• 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:
    Nitrodiarylamines, useful as intermediates, are produced by combining a formyl derivative of an aromatic primary amine with a nitrohaloarene, at condensation temperature for forming nitrodiarylamine, and adding an alkoxide or cycloalkoxide of sodium, potassium, rubidium or cesium.
    公开号:SU1299499A3
    申请号:SU843815211
    申请日:1984-11-30
    公开日:1987-03-23
    发明作者:Уильям Маендер Отто；Людвиг Мертен Хэлмут
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of nidrodiarylamines, which are useful as intermediates for the preparation of dyes, in particular 4-nitrodiphenylamine, is a useful intermediate in the preparation of antiozonants used in rubber formulations.
    The aim of the invention is to simplify the process.
    Example 1. Preparation of potassium 2-methyl-2-butsh1at.
    19.6 g of metallic potassium
    orange crystals weighing 41.8 (0.1951 mol of 4-nitrodiphenylamine) are filtered. The filtrate of the uterine bone (310.5 g) is analyzed. It holds aniline (0.0617 mol), p-nor chlorobenzene (0.0052 mol), forms nilide (0.4448 mol), diphenylforma mid (0.0065 mol), 4-nitrodifine amine (0.0852 mol) triphenylamine (0.0014 mol) and 2-nitrodiphenyls (0.0014 mol). Azo compounds are absent.
    Distillate (294.4 g) is mainly tert-amyl
    467 g of tert-amyl alcohol is added, but it also contains aniline (2-methyl-2-butanol). Alcohol zagru- (0,0021 mol), p-nitrochlorobenzene
    they are poured into a vessel and heated to 60-65 ° C under a nitrogen atmosphere. Potassium is added to the vessel and it is found that it melts at about 60 ° C. The heating jacket maintains the desired temperature in the vessel for 6 hours. The clear product is decanted in a hot state under a nitrogen atmosphere and cooled. It was calculated that this straw-colored liquid presented (0.0012 mol) andformanilide (0.0013 m
    It was calculated that the total conversion (based on p-nitrochlorobenzene is 97.9% and the yield of 4-nitrodi-phenylamine is 93.4%.
    Example 2. In the process according to Ru 1, 4-methylpentane-2-okali was used as an alcoholate for the preparation of 4-nitrodiphenylamine, but instead of 0.87 mol, 0.49 m of anmanilide was added. The reaction temperature of the vessel is 147-150 ° C, the delivery time is 120 min and the total time 210 Turning is 90% and the yield is 73.2%. Both numbers reflect the lowest amount of excess formanilide, but the amount of by-products is also lower than. in example 1.
    It is 13.4% potassium 2-methyl-2-butoxide in t-amyl alcohol.
    The resulting alcoholate is then used to prepare 4-nitrodiphenylamine.
    Example 2. In the method of Example 1, 4-methylpentane-2-potassium oxide was used as an alcoholate to obtain 4-nitrodiphenylamine, but instead of 0.87 mol, 0.49 mol of formanilide was added. The temperature of the reaction vessel is 147-150 ° C, the delivery time is 120 minutes and the total time is 210 minutes. The conversion is 90% and the yield is 73.2%. Both numbers reflect the lowest amount of excess formanilide, but the amount of by-products is also lower than. in example 1.
    35
    PRI me R s 3-10. 0.3 mol of p-nitrochlorobenzene, 0.49 mol of formanilide and 0.3 mol of alcoholate are used in all reactions. A 500 ml three-neck flask with a recess for a thermometer and equipped with a column, a distillation head and a 500 ml addition funnel with a side handle add 47.3 g (0.3 mol) p-nitrochlorobenzene and 105.4 g (0.87 mole) formanilide. To this transfer f If l f r f V ...- “. uf.m - l .v i4- 1.l «. 4, hl 4 111.1 j iw i
    stirring the mixture at 155–160 times, the peraturum is held at 175 ° C, and a solution of 310.9 g (0.33 mol) is continued, drop by drop, for 15 minutes, 2-methyl-2-potassium potassium hydroxide (obtained above) 200 min. The condensate distillate is collected and accumulated 356 ml and the vessel is kept at a temperature of an additional 35 minutes after the addition of the total alcoholate solution and during this time only 9.0 liters of CO are collected. Reaction mas45
    completion of the addition of alcohol.
    Conditions and results are shown in Table 1.
    In examples 3 and 4, the alcoholate solution is added under the surface of the reagents using a perestaltic pump. A comparison of example 4 with example 5 shows that the radiation can then be expected to be distilled off in vacuum, with sharp results. Using a pump, cooled down with 200 ml of xylene and washed. Another series of 200 ml of water with a temperature of 90 ° C. Alternates were applied according to one hundred with 50 ml of xylene used for the method of examples 5-10. The flasks of the reaction flask, the material. The conditions and the results are given in a separatory funnel and in the bottom. 2. Toronically washed with 200 ml of water with a temperature of 90 ° C. The xylene layer was then transferred to example in temperature 16 in a beaker and cooled to 145 ° C, and in example 17 it was cooled to 5 ° C. The resulting light was 160 ° C.
    orange crystals weighing 41.8 g (0.1951 mol of 4-nitrodiphenylamine) are filtered off. The filtrate of the mother liquor (310.5 g) is analyzed. Oy contains aniline (0.0617 mol), p-nitrochlorobenzene (0.0052 mol), forne-nilid (0.4448 mol), diphenylformamide (0.0065 mol), 4-nitrodiphenyl amine (0.0852 mol) triphenylamine (0.0014 mol) and 2-nitrodiphenylamine (0.0014 mol). Azo compounds are absent.
    Distillate (294.4 g) is mainly tert-amyl
    alcohol, but also contains aniline (0,0021 mol), p-nitrochlorobenzene
     alcohol, but also contains aniline (0,0021 mol), p-nitrochlorobenzene

    (0.0012 mol) andformanilide (0.0013 mol.).
    It was calculated that the total conversion (based on p-nitrochlorobenzene) was 97.9% and the yield of 4-nitro-diphenylamine was 93.4%.
    Example 2. In the method of Example 1, 4-methylpentane-2-potassium oxide was used as an alcoholate to obtain 4-nitrodiphenylamine, but instead of 0.87 mol, 0.49 mol of formanilide was added. The temperature of the reaction vessel is 147-150 ° C, the delivery time is 120 minutes and the total time is 210 minutes. The conversion is 90% and the yield is 73.2%. Both numbers reflect the lowest amount of excess formanilide, but the amount of by-products is also lower than. in example 1.
    35
    PRI me R s 3-10. 0.3 mol of p-nitrochlorobenzene, 0.49 mol of formanilide and 0.3 mol of alcoholate are used in all reactions. Reactionary order V ...- ". uf.m - l .v i4- 1.l «. 4, hl 4 111.1 j iw i
    Q peratura is held at 175 ° C and is repeated for 15 min.
    Examples 18-25. Other vari-aHThf reactions are carried out using various reagents. In each reaction, 0.3 mol of nitrogaloarene and 0.49 mol of formanilide are subjected to an interaction and 0.33 mol of the alcoholate (dissolved in the corresponding alcohol) are added dropwise.
    The conditions and the results of the reactions are given in table 3. The following abbreviations have been applied: PNCB p-nitrochlorobenzene PNFB p-nitrofluorobenzene ONCB o-nitrochlrrbenzene FAN formanilide 4-Me FAN 4-methylformanilide 4-CI FAN 4-chloroformedilide 4-NFAN 4-nitroformanilide NaMlBC 4-a-a-a-a-a-a-a-3-NFAN 4-methylformanilide 4-NFAN 4-methylformanilide 4-NFAN 4-nitroformanilide Potassium methyl 2-butoxide KCl Potassium chloride K1P Potassium isoproxide K2B Potassium 2-butalate The proposed method is simpler than the known method, since the latter is
    2-Methyl-2-butylate
    rub 40567,780,0
    Potassium isopropoxide 13286,494.1
    2-Octyloxide potassium 10554,081,7
    tert-Butyl potassium 25287,195.9 n-Butyl potassium 12670,786.0

    external cooling in order to regulate the exothermic heat effect.
    The proposed method eliminates the danger of developing extremely high temperatures in the reaction zone and prevents unwanted side reactions. This process temperature leads to the establishment of the best balance between the reaction rate and obtaining a minimum of by-products.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method for producing nitrodiphenylamine on the basis of nitrohalobenzene, characterized in that, in order to simplify the process, the nitrohalide-benzod is reacted with formanilide, which can be replaced from the p-position by methyl, chlorine or nitro group, at 150-175 ° C, followed by adding to reactionary
    mixtures of C, -Cg-alkyl sodium, potassium, rubidium, or cesium.
    Table 1
    Order 905/63 Circulation 372 Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Production and printing company, Uzhgorod, st. Project, 4
    a b and c a 2
    Table3
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    同族专利:
    公开号 | 公开日
    DE3464485D1|1987-08-06|
    KR850004576A|1985-07-25|
    EP0147379A1|1985-07-03|
    EP0147379B1|1987-07-01|
    AU3607484A|1985-06-27|
    KR870001140B1|1987-06-11|
    JPS60132932A|1985-07-16|
    JPH0455418B2|1992-09-03|
    IN163601B|1988-10-15|
    AU564671B2|1987-08-20|
    CA1225100A|1987-08-04|
    US4614817A|1986-09-30|
    BR8406105A|1985-09-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL246635A|1958-12-22|
    FR1208123A|1959-02-17|1960-02-22|Bayer Ag|Process for preparing 4-nitro-diarylamines|
    NL130294C|1964-05-22|
    US4187248A|1977-11-23|1980-02-05|Monsanto Company|Making a nitrodiarylamine by reacting an alkali metal salt of a formamide with a nitrohaloarene|
    US4209463A|1977-12-27|1980-06-24|Monsanto Company|Promoting the formation of nitrodiarylamines from nitrohaloarenes, activated aryl amines and sodium carbonates|
    US4187249A|1977-12-27|1980-02-05|Monsanto Company|Promoting the reaction of sodium salts of formyl derivatives of aromatic amines to form nitrodiarylamines|
    US4140716A|1978-01-05|1979-02-20|Monsanto Company|Process for making an amide of formic acid and forming nitrodiarylamine therefrom|
    US4196146A|1978-03-13|1980-04-01|Monsanto Company|Making nitrodiarylamines from formyl derivatives of aromatic amines and nitrohaloarenes by admixing with certain aqueous salt solutions|
    US4228103A|1978-03-13|1980-10-14|Monsanto Company|Effecting condensation of nitrohaloarene and formyl derivative of a primary aromatic amine with alkali metal hydroxide|DE3501698A1|1985-01-19|1986-07-24|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 4-NITRODIPHENYLAMINE|
    US5117063A|1991-06-21|1992-05-26|Monsanto Company|Method of preparing 4-aminodiphenylamine|
    EP0566783A1|1992-04-21|1993-10-27|Akzo N.V.|Process for the production of nitrodiarylamines|
    US5252737A|1992-05-22|1993-10-12|Monsanto Company|Process for preparing N-aliphatic substituted p-phenylenediamines|
    US5552531A|1992-05-22|1996-09-03|Monsanto Company|Process for preparing substituted aromatic azo compounds|
    US5331099A|1992-05-22|1994-07-19|Monsanto Company|Process for preparing p-nitroaromatic amides and products thereof|
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    US5380946A|1993-07-30|1995-01-10|Monsanto Company|Process for preparing p-nitroaromatic amides and products thereof|
    US5382691A|1993-11-05|1995-01-17|Monsanto Company|Process for preparing substituted aromatic amines|
    US5840982A|1998-06-04|1998-11-24|Uniroyal Chemical Company, Inc.|Process for preparing para-phenylenediamine derivatives|
    US6495723B1|2000-06-21|2002-12-17|Flexsys America|Zeolite support loaded with a base material for use in the coupling of aniline and nitrobenzene|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/562,767|US4614817A|1983-12-19|1983-12-19|Making nitrodiarylamines|
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