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    • 21. 发明授权
    • Raney nickel catalysis of aromatic amines
    • 阮内镍催化芳香胺
    • US4503251A
    • 1985-03-05
    • US365211
    • 1982-04-05
    • Thomas J. GrayNorman G. MasseRichard A. Hagstrom
    • Thomas J. GrayNorman G. MasseRichard A. Hagstrom
    • C07B61/00B01J25/02B01J35/10C07C67/00C07C209/00C07C211/35C07C211/36C07C85/24
    • B01J25/02
    • Hydrogenation processes utilizing improved Raney nickel alloy catalysts are disclosed. The catalyst comprises a monolithic mesh type structure of a nickel alloy having an integral Beta phase Raney Ni.sub.x M.sub.1-x coating on its outer surfaces, where M is a catalytic activator selected from the group consisting of molybdenum, ruthenium, tantalum and titanium and where x, the weight fraction of nickel in the combined alloy, is between about 0.80 and about 0.95. The catalyst is effective in processes for hydrogenating an amine-substituted aromatic compound of the type ##STR1## wherein K is either benzene or naphthalene, R.sub.1 is a hydrogen atom or an aliphatic chain containing from about 1 to about 12 carbon atoms or a phenyl radical, R.sub.2 is a hydrogen atom, an amine group or an aliphatic chain containing from about 1 to about 3 carbon atoms, R.sub.3 is hydrogen or an amine group, and R.sub.4 is an amine group. When this catalyst is used, substantially higher reactant flow rates and lower operating temperatures are possible as compared to conventional fluidized bed granular catalysts.
    • 公开了利用改进的阮内镍合金催化剂的氢化方法。 催化剂包括在其外表面上具有整体β相拉尼NixM1-x涂层的镍合金的整体网状结构,其中M是选自钼,钌,钽和钛的催化活化剂,其中x, 合金中镍的重量分数在约0.80至约0.95之间。 该催化剂在氢化胺取代的“IMAGE”类型的芳族化合物的方法中是有效的,其中K是苯或萘,R 1是氢原子或含有约1至约12个碳原子的脂族链或苯基 R2为氢原子,胺基或含有约1〜约3个碳原子的脂族链,R3为氢或胺基,R4为胺基。 当使用该催化剂时,与常规流化床颗粒催化剂相比,可以实现更高的反应物流速和较低的操作温度。
    • 22. 发明授权
    • Selective halogenation of 2-fluoroaniline
    • 2-氟苯胺的选择性卤化
    • US4443631A
    • 1984-04-17
    • US340569
    • 1982-01-18
    • Amphlett G. Padilla
    • Amphlett G. Padilla
    • C07C85/24
    • Novel processes for making arylpropionic acids are described. One process comprises carboxylating particular Grignard compounds which are the products of a catalyzed reaction between corresponding arylmagnesium bromides and ethylene. Furthermore, the reaction making the particular Grignard compounds is itself novel. Also, an improved method is disclosed for making coupled aryl compounds useful as intermediates for making compounds having a pharmaceutical use. For example, particular biaryls may be used to make some of the Grignard compounds herein from which the arylpropionic acids are made. Finally, an improved bromination is disclosed giving high yields of 4-bromo-2-fluoroaniline, which is thereafter coupled with benzene, then used to make the arylmagnesium bromide reacted with ethylene to obtain the particular Grignard compound and subsequent desired arylpropionic acid, i.e. 2-(2-fluoro-4-biphenylyl)propionic acid.
    • 描述了制备芳基丙酸的新方法。 一种方法包括羧化特定的格氏化合物,其是相应的芳基溴化镁和乙烯之间的催化反应的产物。 此外,使特定格利雅化合物的反应本身是新颖的。 此外,公开了一种改进的制备偶联芳基化合物的方法,其用作制备具有药物用途的化合物的中间体。 例如,特定的联芳基可以用于制备一些本文的格利雅化合物,其中制备芳基丙酸。 最后,公开了改进的溴化,得到高产量的4-溴-2-氟苯胺,然后与苯偶联,然后用于使芳基溴化镁与乙烯反应,得到特定的格利雅化合物和随后所需的芳基丙酸,即2 - (2-氟-4-联苯基)丙酸。
    • 28. 发明授权
    • Synthesis of amino hydroxy cyclopentenones
    • 氨基羟基环戊烯酮的合成
    • US4304934A
    • 1981-12-08
    • US221523
    • 1980-12-30
    • James R. Bartels-KeithEva R. KargerJean B. Rogers
    • James R. Bartels-KeithEva R. KargerJean B. Rogers
    • C07C45/51C07C55/02C07F7/18G03C5/30C07C85/00C07C85/11C07C85/24
    • G03C5/30C07C45/511C07C55/02C07F7/1856
    • This invention relates to a method of synthesizing 3-amino-2-hydroxy-2-cyclopentenones possessing an aliphatic substituent in the 4-position which comprises reacting cyanoacetamide with an aliphatic aldehyde to yield the corresponding .beta.-substituted-.alpha.,.alpha.'-dicyanoglutaramide, hydrolyzing the amide to the corresponding .beta.-substituted glutaric acid, esterifying the acid to the corresponding dialkyl diester, converting the diester to a 1,2-bis(trimethylsiloxy)-4-substituted cyclopentene by reductive cyclization using chlorotrimethylsilane in the presence of sodium, hydrolyzing and oxidizing the bis(trimethylsiloxy) compound to the 2-hydroxy-4-substituted-2-cyclopentenone in the presence of a cupric salt, nitrosating the 2-cyclopentenone to the 2-hydroxy-4-substituted-5-oximino-2-cyclopentenone, converting the oxime to the 2-acetoxy-3-amino-4-substituted-2-cyclopentenone by reductive acetylation and removing the acetyl group by alkanolysis to yield the 3-amino-2-hydroxy-4-substituted-2-cyclopentenone product.
    • 本发明涉及在4-位上合成具有脂肪族取代基的3-氨基-2-羟基-2-环戊烯酮的方法,该方法包括使氰基乙酰胺与脂族醛反应,得到相应的β-取代-α,α'-二氰基戊酰胺 ,将酰胺水解成相应的β-取代戊二酸,将酸酯化成相应的二烷基二酯,通过在钠存在下使用氯代三甲基硅烷进行还原环化将二酯转化成1,2-双(三甲基甲硅烷氧基)-4-取代的环戊烯 ,在铜盐存在下将双(三甲基甲硅烷氧基)化合物水解和氧化成2-羟基-4-取代-2-环戊烯酮,将2-环戊烯酮亚硝化为2-羟基-4-取代-2-环戊烯-2-酮, 2-环戊烯酮,通过还原乙酰化将肟转化为2-乙酰氧基-3-氨基-4-取代-2-环戊烯酮,通过链烷分解除去乙酰基,得到3-氨基-2-羟基-4- 取代-2-环戊烯酮产物。