Fullerene lipids: Synthesis of novel nitrogen-bridged [60]fullerene fatty ester derivatives

Reactions of methyl 6-azido-hexanoate, 8-azido-octanoate, and 12-azido-dodecanoate with [60]fullerene (1) gave the corresponding aza-[60]fullerene ester derivatives (2a-2c, 22–35% based on the amount of [60]fullerene reacted). The nitrogen atom is bonded to the [60]fullerene cage to yield a “[5,6]-open” type aza substructure. This was confirmed by the appearance of 30–31 sp ² signals at δ_C 133–147 in the carbon nuclear magnetic resonance spectra. Reaction of methyl 11-azido-7-undecynoate with [60]fullerene furnished a mixture of aza-[60]fullerene (2d, 53%) and aziridine-[60]fullerene (2e, 38%) ester derivatives. Compound 2e was identified as the “[6,6]-closed” type aziridine-[60]fullerene derivative, which displayed 10 sp ² signals in the region δ_C 140–145 and one signal at δ_C 85.05 for the sp ³ carbons of the cage. Refluxing a solution of compound 2d in toluene for 50 h gave about 50% yield of compound 2e, but not vice versa.     

亚甲基[6,6]-Fullerene[C60]单羧酸衍生物的合成

以溴乙酸乙酯、硫醚和Fullerene[60]为原料合成Fullerene[60]羧酸乙酯,再经水解、酸化得到亚甲基[6,6]-Fullerene[C60]单羧酸,并进一步反应得其酰胺。这些新化合物的结构经IR和1HNMR确证。     

On an improved pyrolytic synthesis of [60]- and [70]-fullerene

The nickel-catalyzed pyrolysis of two fullerene precursors — (1) naphthalene and (2) 1-bromonaphthalene — at 1200°C in an argon atmosphere has been investigated. Fullerenes, polycyclic aromatic hydrocarbons (PAHs), and polycyclic aromatic brominated species (the latter obtained in pyrolysis of 1-bromonaphthalene only) were extracted from the pyrolysates by reflux in toluene. The toluene extracts were subjected to mass spectrometric analysis using the chemical ionization technique in the negative mode. Mass spectra are included with discussions on fullerene yields and on the mechanism by which fullerenes are formed in pyrolysis. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the toluene-insoluble material.     

富勒烯[60]-曲酸衍生物的合成

富勒烯[60]是由相邻的六元环和五元环组合而成的中空状球形分子,环中含有30个双键,具有缺电子烯烃性质,易发生加成反应。文章通过对甲苯磺酰肼与曲酸缩合反应生成曲酸对甲苯磺酰腙,再与富勒烯[60]发生环加成反应合成了富勒烯[60]-曲酸衍生物,产率32%。目标产物的结构经IR、1H NMR、MS确认。     

C60高分子衍生物的合成与应用价值（上）

综述了近年来Ｃ６０的共价高分子材料化的研究。介绍了一系列Ｃ６０高分子衍生物的合成及表征方法。     

Fullerene lipids: Synthesis of C60 fullerence derivatives bearing a long-chain saturated or unsaturated triester system

Tris(hydroxymethyl)aminomethane was successfully esterified with saturated and unsaturated long-chain fatty acids. The resulting amino-triester intermediates were successively reacted with chloroacetyl chloride, sodium azide, and C₆₀ fullerene. Spectral evidence showed that the aziridine ring is joined to the junction of [6,6]-fused rings of the fullerene. The structures of the various C₆₀ fullerene derivatives bearing a long-chain saturated or unsaturated triester system were characterized by spectroscopic and spectrometric methods.     

富勒烯-C_(60)衍生物与2-溴甲基-3-(二溴甲基)喹喔啉的合成研究

以 2 ,3 二 (溴甲基 )喹喔啉和N 溴代丁二酰亚胺 (NBS)为原料 ,以偶氮二异丁腈 (AIBN)为催化剂 ,在氮气中反应制得 2 溴甲基 3 (二溴甲基 )喹喔啉 (A) ,收率为 2 0 %。以此为中间体与富勒烯C60 反应 ,以 18 冠 6为催化剂 ,按n(A)∶n(C60 ) =1 1∶1 0的物质量比在氮气气氛中经Diels-Alder环加成反应合成了C60 并夹二氮杂蒽 (B) ,收率为 10 6 6 %。并对A和B进行了结构表征。     

Review on the Nitration of [60]Fullerene

[60]Fullerenes continued to attract the interest of a broad scientific community since the method of macroscopic synthesis of fullerenes was discovered in 1990. Studies on the nitration of fullerenes have been carried out under different conditions and nitration reagents. The radical (^˙NO₂) is an excellent reactivity group to make direct multiplet additions with [60]fullerene to get polynitrofullerenes. Radical (^˙NO₂) can be obtained by many different methods.     

咪唑并[1,2-b]哒嗪的合成研究

咪唑并[1，2-b]哒嗪是第四代头孢菌素——头孢唑兰的重要中间体。以3，6-二氯哒嗪为原料，经氨解得到3-氨基-6-氯哒嗪，与溴乙醛成环形成6-氯咪唑并[1，2-b]哒嗪，再在催化剂作用下氢解成咪唑并[1，2-b]哒嗪。考察了反应温度、时间、物料配比、压力、催化剂用量等反应条件对收率的影响。总收率达到41％。用熔点，核磁共振谱和元素分析对产品结构进行表征。     

咪唑并[1, 2-a]吡啶甲酸衍生物的合成与表征

以3-三氟甲基-2-氨基吡啶为原料,通过NBS选择性溴化,再与溴代丙酮酸甲酯通过“一锅法”进行烷基化-环化反应,之后经选择性氯化、Suzuki偶联反应和水解,合成了咪唑并[1,2-a]吡啶甲酸衍生物。反应总收率达到36.5%。并对Suzuki偶联反应的催化剂和反应条件进行了探讨。     

Synthesis and structural assignment of certain pyrimido[1,2-a]benzimidazole derivatives

The pyrimido[1,2-a]benzimidazole derivatives compounds 1–8 were synthesized through cyclocondensation of 2-aminobenzimidazole with the appropriate benzsubstituted benzoylacetone by fusion at 150–170°C for 5 h. Quaternary salts compounds 9–22 were obtained by quaternization of compounds 1–8 with dimethyl or diethyl sulfate and subsequent isolation as the relatively insoluble perchlorate salts. Assignment and confirmation of the structures of the newly synthesized compounds were based upon elemental microanalyses and other spectral evidence.     

[60]Fullerene功能材料的制备研究

由于富勒烯在光、电、磁等方面表现出独特的性质，因此以C60为代表的富勒烯的研究成为最近十几年来研究的一个热点，在C60的功能化研究中，大量的C60衍生物被合成出来；不同的C60衍生物具有更加特殊的性能，使得其在物理、化学、材料学、医学、生物学等方面显示出广阔的应用前景。     

富勒烯C60物理、化学性质的研究进展

介绍了富勒烯的发现、结构及制备方法，比较详尽地阐述了富勒烯在有机溶剂中的溶解性、光学性质、磁性等物理性质以及与金属反应、氧化还原反应、加成反应等化学性质。     

Effects of Pin-up Oxygen on [60]Fullerene for Enhanced Antioxidant Activity

The introduction of pin-up oxygen on C₆₀, such as in the oxidized fullerenes C₆₀O and C₆₀O_n, induced noticeable increase in the antioxidant activity as compared to pristine C₆₀. The water-soluble inclusion complexes of fullerenes C₆₀O and C₆₀O_n reacted with linoleic acid peroxyl radical 1.7 and 2.4 times faster, respectively.

[60]PCBM的合成及纯化工艺

以C₆₀,对甲苯磺酰肼和4-苯甲酰基丁酸为原料,通过一锅法多步骤合成了[60] PCBM,用硅胶柱为载体,甲苯为洗脱剂获得初步纯化的[60] PCBM。经红外光谱图和¹H NMR谱图表征,证明合成产物为目标产物。为进一步纯化产物,结合HPLC分离技术,获得99.5%纯度的[60] PCBM。通过将副产物及回收的C₆₀重新投入合成体系,抑制了新的副产物产生,使得新鲜C₆₀转化为[60]PCBM的收率提高到93.3%。这些措施为降低高纯度[60] PCBM的成本奠定良好的基础。     

6-氯咪唑并[1,2-b]哒嗪的合成

以水合肼和马来酸酐为原料,经缩合、氯化、氨解和关环4步反应合成头孢唑兰的中间体6-氯咪唑并[1,2-b]哒嗪,总收率为65.5%.探讨了影响反应的主要因素,并通过1HNMR对产物结构进行了表征.     

[60]富勒烯三元环化反应及其衍生物功能研究

对[60]富勒烯的三元环化反应及其衍生物的功能研究进行了概述,讨论了[60]富勒烯的三元环化反应的发生机理.重点阐述了[60]富勒烯三元环化典型反应及获得的富勒烯衍生物的生物医药功能等,对今后的工作进行了展望.     

2,6-双-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑吡啶类衍生物的合成及抗菌活性

芳香羧酸酯化、肼解、成盐、环化成3-芳基-4-氨基-5-巯基-1,2,4-三唑与2,6-吡啶二甲酸在相转移催化剂四丁基碘化铵和POCl3作用下,高产率制得8种标题化合物,并利用IR、1HNMR、MS和元素分析对目标化合物的结构进行了表征.初步的抗菌实验表明,部分目标化合物表现出较好的抑菌活性.     

氮杂杯〔4〕芳烃化合物的合成

以对叔丁基杯〔4〕芳烃为原料,对其上沿的叔丁基进行修饰,经不同的合成路线,利用羟基保护、取代、去叔丁基、硝化以及还原合成了尚未报道的新型氮杂杯〔4〕芳烃衍生物。其结构经1 H NMR,13C NMR和GC-MS表征。     

Synthesis of 4-substituted imidazo[1,2-a]quinoxalines

A concise approach to 4-substituted imidazo[1,2-a]quinoxalines 7 is described, starting from 1-fluoro-2-nitrobenzene ( 3 ). The high variability in the functionalization of the imidazo [1,2-a]quinoxaline-4-position is due to the easy introduction of these substituents by N-acylation in the second last step.