N,N-Dimethylformamide-Promoted Synthesis of Fullerene-Fused Oxazoline Derivatives

doi:10.6023/cjoc202307003

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

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

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

Table 2. Substrate scope of amides

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.

Figure 3. Proposed reaction mechanism

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

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

References 42

[1]	Zarrabi, N.; Seetharaman, S.; Chaudhuri, S.; Holzer, N.; Batista, V. S.; Van Der Est, A.; D’Souza, F.; Poddutoori, P. K. J. Am. Chem. Soc. 2020, 142, 10008. doi: 10.1021/jacs.0c01574
[2]	Sun, C.; Yang, P.-P.; Nan, Z.; Tian, C.-B; Cai, Y.-T.; Chen, J.-F.; Qi, F.-F.; Tian, H.-R.; Xie, L.-Q.; Meng, L.-Y.; Wei, Z.-H. Adv. Mater. 2023, 35, 2205603. doi: 10.1002/adma.v35.9
[3]	Li, S.-H.; Xing, Z.; Wu, B.-S.; Chen, Z.-C.; Yao, Y.-R.; Tian, H.-R.; Li, M.-F.; Yun, D.-Q.; Deng, L.-L.; Xie, S.-Y.; Huang, R.-B.; Zheng, L.-S. ACS Appl. Mater. Interfaces 2020, 12, 20733. doi: 10.1021/acsami.0c02119
[4]	Fan, J.-Q.; Fang, G.; Zeng, F.; Wang, X.-D.; Wu, S.-Z. Small 2013, 9, 613. doi: 10.1002/smll.v9.4
[5]	Li, Y.-B.; Biswas, R.; Kopcha, W. P.; Dubroca, T.; Abella, L.; Sun, Y.; Crichton, R. A.; Rathnam, C.; Yang, L.-T.; Yeh, Y.-W.; Kundu, K.; Rodríguez-Fortea, A.; Poblet, J. M.; Lee, K.-B.; Hill, S.; Zhang, J.-Y. Angew. Chem., Int. Ed. 2023, 62, e202211704.
[6]	Ramos-Soriano, J.; Reina, J. J.; Illescas, B. M.; de la Cruz, N.; Rodríguez-Pérez, L.; Lasala, F.; Rojo, J.; Delgado, R.; Martín, N. J. Am. Chem. Soc. 2019, 141, 15403. doi: 10.1021/jacs.9b08003
[7]	Zhu, S.-E.; Dou, L.-F.; Zhang, J.-H.; Wu, Y.; Yang, W.; Lu, H.-D.; Wei, C.-X.; Deng, C.-H.; Dong, Q. Chin. J. Org. Chem. 2021, 41, 2082 (in Chinese). doi: 10.1002/cjoc.v41.17
	(朱三娥, 豆礼锋, 张建辉, 吴缨, 杨伟, 鲁红典, 卫春祥, 邓崇海, 董强, 有机化学, 2021, 41, 2082.)
[8]	Niu, C.; Liu, Z.; Chen, M.-Q.; Yang, S.-F.; Wang, G.-W. Org. Lett. 2022, 24, 3493. doi: 10.1021/acs.orglett.2c01097
[9]	Avila, L. B.; Serrano Arambulo, P. C.; Dantas, A.; Cuevas-Arizaca, E. E.; Kumar, D.; Müller, C. K. Nanomaterials 2022, 12, 2881. doi: 10.3390/nano12162881
[10]	Yan, X.-X.; Niu, C.; Yin, Z.-C.; Lu, W.-Q.; Wang, G.-W. Sci. Bull. 2022, 67, 2406. doi: 10.1016/j.scib.2022.11.023
[11]	Niu, C.; Wang, G.-W. Chin. J. Org. Chem. 2020, 40, 3633 (in Chinese). doi: 10.6023/cjoc202006081
	(牛闯, 王官武, 有机化学, 2020, 40, 3633.)
[12]	Hashiguchi, M.; Obata, N.; Maruyama, M.; Yeo, K. S.; Ueno, T.; Ikebe, T.; Takahashi, I.; Matsuo, Y. Org. Lett. 2012, 14, 3276. doi: 10.1021/ol301186u
[13]	Thiesbrummel, J.; Peña-Camargo, F.; Brinkmann, K. O.; Gutierrez- Partida, E.; Yang, F.-J.; Warby, J.; Albrecht, S.; Neher, D.; Riedl, T.; Snaith, H. J.; Stolterfoht, M.; Lang, F. Adv. Energy Mater. 2023, 13, 2202674. doi: 10.1002/aenm.v13.3
[14]	Guo, Y.; Zhu, H.-X.; Liu, G.-L.; Yan, H.-M.; Zhu, B.-J.; Li, S.; Sun, Y.-J.; Li, G.-H. Chin. J. Org. Chem. 2016, 36, 172 (in Chinese).
	(郭颖, 朱华新, 刘桂林, 严慧敏, 朱冰洁, 李帅, 孙亚军, 李果华, 有机化学, 2016, 36, 172.)
[15]	(a) Yang, W.-W.; Li, Z.-J.; Li, F.-F.; Gao, X. J. Org. Chem. 2011, 76, 1384. doi: 10.1021/jo1023798
	(b) Li, Z.-J.; Li, S.-H.; Sun, T.; Hou, H.-L.; Gao, X. J. Org. Chem. 2015, 80, 3566. doi: 10.1021/acs.joc.5b00253
	(c) Liu, Q.-S.; Qiu, W.-J.; Lu, W.-Q.; Wang, G.-W. Org. Biomol. Chem. 2022, 20, 3535. doi: 10.1039/D2OB00239F
[16]	(a) Banks, M. R.; Cadogan, J. I. G.; Gosney, I.; Hodgson, P. K. G.; Langridge-Smith, P. R. R.; Rankine, D. W. H. J. Chem. Soc., Chem. Commun. 1994, 25, 1365.
	(b) Banks, M. R.; Cadogan, J. I. G.; Gosney, I.; Hodgson, P. K. G.; Langridge-Smith, P. R. R.; Millar, J. R. A.; Taylor, A. T. Tetrahedron Lett. 1994, 35, 9067. doi: 10.1016/0040-4039(94)88429-3
[17]	Averdung, J.; Mattay, J.; Jacobi, D.; Abraham, W. Tetrahedron 1995, 51, 2543. doi: 10.1016/0040-4020(95)00013-X
[18]	Yang, H.-T.; Xing, M.-L.; Zhu, Y.-F.; Sun, X.-Q.; Cheng, J.; Miao, C.-B.; Li, F.-B. J. Org. Chem. 2014, 79, 1487. doi: 10.1021/jo4025573
[19]	(a) Zheng, M.; Li, F.-F.; Ni, L.; Yang, W.-W.; Gao, X. J. Org. Chem. 2008, 73, 3159. doi: 10.1021/jo702678c
	(b) Hou, H.-L. Gao, X. J. Org. Chem. 2012, 77, 2553. doi: 10.1021/jo202616j
[20]	Chang, W.-W.; Li, Z.-J.; Yang, W.-W.; Gao, X. Org. Lett. 2012, 14, 2386. doi: 10.1021/ol300805p
[21]	(a) Li, F.-B.; Liu, T.-X.; Wang, G.-W. J. Org. Chem. 2008, 73, 6417. doi: 10.1021/jo8007868
	(b) Yang, H.-T.; Liang, X.-C.; Wang, Y.-H.; Yang, Y.; Sun, X.-Q.; Miao, C.-B. Org. Lett. 2013, 15, 4650. doi: 10.1021/ol401909z
	(c) Zhang, X.-F.; Li, F.-B.; Shi, J.-L.; Wu, J.; Liu, L. New J. Chem. 2016, 40, 1626. doi: 10.1039/C5NJ02503F
	(d) Liu, T.-X.; Liu, Y.-Q.; Chao, D.; Zhang, P.-L.; Liu, Q.-F.; Shi, L.; Zhang, Z.-G.; Zhang, G.-S. J. Org. Chem. 2014, 79, 11084. doi: 10.1021/jo5020883
	(e) Liu, Q.-S.; Qiu, W.-J.; Lu, W.-Q.; Wang, G.-W. Org. Biomol. Chem. 2022, 20, 3535. doi: 10.1039/D2OB00239F
[22]	Takeda, Y.; Enokijima, S.; Nagamachi, T.; Nakayama, K.; Minakata, S. Asian J. Org. Chem. 2013, 2, 91. doi: 10.1002/ajoc.v2.1
[23]	Yang, H.-T.; Ren, W.-L.; Dong, C.-P.; Yang, Y.; Sun, X.-Q.; Miao, C.-B. Tetrahedron Lett. 2013, 54, 6799. doi: 10.1016/j.tetlet.2013.09.002
[24]	Rosén, A.; Wästberg, B. J. Chem. Phys. 1989, 90, 2525. doi: 10.1063/1.455947
[25]	Xie, Q.-S.; Perez-Cordero, E.; Echegoyen, L. J. Am. Chem. Soc. 1992, 114, 3978. doi: 10.1021/ja00036a056
[26]	(a) Fagan, P. J.; Krusic, P. J.; Evans, D. H.; Lerke, S. A.; Johnston, E. J. Am. Chem. Soc. 1992, 114, 9697. doi: 10.1021/ja00050a081
	(b) Schick, G.; Kampe, K. D.; Hirsch, A. J. Chem. Soc., Chem. Commun. 1995, 19, 2023.
	(c) Wang, G.-W.; Shu, L.-H.; Wu, S.-H.; Wu, H.-M.; Lao, X.-F. J. Chem. Soc., Chem. Commun. 1995, 10, 1071.
[27]	Matsuo, Y.; Iwashita, A.; Abe, Y.; Li, C.-Z.; Matsuo, K.; Hashiguchi, M.; Nakamura, E. J. Am. Chem. Soc. 2008, 130, 15429. doi: 10.1021/ja8041299
[28]	Isobe, H.; Tanaka, T.; Nakanishi, W.; Lemiègre, L.; Nakamura, E. J. Org. Chem. 2005, 70, 4826. doi: 10.1021/jo050432y
[29]	Chang, W.-W.; He, F.-G.; Garcıa-Penas, A.; Shekh, M. I.; Li, Z.-J. RSC Adv. 2022, 12, 14018. doi: 10.1039/D2RA01300B
[30]	Naim, A.; Shevlin, P. B. Tetrahedron Lett. 1992, 33, 7097. doi: 10.1016/S0040-4039(00)60845-6
[31]	Hare, J. P.; Kroto, H. W.; Taylor, R. Chem. Phys. Lett. 1991, 177, 394. doi: 10.1016/0009-2614(91)85072-5
[32]	Khaled, M. M.; Carlin, R. T.; Trulove, P. C.; Eaton, G. R.; Eaton, S. S. J. Am. Chem. Soc. 1994, 116, 3465. doi: 10.1021/ja00087a037
[33]	Rapta, P.; Bartl, A.; Gromov, A.; Stasko, A.; Dunsch, L. ChemPhyChem 2002, 3, 351.
[34]	Subramanian, R.; Kadish, K. M.; Vijayashree, M. N.; Gao, X.; Jones, M. T.; Miller, M. D.; Krause, K. L.; Suenobu, T.; Fukuzumi, S. J. Phys. Chem. 1996, 100, 16327. doi: 10.1021/jp961412q
[35]	Xu, L.-J.; Yang, W.-W.; Han, F.-S.; Gao, X. Org. Biomol. Chem. 2023, 21, 2331. doi: 10.1039/D3OB00039G
[36]	(a) Li, F.-F.; Gao, X.; Zheng, M. J. Org. Chem. 2009, 74, 82. doi: 10.1021/jo801769q
	(b) Yang, W.-W.; Li, Z.-J.; Li, S.-H.; Gao, X. J. Phys. Chem. A 2015, 119, 9534. doi: 10.1021/acs.jpca.5b07932
[37]	(a) Liu, Z.-J.; Larock, R. C. J. Am. Chem. Soc. 2005, 127, 13112. doi: 10.1021/ja054079p
	(b) Sukata, K. Bull. Chem. Soc. Jpn. 1985, 58, 838. doi: 10.1246/bcsj.58.838
[38]	Zhao, H.; Zhu, X.-Y.; Hu, X.-X.; Liu, Y.-G.; Tang, C.-L.; Feng, B.-N. Chin. J. Org. Chem. 2019, 39, 434 (in Chinese). doi: 10.6023/cjoc201807010
	(赵辉, 朱孝云, 胡小霞, 刘延革, 唐春雷, 冯柏年, 有机化学, 2019, 39, 434.)
[39]	Hou, H.-L.; Li, Z.-J.; Li, S.-H.; Chen, S.; Gao, X. Org. Lett. 2013, 15, 4646. doi: 10.1021/ol401834j
[40]	Zhuo, L.-G.; Liao, W.; Yu, Z.-X. Asian J. Org. Chem. 2012, 1, 336. doi: 10.1002/ajoc.v1.4
[41]	(a) Li, D.; Li, Z.-J.; He, F.-G.; Geng, C.; Gao, X. J. Org. Chem. 2019, 84, 14679. doi: 10.1021/acs.joc.9b02272
	(b) Yang, S.-T.; Zhou, X.-Y.; Hu, Y.-J.; Abella, L.; Yao, Y.-R.; Peng, P.; Zhang, Q.-Y.; Rodríguez-Fortea, A.; Poblet, J. M.; Li, F.-F. J. Org. Chem. 2023, 88, 4234. doi: 10.1021/acs.joc.2c02779
[42]	Li, X.-J.; Li, Y.-F. Acta Polym. Sin. 2022, 53, 995 (in Chinese).
	(李骁骏, 李永舫, 高分子学报, 2022, 53, 995.)

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