Multi-stage Reactions in One-pot using Inorganic Supported Reagents

使用无机支持试剂的一锅多级反应

基本信息

批准号：
11650875
负责人：
KODOMARI Mitsuo
金额：
$ 1.86万
依托单位：
Shibaura Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

We have investigated two-stage reactions in one-pot using inorganic supported reagents on the assumption that two reagents reacting each other in homogenous solution are rendered mutually inactive by supporting them onto separate inorganic supports. It should be possible that two-step synthesis, in which a soluble reagent (A) react first with one supported reagent (Y) and the product (B) with the second supported reagent (X) to give the desired final product (C). Typically, 2-aminothiazoles are prepared either by the condensation of α-halo ketones with monosubstituted thioureas or by the reaction of α-thiocyanato carbonyl compounds with aromatic or aliphatic amine hydrochlorides. We have developed a convenient method for the preparation of 2-aminothiazoles in one-pot from readily available α-halo ketones using supported reagents system KSCN/SiO_2-RNH_3AcO/Al_2O_3. α-Halo ketones react first with KSCN/SiO_2 affording α-thiocyanates, the latter moving to RNH_3AcO/Al_2O_3 and reactins with it to give the end product 2-aminothiazoles. We have also developed one-pot synthesis of α-alkylthio-β-diketones from-β-diketones and thiols using supported reagents system CuBr_2/Al_2O_3-NaOH/Al_2O_3. β-Diketones react with CuBr_2/Al_2O_3 to give α-bromo-β-diketones, and then the bromides react with thiols in the presence of the base NaOH/Al_2O_3 to afford the end product α-alkylthio-β-diketones.

我们已经使用无机载体试剂研究了一盘中的两阶段反应，假设两种试剂在同质溶液中相互反应的方法是通过将它们支撑在单独的无机支撑物上，从而使它们相互无效。应有两步合成，其中固体试剂（a）首先与一种支持的试剂（y）和产品（b）与第二个支持的试剂（x）反应，以提供所需的最终产物（c）。通常，通过与单碱成立的thioureAs或α-硫代氨基氨基氨基羰基化合物与芳族或脂肪胺或脂肪族胺盐酸盐的反应来制备2-氨基硫唑。我们已经开发了一种方便的方法，可以使用支持的试剂系统KSCN/SIO_2-RNH_3ACO/AL_2O_3在一锅中从一锅中制备2-氨基硫唑。 α-HALO酮首先与KSCN/SIO_2反应，后者提供α-硫氰酸酯，后者转移到RNH_3ACO/AL_2O_3，并与IT反应蛋白使最终产物2-氨基硫唑。我们还使用支持的试剂系统CUBR_2/AL_2O_3-NAOH/AL_2O_3开发了从-β-二酮和硫醇的α-烷基硫硫代二酮和硫醇的一锅合成。 β-二酮与Cubr_2/al_2o_3反应以产生α-Bromo-β-二酮，然后在基础NaOH/Al_2O_3的情况下，Bromides与硫醇反应，以提供最终产物α-烷基基噻思甲酮。