取代硝基二苯醚的合成

取代硝基二苯醚化合物在农药、染料、颜料和橡胶等领域有广泛应用.硝基二苯醚化合物的经典合成方法是Ullman法,在铜或铜的化合物催化下完成,反应条件苛刻,不易控制.     

N，N’－双（2－硝基苯并双氧化呋咱）－1，3，5－三硝基－2，6－二氨基苯的合成

通过间苯二胺和三硝基三氯苯反应，再经过硝化、叠氮基取代和热解脱氮环化，合成了题称新化合物。     

溴代二羟基硝基二苯醚类化合物的合成与抑菌活性研究

综合考虑二苯醚类杀菌剂结构与活性关系的前期研究结果, 以双羟基二苯醚为原料, 经酸酐保护、硝化、去保护得到含硝基的双羟基二苯醚, 再经过溴代反应合成了7个新的溴代2,2'-, 2,4'-和4,4'-二羟基硝基二苯醚; 所有这些化合物的结构均经¹H NMR, MS, IR和元素分析所证实; 并检测了合成的溴代二羟基硝基二苯醚化合物对两种有害菌的抑菌活性, 结果表明: 它们对所测试菌种具有优良的抑制效果, 其中3个化合物在质量分数为5×10^－6的浓度下抑菌率超过100%, 能完全控制细菌的生长.     

取代二苯醚的新合成反应研究

取代二苯醚是一类重要的高聚物单体，用于制备耐高温塑料、绝缘薄膜以及高强度、高模量、低延伸的液晶纤维等，在国防工业和民用工业上有着宽广的前途。因此研究取代二苯醚的合成方法对我国开发新型的高分子材料有着重要意义。合成取代二苯醚的方法，归纳起来有二     

实用导向基辅助下的邻苯二酚衍生物便捷合成

5-硝基嘧啶作为导向基（DG）能很好的辅助钯催化苯酚邻位乙酰氧基化，研究发现该导向基的引入方且偶联后能在温和条件下移除。该方法操作简单，有良好的底物官能团兼容性，通过一锅法实现导向基的引入和苯酚邻位乙酰氧基化，合成了具有丰富取代基的10种2-[（5-硝基嘧啶-2-基）氧基]芳基乙酸酯新化合物。该类乙酰氧基化产物能够以最高75%收率得到，其结构均经¹H NMR, ¹³C NMR以及HR-MS（ESI）确证。      

借Wohl-Ziegler反应合成1-苯基-1,3-丙二醇及其他1-取代苯基-1,3-丙二醇的衍生物

1,本文叙述从3-苯基丙醇的3′,5′-二硝基苯甲酸酯借 Wohl-Ziegler 溴化反应合成 1-苯基-1,3-丙二醇。2.用相同方法从3-(邻取代基-对硝基苯基)-丙醇酯合成1-(邻取代基-对硝基苯基)-1,3-丙二醇的相应的衍生物。此方法各步产量较高,可以用作在连于苯环的碳原子上引入一个羟基的制备方法。3.含氨基的化合物进行 Wohl-Ziegler 溴化反应时,最好用邻苯二甲酰基,保护氨基。4.3-溴代-3-(邻苯二甲酰亚氨-对硝基苯基)-丙醇乙酸酯在乙酸氢溴酸混合液中水解,获得7-硝基喹啉。     

Na2S还原法合成氨基二苯醚类化合物

用Na2S还原硝基二苯醚类化合物，成功地合成了一系列氨基二苯醚类化合物，产率在70％以上，产物结构经IR，1H NMR和MS表征。     

酰亚胺基取代α,β—不饱和酮的合成及二烯烃环加成反应的研究

在吡啶中肉桂酰氯与相应的酰亚胺化合物反应，分别合成了1－丁二酰亚胺基－3－苯基丙烯酮、1－邻苯二甲酰亚胺基－3－苯基丙烯酮、1－丁二酰亚胺基－3－间硝基苯基丙烯酮和1－邻苯二甲酰亚胺基－3－间硝基苯基丙烯酮。研究了所合成的这些酰亚胺基取代的α，β－不饱和酮分别与环戊二烯和异戊二烯的环加成反应活性。生成的环加成产物均为新的化合物，其结构经元素分析、IR和^1H NMR确证。     

(3-叠氮基-2, 2-二硝基)丙基取代硝胺的合成

本文报道了由(2, 2-二硝基-3-羟基)丙基取代硝胺经相应三氟甲基磺酸酯合成(3-叠氮基-2, 2-二硝基)丙基取代硝胺的合成方法。     

2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成

详细研究了2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成方法。由苯基二硝基甲烷钾盐经羟甲基化，磺酰酯化和叠氮化得到目标化合物：3-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4b)，4-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4c)，m-二(2-叠氮基-1,1-二硝基乙基)苯(10)和p-二(2-叠氮基-1,1-二硝基乙基)苯(15)。     

Na2S还原法合成氨基二苯醚类化合物

氨基二苯醚不仅自身具有良好的杀菌、杀虫功效,广泛地应用到医药及农业领域。一般通过还原硝基二苯醚得到,但现有制备方法存在一些问题。Na2S作为一种较成熟的还原剂,价格低廉,反应后生成的Na2S2O3可作化工原料。本文用Na2S作为还原剂,合成路线如下：     

Twenty-five Years of "Crowning" Around: Synthesis of Crown Ethers at Brigham Young University

A review of the synthesis of crown ethers at Brigham Young University ispresented. Topics include: thiacrown ethers, diestercrown ethers,proton-ionizable crown ethers, chiral crown ethers, azacrown ethers,cryptands and other polycyclic ligands, and the Mannich reaction method toprepare azacrown ethers and cryptands.     

Conversions of Allyl Ethers in a Superbasic Medium

Conversions of alkyl allyl and terpenoid allyl ethers in a superbasic medium (dimethyl sulfoxidepotassium hydroxide) are studied. The ethers with an unbranched alkyl substituent isomerize into propenyl ethers, the ethers with a branched unsaturated substituent decompose to give a hydrocarbon, and diallyl ethers isomerize into allyl vinyl ethers whose Claisen rearrangement gives rise to aldehydes.     

New methodology for the synthesis of benzoazacrown ethers by transformation of the macrocycle of benzocrown ethers

The review summarizes the results of studies aimed at constructing new promising macrocyclic ligands that bind metal and ammonium ions. A new approach to the synthesis of formyl and nitro derivatives of 1-aza-2,3-benzocrown ethers possessing considerable synthetic potential is described. The review presents a radically new methodology for the synthesis of such benzoazacrown ethers based on stepwise transformations of the macrocycle of readily accessible benzocrown ethers. The main structural factors and necessary conditions enabling stepwise transformations of the macrocycle of crown ethers into azacrown ethers were revealed. For the first time, the ability of N-methylbenzoazacrown ethers to form complexes was found, which is much superior to that of widely used N-phenylazacrown ethers and benzocrown ethers with the same size of the macrocycle.     

The synthesis of unique structures of tetra-crown ethers through Michael addition

Unique structures of tetra-crown ethers were successfully synthesized by the reaction of tetramethylolmethane tetraacrylate (TMMT) reacted with crown ethers containing primary amine functional group such as 2-aminomethyl crown ethers and 4-aminobenzo crown ethers; containing secondary amine group like 1-aza crown ethers through Michael reaction. The newly synthesized tetra-crown ethers were characterized by ¹H NMR, ¹³C NMR, FAB mass spectrum, elemental analyses, IR, respectively.     

Synthesis and Complexation Behavior Studies of Novel Bis-crown Ethers

The novel unique structures of bis-crown ethers were successfully synthesized from tri (propylene glycol) di-acrylate with amino- and aza-crown ethers through Michael addition. The crown ethers contained the primary and the secondary amine group such as 2-aminomethyl crown ethers, 4-aminobenzo crown ethers and 1-aza crown ethers. The newly synthesized bis-crown ethers were characterized by elemental analyses, IR, ¹H NMR, ¹³C NMR, mass spectrum, respectively. The newly synthesized host compounds of bis-crown ethers showed complex ability with various sizes of alkali metal cations such as Na⁺, K⁺, Rb⁺ and Cs⁺. The complexation behavior was examined by ¹H NMR spectroscopy and UV spectrometry.     

新型蒽并冠醚的合成及主客体键合行为

以9,10-二溴甲基蒽为原料,经过3步反应合成了2种新型蒽并冠醚;采用核磁共振波谱、紫外光谱和单晶X射线衍射等手段研究了蒽并冠醚与2种π-缺电子客体之间的键合行为.结果表明,蒽并冠醚与客体之间的键合作用主要是π-堆积作用.通过紫外光谱滴定法测得蒽并冠醚与客体之间的键合常数高于经典的苯并冠醚和萘并冠醚,表明蒽结构基团的引入改善了冠醚的主-客体键合能力.     

Potentiometric and AM1d studies of the equilibria between silver(I) and diaza-15-crown and diaza-18-crown ethers with nitrogen in different positions in various solvents

Abstract

Complex formation and stability constants between typical and atypical diaza-15-crown and diaza-18-crown ethers with silver(I) were determined in methanol, acetonitrile and propylene carbonate by the potentiometric method. In two of the diaza crown ethers, AA-diaza-15 and AA-diaza-18-crown, two nitrogens in the macrocyclic ring replaced two consecutive oxygens instead of two opposite ones in the two other diaza crown ethers. It was found that complexes of 1:1 and 1:2 metal-to-ligand stoichiometry were formed. The solvent composition and cavity size of crown ethers significantly influences the stability constants of complexes. AA-diaza-15 and AA-diaza-18-crown ethers were examined for comparison with diaza-15-crown and diaza-18-crown ethers. AA-diaza crown ethers formed less stable 1:1 metal-to-ligand complexes with silver(I) than typical diaza crown ethers but their ability to form 1:2 metal-to-ligand complexes was stronger. The energetically most favorable structures of the 1:1 metal-to-ligand complexes were calculated and visualized by the AM1d method at the semiempirical level of theory.     

Komplexierungseigenschaften von Pyridinokronenethern gegenüber Alkali- und Erdalkaliionen in Methanol

Complexing Properties of Pyridino Crown Ether with Alkali and Alkali-Earth Cations in Methanol The stability constants and thermodynamic values of the complex formation of several pyridino crown ethers with alkali and alkaline-earth cations were determined by calorimetric titration in methanol. The stability of the complexes is lower than with crown ethers. This is mainly caused by a decrease of reaction enthalpies. Compared with other mono substituted crown ethers the complexes with pyridino crown ethers are fare more stable due to entropic effects. With increasing cavity size the stability constants, enthalpies and entropies for the reaction of crown ethers and pyridino crown ethers approach similar values.     

Spectrometrie de masse,problemes de structure et de stereochimie—CCVII Fragmentations des Ethers Insatures

In connection with work on computerized mass spectral interpretation of organic com-pounds, the behavior of three groups of unsaturated ethers was examined: allylic, substituted allylic and unsaturated ethers with 2 or 3 methylene groups between the oxygen atom and the double bond. A total of 36 compounds (11 labelled) were prepared and mechanistic rationalizations presented. The allylic ethers isomerized to vinylic ethers after ionization. No double bond migration was observed, however, before or after electron-impact of allylic and homoallylic ethers or ethers with 3 methylene groups between the oxygen atom and the double bond. The allylic ethers with seven carbon atoms in the saturated chain lost a saturated alcohol molecule [R' + C₃H₆OH] by a uni-directional quadruple hydrogen transfer prior to fragmentation.