[60]富勒烯环加成反应研究进展

综述了[60]富勒烯[2 1]环加成反应、[2 2]环加成反应、[2 3]环加成反应以及[4 2]环加成反应的典型反应、反应试剂以及反应机理,并展望了富勒烯的研究前景和发展方向.     

2-苯基[60]富勒烯吡咯烷衍生物的合成及其性能研究

为了给高能炸药提供钝感剂,以提高其安全性能,用甘氨酸、苯甲醛和C60等为原料合成了2-苯基[60]富勒烯吡咯烷衍生物(产物1),探讨并获得了产物1的适宜合成工艺条件:反应物C60、苯甲醛和甘氨酸物质的量之比为1: 4: 6,温度为105 ℃,反应时间为14 h,此时产率可达到75%(以消耗的C60计).用FT-IR(傅立叶变换红外光谱)、UV-Vis(紫外可见光谱)、1H-NMR(核磁共振氢谱)和MS(质谱)表征了产物1的结构,初步探讨了产物1对HMX(奥克托今)的钝感作用.结果表明,产物1对HMX具有明显的钝感作用,添加质量分数为1%的产物1可使HMX的摩擦感度降低到33%,撞击感度降低到48%.对产物进行了热分析研究,结果表明产物具有很好的热稳定性.     

一步法合成富勒烯[60]-纳米银复合物

AgNO3乙腈溶液注入热的苯甲醛,一步法合成了不同形貌和粒径的纳米银颗粒;硝酸银的乙腈溶液注入热的C60-二甲苯和苯甲醛混合液中,一步原位合成了富勒烯[60]-纳米银复合物。用X射线衍射(XRD)、透射电镜(TEM)、元素分析、傅里叶变换红外光谱(FT-IR)分析证实了富勒烯[60]-纳米银复合物的形成。对纳米银晶粒形成过程和富勒烯[60]-纳米银复合物的形成进行了初步的解释。     

2-[(8-羟基喹啉)-2-基]-5-(2-噻吩基)[60]富勒烯吡咯烷的合成、光学及电化学性能

通过1,3-偶极环加成反应合成出2-[(8-羟基喹啉)-2-基]-5-(2-噻吩基)[60]富勒烯吡咯烷,利用UV-Vis、FT-IR、RAMAN、MALDI-TOF MS、1 HNMR、13C NMR等手段对产物的结构进行了表征,并研究了产物的光学及电化学性能。结果表明,相对于C60来说,该产物的紫外吸收波长及荧光发射波长均发生红移,各对氧化还原峰的半峰电位发生明显的负移,更有利于应用于光电转化领域。     

Fullerene[60]功能材料的潜在应用前景

Fullerene[60]多氢化物可望在储氢材料方面获得应用前景，C60H36催化分解可望出氢气。Fullerene[60]的多硝基化合物可望作为含能材料的添加剂。这方面的研究是Fullerene化学的一个新     

N-甲基-2-(3-羟基苯基)[60]富勒烯吡咯烷衍生物的合成研究

利用1,3-偶极环加成反应,合成分离得到了一种C60吡咯烷衍生物:N-基-2-(3-羟基苯基)[60]富勒烯吡咯烷,通过单因素方法,探讨了反应条件对产物产率的影响,并得到了最佳工艺条件:反应物摩尔比(C60:3-羟基苯甲醛:N-甲基甘氨酸)为1:2:4,反应温度90℃,反应时间2h,产物的产率可达82%(以消耗的C60计).同时用Uv-Vis、FT-IR、1H-NMR、MS等测试手段表征了产物的结构.     

2种富勒烯吡咯烷中间体的合成

利用亚胺叶立德的1,3-偶极环加成法合成了2种带活性基团的富勒烯吡咯烷中间体,即氨基乙基富勒烯吡咯烷和N取代3,4-富勒烯吡咯烷.经基质辅助激光解吸电离飞行时间质谱仪、傅里叶变红外光谱仪和紫外可见光分光光度计表征可知,它们是2种富勒烯吡咯烷中间体.这2种中间体含活性基团,可用于合成更多的富勒烯衍生物,因此在富勒烯化学领域具有广阔的应用前景.     

N-甲基-2-(4-羟基苯基)[60]富勒烯吡咯烷衍生物的合成研究

利用肌氨酸和对羟基苯甲醛所形成的亚胺叶立德与C60发生 1,3-偶极环加成反应,合成了一种新型含羟基C60吡咯烷衍生物:N-甲基-2-(4-羟基苯基)[60]富勒烯吡咯烷.通过UV-vis、1H-NMR、MS、FT-IR确定了产物的结构.探讨了反应条件对产物产率的影响,得到了最佳工艺条件:反应物摩尔比为1:2:6,温度为90℃,反应时间为5h,此时产物的产率可达到87%(以消耗的C60计).     

取代基对8-羟基喹啉锂电子光谱影响的理论研究

运用密度泛函(DFT/B3LYP)方法对4种取代基(-NO2、-CN、-OH、-CH3)在8-羟基喹啉锂(Liq)五位上取代所形成的4种衍生物进行结构优化,并在此基础上应用含时密度泛函(TD-DFT)方法和单激发组态相互作用(CIS)分析了取代基对Liq前线分子轨道和电子光谱的影响.分析结果表明,不同性质的取代基对最高占据轨道(HOMO)电子云分布的影响趋势一致,而对最低空轨道(LUMO)电子云分布影响趋势不同.吸电子基使前线分子轨道能级降低,带隙增大,光谱蓝移.推电子基使前线分子轨道能级升高,带隙减小,电子光谱红移.推吸电子能力强的取代基对前线分子轨道和电子光谱的影响程度较大.     

取代基效应对有机化合物性质的影响

取代基效应是有机结构理论的重要组成部分。取代基效应对有机化合物的物理性质、化学性质和反应活性等都有着重要影响,了解有机化学中的取代基效应及其在有机化学中的作用方式,对于学习有机化学及应用有机化学知识都至关重要。     

Synthesis, Photophysical and Photovoltaic Properties of New [60]Fullerene Pyrrolidine Derivatives

Two new [60]fullerene pyrrolidine derivatives 2 and 3 were synthesized and characterized by ¹H NMR, ¹³C NMR and MS. Their photophysical processes have been investigated by using laser flash photolysis. The experiments show quenching of oligomer singlet excited state and the evidence of the fullerene singlet excited emission. And the intramolecular of electron transfer and also energy transfer of 2 and 3 occurred and the triplet excited state of fullerene moiety in 2 and 3 have different lifetime due to their different structures. A photovoltaic device using compound 2 as the only photoactive material has also been investigated which showed the energy conversion efficiency is 0.011%.     

Synthesis of Heterocycle-Containing [60]Fullerene Derivatives

Fullerene functionalization with heterocycles is reviewed, focusing attention on cycloaddition methodology and oxidative heterocyclization.¹     

Synthesis of Heterocycle-Containing [60]Fullerene Derivatives

Abstract

Fullerene functionalization with heterocycles is reviewed, focusing attention on cycloaddition methodology and oxidative heterocyclization. ^{1 1}This paper was presented before the Symposium 3 on ‘Expanded Horizons of Fullerene Science and Technology’ organized by L. Y. Chiang, E.Osawa, H. Terrones and M. Saunders at the 4th International Conference on Advanced Materials (ICAM-IV), Aug. 27 to Sept. 1, 1995, Cancun, Mexico.

     

[60]Fullerene Amino Acids and Related Derivatives

This paper is a review of the literature concerning the preparation of [60]fullerene amino acid and peptide derivatives. The structure and applications of these derivatives to the biological and Material sciences is also presented.     

[60]Fullerene Amino Acids and Related Derivatives

Abstract

This paper is a review of the literature concerning the preparation of [60]fullerene amino acid and peptide derivatives. The structure and applications of these derivatives to the biological and Material sciences is also presented.     

Preparation of Two Novel C60 and C70 Fullerene Pyrrolidine Derivatives

Abstract

C₆₀ reacted with paraformaldehyde and DL-valine in dry toluene under nitrogen to give a monoadduct. Under the similar conditions,C₇₀ gave a bisadduct. Both products were characterized by FT-IR,UV-Vis,EI-MS and NMR.The studies of the cyclic voltammetry showed that the abilities of donating electron of the products were increased compared to C₆₀ and C₇₀ respectively.     

Preparation of Two Novel C60 and C70 Fullerene Pyrrolidine Derivatives

C₆₀ reacted with paraformaldehyde and DL-valine in dry toluene under nitrogen to give a monoadduct. Under the similar conditions,C₇₀ gave a bisadduct. Both products were characterized by FT-IR,UV-Vis,EI-MS and NMR.The studies of the cyclic voltammetry showed that the abilities of donating electron of the products were increased compared to C₆₀ and C₇₀ respectively.     

Diels-Alder Reaction of [60]Fullerene with Dienes Having an Ester Substituent at 1-Position

Abstract

Treatment of [60]fullerene with ethyl trans, trans-hexa-2,4-dienoate (1) and methyl trans, trans-octa-2,4-dienoate (2) at 70 ～ 100 °C afforded products 3 and 4, respectively, which are resulted from Diels-Alder addition of the dienoates to a 6/6 ring junction of [60]fullerene.     

Diels-Alder Reaction of [60]Fullerene with Dienes Having an Ester Substituent at 1-Position

Treatment of [60]fullerene with ethyl trans, trans-hexa-2,4-dienoate (1) and methyl trans, trans-octa-2,4-dienoate (2) at 70 ∼ 100 °C afforded products 3 and 4, respectively, which are resulted from Diels-Alder addition of the dienoates to a 6/6 ring junction of [60]fullerene.