含甲巯咪唑杂环为端基的非环冠醚的合成

本文以甲巯咪唑杂环为新的端基,在相转移催化条件合成了五个开链冠醚,这些化合物均通过元素分析、UV、IR 、^1H和^13CNMR波谱鉴定.     

中国南海海绵Seletta tenuis lindgren中24-亚甲基-27-甲基胆甾醇的结构鉴定

本研究中国南海海绵生物活性成分的过程中,从南海海绵中分离出24-亚甲基-27-甲基胆甾醇,通过IR,^1HNMR,^13CNMR,^1H-^13CCOSY,MS和MS-MS等波谱分析,确证了其化学结构,并详细报道了波谱数据.     

三苄基锡羧酸酯的合成及其结构表征

本文以(三苄基锡)氧化物和相应的羧酸反应, 合成了20个三苄基锡羧酸酯, 由波谱对结构的研究表明, 红外光谱的酰基振动频率与羧基上取代基的空间和电子效应密切相关, 三苄基锡羧酸酯的结构微小变化, 明显地反映了^1^1^9Sn和^1^3CNMR化学位移的差异, ^1^1^9Sn化学位移与三苄基锡取代的苯甲酸酯的对位取代基Hammett常数(σ)之间存在着良好的线性关系: δ~1~1~9~S~n=15.48σ+14.23, n=7, r=0.995, 去烃基化是这一类化合物质谱裂解的特点。     

α[O-烷基-O'-烷基(苯基)二硫代磷(膦)酸酯基]异戊酸间-苯氧基-α'-氰基苄酯的合成

本文合成了三类十个含磷拟除虫菊酯类新化合物-α-二硫代磷(膦)酸酯基异戊(乙)酸间-苯氧基-α'氰基苄酯,研究了其纯化条件.对部分中间体的制备方法作了改进.产物的结构经IR,^1H NMR 及元素分析证实,测定了部分产物的MS.对波谱中"异常"现象进行了讨论.     

混合三烃基锡衍生物的研究VIII: 甲基二环己基锡(取代)苯氧乙酸酯的合成、结构表征和生物活性

本文合成了二十个混合甲基二环己基锡取代苯氧乙酸酯。研究了这些化合物的IR, NMR (^1H, ^1^3C, ^1^1^9Sn), 结果表明, 除邻甲氧基苯氧乙酸酯外, 这些化合物都可能是以羰基氧为桥连的五配位聚合有机锡化合物。^1^1^9Sn NMR的研究结果表明, ^1^1^9Sn化学位移与苯环上取代基有一线性关系: δ^1^1^9Sn=6.23σ+94.67, r=0.943。农药的初筛表明, 这些化合物除有很好的杀螨活性外, 还有一定的杀菌, 除草和植物激素作用。     

混合三烃基锡衍生物的研究VIII: 甲基二环己基锡(取代)苯氧乙酸酯的合成、结构表征和生物活性

本文合成了二十个混合甲基二环己基锡取代苯氧乙酸酯。研究了这些化合物的IR, NMR (^1H, ^1^3C, ^1^1^9Sn), 结果表明, 除邻甲氧基苯氧乙酸酯外, 这些化合物都可能是以羰基氧为桥连的五配位聚合有机锡化合物。^1^1^9Sn NMR的研究结果表明, ^1^1^9Sn化学位移与苯环上取代基有一线性关系: δ^1^1^9Sn=6.23σ+94.67, r=0.943。农药的初筛表明, 这些化合物除有很好的杀螨活性外, 还有一定的杀菌, 除草和植物激素作用。     

三[(苯基二甲硅基)亚甲基]锡 O,O-二芳基二硫代磷酸酯的研究

本文合成了十五个新的[苯基二甲硅基]锡O,O-二芳基二硫代磷酸酯。测定了它们的IR, ^1H, ^1^3C, ^1^1^9Sn NMR及MS, ^1^1^9Sn NMR的化学位移δ和芳环对位取代基的Hammett常数σ之间存在良好的线性关系。     

四氮[14]轮烯合镍(Ⅱ)配合物的研究 3: 取代四氮[14]轮烯合镍(Ⅱ)及其π配位三羰基合铬多核配合物的合成、表征及电化学性质

制备了三个含有多个苯环的四氮[14]轮烯合镍(Ⅱ)大环配合物, 并将其与Cr(CO)6反应, 合成了四个结构新颖的杂多核配合物, 用IR, UV, ^1H NMR,^1^3C NMR, MS等波谱表征, 确定了化合物的分子结构, 并进行了电化学性质的研究。     

四氮[14]轮烯合镍(Ⅱ)配合物的研究 3: 取代四氮[14]轮烯合镍(Ⅱ)及其π配位三羰基合铬多核配合物的合成、表征及电化学性质

制备了三个含有多个苯环的四氮[14]轮烯合镍(Ⅱ)大环配合物, 并将其与Cr(CO)6反应, 合成了四个结构新颖的杂多核配合物, 用IR, UV, ^1H NMR,^1^3C NMR, MS等波谱表征, 确定了化合物的分子结构, 并进行了电化学性质的研究。     

桥连双-(三氮杂环壬烷)化合物的合成

利用无水碳酸钾作缩合剂,在精制乙腈中使N,N'-二对甲苯磺酰基-1,4,7-三氮杂环壬烷3与双溴甲基化合物4a-4c缩合得到N-对甲苯磺酰基取代的桥连双-(三氮杂环壬烷)5a-5c,经浓硫酸脱去氮原子上的保护基团得到桥连双-(三氮杂环壬烷)6a-6c。化合物5a-5c和6a-6c均经元素分析、IR、^1HNMR、^1^3CNMR、MS等测试手段证实其结构和组成。     

One-pot synthesis and conformational features of n,n'-disubstituted ketene aminals

N,N'-Disubstituted ketene aminals are bioisosteres of thioureas and are useful building blocks in many synthetic operations. A convenient one-pot synthesis of N,N'-disubstituted ketene aminals from activated methylene compounds and isothiocyanates is described. Most of these aminals exist in rotameric equilibrium around the central C=C bonds in solution, and the rotamers are stabilized by intramolecular hydrogen bonding both in solution and in solid states.     

Regiospecific Synthesis of N-Sulfanilyl Heterocyclic Ketene Aminals

Heterocyclic ketene aminals 1 or 2 reacted with N-acetylsulfanilyl chloride 3 in the presence of sodium hydride to afford N-sulfanilyl heterocyclic ketene aminals 4 or 5 regiospecifically.     

Synthetic exploitation of halogenated alkenes containing an electron-withdrawing group: synthesis of α-chlorohydrazones and ketene aminals by regiospecific reactions of in situ generated imide chlorides

A concise approach for the construction of ketene aminals and α-chlorohydrazones has been developed. It involves reactions of the regiodefined gem-dihalo nitrovinyl compound of in situ generated imide chlorides in different media with primary arylamines being dependent on the aryl groups. A range of ketene aminals and α-chlorohydrazones are obtained in good to high yields. In addition, α-aminohydrazones are prepared by using α-chlorohydrazones as the precursors.     

Chelate synthesis of pyrazolyl(ethoxycarbonyl)ketene aminals,the precursors of functionalized pyrazolo[1,5-c]pyrimidines

A scheme for the preparation of novel synthetic reagents. pyrazolyl(ethoxycarbonyl)ketene aminals, from acetyl(ethoxycarbonyl)ketene (N-benzoyl)aminalvia its difluoroboron chelate is suggested. The possibility of cyclization of the ketene aminals obtained into functionally substituted pyrazolo[1,5-c]pyrimidines is shown.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2211–2214, December, 1994.This work was carried out with the support of the International Science Foundation (ISF, Grant No. M5Q 000), and a part of the work was supported by the Russian Foundation for Basic Research (Project No. 94-03-08964).     

THE REACTION OF BENZOYL SUBSTITUTED HETEROCYCLIC KETENE AMINALS WITH ARYL AZIDES.A FACILE APPROACH TO SYNTHSIZE 1, 5-DIARYL-4-(2-IMIDAZOLINYL)-1, 2, 3-TRIAZOLES

Heterocyclic ketene aminals 1 react with aryl azides 2 to give thetitled compounds 3, and in some cases also with the formation offused heterocycles 4.     

A novel and facile synthesis of 2-oxo-1,2-dihydropyridine-fused 1,3-diazaheterocycles via heterocyclic ketene aminals and Konevenagel adducts formed by phthalic anhydride and ethyl cyanacetate

An efficient synthetic pathway to 2-oxo-1,2-dihydropyridine-fused 1,3-diaza heterocycles from heterocyclic ketene aminals,phathalic anhydride and ethyl cyanacetate was established.This protocol involved aza-ene reaction/imine-enamine tautomerization/enamine-ester exchange/ring-opening reaction sequence.     

The regiospecific N‐sulfonylation and N‐phosphorylation of benzoyl‐substituted heterocyclic ketene aminals

The regiospecific N‐sulfonylation and N‐phosphorylation of benzoyl‐substituted heterocyclic ketene aminals have been investigated. In the presence of sodium hydride, benzoyl‐substituted heterocyclic ketene aminals 1 or 2 reacted with p‐toluenesulfonyl chloride 3 to give (E)‐1‐(p‐toluenesulfonyl)‐2‐(aroylmethylene)imidazolidine 4 or (E)‐1‐(p‐toluenesulfonyl)‐2‐(aroylmethylene)hexahydropyrimidine 5, respectively. Under the same condition, 1 reacted with diethyl chlorothiophosphate 6 to give diethyl [2‐(aroylmethylene)imidazolidin‐1‐yl]thiophosphate 7. However, 2 failed to react with 6 to give N‐phosphorylated products. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 297–301, 1999     

Solid-phase Synthesis of a Novel Kind of Hydroxylated Heterocyclic Ketene Aminals

An efficient solid-phase synthesis method for novel heterocyclic ketene aminals containing a hydroxyl group has been developed. The loading of the substrate on the resin through the hydroxyl group and the protection of the amine by the Schiff base were the key steps in the synthesis.     

Recent developments in the heterocyclic ketene aminal-based synthesis of heterocycles

Research on Chemical Intermediates - Small poly-functionalized heterocycles are frequently found in pharmacophores and play important roles in drug discovery. Heterocyclic ketene aminals (HKAs) are...     

烯酮缩胺与芳基异硫氰酸酯的反应: 合成异噻唑化合物 的一个途径

具有不同取代基的五状和非环状的烯酮缩胺与芳基异硫氰酸酯在两酮中回流,可高产率地获得α-碳加成产物,该产物在溴存在下可氧化关环生成异噻唑类化合物。