Reactions of [60]Fullerene with Di(azidomethyl) benzenes

Alargenumberofadditionsto[6O]fullerenehavebeeninvestigated.However,mostoftheworkhaveconcentratedontheformationofthemono-additionproductS0f[60]fullerene'-Thedevelopment0fselechveroutestomultipleadductShascurrentlybecomethefrontierinthechendstryof[60]fuIlerene'~'.FollowingtheaPplicahonoftether-directedremotefunctionalizati0ntotheregi0specificformati0nofthedi-andtriadductSof[60]fullerene,F.Diederichetal6alsodescribed'awayforthedirectdifunctionalizationof[60]fullerenebasedonacyclizationreachono…     

Recent advances in the applications of [1.1.1]propellane in organic synthesis

As a highly strained small molecule, [1.1.1]propellane has been widely used in various synthetic transformations owing to the exceptional reactivity of the central bond between the two bridgehead carbons. Utilizing strain-release approaches, the rapid development of strategies for the construction of bicyclo[1.1.1]pentane (BCP) and cyclobutane derivatives using [1.1.1]propellane as the starting material has been witnessed in the past few years. In this review, we highlight the most recent advances in this field. Accordingly, the reactivity of [1.1.1]propellane can be divided into three pathways, including radical, anionic and transition metal-catalyzed pathways under appropriate conditions.     

CO2 and photo-controlled reversible conversion of supramolecular assemblies based on water soluble pillar[5]arene and coumarin-containing guest

In this communication,a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO₂ responsive tertiary amine unit and a UV responsive coumarin group.When guest molecule 1 dispersed in water,it self-assembled into sheet-like structures.Upon bubbling CO₂,1 transformed into 1 H due to the tertiary amine unit was protonated,accompany the nano-sheets transformed into vesicles.Further irradiation of 1 H with 365 nm light for 3 h,the coumarin group reacted with each other to form bola-type amphiphie 2 H.In this case,vesicles collapsed and re-assembled into nano-tubes.However,when addition of WPS into the solution of 1 H,the vesicles transformed into micelles,this is due to the formation of supramolecular amphiphile WP5&1 H.Upon irradiation of WP5&1 H with 365 nm light for 3 h,nano-ribbons observed instead of micelles in the solution.Notably,nanotubes from 2 H could also transform into nano-ribbons after adding WPS.The selfassembly process and the resultant assemblies were characterized by TEM,SEM,DLS,SAXS and NMR technologies.Due to both CO₂ and light are "green" for living organisms,we anticipated our system can offer the possibilities in "on demand" drug absorption and release.     

1,2,4-三唑并[3,4-b]-1,3,4-噻二唑的合成

近年来稠杂环化合物的合成及其生物活性的研究日益成为杂环化学研究的热门课题。3,6-二取代-1,2,4-三唑并噻二唑衍生物是具有广谱生物活性的稠杂环化合物,如抗菌、消炎、杀微生物、调节植物生长、除草等,因而引起各国化学家的广泛兴趣。此类化合物的生物活性,     

新型间苯二酚杯芳烃硫脲衍生物对阴离子的识别

通过间苯二酚杯芳烃连续三步反应, 以较高产率合成了分子中连有8个和12个硫脲端基的间苯二酚杯芳烃的酰胺衍生物. 用紫外可见光谱法研究了两个代表性化合物4,6,10,12,16,18,22,24-八[6-(苯基硫脲基)-己氨甲酰基甲氧基]-2,8,14,20-四苯基杯[4]间苯二酚芳烃(THBC)和4,6,10,12,16,18,22,24-八[2-(苯基硫脲基)-1-甲基乙基-1-氨甲酰基甲氧基]-2,8,14,20-四苯基杯[4]间苯二酚芳烃(TPBC), 对各种阴离子(AcO^－, H₂PO₄^－, HSO₄^－, H₂PO₄^2－, C₁₂H₂₅-C₆H₄-SO₃^－, Cr₂O₇^2－, B₄O₇^2－, Cl^－, Br^－)的识别性能, 结果表明它们对AcO^－, H₂PO₄^－, HSO₄^－等阴离子有较好的配位作用, 能形成1∶3的配合物.     

Synthesis of 2-chloro-1,1-difluoroallyl mesylates through novel rearrangement and CC bond formation by their Pd-catalyzed reaction with diethylzinc

Treatment of 2-chloro-3,3-difluoroprop-2-en-1-ol derivatives (2) with methanesulfonyl chloride in the presence of a base did not give the expected esters but 2-chloro-1,1-difluoroprop-2-enyl methanesulfonates (4) through a novel [3,3] sigmatropic rearrangement. Reaction of 4 with diethylzinc in the presence of tetrakis(triphenylphosphine) palladium gave 1-alkyl- or 1-aryl-2-chloro-3-fluoropenta-1,3-dienes in moderate to good yields through a CC bond formation followed by dehydrofluorination.     

A,C-Bridged Calix[6]arene： Relationship between the Length of Bridge and Conformation

Three new A,C-diamide bridged p-tert-butylcalix[6]arenes were synthesized from p-tert-butylcalix[6]arenes by bridging ClCH2CONH(CH2)nNHCOCH2Cl(n=3,4,6) in acetonitrile using K2CO3 as a base in 17%-25% yields.It was found that the bridged calix[6]arenes with shorter bridges (n=2,3,4 in N′,N′-bischloroacetodiamines) adopt cone conformation, but the last one (n=6) adopts alternate conformation, i.e., accompanying the lengthening of bridge, the conformation of A,C-bridged calix[6]arenes changes from cone to alternate.     

Chloroaqua Complexes [M3S4(H2O)9?xClx](4?x)+ (M = Mo, W; x = 4, 6, 7) and Their Supramolecular Compounds with Cucur[8]uril

Compounds of trigonal cluster chloroaqua complexes with cucurbit[8]uril were synthesized by slowly evaporating HCl solutions of chalcogenides heterometallic cubane cluster complexes of molybdenum and tungsten with cucurbit[8]uril in air; the complexes were characterized by X-ray diffraction analysis: (H₃O)₈[Mo₃S₄(H₂O)_2.5Cl_6.5]₂Cl(PdCl₄)·(C₄₈H₄₈N₃₂O₁₆)· 29H₂O (a = 13.3183(17) Å, b = 13.7104(18) Å, c = 18.225(3) Å; α = 80.263(3)°, β = 77. 958(3)°, γ = 87.149(4)°, V = 3207.4(7) ų, space group P , Z = 1, ρ(calc) = 1.900 g/cm³), (H₃O)₄ [Mo₃S₄(H₂O)₃Cl₆]₂·(C₄₈H₄₈N₃₂O₁₆)₃·68H₂O (a = 21.413(6) Å, c = 49.832(10) Å; γ = 120°, V = 19788(8) ų, space group R , Z = 3, ρ(calc) = 1.695 g/cm³), (H₃O)₆ [Mo₃S₄(H₂O)₃Cl₆]₂Cl₂·(C₄₈H₄₈N₃₂O₁₆)·12H₂O (a = 15.881(2) Å, b = 17.191(2) Å, c = 23.276(4) Å; β = 98.865(15)°, V = 6278.7(15) ų, space group P2₁/c, Z = 2, ρ(calc) = 1.638 g/cm³), [W₃S₄(H₂O)₅Cl₄]₂·(C₄₈H₄₈N₃₂O₁₆)₃·35H₂O (a = 21.038(3) Å; α = 61.20(1)°, V = 6762.0(14) ų, space group R , Z = 1, ρ(calc) = 1.582 g/cm³). The [Mo₃S₄(H₂O)₃Cl₆]²⁻ anion complex was isolated as three geometrical isomers.Original Russian Text Copyright © 2004 by E. V. Chubarova, D. G. Samsonenko, H. G. Platas, F. M. Dolgushin, A. V. Gerasimenko, M. N. Sokolov, Z. A. Starikova, M. Yu. Antipin, and V. P. Fedin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1049–1058, November–December, 2004.     

Study of nitrogen- and sulfur-containing heterocycles. 54. Properties and conversions of pyrimido[4,5-<Emphasis Type="Italic">b</Emphasis>]-1,4-benzothiazepines. Synthesis of a novel heterocyclic system: Pyrimido[5,4-<Emphasis Type="Italic">c</Emphasis>]isoquinoline

We have studied some properties and conversions of pyrimido[4,5-b]-1,4-benzothiazepines: reduction, oxidation, reactions with nucleophilic reagents (methanol, hydrazine, hydroxylamine, o-methylhydroxylamine, and thiosemicarbazide). We have synthesized derivatives of a novel heterocyclic system: pyrimido[5,4-c]isoquinoline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1863–1872, December, 2004.For Communication 53, see [1].     

The de novo design of median molecules within a property range of interest

Summary In this paper an application is presented of the median molecule workflow to the de novo design of novel molecular entities with a property profile of interest. Median molecules are structures that are optimised to be similar to a set of existing molecules of interest as an approach for lead exploration and hopping. An overview of this workflow is provided together with an example of an instance using the similarity to camphor and menthol as objectives. The methodology of the experiments is defined and the workflow is applied to designing novel molecules for two physical property datasets: mean molecular polarisability and aqueous solubility. This paper concludes with a discussion of the characteristics of this method.