Efficient Route for the Synthesis of New Dinaphthosulfoxide Aza Crowns Using Ethyleneglycol Under Microwave (MW) Irradiation: Macrocyclization is Preferred to Oligomerization Under MW Irradiation

Abstract

New dinaphthosulfoxide aza crowns were prepared from the corresponding dinaphthosulfoxide diester and diamines under reflux conditions (conventional heating) and microwave (MW) irradiation. These reaction routes were used for the synthesis of a series of aza crowns, such as dinaphthosulfide, dinaphthosulfone, dibenzosulfide, and dibenzosulfoxide. The synthesis of aza crowns under MW irradiation in comparison with conventional heating has several advantages, such as shorter reaction times, simpler reaction conditions, and the use of ecofriendly solvents, higher yields, and regioselectivity. In the MW synthesis, macrocyclization is preferred to oligomerization, and thus, the yields of byproducts are low.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

BINOL Aza Macrocycle Derivatives: Synthesis of Dinaphthosulfone Aza Macrocycles Using p-Toluenesulfonic Acid (p-TsOH) in Methanol as an Efficient Route and Evaluation of Their 1H NMR Spectra

Dinaphthosulfone aza macrocycles were synthesized from the reaction of diamines and dinaphthosulfone diester (1,1′-sulfoxobis-(2-naphthoxy(2-methyl acetate))) in methanol in the presence of catalytic amounts of para toluenesulfonic acid (p-TsOH). Dinaphthosulfone diester (1,1′-sulfoxobis-(2-naphthoxy(2-methyl acetate))) was synthesized from the corresponding dinaphthosulfide diester and hydrogen peroxide in formic acid at room temperature. Dinaphthosulfide diester was prepared from initial dinaphtholsulfide diol (1,1′-thio bis(2-hydroxy naphthalene)) and methylchloroacetate. ¹H NMR spectroscopy showed the unusual splittings for these dinaphthosulfone aza macrocycles, and this finding could be proposed as the role of tetrahedral structure of sulfone functional group, hydrogen bonding in the cavity and size of macrocycle.     

2-硝基-1-萘酚的合成

以过氧化氢为氧化剂,在碱性条件下氧化2-亚硝基-1-萘酚合成了2-硝基-1-萘酚,优化了反应条件,改进了分离方法,产品收率达到70%以上.     

Synthesis of New Aza Thia Crowns Bearing 2,2′-Diaminodiphenyl Disulfide

Abstract

New aza thia crowns were prepared from the reaction of 2,2′-diaminodiphenyl disulfide and diacids or diacid chlorides. Diacids are malonic acid, adipic acid, sebacic acid, and 2,2′-thiodiacetic acid and diacid dichlorides are malonyl chloride, adipoyl chloride, sebacoyl chloride, and 2,2′-thiodiacetyl chloride.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures.]     

由(+)-2-氨基丁醇合成氮杂手性冠醚

手性冠醚由于具有手性识别和不对称催化有机反应的性质而受到人们的重视,有关它们的合成及性质,已很多论述。氮杂冠醚则是合成穴醚、双冠醚、套索冠醚(LariatEther)等的重要中间体,也可与高分子材料(高分子载体或高分子基质)连接,用于有机化合物的色谱分离。氮杂手性冠醚兼备手性和氮杂冠醚两种特性,而可能具有广泛的用途。     

Determination of Pentachlorophenol and 1-Naphthol by Peroxyoxalate Chemiluminescence

Abstract

Peroxyoxalate chemiluminescence is used for the determination of pentachlorophenol and 1-naphthol in soil. 1-Naphthol is brominated to make it amenable to the procedure. Calibration curves are linear over concentration ranges spanning four orders of magnitude and limits of detection are at the micromolar level. the processes can be carried out in the soil without prior extraction of the analytes.     

用铝-镍合金还原1-萘酚反应的再研究

文献曾报道以铝-镍合金为还原剂, 在稀碱水溶液中, 可以将1-萘酚(1)以高收率还原为5,6,7,8-四氢-1-萘酚(2). 本研究工作发现, 在相同的条件下该反应除了生成少量2外, 3,4-二氢-2H-萘-1-酮(3)和1,2,3,4-四氢-1-萘酚(4)为主要产物, 该结果明显不同于文献报道, 对反应产物分布及其可能机理进行了探讨. 该还原反应体系为3,4-二氢-1(2H)-萘酮(3)和1,2,3,4-四氢-1-萘酚(4)的合成提供了一条新途径.     

Solid-Liquid Extraction of Some Lanthanide Complexes with 1-Nitroso-2-Naphthol

The extraction behavior of Sm(III), Eu(III) ,Er(III) and Yb(III) with 1- nitroso -2- naphthol (HA) in paraffin has been studied. The composition of extracted complexes has been determined to be LnA3 by slope analysis method. The effect of temperature on extraction system is also investigated and thermodynamic parameters are obtained.     

2-[邻-4,6-二甲氧基嘧啶基-2-氧(硫)代苯基]-1,3,4-噻(噁)二唑类化合物的合成及其除草活性

以取代的邻硝基苯甲醛或水杨醛或邻巯基苯腈为原料,通过几步反应合成得到2-[邻-4,6-二甲氧基嘧啶-2-基-氧(硫)代苯基]-1,3,4-噻(噁)二唑类化合物.初步田间试验证实,30%化合物Ib乳油的使用剂量为2.40～3.60L·hm-2,对试验棉田杂草防除效果达48d,且对棉花较为安全.目标化合物的结构经过1H NMR,MS-ESI,IR以及元素分析等表征.     

三氟甲基侧取代氧、氮、硫杂大环化合物的合成和分子结构

合成了四个三氟甲基侧取代氧、氮、硫杂大环化合物,通过IR、~1H NMR、MS和元素分析作了表征;用AM1方法计算它们的电子结构,并根据计算结果给出了它们的几何构型。     

Efficient Routes for the Synthesis of Dinaphthosulfide (BINOL Derivatives) and Dibenzosulfide Aza Podands Containing Ethanolamine

Four new dinaphthosulfide and dibenzosulfide aza podands were synthesized. The synthesis of these podands was performed under three different reaction conditions: 1) diester, K ₂ CO ₃ , methanol, and RT; 2) diester, ethanolamine, and microwave (MW); and 3) diacid dichloride, ethanolamine, Et ₃ N, CH ₂ Cl ₂ , RT. Two kinds of diester (dinaphthosulfide and dibenzosulfide) were used for the preparation of dihydroxy podands. These dihydroxy podands were reacted with thionyl chloride to afford dichloro podands. The second route gave excellent yields of dihydroxy podands. Dichloro podands are more soluble than dihydroxy podands in conventional solvents such as methanol, chloroform, and acetonitrile.     

Sensitive Synchronous Spectrofluorimetric Methods for the Determination of 1- and 2-Naphthol in Micellar Media

Abstract

The interaction of 1-naphthol and 2-naphthol with several quaternary ammonium salts was studied. Spectrofluorimetric methods were developed for the determination of both naphthols in hexadecyltrimethylammonium bromide micellar medium. The detection limits are 1.4 and 10.2 ng/ml for 1-naphthol, and 6.2 and 5.1 ng/ml for 2-naphthol employing the conventional and synchronous spectrofluorimetric methods, respectively. The use of the first-derivative spectrum allows for the simultaneous determination of both naphthols. The recoveries of 1-naphthol and 2-naphthol in natural waters are acceptable.     

Simultaneous quantitative determination of resorcinol and 1-Naphthol in haircolor products by high-performance liquid chromatography

Summary A high-performance liquid chromatographic method has been developed for the simultaneous quantitative determination of resorcinol and 1-naphthol in hair tonic and haircolor products. The two compounds could be separated on a μBondapak C₁₈ column by elution with 50∶50 (v/v) methanol-water as mobile phase. The retention times of resorcinol and 1-naphthol were 2.5 and 7.0 min, respectively. Seven dye intermediates could be analyzed within 12 min without any interference with the peaks of resorcinol and 1-naphthol from other cosmetic ingredients present in the haircolor liquid or cream. The results obtained were in good agreement with those obtained by a spectrophotometric method.     

聚乙二醇催化合成含三唑大环醚化合物

香草醛(1)和3-取代-4-氨基-5-巯基-1,2,4-均三唑(4)分别与对二氯苄(2)缩合得相应的0,0′-取代二(香草醛)(3)和S,S′-取代双(氨基均三唑)(5).3与5用聚乙二醇-600催化缩环合方便制得含三唑大环醚化合物6.     

N-取代氮杂冠醚的合成和络合萃取性能研究进展

综述了N-取代氮杂冠醚的合成和对金属离子的选择性络合和萃取研究的新进展.     

新显色剂 1-[2,3,5-三氮唑偶氮]-2-萘酚的合成及其与钴(Ⅱ)的分光光度研究

合成了新显色剂 1-[2,3,5-三氮唑偶氮]-2-萘酚(简称TZAN ) ,并研究了其性质及与钴显色反应的条件,测定了试剂有关参数.在 pH 6.08 的 HAc-NaAc 介质中,试剂与钴形成红色络合物,其最大吸收波长为 578.2 nm,摩尔络合比 Co2+∶R=1∶2,用双波长测定,表观摩尔吸光系数为 3.15×104 L/mol.cm,钴量在 0～1.0 μg/mL 范围内遵守比耳定律.     

Synthesis of 2-Aminochromene Derivatives Catalyzed by KF／Al2O3

A series of 2-aminochromene derivatives including 2-amino-ben-zo[ h ] chromene, 2-amino-benzo [ f ] chromene and 2-amino-pyrano [3,2-h ]quinolin derivatives was synthesized from aryl-aldehyde, malononitrile or ethyl cyanoacetate and 1-naphthol or 2-naphthoi or 8-hydroxyquinoline in refluxing ethyl alcohol cat-alyzed by KF-Al2O3. The structures were confirmed by X-ray analysis.     

1-萘酚诱导人血清白蛋白和牛血清白蛋白构象的变化

采用稳态荧光光谱、同步荧光光谱、荧光共振能量转移技术结合分子对接法,探究了1-萘酚(1-OHNap)诱导人血清白蛋白(HSA)和牛血清白蛋白(BSA)构象变化的差异.结果 表明,与1-OHNap的结合作用使HSA中荧光团周围微环境极性发生改变,BSA中Trp残基周围微环境的极性增加;同时,与1-OHNap的结合作用使H...     

1-(2-吡啶偶氮)-2-萘酚-镱二元络合物近红外发光法测定镱

基于金属指示剂 1 (2 吡啶偶氮 ) 2 萘酚 (PAN)对稀土离子Yb3+ 的近红外发光的敏化作用 ,建立了Yb3+ 的定量分析方法。方法的线性范围为 1 .0× 1 0 - 6 ～ 8.0× 1 0 - 6 mol L,检测下限为 1 .0× 1 0 - 6 mol L ,相对标准偏差为 3 .2 %。该方法适用于在混合稀土样品中选择性地测定Yb3+ 的含量。     

阳离子型微乳液对显色剂1—（2—吡啶偶氮）—2—萘酚的增溶作用

以光度法研究了阳离子型微乳液对显色剂１－（２－吡啶偶氮）－２－萘酚（ＰＡＮ）的增溶作用，通过测定ＰＡＮ在阳离子型ＣＴＭＡＢ／ｎ－Ｃ５Ｈ１１ＯＨ／ｎ－Ｃ９Ｈ２０微乳液中的“胶束位”ｎ和结合常数Ｋ，并与相同表面活性剂胶束体系比较，探讨了微乳液对显色剂ＰＡＮ的增溶作用。