Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.     

New Approach to Synthesis of Tetrahydroisoquino[2,l-c] [1,3]-benzodiazepine

A concise and efficient synthesis of the new compounds tetrahydroisoquino [2,1-c] [1,3] benzodiazepine 5 and 7 is reported.     

Novel Synthesis of Pyrano[2,3-d]Thiazole,Thiazolo[3,2-a]Pyridine,and Pyrazolo [3′,4′:4,5] Thiazolo[3,2-a]Pyridine Derivatives

Cyclocondensation of 2-cyanomethyl-4-thiazolidinone (1) with tetracyanoethylene (2) furnished pyrano[2,3-d]thiazole derivative (4) . Benzo[e]pyrano[2,3-d]thiazole derivative (6) was obtained by cyclization of compound (1) with salicylaldehyde. In a similar manner, condensation of compound (1) with 2-hydroxy-1-naphthaldehyde in refluxing ethanol yielded naphtho[e]pyrano[2,3-d]thiazole derivative (7) . Interaction of compound (9) with benzylidenemalononitriles (10) (1 : 1 molar ratio) at reflux temperature in ethanol in the presence of piperidine afforded thiazolo[3,2-a]pyridines (12a-c) . Treatment of compound (12a) with hydrazines furnished pyrazolo[3′,4′:4,5] thiazolo[3,2-a]pyridines (14a,b) . The reaction of compound (1) with benzyli-denecyanoacetate (16) yielded 5-hydroxythiazolo[3,2-a]pyridine derivative (21) . Cyclization of bis(thiazolinone) (23) with benzylidenemalononitriles (10) produced bis(thiazolopyridine) derivatives (25a,b) .     

Thieno[2,3-b]pyridine-2-carbohydrazide in Polyheterocyclic Synthesis: The Synthesis of Pyrido[3′,2′:4,5]thieno[3,2-d]pyrimidine,Pyrido[3′,2′:4,5]thieno[3,2-d][1,2,3]triazine,and Pyrazolyl,Oxadiazolylthieno[2,3-b]pyridine Derivatives

Pyrdine-2(1H)-thione 1 reacted with ethyl chloroacetate 2 to give 2-S-ethoxy-carbonylmethylpyridine derivative 3, which could be cyclized into thieno[2,3-b]-pyridine-2-carbohydrazide derivative 5 by boiling with hydrazine hydrate. The latter compound reacted with cinnamonitrile derivatives 6a, b, triethylorthoformate, formic acid, dimethylformamide-dimethylacetal, and diethyl carbonate to give the corresponding shiff base 7a, b and pyrido[3′,2′;-4,5]thieno[3,2-d]pyrimidine derivatives 10–13 in respective manner. On the other hand, compound 5 also reacted with carbondisulphide and phenyl isothiocyanate to afford the corresponding 2-(1,3,4-oxadiazolo-2-yl)thieno[2,3-b]pyridine derivatives 18 and 22. Finally, compound 5 reacted with some β-dicarbonyl compounds, such as ethyl acetoacetate, acetylacetone and ethyl β-arylazoacetoacetate, to yield the corresponding 2-(pyrazol-1-yl-carbonyl)thieno[2,3-b]pyridine derivatives 24, 25, and 27 respectively.     

Phase Transfer Catalyzed Synthesis of 1, 2-Bis[（3-aryl）-s-triazolo- [3, 4-b]-[1, 3, 4]thiadiazole-6-yl]ethanes

s-Triazolo[3, 4-b]-[1, 3, 4]thiadiazole derivatives have been paid attractive attention due to their significantly biological activities1-5, including antibacterial, antifungal, anticancer, relaxing vascular activities. They are highly important heterocyc…     

Synthesis of [125I]‐, [2H]‐, and [3H]‐Labeled 3‐Iodothyronamine (T1AM)

3‐Iodothyronamine (T₁AM) is a novel metabolite of thyroid hormone. In HEK‐293 cells expressing an orphan G‐protein coupled receptor, the trace amine receptor, T₁AM, potently increased cAMP accumulation. In mice, T₁AM rapidly induced hypothermia and bradycardia within minutes of administration. These results suggest the existence of a new signaling pathway, the stimulation of which leads to rapid physiological and behavioral consequences. Isotope‐labeled T₁AM derivatives would be useful to study the biology and pharmacology of T₁AM. Herein we describe efficient syntheses of [¹²⁵I]‐, [²H]‐, and [³H]‐T₁AM.     

One-step synthesis of some polyfluoroalkylated 1,3-benzodioxoles, 4H-l,3-benzodioxins anddibenzo[d,f] [l,3]dioxepins

Several polyfluoroalkylated heterocyclic compounds containing methylenedioxy group such as 2-(F-alkyl) substituted 1,3-benzodioxole, piperonal, 4H-1,3-benzodioxin, 1,3-dioxolane and 6-(F-alkyl) substituted dibenzo[d,f][1,3]dioxepin have been prepared through double Michael-addition reactions of 2,2-dihydropolyfluoroalkanoates with the corresponding diphenols or diols in high yields.     

Synthesis of Spiro[benzo[h]chromene-4,3′-indoles] and Spiro[benzo[f]chromene-1,3′-indoles]

Russian Journal of Organic Chemistry - New spiro heterocycles, spiro[benzo[h]chromene-4,3′-indoles] and spiro[benzo[f]chromene-1,3′-indoles], have been synthesized in 50–60% yield...     

Pyridazines,LIV: On the synthesis of pyridazine-fused S-heterocycles: Thieno[2,3-c]pyridazine,pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine,and pyridazino[3,4-b][1,4]benzothiazine

Summary Starting from 3-chloro-4-pyridazinecarbonitrile (1), the thienopyridazine derivatives2 and3 were prepared. Condensation of3 with triethyl orthoformate afforded the novel tricyclic system4. Reaction of1 with 2-aminothiophenol, followed by treatment with NaH/DMSO was found to give the diaza-phenothiazine6 instead of the expected condensed thiazepine.Dedicated with best wishes to Prof. Dr. G. Zigeuner on the occasion of his 70^th anniversary     

铁液中[Ce]-[O]-[S]沉淀图及其应用

选用近期实验所测较为准确的稀土-氧、稀土-硫、稀土-氧-硫体系的热力学数据建立了纯铁液中的[Ce]-[O]-[S]空间沉淀图。应用热力学理论计算了铁液中氧硫活度与生成的稀土夹杂物间的定量关系。确定了铁水初始氧硫活度与生成稀土夹杂物类型的关系,并验证了理论计算结果。     

穴醚[2, 2, 2]和穴醚[2, 2]对镉离子萃取行为的研究

本文研究了穴醚[2,2,2]和穴醚[2,2]在硝基甲烷中对镉的萃取行为。探讨了溶剂、穴醚浓度,碱浓度,无机酸浓度,盐效应及共存离子对镉萃取的影响。实验结果表明,硝基甲烷ε=35.6,μ=3.4德拜宜作为穴醚的溶剂。当穴醚[2,2,2]——硝基甲烷的浓度为2×10~(-3)M,Me_4NOH浓度为4×10~(-2)M时对镉的萃取最为有利。无机酸的引入使穴醚质子化程度加大,盐效应对镉的萃取无明显影响。十八种共存离子对镉萃取无干扰,因而选择性高。实验结果为用穴醚[2,2,2]萃取镉提供了依据。     

预测[C,O,S]体系的稳定异构体

采用 DFT, QCISD及CCSD(T)方法对单重态和三重态的COS分子体系势能面进行了理论计算, 在 QCISD/6-311G(d) 水平上得到4个过渡态连接的6个稳定构型. 经动力学及热力学分析发现只有一个单重态线性的分子11(O—C—S) 能够稳定存在.     

Synthesis of Some New Thieno[2,3-b]pyridines,Pyrimidino[4′,5′:4,5]thieno[2,3-b]-pyridines,and 2,3-Dihydro-1,3,4-thiadiazoles

Thieno[2,3-b]pyridines were synthesized from 6-benzofuran-2-yl-4-phenyl-2-sulfanylpyridine-3-carbonitrile and each of chloro acetone, ethyl chloroacetate, ω -bromoacetophenone, and chloroacetonitrile. These compounds were conveniently converted into novel pyrido[4′,5′:4,5]thieno[3,2-d]pyrimidines. Also, 2,3-dihydro-1,3,4-thiadiazole was synthesized from hydrazonoyl halides and 2-benzofuran-2-yl-3-(phenylamino)-3-thioxopropanenitrile. The structures of the products have been elucidated by elemental analyses, spectral data studies, and alternative syntheses whenever possible. The newly synthesized compounds were tested towards microorganisms.     

Pyridine-2(1H)-thione in Heterocyclic Synthesis: Synthesis of Some New Nicotinic Acid Ester,Thieno[2, 3-b]pyridine,Pyrido[3′, 2′: 4, 5]thieno [3, 2-d]pyrimidine,and Thiazolylpyrazolo[3, 4-b]pyridine Derivatives

Nicotinic acid esters 3a–c were prepared by the reaction of pyridine-2(1H)-thione derivative 1 with α-halo-reagents 2a–c. Compounds 3a–c underwent cyclization to the corresponding thieno[2, 3-b]pyridines 4a–c via boiling in ethanol/piperidine solution. Compounds 4a–c condensed with dimethylformamide-dimethylacetal (DMF-DMA) to afford 3-{[(N,N-dimethylamino)methylene]amino}thieno[2, 3-b]- pyridine derivatives 6a–c. Moreover, compounds 4a–c and 6a–c reacted with different reagents and afforded the pyrido[3′,2′:4, 5]thieno[3, 2-d]pyrimidine derivatives 10a–d, 11a–c, 12a,b, 14a,b, 17, and 19. In addition, pyrazolo[3, 4-b]pyridine derivative 20 (formed via the reaction of 1 with hydrazine hydrate) reacted with ethylisothiocyanate yielded the thiourea derivative 21. Compound 21 reacted with α-halocarbonyl compounds to give the 3-[(3H-thiazol-2-ylidene)amino]-1H-pyrazolo[3, 4-b]pyridine derivatives 23a–c, 25, and 27a,b.     

Synthesis of 2,4-disubstituted pyrimido[4,5-b]-indoles,pyrano[4′,3′:4,5]pyrrolo[2,3-d]pyrimidines and some conversions of pyrimido[4,5-d]indoles

Methods have been developed for the production of 2,4-disubstituted 5,6,7,8-tetrahydro-9H-pyrimido[4,5-b]indoles and pyrano[43:4,5]pyrrolo[2,3-d]pyrimidines. Heterocyclization reactions were carried out on 4-hydrazinopyrimido[4,5-b]indoles.A. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Erevan, 375014. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10. pp. 1413–1416, October, 1996. Original article submitted June 21, 1996.     

The pH-controlled[2]or [3]pseudorotaxanes based on stilbene dye SD⊂CB[7]

We studied characteristics of [2] or [3]pseudorotaxanes based on stilbene dye SD?CB[7] . In neutral or weak alkaline conditions, SD could be encapsulated inside the stilbene site of CB[7] with 1:1 stoichiometry, whereas, with the pH changing to acidity, the hydrogen bonding between the carboxyl group and the carbonyl of CB[7] maked another CB[7] molecule include into hexanoic acid site, these processes were confirmed by fluorescence spectra,UV–Vis spectra and 1H NMR.     

Polarity of [sgrave]3,λ5-Phosphoranes

Abstract

Tricoordinated pentavalent phosphorus compounds- [sgrave]³,λ⁵-phosphoranes-present a new field in unusually (low) coordinated phosphorus chemistry. Our current interest in these compounds is stimulated by the possibility of actual determination of unknown phosphorus bond polarities, using electrical methods in subsequent investigations of the spatial and electronic structure of [sgrave]³,λ⁵ -phosphoranes. We have studied the series of bis(imino)phosphoranes by the method of dipole moments R²N=P (R¹)=NR³ (I-VI) R¹ R² R³,^μexp.^{(D): (I) N}(^SiMe ₃)₂, ^SiMe ₃, SiMe₃, 2.16; (11) t-Bu, t-Bu, 2.36; (111) N(SiMe₃)₂, SiMe₃, t-Bu, 2.26; (IV) 2,4,6-Me₃C₆H₂, t-Bu, 2,4,6-t-Bu₃C₆H₂, 2.44; (V) t-Bu(Me₃Si)N, t-Bu, t-Bu, 2.74; (VI) c-2,2,6,6-Me4C5H6N, SiMe₃, SiMe₃, 2.82 and defined P=N bond polarity (3.14D). Dipole monents (I-VI) are described by the given values, the group moments R-P and R-N were previously found from dicoordinated phosphorus compounds. The tendency of increasing ^μexp, with the growth of n,Π-donor abilities of ^μexP,₁ substituent R in row (I-III)-(V)-(VI) is possibly caused by the increase of the conjugative effect contribution in stabilization of the 4-electron 3-centre Π-system N=P=N.     

[Si,N,N,P]体系异构体结构与稳定性

在B3LYP/6-311G(d)和QCISD(t)/6-311+G(2df)(单点)水平下计算得到了[Si,N,N,P]体系势能面上的一些驻点, 研究了异构体之间的异构化过程, 并讨论了该体系异构体的结构与稳定性. 结果表明在[Si,N,N,P]体系中的11个异构体中只有含有Si-P交叉成键的类蝶型四元环异构体SiNPN(E1, ²A″)是稳定的, 其他异构体由于易于重排或是解离, 稳定性较低. 研究同时给出了E1的电子与几何结构、振动频率及指认、偶极矩和转动常数等相关数据. 分析结果表明通过中间体E3(SiNPN)的反应SiN(²Π) + PN(¹Σ)→E1是由SiN(²Π)和PN(¹Σ)碎片产生E1的最有利途径, 因此E1可成为星际观测的目标. G2级别下此反应的反应焓变为215.25 kJ/mol (298.15 K), 而异构体E1在298.15 K下的标准生成焓为457.99 kJ/mol.     

[C, N, N, P]体系异构体结构与稳定性

在B3LYP/6-311G(d)和QCISD(t)/6-311+G(2df)水平下计算得到了[C, N, N, P]体系的9个异构体、20个过渡态及一些相关的解离碎片, 并研究了异构体之间的异构化过程, 讨论了该体系异构体的结构与稳定性. 结果表明在得到的9个异构体中, 具有2A′电子态的、非线型链状NCNP, NCPN, CNPN和CNNP 4个异构体是较稳定的. 其余异构体由于易于重排或是解离, 稳定性较低. 研究同时给出了这4个异构体的振动频率、转动常数、偶极矩、第一绝热电离能和绝热电子亲合能等相关数据, 为可能的实验和星际光谱观测提供相关的理论数据. 得到的计算结果与等价电子体系SiNNP进行了比较.     

Bi3GaS5]2[Ga3Cl10]2[GaCl4]2·S8 containing heterocubane-type [Bi3GaS5]2+, star-shaped [Ga3Cl10]-, monomeric [GaCl4]- and crown-like S8

By reaction of elemental bismuth, sulfur, bismuth(III) chloride and gallium(III) chloride in the ionic liquid (BMIm)Cl (BMIm: 1-butyl-3-methylimidazolium), [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is obtained as red transparent crystals. According to X-ray structure analysis based on single crystals, the title compound crystallizes with triclinic lattice symmetry and is composed of heterocubane-type [Bi(3)GaS(5)](2+) cations, trimeric star-shaped [Ga(3)Cl(10)](-) anions with three (GaCl(4)) tetrahedra sharing a single central chlorine atom, monomeric [GaCl(4)](-) tetrahedra and neutral, crown-shaped S(8)-rings. Here, the heterocubane [Bi(3)GaS(5)](2+) as well as the star-shaped [Ga(3)Cl(10)](-) are observed as building units for the first time. [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is further characterized by X-ray powder diffraction as well as by thermogravimetry/differential thermal analysis.