One-Pot Synthesis of Secondary and Tertiary Amines by Carbonylative Hydroaminomethylation of Alkenes Catalyzed by Di(μ-chloro)bis(η4-1,5-cyclooctadiene)dirhodium
作者:Thorsten Rische、Peter Eilbracht
DOI:10.1055/s-1997-1338
日期:1997.11
Secondary and tertiary amines are selectively prepared with high yields by the reaction of alkenes with primary or secondary amines, carbon monoxide and hydrogen in the presence of [Rh(cod)Cl]2 as catalyst via a one-pot hydroformylation - amine condensation - reduction sequence.
N-alkylation of amines by using secondary amides as the alkyl source was developed. A versatile type of carboxamide functioned as an N-alkylation reagent in the presence of an indium(III) catalyst and a hydrosilane to provide alkylated tertiary aminesefficiently. This amide-based catalytic N-alkylation strategy is considered to be a highly useful protocol to access unsymmetrical tertiary amines.
An iron(0)-catalysed cascade synthesis of N-alkylated anilines from allylic or homoallylic alcohols and primary and secondary anilines under hydrosilylation conditions has been developed. Notably, a simple Fe(cod)(CO)3 complex (cod = cycloocta-1,5-diene) was used as a precatalyst under visible light activation in ethanol in the presence of the inexpensive and non-toxic PMHS (polymethylhydrosiloxane) as the hydrosilane source. This methodology is based on a three step-one sequence process involving isomerisation of allylic alcohols/condensation with anilines/reduction reactions.
GROUP-15 CATIONIC COMPOUNDS FOR OLEFIN POLYMERIZATION CATALYSTS
申请人:——
公开号:US20020111265A1
公开(公告)日:2002-08-15
This description addresses fluorinated amine compounds meeting the general formula R′
i
ArF-ER
2
, where ArF is a fluoroaryl group, E is nitrogen or phosphorous, each R is independently a C
1
-C
20
hydrocarbyl group, or the two Rs may connect to form an unsubstituted or substituted C
2
-C
20
cycloaliphatic group, R′ is a C
1
-C
20
hydrocarbyl or halogenated hydrocarbyl, and i is 0, 1 or 2. These compounds may be protonated with strong Bronsted acids to form protonated amine compounds that are useful for the preparation of organometallic catalyst-cocatalyst compounds comprising noncoordinating or weakly coordinating anions. The resulting organometallic catalyst-cocatalyst complexes can be effectively used as olefin polymerization catalysts. High number-average molecular weight polymers at high rates of productivity were observed from the use of metallocene catalyst complexes prepared with [N-pentafluorophenyl pyrrolidinium][tetrakis(pentafluorophenyl)borate] of [N-pentafluorophenyl pyrrolidinium][chloride].
本说明涉及符合通式 R′ 的氟化胺化合物
i
ArF-ER
2
其中 ArF 是氟芳基,E 是氮或磷,每个 R 独立地是 C
1
-C
20
烃基,或两个 R 可连接形成未取代或取代的 C
2
-C
20
环脂族基团,R′是一个 C
1
-C
20
烃基或卤代烃基,i 为 0、1 或 2。这些化合物可以用强勃朗斯特酸质子化,形成质子化胺化合物,用于制备包含非配位或弱配位阴离子的有机金属催化剂-催化剂化合物。由此得到的有机金属催化剂-催化剂复合物可有效地用作烯烃聚合催化剂。使用 [N-pentafluorophenyl pyrrolidinium][tetrakis(pentafluorophenyl)borate] of [N-pentafluorophenyl pyrrolidinium][chloride] 制备的茂金属催化剂络合物,可以观察到生产率高的高平均分子量聚合物。
Olefin polymerization catalysts derived from Group-15 cationic compounds and processes using them
申请人:——
公开号:US20020115806A1
公开(公告)日:2002-08-22
Fluorinated amine compounds, R′
i
ArF-ER
2
, where ArF is a fluoroaryl substituent, E is nitrogen or phosphorous, each R is independently a C
1
-C
20
hydrocarbyl substituent, or the two R's may be connected to form an unsubstituted or substituted C
2
-C
20
cycloaliphatic substituent, R′ is a C
1
-C
20
hydrocarbyl or halogenated hydrocarbyl, and i is 0, 1 or 2 are disclosed. These compounds may be protonated and complexed with suitable substantially noncoordinating anions to prepare polymerization catalyst components. When these catalyst components are combined with organometallic catalyst precursors, the catalyst precursor is activated to a catalyst. This catalyst is combined with monomer under olefin polymerization conditions to prepare polymer. High number-average molecular weight polymers at high productivity rates were observed from using metallocene catalysts activated with [N-pentafluorophenyl pyrrolidinium][tetrakis(pentafluorophenyl)borate].
氟化胺化合物,R′ i
i
ArF-ER
2
其中 ArF 是氟芳基取代基,E 是氮或磷,每个 R 独立地是 C
1
-C
20
烃基取代基,或者两个 R 可以连接形成未取代或取代的 C
2
-C
20
环脂族取代基,R′是 C
1
-C
20
烃基或卤代烃基,i 为 0、1 或 2。这些化合物可以质子化并与合适的基本上不配位的阴离子络合,制备聚合催化剂组分。当这些催化剂组分与有机金属催化剂前体结合时,催化剂前体被活化成催化剂。催化剂在烯烃聚合条件下与单体结合,制备聚合物。使用经 N-五氟苯基吡咯烷硼酸酯和四(五氟苯基)硼酸酯活化的茂金属催化剂,可以观察到生产率高、平均分子量高的聚合物。