CN1230417C - 从腈制备伯胺和仲胺的方法 - Google Patents
从腈制备伯胺和仲胺的方法 Download PDFInfo
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- CN1230417C CN1230417C CNB02104788XA CN02104788A CN1230417C CN 1230417 C CN1230417 C CN 1230417C CN B02104788X A CNB02104788X A CN B02104788XA CN 02104788 A CN02104788 A CN 02104788A CN 1230417 C CN1230417 C CN 1230417C
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- Prior art keywords
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- weight
- amine
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- methyl
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- C07—ORGANIC CHEMISTRY
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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Abstract
在载体上含有基于催化剂总重量为0.1～10%(重量)Pd的含Pd催化剂存在下，在50～250℃温度和5～350bar压力下，通过将通式(III)的腈X-CN (III)与氢反应，制备通式(I)的伯胺X-CH2-NH2 (I)和通式(II)的仲胺的混合物。(X-CH2-)2NH (II)其中X是未取代或被C1-20-烷基、C3-8-环烷基、C4-20-烷基环烷基、C4-20-环烷基烷基、C2-20-烧氧基烷基、C6-14-芳基、C7-20-烷芳基、C7-20-芳烷基、C1-20-烷氧基、羟基、C1-20-羟烷基、氨基、C1-20-烷氨基、C2-20-二烷氨基、C2-12-链烯基氨基、C3-8-环烷氨基、芳氨基、二芳氨基、芳基-C1-8-烷氨基、卤素、巯基、C2-20-链烯氧基、C3-8-环烷氧基、芳氧基和/或C2-8-烷氧基羰基取代C1-20-烷基、C2-20-链烯基或C3-8-环烷基。
Description
本发明涉及从腈通过钯催化剂制备伯胺和仲胺混合物的方法。
从腈通过特定的钯催化剂制备胺的方法是公知的。
DE-A-3935641描述了从3-(二甲基氨基)丙腈(DMAPN)制备胺的方法。形成的产品是双(3-(二甲基氨基)丙基)胺(双-DMAPA)和三(3-(二甲基氨基)丙基)胺(三-DMAPA)。该反应是通过氧化铝上的钯作为催化剂进行的。双-DMAPA的产率不超过32％。
EP-A-0869113涉及从腈和仲胺制备叔胺的方法。此处，仲胺通过在氧化锌载体上含有0.9％的Pd和0.1％Pt的催化剂、在氢的存在下进行反应。
WO 99/32429涉及从腈和伯胺制备仲胺的方法。该反应通过在氧化锌上含有0.9％Pd和0.1％Pt的上述催化剂、在氢等的存在下进行。
本发明一个目的是提供在催化剂存在下通过腈与氢反应制备伯胺和仲胺的混合物的方法。
特别是，制备伯胺和对称的仲胺的混合物。
我们已发现该目的通过这样的制备方法达到：在载体上含有基于催化剂总重量为0.1～10％(重量)Pd的含Pd催化剂存在下，在50～250℃温度和5～350bar压力下，通过通式(III)的腈
X-CN (III)
与氢反应，制备通式(I)的伯胺
X-CH2-NH2 (I)和通式(II)的仲胺的混合物。
(X-CH2-)2NH (II)其中X是未取代或被C1-20-烷基、C3-8-环烷基、C4-20-烷基环烷基、C4-20-环烷基烷基、C2-20-烷氧基烷基、C6-14-芳基、C7-20-烷芳基、C7-20-芳烷基、C1-20-烷氧基、羟基、C1-20-羟烷基、氨基、C1-20-烷氨基、C2-20-二烷氨基、C2-12-链烯基氨基、C3-8-环烷氨基、芳氨基、二芳氨基、芳基-C1-8-烷氨基、卤素、巯基、C2-20-链烯氧基、C3-8-环烷氧基、芳氧基和/或C2-8-烷氧基羰基取代的C1-20-烷基、C2-20-链烯基或C3-8-环烷基。
该催化剂优选还含有0.1～10％(重量)选自元素周期表的IB族和VIII族、铈和镧的至少一种附加金属。
根据本发明，发现使用以上定义的催化剂将腈与氢反应制备伯胺和仲胺的混合物能提高催化剂的使用寿命或长期稳定性。
本发明使用的催化剂含有基于催化剂总重量为0.1～10％(重量)，优选0.1～5％(重量)，尤其优选0.2～1％(重量)的钯。
此外，该催化剂还可以含有基于催化剂总重量为0.1～10％(重量)，优选0.1～5％(重量)，尤其优选0.2～1％(重量)的选自元素周期表的IB族和VIII族、铈和镧的至少一种附加金属。可以使用其他一种金属或其他许多金属的混合物。优先选择铜、铂和它们的混合物，尤其优选铂。尤其优先选择含有基于催化剂总重量为0.2～1％(重量)钯和0.2～1％(重量)铂，特别是0.3～0.5％(重量)钯和0.3～0.5％(重量)铂的催化剂。
尤其优先选择在载体ZrO2上含有基于催化剂总重量为约0.4％(重量)钯和约0.4％(重量)铂的催化剂。
该催化剂优选含有Pd和Pt作为仅有的活性成分。该催化剂尤其优选由载体上的Pd和Pt构成。此处Pd和Pt优选以近似等重量或精确等重量的量存在。
众所周知，可以用合适的载体作为载体。例如，载体选自活性碳、碳化硅和金属氧化物。优选金属氧化物是氧化铝、二氧化硅、二氧化钛、二氧化锆、氧化锌、氧化镁或它们的混合物，它们可非必需地掺杂碱金属氧化物和/或碱土金属氧化物。尤其优先选择γ-氧化铝、二氧化硅、二氧化锆或氧化钛或它们的混合物，尤其是ZrO2。所用载体可具有任何形状；例如它们可以呈挤出物、丸状或片状使用。该催化剂可通过通常公知的方法制备，如通过用所用金属化合物的溶液浸溃载体来制备。例如可通过用PdCl2或Pd(NO3)2溶液浸溃载体来施加钯。
例如载体可用金属前体涂覆。合适的金属前体是诸如硝酸盐、亚硝酰硝酸盐、卤化物、碳酸盐、羧酸盐、乙酰乙酸盐、氯代络合物、亚硝酸络合物和胺络合物的金属盐。优先选择硝酸盐、氯化物、氯代络合物和胺络合物。优选通过共沉淀或共同浸渍进行施加。金属前体可同时施加或顺续施加。活性成分的施加顺序可自由选择。
制备本发明所用催化剂的其他制备方法是本领域普通技术人员公知的，包括气相沉积、溅射和共沉淀。
催化剂的表面积、孔容积和孔尺寸分布在宽范围内要求不是很严格。
本发明的方法在50～200℃、优选90～170℃、尤其优选120～160℃温度，5～300bar、优选50～250bar、尤其优选70～210bar压力下，在诸如高压釜的加压装置或优选在管式反应器中分批或优选连续进行。压力优选是反应器中氢的压力。当使用管式反应器时，采用的催化剂也可以作为固定床催化剂存在。
反应优选以上升流或下降流模式，尤其优选是以上升流模式在液相下进行。具体的，优先选择不使用氨进行反应。
基于所用的腈，通过催化剂的空速优选为0.1～2kg/(l·h)，尤其是约0.1kg/(l·h)。从反应器排出的部分液体可回流到反应中。反应优选在反应器排出液体回流量为1～20kg/(lcat·h)，尤其是5～10kg/(lcat·h)下进行。
本发明的方法可不在溶剂中或在诸如水、甲醇、乙醇、四氢呋喃、甲基叔丁基醚或N-甲基吡咯烷酮的溶剂中进行。通式(III)的腈可溶解在溶剂中。溶剂也可以在任何点单独送入反应器中。优先选择不在溶剂中进行反应。
本发明方法中获得的通式(I)和(II)的胺可从反应混合物中分离出，并以公知的方式如通过蒸馏进行提纯。
例如可能通过精馏得到含有纯仲胺的气流和含有伯胺的气流，含有伯胺的气流回到合成中。
根据本发明，通式(I)的伯胺和通式(II)的仲胺优选以10∶1～1∶10，更优选2～4∶5的重量比形成。形成叔胺的量优选很少；尤其优选不形成叔胺。形成叔胺的量以反应器的产出(没有溶剂)计优选低于15％(重量)，尤其优选低于10％(重量)。
在本发明方法中，用通式(III)的腈进行反应。
X-CH (III)
其中X是未取代或被C1-20-烷基、C3-8-环烷基、C4-20-烷基环烷基、C4-20-环烷基烷基、C2-20-烷氧基烷基、C6-14-芳基、C7-20-烷芳基、C7-20-芳烷基、C1-20-烷氧基、羟基、C1-20-羟烷基、氨基、C1-20-烷氨基、C2-20-二烷氨基、C2-12-链烯基氨基、C3-8-环烷氨基、芳氨基、二芳氨基、芳基-C1-8-烷氨基、卤素、巯基、C2-20-链烯氧基、C3-8-环烷氧基、芳氧基和/或C2-8-烷氧基羰基取代的C1-20-烷基、C2-20-链烯基或C3-8-环烷基。
X优选是支链或非支链、优选非支链的C1-12-烷基，尤其优选C1-8-烷基，尤其是C1-6-烷基，特别是C1-4-烷基。实例是由1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20亚甲基单元构成的，以C(C)-C-C、C-C(C)-C、C-C(C)2-C作为结构单元的非支链基团。优选结构单元是C、C-C、C-C-C、C-C-C-C、C-C-C-C-C-C、C-C(C)-C-C、C-C(C)-C-C、C-C-C(CN)-C-C-C，尤其优选是C、C-C、C-C-C、C-C-C-C。
如上指出的，X可以被取代。此时，取代基的数量可达到X中可替换的氢原子的数量。不管基团的类型如何，可存在1～5个，优选1～3个，尤其是0、1或2个取代基。可能的取代基是：
-C1-20-烷氧基，优选C1-8-烷氧基如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、异戊氧基、仲戊氧基、新戊氧基、1，2-二甲基丙氧基、正己氧基、异己氧基、仲己氧基、正庚氧基、异庚氧基、正辛氧基、异辛氧基，尤其优选C1-4-烷氧基如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基和叔丁氧基，
-羟基，
-C1-20-羟烷基，优选C1-8-羟烷基，尤其优选C1-4-羟烷基如羟甲基、1-羟乙基、2-羟乙基、2-羟基-2-丙基和3-羟基正丙基，
-氨基，
-C1-20-烷氨基，优选C1-8-烷氨基，尤其优选C1-4-烷氨基如甲氨基，或对应的氨烷基，1-氨乙基、2-氨乙基、2-氨基正丙基和3-氨基正丙基，
-C2-20-二烷氨基，优选C2-12-二烷氨基，尤其优选C2-8-二烷氨基如N，N-二甲氨氐、N，N-二乙氨基、N，N-二丙氨基、N，N-二(1-甲基乙基)氨基、N，N-二丁氨基、N，N-二(1-甲基丙基)氨基、N，N-二(2-甲基丙基)氨基、N，N-二(1，1-二甲基乙基)氨基、N-乙基-N-甲氨基、N-甲基-N-丙氨基、N-甲基-N-(1-甲基乙基)氨基、N-丁基-N-甲氨基、N-甲基-N-(1-甲基丙基)氨基、N-甲基-N-(2-甲基丙基)氨基、N-(1，1-二甲基乙基)-N-甲氨基、N-乙基-N-丙氨基、N-乙基-N-(1-甲基乙基)氨基、N-丁基-N-乙氨基、N-乙基-N-(1-甲基丙基)氨基、N-乙基-N-(2-甲基丙基)氨基、N-乙基-N-(1，1-二甲基乙基)氨基、N-(1-甲基乙基)-N-丙氨基、N-丁基-N-丙氨基、N-(1-甲基丙基)-N-丙氨基、N-(1-甲基丙基)-N-丙氨基、N-(2-甲基丙基)-N-丙氨基、N-(1，1-二甲基乙基)-N-丙氨基、N-丁基-N-(1-甲基乙基)氨基、N-(1-甲基乙基)-N-(1-甲基丙基)氨基、N-(1-甲基乙基)-N-(1-甲基丙基)氨基、N-(1-甲基乙基)-N-(2-甲基丙基)氨基、N-(1，1-二甲基乙基)-N-(1-甲基乙基)氨基、N-丁基-N-(1-甲基丙基)氨基、N-丁基-N-(2-甲基丙基)氨基、N-丁基-N-(1，1-二甲基乙基)氨基、N-(1-甲基丙基)-N-(2-甲基丙基)氨基、N-(1，1-二甲基乙基)-N-(1-甲基丙基)氨基和N-(1，1-二甲基乙基)-N-(2-甲基丙基)氨基，
-C3-12-氮杂环烷基，优选C3-8-氮杂环烷氨基，尤其优选C5-8-氮杂环烷基如吡咯烷、哌啶、氮杂(azepane)、哌嗪、N-烷基哌嗪和吗啉，
-C3-8-环烷氨基如环丙氨基、环丁氨基、环戊氨基、环己氨基、环庚氨基和环辛氨基，优选环戊氨基、环己氨基和环辛氨基，尤其优选环戊氨基和环己氨基，
-C3-8-二环烷氨基，
-芳氨基如苯氨基、1-萘氨基和2-萘氨基，优选苯氨基，
-芳基-C1-8-烷氨基，优选苯基-C1-8-烷氨基，尤其优选苯基-C1-4-烷氨基如苯基甲氨基和苯基乙氨表，
-卤素，优选氟、氯和溴，尤其优选氟和氯。
-巯基，
-C2-20-氧杂环烷基，优选C2-8-氧杂环烷基，尤其优选C2-8-氧杂环烷基如2-四氢呋喃基、3-四氢呋喃基、2-呋喃基和3-呋喃基，
-C3-8-环烷氧基如环丙氧基、环丁氧基、环戊氧基、环己氧基、环庚氧基和环辛氧基，优选环戊氧基和环己氧基，尤其优选环戊氧基和环己氧基，
-芳氧基如苯氧基、1-萘氧基和2-萘氧基，优选苯氧基。
优选存在0、1或2OH或C2-12-二烷氨基，优选C2-8-二烷氨基，尤其是C2-4-二烷氨基取代基。尤其是取代基是二甲氨基或OH。
优选通式(III)的腈是乙腈、丙腈、异丙腈、丁腈、戊腈、戊烯腈、惹烯腈、3-羟基丙腈、3-甲氧基丙腈、3-乙氧基丙腈、3-丙氧基丙腈、3-异丙氧基丙腈、3-环己氧基丙腈、2-甲基-3-羟基丙腈、3-甲氧基-2-甲基丙腈、3-乙氧基-2-甲基丙腈、2-甲基-3-丙氧基丙腈、3-异丙氧基-2-甲基丙腈、3-环己氧基-2-甲基丙腈、3-甲基-3-羟基丙腈、3-甲氧基-3-甲基丙腈、3-乙氧基-3-甲基丙腈、3-甲基-3-丙氧基丙腈、3-异丙氧基-3-甲基丙腈、3-环己氧基-3-甲基丙腈、3-氨基丙腈、3-甲基氨基丙腈、3-二甲基氨基丙腈、3-乙基氨基丙腈、3-二乙基氨基丙腈、3-丙基氨基丙腈、3-二丙基氨基丙腈、3-异丙基氨基丙腈、3-二异丙基氨基丙腈、3-环己基氨基丙腈、3-二环己基氨基丙腈、N-(氰乙基)-N-甲基苯胺。尤其优先选择3-羟基丙腈、3-甲氧基丙腈、3-二甲基氨基丙腈、3-二乙基氨基丙腈、3-环己基氨基丙腈和3-甲基氨基丙腈，尤其是双氰乙基醚、双氰乙基胺、N-甲基双氰乙基胺、N-乙基双氰乙基胺、N-正丙基双氰乙基胺、聚异丁烯腈、N-聚异丁烯氨基丙腈、三氰乙基胺、5-氨基戊腈、5-甲基氨基戊腈、5-二甲基氨基戊腈、6-氨基己腈、6-甲基氨基己腈、6-二甲基氨基己腈、5-氨基-4-甲基戊腈、5-甲氨基-4-甲基戊腈、5-二乙氨基-4-甲基戊腈、5-乙氨基-4-甲基戊腈、5-二乙氨基-4-甲基戊腈、5-氨基-2-甲基戊腈、5-甲氨基-2-甲基戊腈、5-二甲氨基-2-戊腈、5-乙氨基-2-甲基戊腈、5-二乙氨基-2-甲基戊腈、4-氰基辛二腈、丙烯腈。
尤其优先选择己二腈、3-二甲基氨基丙腈(DMAPN)和3-羟基丙腈，特别是DMAPN。
胺混合物，尤其是DMAPN和双-DMAPN是环氧树脂的硬化剂、聚氨酯的催化剂、制备季铵化合物的中间产品、增塑剂、缓蚀剂、纺织助剂、染料和乳化剂。多功能化叔胺也用于制备合成树脂、离子交换剂、药物、谷物保护剂和杀虫剂。
本发明通过以下实施例描述。
实施例
向内径30mm、总长2.0m并在中心装有12mm直径热偶的电热管式反应器中装入570g(＝500ml)催化剂和450ml不锈钢填充物的混合物。催化剂在作为载体材料的二氧化锆上含有0.4％(重量)Pt和0.4％(重量)Pd，呈直径7mm、厚3mm、孔直径3mm的环状形式。
反应前，将催化剂在大气压160℃下，用纯氢气还原12小时。
将500g/h 3-(二甲基氨基)丙腈(DMAPN)、4.0kg/h自反应器的排出液体和0.38标准m3/h氢气从反应器底部向上顺流穿过反应器。将起始原料在反应器上游加热到140℃。反应器保持140℃和80bar总压。
离开反应器的混合物被冷却，部分液体再回到反应器入口，将剩余物降压到大气压。用气相色谱分析发现50％(重量)双(3-二甲基氨基丙基)胺(双-DMAPA)、30％(重量)3-二甲基氨基丙基胺(DMAPA)、3.0％(重量)DMAPN和17％(重量)从反应器排出的各种副产品。DMAPN的转化率为97％。
在最高压力30mbar(abs.)、回流比5∶1下，用含有随意堆放的(20个理论塔板)柱的实验室蒸馏装置连续分批蒸馏2300g反应器的排出液体。得到包括90.0％(重量)DMAPA、5.5％(重量)DMAPN和4.5％(重量)副产品的730g第一馏分(45℃得到)，以及包括99.3％(重量)双-DMAPA的960g第二馏分(125℃得到)。
Claims (9)
1、一种制备通式(I)的伯胺和通式(II)的仲胺的混合物的方法，
X-CH2-NH2 (I)
(X-CH2-)2NH (II)
其中X是未取代或被C1-20-烷基、C3-8-环烷基、C4-20-烷基环烷基、C4-20-环烷基烷基、C2-20-烷氧基烷基、C6-14-芳基、C7-20-烷芳基、C7-20-芳烷基、C1-20-烷氧基、羟基、C1-20-羟烷基、氨基、C1-20-烷氨基、C2-20-二烷氨基、C2-12-链烯基氨基、C3-8-环烷氨基、芳氨基、二芳氨基、芳基-C1-8-烷氨基、卤素、巯基、C2-20-链烯氧基、C3-8-环烷氧基、芳氧基和/或C2-8-烷氧基羰基取代的C1-20-烷基、C2-20-链烯基或C3-8-环烷基，
通过在载体上含有基于催化剂总重量为0.1～10％(重量)Pd的含Pd催化剂存在下，在50～250℃温度和5～350bar压力下，将通式(II)的腈
X-CN (III)
与氢反应制得。
2、权利要求1的方法，其中催化剂还含有0.1～10％(重量)选自元素周期表的IB族和VIII族、铈和镧的至少一种附加金属。
3、权利要求2的方法，其中催化剂含有0.2～1％(重量)的Pd和0.2～1％(重量)的Pt。
4、权利要求1的方法，其中载体选自活性碳、碳化硅和金属氧化物。
5、权利要求4的方法，其中载体是ZrO2。
6、权利要求1到5的任何一个的方法，其中X是至多带有2个取代基的直链C1-6-烷基。
7、权利要求6的方法，其中取代基是C2-12-二烷氨基或OH。
8、权利要求7的方法，其中通式(III)的腈是转化为双(3-二甲基氨基)丙基)胺和3-(二甲基氨基)丙基胺的混合物的3-(二甲基氨基)丙腈。
9、权利要求1到5的任何一个的方法，其中通式(I)的伯胺和通式(II)的仲胺以10∶1～1∶10的重量比形成。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10100313A DE10100313A1 (de) | 2001-01-05 | 2001-01-05 | Verfahren zur Herstellung von primären und sekundären Aminen aus Nitrilen |
| DE10100313.7 | 2001-01-05 |
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| Publication Number | Publication Date |
|---|---|
| CN1365965A CN1365965A (zh) | 2002-08-28 |
| CN1230417C true CN1230417C (zh) | 2005-12-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB02104788XA Expired - Fee Related CN1230417C (zh) | 2001-01-05 | 2002-01-04 | 从腈制备伯胺和仲胺的方法 |
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| Country | Link |
|---|---|
| US (1) | US6790995B2 (zh) |
| EP (1) | EP1221437B1 (zh) |
| JP (1) | JP3836374B2 (zh) |
| CN (1) | CN1230417C (zh) |
| AT (1) | ATE299133T1 (zh) |
| DE (2) | DE10100313A1 (zh) |
| ES (1) | ES2243600T3 (zh) |
| HU (1) | HUP0200036A2 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE602006004279D1 (de) | 2005-09-09 | 2009-01-29 | Mitsubishi Gas Chemical Co | Verfahren zur Herstellung von Aminoverbindungen mit einem aromatischen Ring unter Verwendung eines Schalenkatalysators |
| US8063239B2 (en) * | 2006-05-09 | 2011-11-22 | Basf Se | Process for preparing aminoalkylnitriles and diamines from such nitriles |
| EP2688861B1 (de) * | 2011-03-22 | 2016-08-17 | Basf Se | Verfahren zur hydrierung von nitrilen |
| US20150152043A1 (en) * | 2012-06-05 | 2015-06-04 | Stefan J. Pastine | Synthesis of and compositions containing diaminoacetals and diaminoketals |
| CN106866431B (zh) * | 2017-02-22 | 2018-07-10 | 浙江新化化工股份有限公司 | 一种n-(2-甲氧基环己基)-1,3-丙二胺的生产方法 |
| US10919839B2 (en) | 2017-07-11 | 2021-02-16 | Aditya Birla Chemicals (Usa) Llc | Silicon-containing compositions and their methods of use |
| CN110790669B (zh) * | 2019-11-15 | 2021-10-15 | 中国科学院金属研究所 | 纳米碳负载单原子钯基催化剂在腈类化合物催化加氢制备仲胺中的应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3739260A1 (de) * | 1987-11-18 | 1989-06-01 | Bayer Ag | Verfahren zur herstellung von n,n-dimethyldiaminopropan |
| DE3935641A1 (de) | 1989-10-26 | 1991-05-02 | Bayer Ag | Verfahren zur herstellung von bis- und tris-(3-dimethylaminopropyl)-amin |
| DE19713383A1 (de) | 1997-04-01 | 1998-10-08 | Basf Ag | Verfahren zur Herstellung tertiärer Amine aus Nitrilen und sekundären Aminen |
| KR100447695B1 (ko) * | 1997-08-08 | 2004-09-08 | 더 프록터 앤드 갬블 캄파니 | 개질된 알킬아릴의 제조방법 |
| US5869653A (en) * | 1997-10-30 | 1999-02-09 | Air Products And Chemicals, Inc. | Hydrogenation of nitriles to produce amines |
| DE19756947A1 (de) | 1997-12-22 | 1999-06-24 | Basf Ag | Verfahren zur Herstellung sekundärer Amine aus Nitrilen und primären Aminen |
-
2001
- 2001-01-05 DE DE10100313A patent/DE10100313A1/de not_active Withdrawn
-
2002
- 2002-01-03 US US10/033,912 patent/US6790995B2/en not_active Expired - Fee Related
- 2002-01-04 EP EP02000129A patent/EP1221437B1/de not_active Expired - Lifetime
- 2002-01-04 AT AT02000129T patent/ATE299133T1/de not_active IP Right Cessation
- 2002-01-04 ES ES02000129T patent/ES2243600T3/es not_active Expired - Lifetime
- 2002-01-04 HU HU0200036A patent/HUP0200036A2/hu unknown
- 2002-01-04 DE DE50203537T patent/DE50203537D1/de not_active Expired - Fee Related
- 2002-01-04 CN CNB02104788XA patent/CN1230417C/zh not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| ATE299133T1 (de) | 2005-07-15 |
| JP2002226440A (ja) | 2002-08-14 |
| EP1221437A1 (de) | 2002-07-10 |
| HUP0200036A2 (hu) | 2002-12-28 |
| CN1365965A (zh) | 2002-08-28 |
| EP1221437B1 (de) | 2005-07-06 |
| JP3836374B2 (ja) | 2006-10-25 |
| US20020091194A1 (en) | 2002-07-11 |
| DE50203537D1 (de) | 2005-08-11 |
| ES2243600T3 (es) | 2005-12-01 |
| HU0200036D0 (en) | 2002-03-28 |
| US6790995B2 (en) | 2004-09-14 |
| DE10100313A1 (de) | 2002-07-11 |
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