甲烷与三氯化铁的光化学反应在环境温度下实现甲烷的选择性氯化反应

doi:10.6023/cjoc202009044

摘要/Abstract

在温和条件下选择性活化与转化甲烷具有可观的经济效益, 但同时也是难点. 报道在环境温度条件下, 无水三氯化铁(FeCl₃)与甲烷在环境温度下的光化学反应, 这是一种有效的选择性活化甲烷生成一氯甲烷的方法. 在300 W的高压汞灯或者太阳光的照射下, 由甲烷转化的产物为单一的一氯甲烷, 而没有其它多氯代物, 最大初始生成效率为43 g_MeCl?(kg_Fe?h)^–1. 氯化铁既作为氯自由基源, 也作为氧化剂, 并在反应中被还原为氯化亚铁. 高压汞灯功率增加以及氯化铁浓度增加都会加快初始反应速率. 而反应温度以及甲烷的压力对反应的初始速率影响很小. 氯甲烷可以被水解为甲醇, 亚铁在空气以及盐酸存在下也可以被重新氧化为三价铁, 从而完成铁和氯的循环.

关键词: C—H活化, 甲烷活化与转化, 金属催化合成反应, 光催化

Selective activation of methane under mild conditions to produce functionalized products is highly lucrative but remains challenging. The photochemical reaction of anhydrous ferric chloride (FeCl₃) with methane at ambient temperature is an efficient process to selectively chlorinate methane to methyl chloride. An exclusive formation of methyl chloride instead of other multi-chlorinated products is observed, and a maximum initial productivity of 43 g_MeCl?(kg_Fe?h)^–1 was obtained under irradiation with a 300-watt high-pressure mercury lamp or solar light. Ferric chloride functions both as the source of reactive chlorine radicals and as the oxidant, and it was concomitantly reduced to ferrous chloride. The reaction rate increases with the power of the lamp and the concentration of ferric chloride. Interestingly, the reaction temperature from 25 to 75 ℃ and the methane pressure in the range of 1~4 MPa had little influence on the reaction rate. Methyl chloride was hydrolyzed to methanol with elimination of hydrogen chloride, and the ferrous product was re-oxidized to the ferric analog by oxygen in the air in the presence of hydrogen chloride, thus completing the loop of both iron and chlorine.

Key words: C—H activation, methane activation and functionalization, metal-catalyzed synthetic reaction, photocatalysis

引用此文

霍尚飞, 陈鸿, 左伟伟. 甲烷与三氯化铁的光化学反应在环境温度下实现甲烷的选择性氯化反应[J]. 有机化学, 2021, 41(4): 1683-1690.

Shangfei Huo, Hong Chen, Weiwei Zuo. Selective Chlorination of Methane Photochemically Mediated by Ferric Chloride at Ambient Temperature[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1683-1690.

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图/表 5

Figure 1. GC chromatogram of the methyl chlorination reaction in CH3CN GC analysis conditions: oven temperature (80 ℃), SPL1 temperature (275 ℃); retention times: methane 1.000 min, methyl chloride 1.044 min, chloroform 1.784 min, carbon tetrachloride 1.650 min.

Figure 2. 1H NMR (600 MHz, CD3CN) and HSQC spectra of methyl chloride in acetonitrile-d3 after being produced by a photochemical reaction in this solvent In 1H NMR spectrum, in addition to the signals at δ 0.22, 3.05 and 4.79 that are assigned to methane, methyl chloride and hydrogen chloride, respectively, no other resonances are observed, indicating no formation of methylene chloride, chloroform

Figure 3. (a) Molecular structure of [Fe(MeCN)2Cl2]2 produced by the photochemical reduction of FeCl3 in acetonitrile (Thermal ellipsoids are drawn at 30% probability) and (b) zero-field 57Fe M?ssbauer spectrum of [Fe(MeCN)2Cl2]2 recorded at 298 K

Figure 4. Effect of reaction parameters on the initial consumption rate of FeCl3 in the photochemical chlorination of methane (a) Effect of FeCl3 concentration. Conditions: acetonitrile as solvent, methane pressure=4 MPa, 25 ℃, 300-watt lamp; (b) effect of the power of the lamp. Conditions: [FeCl3]=0.130 mol?L–1 in acetonitrile, methane pressure=4 MPa, 25 ℃; (c) effect of methane pressure. Conditions: [FeCl3]=0.130 mol?L–1 in acetonitrile, 25 ℃, 300-watt lamp; (d) effect of reaction temperature. Conditions: [FeCl3]=0.130 mol?L–1 in acetonitrile, methane pressure=4 MPa, 300-watt lamp

Figure 5. (a) Molecular structure of H2Fe(H2O)Cl5 produced by oxidation of [Fe(MeCN)2Cl2]2 with air or hydrogen peroxide in dilute hydrochloric acid (Thermal ellipsoids are drawn at 30% probability) and (b) zero-field 57Fe M?ssbauer spectrum of H2Fe(H2O)Cl5 recorded at 298 K

参考文献 24

[1]	Lamarche-Gagnon, G.; Wadham, J.L.; Sherwood Lollar, B.; Arndt, S.; Fietzek, P.; Beaton, A.D.; Tedstone, A.J.; Telling, J.; Bagshaw, E.A.; Hawkings, J.R.; Kohler, T.J.; Zarsky, J.D.; Mowlem, M.C.; Anesio, A.M.; Stibal, M. Nature 2019, 565,73. doi: 10.1038/s41586-018-0800-0 pmid: 30602750
[2]	(a) McFarland, E. Science 2012, 338,340. pmid: 28150944
	(b) Gunsalus, N.J.; Koppaka, A.; Park, S.H.; Bischof, S.M.; Hashiguchi, B.G.; Periana, R.A. Chem. Rev. 2017, 117,8521. doi: 10.1021/acs.chemrev.6b00739 pmid: 28150944
	(c) Lin, R.; Amrute, A.P.; Perez-Ramirez, J. Chem. Rev. 2017, 117,4182. doi: 10.1021/acs.chemrev.6b00551 pmid: 28150944
	(d) Ravi, M.; Ranocchiari, M.; van Bokhoven, J.A. Angew. Chem., nt. Ed. 2017, 56,16464. pmid: 28150944
[3]	(a) Fletcher, S.E. M.; Schaefer, H. Science 2019, 364,932. doi: 10.1126/science.aax1828 pmid: 12037558
	(b) Labinger, J.A.; Bercaw, J.E. Nature 2002, 417,507. pmid: 12037558
	(c) Shilov, A.E.; Shul'pin, G.B. Chem. Rev. 1997, 97,2879. pmid: 12037558
	(d) Cavaliere, V.N.; Wicker, B.F.; Mindiola, D.J. Adv. Organomet. Chem. 2012, 60,1. pmid: 12037558
[4]	(a) Alvarez-Galvan, M.C.; Mota, N.; Ojeda, M.; Rojas, S.; Navarro, R.M.; Fierro, J.L. G. Catal. Today 2011, 171,15.
	(b) Olsbye, U. Angew. Chem., nt. Ed. 2016, 55,7294.
[5]	(a) Zimmermann, T.; Soorholtz, M.; Bilke, M.; Schuth, F. J. Am. Chem. Soc. 2016, 138,12395. doi: 10.1021/jacs.6b05167 pmid: 9554841
	(b) Periana, R.A.; Taube, D.J.; Evitt, E.R.; Loffler, D.G.; Wentrcek, P.R.; Voss, G.; Masuda, T. Science 1993, 259,340. pmid: 9554841
	(c) Periana, R.A.; Taube, D.J.; Gamble, S.; Taube, H.; Satoh, T.; Fujii, H. Science 1998, 280,560. doi: 10.1126/science.280.5363.560 pmid: 9554841
	(d) Lin, M.; Sen, A. Nature 1994, 368,613. pmid: 9554841
	(e) Periana, R.A.; Mironov, O.; Taube, D.; Bhalla, G.; Jones, C.J. Science 2003, 301,814. pmid: 9554841
	(f) Gretz, E.; Oliver, T.F.; Sen, A. J. Am. Chem. Soc. 1987, 109,8109. pmid: 9554841
	(g) Vargaftik, M.N.; Stolarov, I.P.; Moiseev, I.I. J. Chem. Soc., hem. Commun. 1990,1049. pmid: 9554841
	(h) Kao, L.C.; Hutson, A.C.; Sen, A. J. Am. Chem. Soc. 1991, 113,700. pmid: 9554841
[6]	(a) Takanabe, K.; Iglesia, E. Angew. Chem., nt. Ed. 2008, 47,7689. pmid: 30924338
	(b) Hammond, C.; Conrad, S.; Hermans, I. ChemSusChem 2012, 5,1668. pmid: 30924338
	(c) Lunsford, J.H. Angew. Chem., nt. Ed. Engl. 1995, 34,970. pmid: 30924338
	(d) Meng, L.; Chen, Z.; Ma, Z.; He, S.; Hou, Y.; Li, H.-H.; Yuan, R.; Huang, X.-H.; Wang, X.; Wang, X.; Long, J. Energy Environ. Sci. 2018, 11,294. pmid: 30924338
	(e) Wu, S.; Tan, X.; Lei, J.; Chen, H.; Wang, L.; Zhang, J. J. Am. Chem. Soc. 2019, 141,6592. pmid: 30924338
[7]	Horn, R.; Schloegl, R. Catal. Lett. 2015, 145,23.
[8]	(a) Bilke, M.; Losch, P.; Vozniuk, O.; Bodach, A.; Schuth, F. J. Am. Chem. Soc. 2019, 141,11212. doi: 10.1021/jacs.9b04413 pmid: 17295483
	(b) Olah, G.A.; Gupta, B.; Farina, M.; Felberg, J.D.; Ip, W.M.; Husain, A.; Karpeles, R.; Lammertsma, K.; Melhotra, A.K.; Trivedi, N.J. J. Am. Chem. Soc. 1985, 107,7097. pmid: 17295483
	(c) Zhou, X.P.; Yilmaz, A.; Yilmaz, G.A.; Lorkovic, I.M.; Laverman, L.E.; Weiss, M.; Sherman, J.H.; McFarland, E.W.; Stucky, G.D.; Ford, P.C. Chem. Commun. 2003,2294. pmid: 17295483
	(d) Paunovic, V.; Zichittella, G.; Moser, M.; Amrute, A.P.; Perez-Ramirez, J. Nat. Chem. 2016, 8,803. doi: 10.1038/nchem.2522 pmid: 17295483
	(e) Podkolzin, S.G.; Stangland, E.E.; Jones, M.E.; Peringer, E.; Lercher, J.A. J. Am. Chem. Soc. 2007, 129,2569. pmid: 17295483
	(f) He, J.; Xu, T.; Wang, Z.; Zhang, Q.; Deng, W.; Wang, Y. Angew. Chem., nt. Ed. 2012, 51,2438. pmid: 17295483
[9]	(a) Li, F.; Yuan, G. Angew. Chem., nt. Ed. 2006, 45,6541. pmid: 29199824
	(b) Batamack, P.T. D.; Mathew, T.; Prakash, G.K. S. J. Am. Chem. Soc. 2017, 139,18078. doi: 10.1021/jacs.7b10725 pmid: 29199824
[10]	(a) Paunovic, V.; Lin, R.; Scharfe, M.; Amrute, A.P.; Mitchell, S.; Hauert, R.; Perez-Ramirez, J. Angew. Chem., nt. Ed. 2017, 56,9791.
	(b) Shalygin, A.; Paukshtis, E.; Kovalyov, E.; Bal'Zhinimaev, B. Front. Chem. Sci. Eng. 2013, 7,279.
[11]	(a) Maldotti, A.; Molinari, A.; Amadelli, R. Chem. Rev. 2002, 102,3811. doi: 10.1021/cr010364p pmid: 12371903
	(b) Wu, W.; Fu, Z.; Wen, X.; Wang, Y.; Zou, S.; Meng, Y.; Liu, Y.; Kirk, S.R.; Yin, D. Appl. Catal. A: Gen. 2014, 469,483. pmid: 12371903
[12]	Blanksby, S.J.; Ellison, G.B. Acc. Chem. Res. 2003, 36,255. pmid: 12693923
[13]	(a) Minisci, F.; Fontana, F. Tetrahedron Lett. 1994, 35,1427. pmid: 17737550
	(b) Kochi, J.K. Science 1967, 155,415. doi: 10.1126/science.155.3761.415 pmid: 17737550
[14]	Bach, R.D.; Shobe, D.S.; Schlegel, H.B.; Nagel, C.J. J. Phys. Chem. 1996, 100,8770.
[15]	Chang, P. K. A.J.-H. C. J. Org. Chem. 1971, 36,3138.
[16]	Miller, J. WO 9959946, 1999.
[17]	(a) Roberts, B.P. Chem. Soc. Rev. 1999, 28,25. pmid: 28636596
	(b) Le, C.; Liang, Y.; Evans, R.W.; Li, X.; Mac-Millan, D.W. C. Nature 2017, 547,79. pmid: 28636596
[18]	(a) Sorokin, A.B.; Kudrik, E.V.; Alvarez, L.X.; Afanasiev, P.; Millet, J.M. M.; Bouchu, D. Catal. Today 2010, 157,149. pmid: 17676842
	(b) An, Z.-J.; Pan, X.-L.; Liu, X.-M.; Han, X.-W.; Bao, X.-H. J. Am. Chem. Soc. 2006, 128,16028. pmid: 17676842
	(c) Bar-Nahum, I.; Khenkin, A.M.; Neumann, R. J. Am. Chem. Soc. 2004, 126,10236. doi: 10.1021/ja0493547 pmid: 17676842
	(d) Muehlhofer, M.; Strassner, T.; Herrmann, W.A. Angew. Chem., nt. Ed. 2002, 41,1745. pmid: 17676842
	(e) Kirillova, M.V.; Kuznetsov, M.L.; Reis, P.M.; da Silva, J.A. L.; da Silva, J. J., R.F.; Pombeiro, A.J. L. J. Am. Chem. Soc. 2007, 129,10531. doi: 10.1021/ja072531u pmid: 17676842
[19]	(a) Lange, J.-P. ChemSusChem 2017, 10,245. doi: 10.1002/cssc.201600855 pmid: 27763723
	(b) Lange, J.P. CATTECH 2001, 5,82. pmid: 27763723
[20]	Lange, J.-P. Catal. Sci. Technol. 2016, 6,4759.
[21]	Lange, J.-P.; Sushkevich, V.L.; Knorpp, A.J.; van Bokhoven, J.A. Ind. Eng. Chem. Res. 2019, 58,8674.
[22]	Knuuttila, P.T.; Jokinen, S.S.; Judin, V.O.; Vuorisalo, J.T.; Salanne, S.S. EP 0493023, 1992.
[23]	Horvath, I.T.; Pa, N.H.; Summit, J.M. M.; Cook, R.A. US 5354916, 1994.
[24]	Mizuta, S.; Kondo, W.; Fujii, K.; Iida, H.; Isshiki, S.; Noguchi, H.; Kikuchi, T.; Sue, H.; Sakai, K. Ind. Eng. Chem. Res. 1991, 30,1601.