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    • 3. 发明授权
    • Process for the preparation of carboxylic acid salts from primary alcohols
    • 从伯醇制备羧酸盐的方法
    • US06646160B2
    • 2003-11-11
    • US09563683
    • 2000-05-03
    • Thaddeus S. Franczyk, IIWilliam L. Moench, Jr.
    • Thaddeus S. Franczyk, IIWilliam L. Moench, Jr.
    • C07C51291
    • C07C227/02C07C229/08C07C229/12C07C229/16
    • The present invention provides a new and useful improvement in the process to manufacture a carboxylic acid salt, particularly an amino carboxylic acid salt, from a primary alcohol, particularly a primary aminoalcohol. The process of manufacturing amino carboxylic acid salts comprises contacting an aqueous solution of a primary aminoalcohol with a strong hydroxide base selected from the group consisting of an alkali metal hydroxide, an alkaline earth metal hydroxide, an ammonium hydroxide compound including a tetraalkyl ammonium hydroxide, or the like, in the presence of an effective amount of a catalyst. The catalyst comprises one or more of elements selected from the group consisting of copper, cobalt, nickel, and cadmium as well as optionally lesser amounts of chromium, titanium, niobium, tantalum, zirconium, vanadium, molybdenum, manganese, tungsten, cobalt, nickel, or mixtures thereof. The reaction mixture contains less than about 3000 ppm, preferably less than about 500 ppm, more preferably less than about 100 ppm of oxidized copper (Cu+ and/or Cu2+) during the reaction. The concentration of oxidizing agents in the reactants is minimized to prevent formation of oxidized copper from metallic copper catalyst.
    • 本发明提供了从伯醇,特别是伯氨基醇制备羧酸盐,特别是氨基羧酸盐的方法中的新的和有用的改进。 制备氨基羧酸盐的方法包括将伯氨基醇的水溶液与选自碱金属氢氧化物,碱土金属氢氧化物,氢氧化铵,氢氧化四烷基铵或氢氧化四烷基铵的强氢氧化物碱 在有效量的催化剂存在下进行。 催化剂包含一种或多种选自铜,钴,镍和镉的元素,以及任选少量的铬,钛,铌,钽,锆,钒,钼,锰,钨,钴,镍 ,或其混合物。 反应混合物在反应期间含有小于约3000ppm,优选小于约500ppm,更优选小于约100ppm的氧化铜(Cu 2+和/或Cu 2+)。 反应物中氧化剂的浓度被最小化以防止金属铜催化剂形成氧化铜。
    • 6. 发明授权
    • Method of making phosphorus-containing compounds and products thereof
    • 制造含磷化合物及其制品的方法
    • US06864218B2
    • 2005-03-08
    • US10192709
    • 2002-07-09
    • Thaddeus S. Franczyk, II
    • Thaddeus S. Franczyk, II
    • C07F9/38C07F9/40A01N57/18C07C9/22C07F9/02
    • C07F9/4065C07F9/3813C07F9/3891C07F9/4006
    • A process for oxidizing a hydroxymethylphosphonic acid compound to produce a formylphosphonic acid compound is described. The oxidation reaction is carried out in the presence of an oxidant and a catalyst. For example, hydroxymethylphosphonic acid (HMPA) is oxidized by oxygen or hydrogen peroxide in the presence of a copper-containing catalyst to give formylphosphonic acid (FPA). Formylphosphonic acid can then be reacted with glycine to produce a condensation product which, upon hydrogenation, yields glyphosate. Glyphosate can be incorporated into various formulations for use as a herbicide. In addition to glycine, formylphosphonic acid can also be reacted with ammonia, ethanolamine, or other primary amines to form a precursor compound, which can be converted to glyphosate.
    • 描述了氧化羟甲基膦酸化合物以产生甲酰膦酸化合物的方法。 氧化反应在氧化剂和催化剂的存在下进行。 例如,羟基甲基膦酸(HMPA)在含铜催化剂存在下被氧或过氧化氢氧化,得到甲酰基膦酸(FPA)。 然后可以将甲基膦酸与甘氨酸反应以产生缩合产物,其在氢化时产生草甘膦。 草甘膦可以并入用作除草剂的各种制剂中。 除了甘氨酸之外,甲酰基膦酸还可以与氨,乙醇胺或其它伯胺反应形成前体化合物,其可以转化成草甘膦。
    • 10. 发明授权
    • Continuous process for the preparation of N-(phosphonomethyl)
iminodiacetic acid
    • 连续制备N-(膦酰基甲基)亚氨基二乙酸的方法
    • US6130351A
    • 2000-10-10
    • US373106
    • 1999-08-12
    • Michael K. SternTodd J. JohnsonAmy L. JorgensonMichael D. RogersThaddeus S. Franczyk, II
    • Michael K. SternTodd J. JohnsonAmy L. JorgensonMichael D. RogersThaddeus S. Franczyk, II
    • B01J20/26B01J20/34B01J31/20B01J31/40B01J38/00C07B61/00C07C233/47C07D241/08C07F9/38
    • C07D241/08C07C233/47C07F9/3808
    • A process for the production of N-(phosphonomethyl)iminodiacetic acid. N-(acetyl)iminodiacetic acid is formed in a amidocarboxymethylation reactor system, into which a source of each of the following is continuously fed: (1) acetamide or an acetamide derivative, (2) formaldehyde or a formaldehyde generator or derivative, (3) a carbonylation catalyst, (4) carbon monoxide, and optionally (5) hydrogen. In turn, an amidocarboxymethylation reaction product stream, which contains N-(acetyl)iminodiacetic acid and the carbonylation catalyst, is withdrawn from the amidocarboxymethylation reactor system. The carbonylation catalyst is separated from the amidocarboxymethylation reaction product stream to recover the carbonylation catalyst and form a catalyst depleted product stream which contains N-(acetyl)iminodiacetic acid. The separated carbonylation catalyst is returned to the amidocarboxymethylation reactor system, and the N-(acetyl)iminodiacetic acid in the catalyst depleted product stream is either: (1) reacted with a source of phosphorous and a source of formaldehyde in the presence of an acid to form a phosphonomethylation reaction product stream containing N-(phosphonomethyl)iminodiacetic acid and acetic acid; or (2) deacylated and cyclized to form a 2,5-diketopiperazine, and then reacted with a source of phosphorous and a source of formaldehyde in the presence of an acid to form a phosphonomethylation reaction product stream containing N-(phosphonomethyl)iminodiacetic acid and acetic acid. Either way, the N-(phosphonomethyl)iminodiacetic acid is precipitated from the phosphonomethylation reaction product stream in the presence of acetic acid, and the precipitate is recovered to form a filtrate stream.
    • 一种生产N-(膦酰基甲基)亚氨基二乙酸的方法。 在酰胺羧甲基化反应器系统中形成N-(乙酰基)亚氨基二乙酸,其中连续供给以下各项的源:(1)乙酰胺或乙酰胺衍生物,(2)甲醛或甲醛发生剂或衍生物,(3 )羰基化催化剂,(4)一氧化碳和任选的(5)氢。 反过来,含有N-(乙酰基)亚氨基二乙酸和羰基化催化剂的酰胺甲基甲基化反应产物流从酰胺羧甲基化反应器系统中排出。 从酰胺羧甲基化反应产物流中分离羰基化催化剂以回收羰基化催化剂并形成含有N-(乙酰基)亚氨基二乙酸的催化剂贫化产物流。 将分离的羰基化催化剂返回到酰胺羧甲基化反应器系统中,催化剂贫化产物流中的N-(乙酰基)亚氨基二乙酸是:(1)在酸存在下与磷源和甲醛源反应 以形成含有N-(膦酰基甲基)亚氨基二乙酸和乙酸的膦酰基甲基化反应产物流; 或(2)脱酰基并环化形成2,5-二酮哌嗪,然后在酸存在下与磷源和甲醛源反应,形成含有N-(膦酰基甲基)亚氨基二乙酸的膦酰基甲基化反应产物流 和乙酸。 无论哪种方式,在乙酸存在下,从膦酰基甲基化反应产物流中沉淀N-(膦酰基甲基)亚氨基二乙酸,并回收沉淀物以形成滤液流。