[6O]富勒烯的化学修饰

对近年来一些新的[60]富勒烯的化学修饰方法进行了综述。参考文献76篇。     

Phosphate Doubly Capped Tetrahomodioxacalix[6] arene

A bisphosphate-bridged tetrahomodioxacalix[6] arene with a C2v symmetry at the ambient temperature was obtained by the reaction of tetrahomodioxacalix[6] arene with POCl3。     

桥联杯[6]芳烃研究进展

综述了桥联杯[6]芳烃的合成及构象固定等方面的研究进展,并以下缘1,4位桥联杯[6]芳烃,杯[6]冠醚和杯[6]穴醚及其类似物等主体分子为重点,综述了桥联杯[6]芳烃在分子识别和超分子化学领域中的应用研究的最新进展。     

An Interesting Approach to Bis-calix[5]arene Analogue from Calix[6]arene

Calix [n] arenas {n = 4, 6 or 8} are easily prepared from formaldehyde and para-substituted phenols via cyclic condensation under alkaline conditions in one step. It is not surprising that the calyx [n] arene (n = 4, 6, 8) chemistry has been developing very rapidly during the latest 20 years1. However, it is not the case for calixarenes with odd benzene rings (for example, n = 5). The yield of p-tert-butylcalix [5] arene synthesized in one-step from p-tert-butylphenol and formaldehyde was a…     

Competitive [2,3]- and [1,2]-oxonium ylide rearrangements. Concerted or stepwise?

The axial-equatorial conformational isomer distribution of the reactant diazoacetoacetate or its metal carbene intermediate is reflected in Rh(II) catalyzed oxonium ylide forming reactions of 3-(trans-2-arylvinyl)tetrahydropyranone-5-diazoacetoacetates that afford diastereoisomeric products for both the symmetry-allowed [2,3]- and the formally symmetry-forbidden [1,2]-oxonium ylide rearrangements.     

An Interesting Approach to Bis—calix [5] arene Analogue from Caxlix[6] arene

By 1,4-bridgine of p-tert-butylcalix [6] arene with 2,6-bis(bromomethyl)-4-methyl-anisole,a new type of bis-calix [5] arene analogue was obtained in high yield.     

Calix[4]dithiacrown-6 and Its Platinum Complex

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Bio-inspired Calix[6]Arene–Zinc Funnel Complexes

A bio-inspired supramolecular system is presented. A calix[6]arene possessing three imidazolyl arms on alternate phenolic positions binds a zinc ion. The resulting complex contains a hydrophobic pocket, which has a flattened conic shape. The system behaves as a selective molecular funnel for neutral guests that bind the metal centre. The exceptional stability of these tetrahedral dicationic complexes is exemplified by the acetaldehyde ternary adduct that was analysed by X-ray crystallography. The ligand is deeply buried in the heart of the calixarene cavity, pointing its methyl group selectively towards the centre of one of the aromatic walls, thereby establishing a stabilizing CH/π interaction. Protic guests undergo hydrogen bonding with the phenolic oxygens of the calixarene structure. The selectivity of the binding in the cavity is based on both the affinity of the donor atom of the guest ligand for the zinc ion and the relative host–guest geometries. The helical shape of the tris-imidazolyl groups binding the metal centre is the base of the chirality of the system. The twisted calix[6]arene structure of the zinc funnel complexes is shown to provide a new example of a cavity suitable for host–guest chiral induction.     

Cucurbit[6]uril的简便合成及其硝化

Cucurbituril(葫芦脲,CB[6])是迄今已知的类似于Fullerene(C60)的另一个高度对称中空的刚性分子.C60已经成为当前化学研究的一个重要热点,而后者尚处于起步阶段[1,2].目前已经发现CB[6]的许多独到的重要用途,特别是超分子载体等[3].     

One-Pot Method for Synthesis of Calix[6]biscrowns

p-tert-Butylcalix[6]-1,4-2,5-biscrown-4 is a typical member of the family of calix[6]crowns. In the literature, the compound was synthesized from calix[6]arene by two steps and the overall yield based on calix[6]arene was 24%.Herein we wish to report a one-pot method to do this work. By this method the yield was up to 48% and the reaction time was greatly reduced.     

叔丁基杯[6]芳烃的去叔丁基反应

报道了以对叔丁基杯[6]芳烃为原料,室温时,在三氯化铝催化下选择性脱去叔丁基的工艺.探讨了在合成去叔丁基杯[6]芳烃实验中催化剂用量对反应结果的影响,并对反应机理进行了讨论.结果表明,当n(AlCl3)∶n(p-tert-calix[6]arene)=8~9.5∶1时,分离得到了两种去叔丁基杯[6]芳烃:5-叔丁基-37,38,39,40,41,42-六羟基杯[6]芳烃和37,38,39,40,41,42-六羟基杯[6]芳烃,当n(AlCl3)∶n(p-tert-calix[6]arene)=10.5∶1时,得到37,38,39,40,41,42-六羟基杯[6]芳烃,产率90.8%.     

Some reactions of [(η6-C6Me6)Ru(η6-[2.2]paracyclophane)]-[BF4]2 with nucleophiles

Single addition of the nucleophiles X⁻ (X = H, CN, OH) to the less sterically hindered ring in [(η⁶-C₆Me₆)Ru(η⁶-C₁₆H₁₆)][BF₄]₂ (1) proceeds smoothly to produce, as the sole product, [(exo-η⁵-C₆Me₆X)Ru(η⁶-C₁₆H₁₆)][BF₄]. Use of Na[BD₄] in place of Na[BH₄] gives the expected shift in ν(C-H_exo) in the infrared spectrum.     

Synthesis of Green Colored Photochromic 6′-Arylamino Spiro [2H]Naphth[1,2-b]oxazines

The published route to a series of 6′-arylamino substituted photochromic spirooxazines has been investigated with improvements made to perform the synthesis in satisfactory yield. The route has been exemplified with several novel derivatives prepared (including hydroxyl functionalised). Additionally, a one-pot procedure for the conversion of suitably functionalized 1,2-naphthoquinones into the photochromic compounds is reported.     

A Novel Type of Lower-Rim-Connected Double-Calix[6]arenes Composed of A 1,2,4-Triply Bridged and A Normal Calix[6]arene

Calixareneshavebeenprovedtobeusefulbuildingblockstoconstructmolecularreceptorsinsupramolecularchemistry.Chemicalmodificationsofcalixarenesattheupperrimorthelowerrimcanaffordpreorganizedligandsabletocomplexmetalionsandneutralmolecules,oftenwithspecialselectivitiesl.Inordertoimprovethebindingpropertiesofcalixarenes,double-calixareneshavebeenpreparedandattractedmuchmoreattentionduetothecombinationoftwobuildingblockswithenforcedcavitiesandspecialmolecularrecognitionabilitiesbyco-operationeffects2.…     

σ-Aromaticity-Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−

In this work, the largest heterometallic supertetrahedral clusters, [Zn₆Ge₁₆]⁴⁻ and [Cd₆Ge₁₆]⁴⁻, were directly self-assembled through highly-charged [Ge₄]⁴⁻ units and transition metal cations, in which 3-center–2-electron σ bonding in Ge₂Zn or Ge₂Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures have an open framework with a large central cavity of diameter 4.6 Å for Zn and 5.0 Å for Cd, respectively. Time-dependent HRESI-MS spectra show that the larger clusters grow from smaller components with a single [Ge₄]⁴⁻ and ZnMes₂ units. Calculations performed at the DFT level indicate a very large HOMO–LUMO energy gap in [M₆Ge₁₆]⁴⁻ (2.22 eV), suggesting high kinetic stability that may offer opportunities in materials science. These observations offer a new strategy for the assembly of heterometallic clusters with high symmetry.     

Condensed pyridopyrimidines. 1. Synthesis of new derivatives of pyrano[3′,4′∶5,6]pyrido[2,3-d]pyrimidines

New derivatives of pyrano[3,45,6]pyrido[2,3-d]pyrimidines were synthesized from ethyl 2-amino-7,7-dimethyl-7,8-dihydro-5H-pyrano[4,3-b]pyridine-3-carboxylate.A. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Erevan. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1239–1241, September, 1999.     

Substituted benzoquinazolinones. Part 1: Synthesis of 6-aminobenzo[h]quinazolinones via Buchwald–Hartwig amination from 6-bromobenzo[h]quinazolinones

6-(Morpholin-4-yl)benzo[h]quinazolin-4(3H)-one derivatives 18a,b were prepared under Buchwald–Hartwig conditions by reacting 6-bromobenzo[h]quinazolin-4(3H)-ones 13a,b with morpholine in the presence of a Pd(OAc)₂/XantPhos system in 1,4-dioxane as solvent. The starting 6-bromobenzo[h]quinazolin-4(3H)-ones 13 were synthesized via condensation of the ethyl 1-amino-4-bromonaphthalene-2-carboxylate (11) with formamide (Niementowski reaction), and then reaction of the obtained benzoquinazolinone 9 with appropriates benzyl bromides. Compound 11 was prepared using a three-step procedure involving (a) metalation of the N-Boc- or N-Piv-protected 1-aminonaphthalenes with t-BuLi, followed by reaction with ethyl chloroformate, (b) bromination of the naphthalene ring of ester 3 using NBS, and next (c) deprotecion of the amine group with TFA or HCl. Biological screening of the potential cytotoxicity of compounds 8, 9, 18b on A549 and HT29 cell lines, as well as on the lymphocytes showed that compound 18b has interesting anticancer activities. The detailed synthesis, spectroscopic data, and biological assays were reported.     

Synthesis and structures of zirconium complexes [Et2H2N]+2[ZrCl6]2–, [Me3NCH2Ph]+2[ZrCl6]2–•MeCN, [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–•2 MeCN,and [Ph4Sb]+2[ZrCl6]2–

Russian Chemical Bulletin - The complexes [Et2H2N]+2[ZrCl6]2– (1), [Me3NCH2Ph]+2[ZrCl6]2–?MeCN (2), [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–?2 MeCN (3), and...     

[Mo(S_2CNEt_2)_4]·[FeCl_4]·[C_6H_5SH]_2包合物晶体的合成、结构和性质研究Ⅱ.

用MoCl_5,FeCl_3,二乙胺基硫代甲酸钠和苯硫酚在甲醇中反应,得到[Mo(S_2CNEt_2)_4]·[FeCl_4]·[C_6H_5SH]_2三元包合物晶体,并测定其结构.晶体属正交晶系,空间群C_(2V)~7-P_(mn)2_1,晶胞参数:α=18.518A,b=7.282A,c=18.518A,V=2496.96A~3,Z=2.结构参数经块矩阵最小二乘法精修后,最后的偏离因子R=0.069.此外,还进行了红外光谱、紫外一可见光谱,EPR谱及电化学性质等研究.