An efficient homogeneous gold(I) catalyst for N-alkylation of amines with alcohols by hydrogen autotransfer

A new and highly efficient homogeneous [Ph₃PAuCl]/AgOTf catalytic system was developed in N-alkylation reaction of primary amines with alcohols through a hydrogen autotransfer process. This Au(I) catalytic system shows excellent selectivity for mono-alkylation of primary amines with benzyl alcohol under moderate temperature of 100 °C (only secondary amines as product). The possible mechanism of this hydrogen autotransfer reaction with the catalytic system was proposed.     

抗过敏药物盐酸松齐拉敏的合成

以2-氨基嘧啶、对甲氧基氯苄和N,N-二甲基-2-氯乙胺为原料,经两步N-烃基化反应合成了抗过敏药物盐酸松齐拉敏,总收率75.1%,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)确证。     

二(N-十二烷基-N,N-二羧甲基铵基)-联苯二苄的合成

在氯乙酸钠存在下,二(N-十二烷基)-联苄胺经N-烷基化反应合成了新型双子表面活性剂——二(N-十二烷基-N,N-二羧甲基铵基)-联苯二苄(1)。1的结构经IR确证。     

Efficient synthesis of tertiary amine by direct N-alkylation of secondary amine with carboxylic acid using Ni (0) encat catalyst

In this article, direct N-alkylation of secondary amines with carboxylic acid is described. Readily available diversified carboxylic acid has been explored on variant secondary amines using encapsulated Nickel as catalyst and inexpensive sodium borohydride as the hydride source. High yields, mild reaction conditions, tolerance to sensitive functional group and facile operational procedure are the significance of the present methodology.     

2种吲哚衍生物的N-烷基化产物的制备

吲哚-3-乙醛酸甲酯和3-吲哚乙腈在碱存在下,以烷基卤或硫酸烷基酯为亲电试剂进行N-烷基化反应,合成了6种新的N-烷基化吲哚化合物。 研究了吲哚化合物及烷基化试剂的结构、溶剂和碱对N-烷基化反应的影响。 具有强吸电子取代基的吲哚-3-乙醛酸甲酯使用弱碱Cs2CO3在室温就可顺利进行烷基化反应,产率达到93%;而具有较弱吸电子取代基的3-吲哚乙腈,需要使用强碱NaH才能进行烷基化反应。     

N-十六烷基聚己内酰胺的红外光谱研究

以聚己内酰胺(PA6)和1-溴正十六烷为原料,利用N-烷基化方法制备了具有不同烷基取代度的N-十六烷基聚己内酰胺(PA6C16)。采用DSC和FTIR方法研究了具有不同烷基取代度的PA6C16的热转变行为。DSC结果表明N-十六烷基聚己内酰胺的十六烷基侧链可以结晶,且低取代度的N-十六烷基聚己内酰胺(PA6C16-L)侧链结晶的熔点高于高取代度的N-十六烷基聚己内酰胺(PA6C16-H)。红外光谱结果表明,PA6C16-L侧链的亚甲基呈正交晶堆积,而PA6C16-H的侧链亚甲基则呈六方晶堆积。变温红外光谱结果显示,伴随着侧链结晶的熔融,PA6C16-H的主链构象发生明显改变,而PA6C16-L主链的构象则未显示出明显改变。     

Selective Iron Catalyzed Synthesis of N-Alkylated Indolines and Indoles

Whereas iron catalysts usually promote catalyzed C3-alkylation of indole derivatives via a borrowing-hydrogen methodology using alcohols as the electrophilic partners, this contribution shows how to switch the selectivity towards N-alkylation. Thus, starting from indoline derivatives, N-alkylation was efficiently performed using a tricarbonyl(cyclopentadienone) iron complex as the catalyst in trifluoroethanol in the presence of alcohols leading to the corresponding N-alkylated indoline derivatives in 31–99 % yields (28 examples). The one-pot, two-step strategy for the selective N-alkylation of indolines is completed by an oxidation to give the corresponding N-alkylated indoles in 31–90 % yields (15 examples). This unprecedented oxidation methodology involves an iron salt catalyst associated with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and a stoichiometric amount of t-BuOOH at room temperature.     

Cyclometalated palladium pre-catalyst for N-alkylation of amines using alcohols and regioselective alkylation of sulfanilamide using aryl alcohols

Simple pyrazole based palladacycle-phosphine with a high turnover has been developed and applied for the N-alkylation of amines and sulfanilamide using alcohols as substrates by hydrogen borrowing strategy. N-alkylation of primary and secondary amines resulted in high isolated yields at 100–130 °C, under solvent free conditions. More challenging secondary aliphatic as well as aromatic alcohols were also successfully utilized as alkylating agents under similar reaction conditions. The turn over number reached up to 43000 for N-benzylation of aniline using benzyl alcohol. Notably, regioselective N-alkylation of 2-aminobenzothiazole and 4-aminobenzenesulfonamide to the corresponding 2-N-(alkylamino)azoles and 4-amino-(N-alkyl)benzenesulfonamides using alcohols as alkylating agents have been achieved using our new pre-catalyst-phosphine system.     

相转移催化2－甲基吲哚的N－烷基化反应

考察了不同相转移催化剂、反应时间、反应温度、氢氧化钾浓度、溴乙烷用量诸因素对２－甲基吲哚进行Ｎ－烷基化反应的影响。研究了催化剂浓度和结构与该反应速度的定量关系。     

氮杂环卡宾的合成及在氢转移反应中的应用

利用氯甲基吡啶与咪唑反应制备了一系列含吡啶取代咪唑L1～L5,考察了所得咪唑衍生物与钌化合物在碱性条件下原位形成的氮杂卡宾钌络合物对苯胺与醇氢转移反应的催化活性.研究了碱的种类、钌前体、温度等对反应的影响,结果表明RuCl3 H2O/1-(2-吡啶甲基)-3-甲基碘化咪唑(L3)/KOH催化体系在185℃时对苯胺与乙二醇反应的催化活性较高,选择性生成N-羟乙基苯胺,TON(单位活性转化的底物分数)可达2130.此外,还考察了RuCl3 H2O/L3/KOH催化体系对苯胺与丁醇、环己醇、异丙醇、苯甲醇反应的催化性能.在催化剂作用下,醇与苯胺可形成亚胺及仲胺,伯醇可以自氢转移反应形成酯,反应产物的结构及选择性取决于醇的结构及反应条件.