聚合物支载相转移催化剂的研究2.聚苯乙烯支载苯并-15-冠-5-与无环冠醚

本文报道了三种聚苯乙烯支载苯并-15-冠-5与两种聚苯乙烯支载无环冠醚的合成,并研究了它们对K~+与Na~+的络合性能与相转移催化性能。     

聚苯乙烯支载聚乙二醇二苯并-18-冠-6的合成及催化性能研究

叙述了几种聚苯乙烯支载聚乙二醇二苯并-18-冠-6高聚物冠醚的合成,并研究了它们对n-溴辛烷与碘化钾及苯酚钾盐取代反应时的相转移催化性能。     

二氧化硅固载苯并冠醚的合成与性能

3-烯丙基邻苯二酚与氯乙醇反应,得到3-烯丙基-1,2-双羟乙氧基苯,它与二缩三乙二醇双对甲苯磺酸酯反应,得到3-丙烯基苯并18-冠-6。从4-烯丙基邻苯二酚类似地制得4-烯丙基1,2-双羟乙氧基苯。它与1,2-双羟乙氧基苯双对甲苯磺酸酯反应,合成了4-丙烯基二苯并-18-冠-6。二种丙烯基取代冠醚与三氯硅烷反应,以二氧化硅固载化,得到二氧化硅固载苯并冠醚,它们皆可与铂形成配合物,是一类新型烯烃硅氢化催化剂。     

聚合物支载相转移催化剂的研究1.聚苯乙烯支载二苯并-18-冠-6及聚乙二醇长链烷基醚的合成

本文叙述了聚苯乙烯支载二苯并-18-冠-6及聚乙二醇长链烷基醚的合成,并研究了n-溴辛烷与碘化钾及苯酚钾盐的相转移催化取代反应。     

双冠醚的研究(Ⅶ)——Schiff碱型和仲胺型双(苯并-18-冠-6)的合成

4′-氨基苯并-18-冠-6分别与间-硝基苯甲醛、对-硝基苯甲醛、间-苯二甲醛及其取代物和对-苯二甲醛缩合制得6种新的Schiff碱型单冠醚和双冠醚。4′-甲酰基苯并-18-冠-6分别与4′-氨基苯并-15-冠-5、4′-氨基苯并-18-冠-6作用制得2个醚环大小相同和不同的Schiff碱型双(苯并冠醚)。这些双冠醚经硼氢化钠还原得到相应的6种新的仲按型双冠醚。     

叔丁基取代二苯并-18-冠-6的合成

以二甘醇和邻苯二酚为原料制得二苯并-18-冠-6;以多聚磷酸为催化剂和溶剂,将二苯并-18-冠-6与叔丁醇反应实现叔丁基化;利用正庚烷重结晶对叔丁基化反应产物进行纯化,得到4,4′-二叔丁基二苯并-18-冠-6和4,5′-二叔丁基二苯并-18-冠-6两种对称的二叔丁基二取代苯并冠醚产品.利用红外光谱和核磁共振谱表征了二叔丁基二取代苯并冠醚产物的结构。     

含二苯并-18-冠-6冠醚环的偶氮型液晶冠醚的合成

含二苯并-18-冠-6冠醚环的偶氮型液晶冠醚的合成;偶氮型;冠醚;热致性液晶;合成     

酚醛冠醚共缩聚物的合成与性能

用2,6-二羟甲基-4-苯基苯酚分别与二苯并-18-冠-6(2B18C6)、二苯并-24-冠-8(2B24C8)、二苯并-30冠-10(2B30C10)、苯并-15-冠-5(B15C5)、苯并-18-冠-6(B18C6)缩聚合成了五种酚醛型冠醚共聚物。我们用聚冠醚的氯仿溶液萃取苦味酸碱金属盐水溶液,研究了它们对金属离子的络合性能。结果表明,聚冠醚(PB15C5)和(PB18C6)的萃取能力和选择性显著优于相应的单冠醚。     

3′-甲酰基苯并冠醚的合成

4′位取代苯并冠醚已有很多报道,3′位取代苯并冠醚却很少见。见诸文献的3′位取代基仅有甲基、芳甲酰基、甲氧基、正十五烷基、氰基和叔丁基等。鉴于苯环     

反式-二硝基-二苯并-18-冠醚-6的合成及结构测定

本文对二苯并-18-冠醚-6进行硝化,然后将产物与钾盐反应,生成了二硝基-二苯并-18-冠醚-6-硫氰化钾一水络合物。用元素分析、红外光谱及X光衍射法测定了结构。     

Thermochemical behaviour of crown ethers in the mixtures of water with organic solvents: Part VII. Enthalpy of solution of 15-crown-5 and benzo-15-crown-5 in the mixtures of water with acetone at 298.15 K

Enthalpy of solution of crown ethers (15-crown-5 and benzo-15-crown-5) in water-acetone mixtures have been measured within the whole range of mole fraction at 298.15 K. The obtained data have been compared with those of the solution enthalpy of both crown ethers in the mixtures of water with dimethyl sulfoxide. The replacement of SO group with CO in the molecule of the organic solvent brings about an increase in the exothermic effect of the solution of 15-crown-5 and benzo-15-crown-5 ethers, especially in the mixtures with a medium water content. The observed effect is connected with the preferential solvation of the molecules of both crown ethers by acetone molecules in the water-acetone mixtures. The process of preferential solvation of 15-crown-5 and benzo-15-crown-5 ethers does not take place in the water-dimethyl sulfoxide mixture.     

Perfluoroalkylation of benzo crown ethers with sodium perfluoroalkanesulfinates in the presence of oxidant

Using Ce(SO4)2 or Mn(OAc)3 as oxidant, dibenzo crown ethers such as dibenzo-18-crown-6 (1) and dibenzo-24-crown-8 (5) and benzo-12-crown-4 (7) reacted smoothly with sodium perfluoroalkanesulfinates (2a-2e) to give the corresponding perfluoroalkylated products (3,4,6,7) in good yields with two isomers obtained in the case of dibenzo crown ethers. This provides a facile synthesis of perfluoroalkyl-containing crown ethers.     

Allylation of phenoxides by crown ethers and their polymers

Allylation of sodium phenoxide in the presence of crown ethers produces a high ratio of O/O + C allylation when conducted in water, phenol, benzene, or diethyl ether. The striking increase in the product ratios is attributed to specific complexation of the crown ethers that facilitate the dissociation of the ion pair aggregate of the sodioderivative in benzene or diethyl ether. The crown ethers may act as a phase transfer catalyst when the reaction is run in water. Furthermore, the O/O + C ratios of the allylation strongly depend on the kind of crown ethers used. To examine their effect the allylation of sodium phenoxide was studied with various crown ethers, such as 18-crown-6, benzo-18-crown-6, benzo-15-crown-5, poly(vinylmonobenzo-15-crown-5), and poly(vinylmono-benzo-18-crown-6), as catalysts. It was found that among these crown ethers poly(vinylmono-benzo-15-crown-5) was the most effective catalyst.     

The Effect of Crown Ethers on the Oxidation of Triethylamine by Ferricyanide Ion in Aqueous Solutions at Different pH Values

The effect of benzo-15-crown-5,15-crown-5 and 12-crown-4 on the oxidation of triethylamine by aqueous ferricyanide ion has been studied at pH 4, 7 and 11. The crown ethers retard the normal oxidation process at all pH values, the effect depending on the crown ether concentration. The three crown ethers show the same retardation effect at pH 4 and 7, while at pH 11 the retardation decreases in the order B15C5 > 12C4 > 15C5.     

Nitration of Benzo Crown Ethers with Potassium Nitrate in Polyphosphoric Acid

A general method for the nitration of benzo crown ethers with potassium nitrate in polyphosphoric acid has been developed. Mono- and dinitro derivatives of benzo-12-crown-4, benzo-15-crown-5, dibenzo-18-crown-6, and dibenzo-24-crown-8 have been prepared. The role of complex formation in the regioselective tendency for the nitration of dibenzo-18-crown-6 has been demonstrated.     

腙型双冠醚对碱金属的配位性能

本文报道了五个腙型双冠醚的合成。电导测定结果表明含苯并-15-冠-5单元的双冠醚与四苯基硼酸钾、铷、铯,含苯并-18-冠-6单元的双冠醚与四苯基硼酸铯生成2:1夹心型配合物(冠醚单元:金属离子)。并用这些双冠醚的氯仿溶液萃取苦味酸碱金属盐水溶液,测定了萃取百分率和计算了萃取平衡常数,结果表明腙型双冠醚的萃取能力及选择性优于相应的单冠醚。     

Extraction and determination of crown ethers from water samples using a membrane disk and gas chromatography

A method for rapid extraction and determination of some crown ethers in aqueous matrices using octadecyl-bonded silica membrane disks and gas chromatography is presented. Extraction efficiency and the influence of vacuum pressure. pH, and type and least amount of eluting solvent used to extract the crown ethers from the membrane disks were evaluated. Extraction efficiencies > 95% were obtained for benzo-15-crown-5, benzo-18-crown-6 and dicyclohexyl-18-crown-6 using 5 ml of acetonitrile as eluting solvent. The limit of detection of the proposed method for the determination of the crown ethers is reported.     

含1,3-亚丙基冠醚的合成

为了进一步研究亚丙基冠醚的络合行为,合成了三种含1,3-亚丙基冠醚,即2,3-苯并-1,4,7,11-四氧-环十三-2-烯(苯并-13-冠-4)(1)、2,3-苯并-1,4,8,11,14-五氧-环十七-2-烯(苯并-17-冠-5)(2)、2,3-苯并-1,4,7,10,14,17-六氧-环十九-2-烯(苯并-19-冠-6)(3)。通过元素分析、红外光谱、质谱、核磁共振谱和 X-衍射晶体结构分析,确证了它们的结构。     

Complexes of sodium and lithium borohydrides with macrocyclic polyethers

A method for the synthesis of complexes of sodium and lithium borohydrides with crown ethers is proposed. The complexes of sodium borohydride with benzo-15-crown-5, 4′-aminobenzo-15-crown-5, dibenzo-18-crown-6, and diaza-18-crown-6 and the complexes of lithium borohydride with benzo-15-crown-5 and dibenzo-18-crown-6 are synthesized. These complexes can be used for the preparation of hydrogen in their reactions with methanol. The complex formation does not affect the purity of hydrogen formed.