N,N-二甲基甲酰胺促进的富勒烯稠合噁唑啉衍生物的合成

doi:10.6023/cjoc202307003

摘要/Abstract

富勒烯稠合噁唑啉衍生物的合成已建立多种方法, 但绝大多数方法仅限于芳香族类底物. 发展了一种N,N-二甲基甲酰胺(DMF)促进富勒烯C₆₀与酰胺类底物在碱性条件下合成富勒烯稠合噁唑啉的方法, 该方法对脂肪族和芳香族酰胺均具有较好的兼容性, 能以27%~62%的收率成功合成了一系列富勒烯稠合噁唑啉衍生物. 实验结果表明N,N-二甲基甲酰胺(DMF)在此反应中作为共溶剂, 可以显著提高目标化合物的收率. 现场可见近红外吸收光谱和对照实验研究表明, 富勒烯稠合噁唑啉二负离子是反应的关键中间体, DMF有利于此二负离子的生成并对此二负离子起到稳定作用. 电化学性质研究显示, 富勒烯稠合噁唑啉产物的噁唑啉环上不含取代基和含芳基取代基的衍生物, 其起始还原电位相对于C₆₀无明显变化, 但噁唑啉环上含脂肪烷基的衍生物的起始还原电位有较大负移, 达到0.1 V.

关键词: 富勒烯稠合噁唑啉衍生物, 亲核反应, N,N-二甲基甲酰胺, 现场可见近红外吸收光谱, 电化学性质

Fullerene-fused oxazoline derivatives have been synthesized by many methods, however, the range of substrates is mainly limited to the aromatic substrates. Herein, a method for the synthesis of fullerene-fused oxazoline derivatives has been developed through the N,N-dimethylformamide (DMF)-promoted reaction of C₆₀ with amides under basic conditions. The method was viable for both aliphatic and aromatic amides, providing the corresponding products in 27%~62% yields. It was found that DMF as a cosolvent could significantly improve the yield of the products. Mechanistic studies indicate that dianionic [60]fullero-oxazoline is key intermediate, and DMF plays a role in stabilizing dianion as demonstrated by in situ visible near infrared spectroscopy and control experiments. The electrochemical property study showed that, to compare with C₆₀, fullerene-fused oxazoline derivatives of unsubstituted or substituted with an aryl group on oxazoline ring displayed only a slightly changed onset reduction potential, however, that for the derivatives decorated by an alkyl group such as Et on the oxazoline ring was apparently negatively shifted of up to 0.1 V.

Key words: fullerene-fused oxazoline derivatives, nucleophilic reaction, N,N-dimethylformamide, in situ visible near infrared spectroscopy, electrochemical property

引用此文

徐利军, 李宗军, 韩福社, 高翔. N,N-二甲基甲酰胺促进的富勒烯稠合噁唑啉衍生物的合成[J]. 有机化学, 2024, 44(1): 242-250.

Lijun Xu, Zongjun Li, Fushe Han, Xiang Gao. N,N-Dimethylformamide-Promoted Synthesis of Fullerene-Fused Oxazoline Derivatives[J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 242-250.

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图/表 7

图1. 已报道的合成富勒烯稠合噁唑啉的方法

Figure 1. Reported methods for the synthesis of fullerene-fused oxazoline derivatives

Entry	Amide (1a)/equiv.	Solvent	TBAOH/equiv.	I₂/equiv.	Temp./℃	Time/h	Yield^b/% of 2a
1	80	o-DCB	3	2	30	2	0
2	80	V(o-DCB)∶V(DMF)=1∶1	3	2	30	2	Trace
3	80	V(o-DCB)∶V(DMF)=3∶1	3	2	30	2	9
4	80	V(o-DCB)∶V(DMF)=3∶1	5	2	30	2	13
5	80	V(o-DCB)∶V(DMF)=3∶1	10	2	30	2	Trace
6	80	V(o-DCB)∶V(DMF)=3∶1	5	5	30	2	13
7	80	V(o-DCB)∶V(DMF)=3∶1	10	5	30	2	17
8	80	V(o-DCB)∶V(DMF)=3∶1	10	10	30	2	19
9	80	V(o-DCB)∶V(CH₃CN)=3∶1	10	10	30	2	0
10	80	V(o-DCB)∶V(THF)=3∶1	10	10	30	2	13
11	80	V(o-DCB)∶V(DMSO)=3∶1	10	10	30	2	13
12	80	V(o-DCB)∶V(Toluene)=3∶1	10	10	30	2	3
13	80	V(o-DCB)∶V(DMF)=3∶1	10	10	70	2	25
14	80	V(o-DCB)∶V(DMF)=3∶1	10	10	90	2	0
15	80	V(o-DCB)∶V(DMF)=3∶1	10	10	70	1	31
16	80	V(o-DCB)∶V(DMF)=3∶1	10	10	70	0.5	23
17	40	V(o-DCB)∶V(DMF)=3∶1	10	10	70	1	25
18	100	V(o-DCB)∶V(DMF)=3∶1	10	10	70	1	31

表1. 合成化合物2a的反应条件优化a

Table 1. Optimization of the reaction conditions for the synthesis of 2a

表2. 酰胺底物的适用范围a

Table 2. Substrate scope of amides

图2. 现场可见?近红外吸收光谱

Figure 2. In situ vis-NIR spectroscopy Conditions: The reactions were performed in o-DCB solvent (80 mL) for (a) and in a mixed o-DCB/DMF (V∶V=3∶1, 80 mL) solvent for (b), respectively, with C60 (100 mg, 1.0 equiv.), TBAOH (10.0 equiv.) and formamide (80.0 equiv.) at 70 ℃ under Ar atmosphere for 1.5 h. Then I2 (10.0 equiv.) was added. Curves 1-1/2-1, only C60; curves 1-2/2-2, in the presence of amide and TBAOH; curves 1-3/2-3, after 0.5 h; curves 1-4/2-4, after 1 h; curves 1-5/2-5, after 1.5 h; curves 1-6/2-6, after adding I2. All measurements were carried out under an Ar atmosphere with a 1 mm cuvette.

图3. 可能的反应机理

Figure 3. Proposed reaction mechanism

图4. 化合物的循环伏安测试图

Figure 4. Cyclic voltammograms of compounds Conditions: Cyclic voltammograms of 2a, 2c, 2f, 2g, 2i, 2j and C60 in o-DCB solution (1×10－3 mol/L) with Bu4NClO4 (0.1 mol/L) as an electrolyte at the scanning rate of 100 mV/s. Glassy carbon, platinum wire, and saturated calomel electrodes (SCE) were used as the working, counter, and reference electrodes, respectively.

Compound	E₁^red^a/V	ε_LUMO^b/eV
2a	－0.99	－3.81
2c	－1.07	－3.73
2f	－1.01	－3.79
2g	－1.00	－3.80
2i	－1.01	－3.79
2j	－0.99	－3.81
C₆₀	－0.97	－3.83

表3. 富勒烯稠合噁唑啉化合物和C60的E1red以及εLUMO

Table 3. E1red and εLUMO for fullerene-fused oxazoline derivatives and C60

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