bronsted酸性离子液体催化合成阿司匹林

以邻苯二胺和环丙基甲酸为原料,以多聚磷酸(PPA)为催化剂,在微波辐射下合成了环丙基苯并咪唑,用碘甲烷季胺化得到未见文献报道的环丙基苯并咪唑盐,通过苯并咪唑盐与Grignard试剂加成后水解反应制备环丙基甲基酮。经元素分析和红外光谱、质谱、核磁共振测试技术表征确证了结构。环丙基甲基酮为无色液体,合成环丙基甲基酮方法的产率为67%,为环丙基甲基酮提供了一种未见文献报道的合成方法。     

Novel Synthetic Method for Triacetylbenzene

Triketones are an important class of compounds in view of the distinct structure feature and wide utility in macromolecular material, organic synthesis and coordination chemistry1. The synthetic method for preparing symmetrical triketones 1, 3, 5- triacetylbenzene reported by Robert et al. is via condensation of acetone with ethyl formate followed by the trimerization of the intermediate acetylacetaldehyde2. We reported the reaction of benzimidazolium salts with Grignard reagents, providing a …     

Novel synthetic method for ketones from substituted benzimidazolium salts and Grignard reagents

A new synthetic method of ketones from substituted benzimidazolium salts and Grignard reagents is reported. The influences of the various Grignard reagents on the yield of ketones and the mechanism are discussed.     

Novel Synthetic Method for Muscone

Muscone is a precious fragrant compound scarce in nature. Many attempts to synthesize this unique natural product have been carried out. In this work, a novel synthetic method for the preparation of muscone from 3‐methyl‐15‐hydroxypentadecanoate is provided. Benzimidazolium salt was used as tetrahydrofolate coenzyme model at formic acid oxidation level and Grignard reagent as nucleophile to which a one‐carbon unit was transferred. The biomimetic synthesis of muscone was successfully accomplished using the addition‐hydrolysis reaction of benzimidazolium salt with the Grignard reagent.     

The Synthesis of Dialdehyde from Sodium Hydrogen Telluride with 1,1'''',3,3''''-Tetramethyl-2,2''''-bis-benzimidazolium Salt

Dialdehydes are important chemical industrial materials. An efficient preparation method of dialdehydes has been interested. We have reported two novel synthetic methods of dialdehyde via the addition-hydrolysis reaction of benzimidazolium salt with bis-Grignard reagent1 and the reduction-hydrolysis reaction of diimidazoline2. Sodium hydrogen telluride has been shown to be a convenient reagent for the reduction of unsaturated nitro-compounds to saturated ones3. The reduction of N-methylpy…     

Novel Synthesis of α‐Diketones from Bisbenzimidazolium Salt and Grignard Reagents

The reaction of bisbenzimidazolium salt with Grignard reagents and a new synthetic method of a‐diketones from bis‐benzimidazolium salt and Grignard reagents are reported. The structures of all a‐diketones are characterized by elemental analyses, infrared spectroscopy and ¹H NMR spectroscopy. The influences of the various Grignard reagents on the yield of a‐diketones and the mechanism are discussed, and a new convenient synthetic method for a‐diketones is provided.     

龙葵醛的新合成方法研究

龙葵醛是一种珍贵的香料 ,也是重要的化工原料 ,广泛应用于香料、医药、染料及农药等行业 .龙葵醛的工业生产以苯乙酮和一氯醋酸乙酯为原料 ,按 Darzens法合成[1,2 ] .苯乙酮与一氯醋酸乙酯在强碱作用下制得甲基苯基环氧丙酸酯 ,该酯经皂化、中和、水解成酸 ,再将该酸加热分解 ,得龙葵醛 .该方法操作比较复杂 ,产率和产品纯度也不高 .为了寻找产率高、纯度好且成本低的新制备方法已有广泛的研究 .Rivero等 [3]提出的 2 -甲基苯乙醇氧化法 ,尽管产率较高 ,但反应温度要在 -78℃ ,不利于工业化生产 .陈万之等[4 ] 利用各种铑螯合物作为催化剂…     

A novel method for the formylation of Grignard reagent

A facile and efficient method for the formylation of Grignard reagent was reported, and a new approach for the preparation of aldehydes from Grignard reagent and benzimida-zolium salts was provided.     

4－十二烷基二亚乙基三胺的合成

４－十二烷基二亚乙基三胺的合成史真，范乃丽，赵莉（西北大学化学系西安７１００６９））（陕西教育学院化学系西安）关键词咪唑啉，十二烷基二亚乙基三胺，合成４－十二烷基二亚乙基三胺作为一种表面活性剂在废水处理、医药卫生等方面有广泛用途，可以从废水中除去痕量...     

A New Synthetic Method for N—Substituted Selenoamides

Benzotriazole,aldehydes and primary selenoamides react together with elimination of water to form 1:1:1 adducts which are reduced smoothly by NaBH4 to give the N-substituted selenoamides in good yield.     

盐酸吡格列酮的合成新方法研究

报道了治疗糖尿病药物盐酸吡格列酮的合成新方法.在六氢吡啶作用下,对羟基苯甲醛和2,4-噻唑烷二酮缩合生成5-[(4-羟苯基)亚甲基]-2,4-噻唑烷二酮,经钯炭催化氢化还原生成5-[(4-羟苯基)甲基]-2,4-噻唑烷二酮,再和氢氧化钾反应生成相应的钾盐,然后与5-乙基-2-羟乙基吡啶和甲基磺酰氯反应得到的磺酸酯作用生成吡格列酮,最后用盐酸酸化得到其盐酸盐.产品结构经1H NMR和IR确证.     

Synthesis of Cyclohexyl and Isopropyl Ketones from Benzimidazole Methiodide Salt and Grignard Reagents

The reaction of 2-alkyl-l, 3-dimethylbenzimidazolinm salts with Grignard reagents gave addition products which were hy-drelyzed to give ketones. A new method for the preparation of cyclohexyl ketones and isopropyl ketones is provided.     

New synthetic method for cycloalkanedione

Ｔｈｅｓｙｎｔｈｅｔｉｃｍｅｔｈｏｄｓｉｎｌｉｔｅｒａｔｕｒｅｆｏｒｐｒｅｐａｒｉｎｇｃｙｃｌｏａｌｋａｎｅｄｉｏｎｅｃｏｍｐｏｕｎｄｓｕｓｅｄａｓｖａｌｕａｂｌｅｐｅｒｆｕｍｅｕｓｕａｌｌｙａｒｅｓｐｅｃｉａｌ,ｔｈｅｓｙｎｔｈｅｓｅｓｏｆｓｏｍｅｃｙｃｌｏａｌｋａｎｅｄｉｏｎｅｃｏｍｐｏｕｎｄｓａｒｅｅｘｔｒｅｍｅｌｙｄｉｆｆｉｃｕｌｔ.1,6ＣｙｃｌｏｄｏｄｅｃａｎｅｄｉｏｎｅｗａｓｐｒｅｐａｒｅｄｐｒｅｖｉｏｕｓｌｙｂｙＦｏｎｋｅｎｅｔａｌ.[1]ｖｉａｍｉｃｒｏｂｉｏｌｏｇｉｃａｌｈｙｄｒｏｘ…     

环己基甲酮类化合物的仿生合成新方法

以2位环己基取代苯并咪唑盐作为甲酸氧化态的四氢叶酸辅酶模型, 与亲核Grignard试剂作用, 将甲酸氧化态的一碳单元转移给亲核试剂, 成功地实现了6类具有潜在应用价值的环己基甲酮的绿色仿生合成, 其结构用元素分析、1H NMR、IR和MS等方法进行了表征, 并对反应机理和反应条件进行了讨论.     

甲基酮香料的仿生合成新方法研究

四氢叶酸辅酶在生物体内的作用是转移不同氧化态的一碳单元, 当一碳单元处于甲酸氧化态时, 活性部位是具有五元环状结构的咪唑啉环. 模拟四氢叶酸辅酶转移一碳单元的反应, 以苯并咪唑甲基碘盐作为四氢叶酸辅酶甲酸氧化态模型, 以格利雅试剂甲基碘化镁作为接收一碳单元的亲核试剂, 将甲酸氧化态的一碳单元转移给甲基碘化镁, 成功合成了三种重要的甲基酮香料甲基己基酮、甲基壬基酮和甲基十一烷基酮, 其结构用元素分析, 1H NMR, IR和MS等方法进行了表征, 并对反应机理和反应条件进行了讨论, 为甲基酮香料提供了一种仿生合成新方法.     

密闭高压法合成桥连金属四苯基卟啉多聚物

采用密闭高压法合成出一系列桥连金属四苯基卟啉多聚物[M(TPP)L]_n[M＝Fe(Ⅲ),Co(Ⅱ),Mn(Ⅱ),Cu(Ⅱ),Ni(Ⅱ);L＝吡嗪,咪唑,联吡啶].通过固体紫外反射、光电压和红外等方法予以表征.在固体紫外反射和光电压光谱中,金属卟啉聚合物的Soret带均发生了显著蓝移.在红外光谱中,单体Co(TPP)(pyz)₂在1598cm^-1处显示一个强吸收,而聚合物[Co(TPP)(pyz)]_n在1600cm^-1附近仅有极弱的吸收,单体在3482,3423,2921,2854,1004,792和611cm^-1处出现的强吸收在聚合物中接近消失,说明此聚合物与单体相比对称性增加,而单体在1644,1353和1070cm^-1处的吸收分别向高场方向位移13,25和15cm^-1.实验中还发现,对于不同中心金属离子,反应完成的时间不同,时间由短到长的顺序为:Co(Ⅱ)＞Fe(Ⅲ)＞Ni(Ⅱ)＞Cu(Ⅱ)＞Mn(Ⅲ);不同桥连配体反应完成的时间由短到长顺序是联吡啶＞吡嗪＞咪唑.     

Dialdehyde in Heterocyclic Synthesis： Synthesis of Compounds Containing Two 4H-Benzopyran Building Blocks under Microwave Irradiation

The syntheses of 4H-benzopyran derivatives were investigated using dialdehyde as a key starting material. The reaction proceeds under microwave irradiation in good yield (87%--95%) with short reaction time (5--8 min),therefore providing a rapid and efficient method of synthesizing a variety of compounds containing two 4H-benzopyran units.     

二茂钛氨基酸配合物的合成新方法

二茂钛衍生物在催化烯烃聚合、氢化、异构化等领域具有重要应用价值[1] ,同时 ,因该类衍生物还具有良好的抗癌性能 ,且其毒性远远低于顺铂类化合物[2 ] ,使人们对这类配合物的研究一直非常重视 .有文献报道 [3] ,以具有生物活性的配体取代二氯二茂钛中的氯原子 ,可以改善其生物利用率 ,提高二茂钛的抗癌活性 .二茂钛配合物的合成绝大多数都是在无水无氧的有机相中进行的 ,在两相(水相 /有机相 ) [4 ,5] 中则很少 .我们曾经在有机相和水相中合成了一些新的二茂钛氨基酸配合物 [6] ,但操作繁杂 ,反应速度慢 ,影响因素多 ,产率低等是这两种体系…     

尼达尼布的合成新方法

以N-甲基-4-硝基苯胺作为起始原料,依次经氯乙酰化、取代及氢化还原反应制得关键中间体N-(4-氨基苯基)-甲基-2-(4-甲基-1-哌嗪基)乙酰胺（4）;以4-氯-3-硝基苯甲酸为原料,依次经酯化、取代、氢化还原及环合反应制得6-甲氧羰基-2-吲哚酮（8）; 8与原苯甲酸三乙酯和乙酸酐经“一锅煮”反应制得中间体1-乙酰基-3-甲氧基(苯基)亚甲烯基-2-氧代吲哚环-6-羧酸甲酯（9）; 4和9进行取代反应的同时脱除保护,经“一锅煮”反应合成尼达尼布,总收率57.2%,其结构经¹H NMR,¹³C NMR和MS(ESI)确证。