whose dimensions correspond to the amount of the initial mixture, p-nitrosodiphenylgpdroxylamine and the catalyst are suspended with an appropriate amount of the selected solvent, then the air is removed by pumping and purging with nitrogen and stirring is maintained at the selected hydrogen pressure. Next, the reaction mixture is heated until appropriate, its self-heating due to the exothermic reaction. The reaction temperature is maintained by cooling. After cessation of heat release, the reaction mass is left at elevated temperature for a short time.
    The catalyst is usually moistened with water; when used, l-nitrosodiphenylhydroxylamine is also recommended to be moistened with water. Water introduced with the above substances is not a hindrance, just like the water formed during the reaction. It does not matter whether there is already an aqueous phase in the reaction mixture or water is formed during the reaction.
    Upon completion of the reaction, the reaction mixture is treated in the usual manner. The contents of the reactor are first cooled, the pressure in the reaction vessel is reduced, and the catalyst is filtered off at 20-60 ° C. The water formed during the reaction is separated and the desired product is isolated by distilling the reaction mixture.
    The method according to the invention differs in a relatively short reaction time of about 15-45 minutes and provides a high (more than 90%) yield of the desired product.
    Examples 1-5. The process is carried out in a 1 liter glass autoclave.
    equipped with a drain valve and bottom part, a gas inlet, a paddle stirrer and a manometer. The reaction is carried out at a temperature of 40-150 ° C, the hydrogen pressure is 5-30 atm, the reaction time is 30 minutes, and the stirring speed is 1500 rpm. First, gases are removed from the autoclave, then hydrogen is purged with hydrogen, and finally, half volume is charged with a solvent; g-nitrosodiphenylhydroxylamine together with the catalyst is suspended, the pressure of hydrogen is brought to the working pressure through the inlet valve and the autoclave is gently heated. Depending on the other parameters of the reaction, it is carried out at 20-70 ° C. After 30 minutes, the pressure in the autoclave is released, and the catalyst is filtered off at 30–50 ° C. The catalyst, moistened with a solvent, when reuse is necessary, is again washed into the reaction chamber. From the filtrate by fractional distillation, first get the first reactionary water, and then the solvent and, finally, α-aminodiphenylamine. When obtaining significantly larger amounts of α-aminodiphenylamine, it is recommended to connect a desiccant, which is a roll mill for flakes, to the hierogony column. In this case, p-aminodiphenylamine is formed in the form of white flakes, with a slightly beige tint.
    The table presents the conditions for carrying out the process, as well as the yields of p-aminodiphenylamine. In each run, 20.0 g (93.2 mmol) of p-nitrosodiphenylhydroxylamine was used.
    DNA-ha-nitrosodipheny. Hydroxy.chamin.
    Note. ADA-p-aminodiphenylamine. SRRD-Y-cyclohexnyl-phenylenediamine.
    权利要求:
    Claims (5)
    [1]
    1. A method of producing l-aminodiphenylamine by catalytic hydrogenation of p-nitrosodiphenylhydroxylamine in the presence of an organic solvent and a catalyst based on one or more Vni metals of the ruthenium group, rhodium, palladium, osmium, iridium and platinum or their sulfide compounds and temperatures
    20-200 ° C, characterized in that, in order to increase the yield of the target product, aniline or its homolog with 7-12 carbon atoms, their monoalkylamino or dialkylamino derivatives with 1-6 carbon atoms in one or more N, are used as a solvent. -alkyl groups.
    [2]
    2. A method according to claim 1, characterized in that palladium on activated carbon, platinum on activated carbon or platinum sulfide on activated carbon is used as a catalyst.
    [3]
    3. Method according to paragraphs. 1 and 2, characterized in that the hydrogenation was carried out at 30-125 ° C.
    [4]
    4. Method according to paragraphs. 1-3, characterized in that anep, o-toluidine or g-toluidine is used as a solvent. 10
    [5]
    5. Method but paragraphs 1-4, characterized in that the hydrogenation is carried out 6 under a hydrogen pressure of from 1 to 30 atm. 6, the Method according to PP. 1-5, characterized in that the amount of catalyst is 0.001-0.5 sec. % of iio metal to the rest to applied p-nitrosodiphenylhydroxylamine. Sources of information taken into account during the examination 1. German patent No. 1941008, Cl. C 07 C, publ. 1969. 2. Patent of Great Britain No. 1296211, cl. C 07 C, publ. 1971 (prototype).
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    同族专利:
    公开号 | 公开日
    CA1127666A|1982-07-13|
    NL7901809A|1979-09-13|
    DD142331A5|1980-06-18|
    JPS54128530A|1979-10-05|
    FR2419276A1|1979-10-05|
    DE2810666B2|1981-01-29|
    ES478478A1|1979-06-01|
    PL113863B1|1981-01-31|
    ATA180079A|1981-10-15|
    DE2810666A1|1979-09-27|
    GB2015998A|1979-09-19|
    AT367017B|1982-05-25|
    IT1114098B|1986-01-27|
    CH639937A5|1983-12-15|
    ZA791041B|1980-03-26|
    BR7901401A|1979-10-09|
    BE874713A|1979-07-02|
    IT7948277D0|1979-03-09|
    RO76866A|1982-03-24|
    GB2015998B|1982-07-14|
    CS203035B2|1981-02-27|
    PL214043A1|1979-11-05|
    HU180419B|1983-03-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1296211A|1969-01-27|1972-11-15|
    DE2355737C2|1973-11-08|1982-10-21|Bayer Ag, 5090 Leverkusen|Process for the preparation of 4-amino-diphenylamine|US8486223B2|2003-07-04|2013-07-16|Jiangsu Sinorgchem Technology Co., Ltd.|Falling film evaporator|
    CA2515238C|2003-07-04|2011-06-28|Nongyue Wang|Process for preparing 4-aminodiphenylamine|
    CA2531074C|2003-07-04|2011-10-11|Shi, Guangqiang|Process for preparing 4-aminodiphenylamine|
    US8686188B2|2003-07-04|2014-04-01|Jiangsu Sinorgchem Technology Co., Ltd.|Process for preparing 4-aminodiphenylamine|
    CN102259029B|2010-05-24|2014-12-10|江苏圣奥化学科技有限公司|Solid alkali catalyst|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19782810666|DE2810666B2|1978-03-11|1978-03-11|Process for the preparation of p-amino-diphenylamine|
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