Catalytic dehydrogenation of aliphatic amines to nitriles, imines, or vinylamines and dealkylation of tertiary aliphatic amines over halide cluster catalysts of group 5 and 6 transition metals
Catalytic dehydrogenation of aliphatic amines to nitriles, imines, or vinylamines and dealkylation of tertiary aliphatic amines over halide cluster catalysts of group 5 and 6 transition metals
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DOI：
10.1016/j.jcat.2004.11.034
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发表时间：
2005-02-15
影响因子：
7.3
通讯作者：
Chihara, T
中科院分区：
文献类型：
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作者：
Kamiguchi, S;Nakamura, A;Chihara, T
卤化钼簇合物（H_3O）（2）[（Mo_6Cl_8）Cl-_6]（.）以八面体金属骨架的6 H（2）O为催化剂，在氢气或氦气气氛下，在气流反应器中进行催化反应。二乙胺在300 ℃以上开始反应，在350 ℃以上选择性地脱氢为N-亚乙基乙胺。二丁胺生成相应的脱氢产物，吡咯烷和哌啶脱氢生成1-吡咯啉和2，3，4，5-四氢吡啶。伯胺脱氢得到相应的腈和缩合产物N-亚烷基烷基胺。将三丙胺和三丁胺脱氢，得到大部分N-乙烯基二烷基胺。相反，三乙胺被脱烷基化为二乙胺。因此，卤化物簇表现出对脂肪族胺的特征催化作用：氮键合的氢被完全去除以产生腈或亚胺，并且当没有这样的氢时，相邻的氢或氮键合的烷基被去除。铌，钽，钨氯化物簇的相同的金属框架也是活性催化剂的脱烷基化和脱氢的二乙胺。(C)2004爱思唯尔公司All rights reserved.
A molybdenum halide cluster, (H3O)(2)[(Mo6Cl8)Cl-6](.)6H(2)O, with an octahedral metal framework was used as a catalyst in a gas-flow reactor under hydrogen or helium. Diethylamine started to react above 300 degreesC, and dehydrogenation to N-ethylideneethylamine proceeded selectively above 350 degreesC. Dibutylamine yielded the corresponding dehydrogenation product, and pyrrolidine and piperidine were dehydrogenated to 1-pyrroline and 2,3,4,5-tetrahydropyridine. Dehydrogenation of primary amines yielded the corresponding nitriles and the condensation product N-alkylidenealkylamine. Tripropylamine and tributylamine were dehydrogenated to yield, for the most part, N-vinyldialkylamines. In contrast, triethylamine was dealkylated to diethylamine. Thus, the halide cluster exhibited a characteristic catalysis for aliphatic amines: nitrogen-bonded hydrogens were removed completely to yield nitrile or imine, and when there was no such hydrogen, a neighboring hydrogen or the nitrogen-bonded alkyl group was removed. Niobium, tantalum, and tungsten chloride clusters of the same metal framework were also active catalysts for dealkylation and dehydrogenation of diethylamine. (C) 2004 Elsevier Inc. All rights reserved.