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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650875/
• 关键词: Supported reagent; One-pot synthesis; 2-Aminothiazole; Potassium thiocyanate; silica gel; alumina; sulfide; thiol; アミン; ハロケトン; アルミナ担持臭化銅; β-カルボニル化合物; アルミナ担持水酸化ナトリウム; アルミナ担持酢酸アンモニウム; シリカゲル担持チオシアン酸カリウム

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.

我们研究了使用无机负载试剂的一锅两步反应，假设在均质溶液中相互反应的两种试剂通过负载到单独的无机载体上而相互失活。两步合成应该是可能的。其中可溶性试剂(A)首先与一种负载试剂(Y)反应，产物(B)与第二种负载试剂(X)反应，得到所需的最终产物(C)，通常为2-氨基噻唑。通过 α-卤代酮与单取代硫脲的缩合或通过 α-氰硫基羰基化合物与芳香族或脂肪族胺盐酸盐的反应来制备。我们开发了一种简便的方法，可以轻松地一锅制备 2-氨基噻唑。使用支持的试剂系统KSCN/SiO_2-RNH_3AcO/Al_2O_3可得到α-卤代酮。酮首先与 KSCN/SiO_2 反应，生成 α-硫氰酸酯，后者转移到 RNH_3AcO/Al_2O_3 并与其反应，得到最终产物 2-氨基噻唑 我们还开发了 α-烷硫基-β-二酮的一锅法合成。使用支持的试剂系统测定 β-二酮和硫醇CuBr_2/Al_2O_3-NaOH/Al_2O_3与CuBr_2/Al_2O_3反应生成α-溴-β-二酮，然后溴化物在碱NaOH/Al_2O_3存在下与硫醇反应得到最终产物α-烷硫基。 -β-二酮。

项目成果

Y.Suzuki,M.Kodomari: "One-Pot Synthesis Using Supported Reagents System"Chemistry Letters. 1091-1092 (1998)

Y.Suzuki，M.Kodomari：“使用支持的试剂系统进行一锅合成”化学快报。