Alternative Approach for the Synthesis of Nitroaromatic Olefins via Dehydrogenative Nitration of Easily Available Arylethanes

doi:10.6023/cjoc202008041

Abstract

Nitroolefin is a common and versatile reagent, synthesis of which from aldehydes/ketones, α, β-unsaturated carboxylic acids or olefins is generally limited by the high cost of raw materials in industrial processes in the future. Herein, an alternative and economical protocol for the synthesis of nitroaromatic olefins directly from easily available arylethanes with barium nitrate using Cu/Ag as cocatalyst and ammonium persulfate as the terminal oxidant is reported. Additionally, 1,1-diphenylethanes, phenylethanes, 4-ethyl-1,1'-biphenyl and ethylnaphthalenes were suitable substrates for the current dehydrogenative nitration, and provided E-nitroaromatic olefins in moderate to good yields.

Key words: nitroaromatic olefins, arylethanes, barium nitrate, dehydrogenative nitration, ammonium persulfate

Cite this article

Bing Mu, Junliang Wu, Guang'an Zhang. Alternative Approach for the Synthesis of Nitroaromatic Olefins via Dehydrogenative Nitration of Easily Available Arylethanes[J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 250-257.

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References 67

[1]	Reddy M.A.; Jain N.; Yada D.; Kishore C.; Reddy V.J.; Reddy P.S.; Addlagatta A.; Kalivendi S.V.; Sreedhar B. J. Med. Chem. 2011, 54, 6751.
[2]	Lu L.Q.; Chen J.R.; Xiao W.J. Acc. Chem. Res. 2012, 45, 1278.
[3]	Kaap S.; Quentin I.; Tamiru D.; Shaheen M.; Eger K.; Steinfelder H.J. Biochem. Pharmacol. 2003, 65, 603.
[4]	Uehara H.; Imashiro R.; Hernández-Torres G.; Barbas III, C.F.Proc. Natl. Acad. Sci. U. S. A. 2010, 107, 20672.
[5]	Meah Y.; Massey V. Proc. Natl. Acad. Sci. U. S. A. 2000, 97, 10733.
[6]	Ishii T.; Fujioka S.; Sekiguchi Y.; Kotsuki H. J. Am. Chem. Soc. 2004, 126, 9558.
[7]	Huang H.B.; Jacobsen E.N. J. Am. Chem. Soc. 2006, 128, 7170.
[8]	Tripathi C.B.; Kayal S.; Mukherjee S. Org. Lett. 2012, 14, 3296.
[9]	Bai B.; Wang L.; Yang J.; Cai L.L.; Liu Q.J.; Xi, Gao. L.; Zhao, Z.W.; Mao, D.B.; Chen, Z.F. Chin. J. Org. Chem. 2019, 39, 1053. (in Chinese)
	( 白冰, 王龙, 杨静, 蔡莉莉, 刘前进, 席高磊, 赵志伟, 毛多斌, 陈芝飞, 有机化学, 2019, 39, 1053.).
[10]	Luo S.P.; Wang L.P.; Yue H.D.; Le Z.G.; Yang W.L.; Xu D.Q.; Xu Z.Y. Acta Chim Sinica. 2006, 64, 1483.
[11]	Evans D.A.; Mito S.; Seidel D. J. Am. Chem. Soc. 2007, 129, 11583.
[12]	March J. Advanced Organic Chemistry, 3rd ed., John Wiley & Sons, New York, 1985.
[13]	Albrecht L.; Dickmeiss G.; Acosta F.C.; Rodríguez-Escrich C.; Davis R.L.; Jorgensen K.A. J. Am. Chem. Soc. 2012, 134, 2543.
[14]	Liu Y.K.; Nappi M.; Arceo E.; Vera S.; Melchiorre P. J. Am. Chem. Soc. 2011, 133, 15212.
[15]	Arai T.; Mishiro A.; Yokoyama N.; Suzuki K.; Sato H. J. Am. Chem. Soc. 2010, 132, 5338.
[16]	Denmark S.E.; Thorarensen A. Chem. Rev. 1996, 96, 137.
[17]	Yan L.J.; Xu H.; Wang Y.; Dong J.W.; Wang Y.C. Chin. J. Org. Chem. 2020, 40, 284. (in Chinese)
	( 严丽君, 徐菡, 王艳, 董建伟, 王永超, 有机化学, 2020, 40, 284.).
[18]	Basavaiah D.; Reddy B.S.; Badsara S.S. Chem. Rev. 2010, 110, 5447.
[19]	Nair D.K.; Mobin S.M.; Namboothiri I.N.N. Org. Lett. 2012, 14, 4580.
[20]	Quan X.J.; Ren Z.H.; Wang Y.Y.; Guan Z.H. Org. Lett. 2014, 16, 5728.
[21]	Chen Y.F.; Nie G.; Zhang Q.; Ma S.; Li H.; Hu Q.Q. Org. Lett. 2015, 17, 1118.
[22]	Kurti L.; Czako B. Strategic Applications of Named Reactions in Organic Synthesis, Elsevier Academic Press, London , 2005.
[23]	Fioravanti S.; Pellacani L.; Tardella P.A.; Vergari M.C. Org. Lett. 2008, 10, 1449.
[24]	Hassner A.; Kropp J.E.; Kent G.J. J. Org. Chem. 1969, 34, 2628.
[25]	Ranganathan S.; Kar S.K. J. Org. Chem. 1970, 35, 3962.
[26]	Corey E.J.; Estreicher H. J. Am. Chem. Soc. 1978, 100, 6294.
[27]	Barluenga J.; Rodríguez M.A.; Campos P.J.; Asensio G. J. Chem. Soc., Chem. Commun. 1987, 1491.
[28]	Barluenga J.; Rodríguez M.A.; Campos P.J. J. Chem. Soc., Perkin Trans. 1 1990, 2807.
[29]	Sy W.W.; By A.W. Tetrahedron Lett. 1985, 26, 1193.
[30]	Jew S.S.; Kim H.D.; Cho Y.S.; Cook C.H. Chem. Lett. 1986, 15, 1747.
[31]	Hwu J.R.; Chen K.L.; Ananthan S.; Patel H.V. Organometallics 1996, 15, 499.
[32]	Ghosh D.; Nichols D.E. Synthesis 1996, 195.
[33]	Suzuki H.; Mori T. J. Org. Chem. 1997, 62, 6498.
[34]	Mukaiyama T.; Hata E.; Yamada T. Chem. Lett. 1995, 24, 505.
[35]	Hata E.; Yamada T.; Mukaiyama T. Bull. Chem. Soc. Jpn. 1995, 68, 3629.
[36]	Jovel I.; Prateeptongkum S.; Jackstell R.; Vogl N.; Weckbecker C.; Beller M. Adv. Synth. Catal. 2008, 350, 2493.
[37]	Varma R.S.; Naicker K.P.; Liesent P.J. Tetrahedron Lett. 1998, 39, 3977.
[38]	Manna S.; Jana S.; Saboo T.; Maji A.; Maiti D. Chem. Commun. 2013, 49, 5286.
[39]	Rokade B.V.; Prabhu K.R. Org. Biomol. Chem. 2013, 11, 6713.
[40]	Das J.P.; Sinha P.; Roy S. Org. Lett. 2002, 4, 3055.
[41]	Baruah D.; Pahari P.; Konwar D. Tetrahedron Lett. 2015, 56, 2418.
[42]	Yang Z.; Li J.; Hua J.; Yang T.; Yi J.M.; Zhou C.S. Synlett 2017, 28, 1079.
[43]	Luo Z.G.; Xu F.; Fang Y.Y.; Liu P.; Xu X.M.; Feng C.T.; Li Z.; He J. Res. Chem. Intermed. 2016, 42, 6079.
[44]	Maity S.; Manna S.; Rana S.; Naveen T.; Mallick A.; Maiti D. J. Am. Chem. Soc. 2013, 135, 3355.
[45]	Naveen T.; Maity S.; Sharma U.; Maiti D. J. Org. Chem. 2013, 78, 5949.
[46]	Maity S.; Naveen T.; Sharma U.; Maiti D. Org. Lett. 2013, 15, 3384.
[47]	Zhao A.; Jiang Q.; Jia J.; Xu B.; Liu Y.F.; Zhang M.Z.; Liu Q.; Luo W.P.; Guo C.C. Tetrahedron Lett. 2016, 57, 80.
[48]	Whiting K.; Carmona L.G.; Sousa T. Renewable Sustainable Energy Rev. 2017, 76, 202.
[49]	Degnan T.F. J. Catal. 2003, 216, 32.
[50]	Grant J.T.; Venegas J.M.; McDermott W.P.; Hermans I. Chem. Rev. 2018, 118, 2769.
[51]	Kumar A.; Bhatti T.M.; Goldman A.S. Chem. Rev. 2017, 117, 12357.
[52]	Wang Y.L.; Qian L.; Huang Z.D.; Liu G.X.; Huang Z. Chin. J. Chem. 2020, 38, 837.
[53]	Sathyamoorthi S.; Banerjee S. ChemistrySelect 2017, 2, 10678.
[54]	Sathyamoorthi S.; Du Bois, J. Org. Lett. 2016, 18, 6308.
[55]	Banerjee S.; Sathyamoorthi S.; Du Bois J.; Zare R.N. Chem. Sci. 2017, 8, 7003.
[56]	Manna S.; Antonchick A.P. Chem. -Eur. J. 2017, 23, 7825.
[57]	Burkhard C.A.; Brown J.F., Jr. US 2867669, 1959.
[58]	Tang X.J.; Dolbier Jr.W.R. Angew. Chem. Int. Ed. 2015, 54, 4246.
[59]	Ambala S.; Singh R.; Singh M.; Cham P.S.; Gupta R.; Munagala G.; Yempalla K.R.; Vishwakarma R.A.; Singh P.P. RSC Adv. 2019, 9, 30428.
[60]	Huie R.E.; Clifton C.L.; Kafafi S.A. J. Phys. Chem. 1991, 95, 9336.
[61]	Huie R.E.; Clifton C.L. J. Phys. Chem. 1990, 94, 8561.
[62]	Liu Y.; Wang Q.L.; Chen Z.; Zhou Q.; Zhou C.S.; Xiong B.Q.; Zhang P.L.; Yang C.A.; Tang K.W. Org. Biomol. Chem. 2019, 17, 1365.
[63]	Manna S.; Jana S.; Saboo T.; Maji A.; Maiti D. Chem. Commun. 2013, 49, 5286.
[64]	Gross Z.; Hoz S. J. Am. Chem. Soc. 1988, 110, 7489.
[65]	Hsieh T.H.H.; Dong V.M. Tetrahedron 2009, 65, 3062.
[66]	Zhao A.; Jiang Q.; Jia J.; Xu, Bin.; Liu, Y.F.; Zhang, M.Z.; Liu, Q.; Luo, W.P.; Guo, C.C. Tetrahedron Lett. 2016, 57, 80.
[67]	Ambala S.; Singh R.; Singh M.; Cham P.S.; Gupta R.; Munagala G.; Yempalla K.R.; Vishwakarma R.A.; Singh P.P. RSC Adv. 2019, 9, 30428.

Entry	Nitro source	[Cu]	Ligand	Oxidant	[Ag]	Additive	Solvent	Yield/%
1	NaNO ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	30
2	NaNO ₃	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	66
3	KNO ₃	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	56
4	AgNO ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	39
5	^t BuNO ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	8
6	Bi(NO ₃) ₃•5H ₂O	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	57
7	Ca(NO ₃) ₂•4H ₂O	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	51
8	Cd(NO ₃) ₂•4H ₂O	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	54
9	Co(NO ₃) ₂•6H ₂O	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	25
10	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	80
11	Pb(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	86
12	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	CF ₃COOH	22
13	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	Dioxane	11
14	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DCE	12
15	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMSO	14
16	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMA	8
17	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	NMP	NR
18	Ba(NO ₃) ₂	CuBr	L ₁	Na ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	59
19	Ba(NO ₃) ₂	CuBr	L ₁	DDQ	CF ₃COOAg	CF ₃SO ₃H	DMF	10
20	Ba(NO ₃) ₂	CuBr	L ₁	^t BuOO ^t Bu	CF ₃COOAg	CF ₃SO ₃H	DMF	6
21	Ba(NO ₃) ₂	CuBr	L ₁	^t BuOOH	CF ₃COOAg	CF ₃SO ₃H	DMF	NR
22	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	AgNO ₃	CF ₃SO ₃H	DMF	78
23	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CH ₃COOAg	CF ₃SO ₃H	DMF	75
24	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	Ag ₂SO ₄	CF ₃SO ₃H	DMF	73
25	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	Ag ₂CO ₃	CF ₃SO ₃H	DMF	NR
26	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃COOH	DMF	42
27	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	TsOH	DMF	16
28	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	^t BuCOOH	DMF	27
29	Ba(NO ₃) ₂	CuBr	L ₂	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	75
30	Ba(NO ₃) ₂	CuBr	L ₃	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	76
31	Ba(NO ₃) ₂	CuBr	L ₄	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	64
32	Ba(NO ₃) ₂	CuBr	L ₅	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	72
33	Ba(NO ₃) ₂	CuBr	L ₆	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	79
34	Ba(NO ₃) ₂	CuOAc	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	92 (89) ^b
35	Ba(NO ₃) ₂	CuI	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	80
36	Ba(NO ₃) ₂	(CF ₃SO ₃) ₂Cu	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	80
37	Ba(NO ₃) ₂	[CF ₃SO ₃Cu] ₂• C ₆H ₅CH ₃	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	82
38	Ba(NO ₃) ₂	Cu ₂O	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	73
39	Ba(NO ₃) ₂	CuCl	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	76
40	Ba(NO ₃) ₂	CuBr ₂	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	77

Entry	Nitro source	[Cu]	Ligand	Oxidant	[Ag]	Additive	Solvent	Yield/%
1	NaNO ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	30
2	NaNO ₃	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	66
3	KNO ₃	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	56
4	AgNO ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	39
5	^t BuNO ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	8
6	Bi(NO ₃) ₃•5H ₂O	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	57
7	Ca(NO ₃) ₂•4H ₂O	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	51
8	Cd(NO ₃) ₂•4H ₂O	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	54
9	Co(NO ₃) ₂•6H ₂O	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	25
10	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	80
11	Pb(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	86
12	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	CF ₃COOH	22
13	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	Dioxane	11
14	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DCE	12
15	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMSO	14
16	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMA	8
17	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	NMP	NR
18	Ba(NO ₃) ₂	CuBr	L ₁	Na ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	59
19	Ba(NO ₃) ₂	CuBr	L ₁	DDQ	CF ₃COOAg	CF ₃SO ₃H	DMF	10
20	Ba(NO ₃) ₂	CuBr	L ₁	^t BuOO ^t Bu	CF ₃COOAg	CF ₃SO ₃H	DMF	6
21	Ba(NO ₃) ₂	CuBr	L ₁	^t BuOOH	CF ₃COOAg	CF ₃SO ₃H	DMF	NR
22	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	AgNO ₃	CF ₃SO ₃H	DMF	78
23	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CH ₃COOAg	CF ₃SO ₃H	DMF	75
24	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	Ag ₂SO ₄	CF ₃SO ₃H	DMF	73
25	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	Ag ₂CO ₃	CF ₃SO ₃H	DMF	NR
26	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃COOH	DMF	42
27	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	TsOH	DMF	16
28	Ba(NO ₃) ₂	CuBr	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	^t BuCOOH	DMF	27
29	Ba(NO ₃) ₂	CuBr	L ₂	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	75
30	Ba(NO ₃) ₂	CuBr	L ₃	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	76
31	Ba(NO ₃) ₂	CuBr	L ₄	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	64
32	Ba(NO ₃) ₂	CuBr	L ₅	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	72
33	Ba(NO ₃) ₂	CuBr	L ₆	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	79
34	Ba(NO ₃) ₂	CuOAc	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	92 (89) ^b
35	Ba(NO ₃) ₂	CuI	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	80
36	Ba(NO ₃) ₂	(CF ₃SO ₃) ₂Cu	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	80
37	Ba(NO ₃) ₂	[CF ₃SO ₃Cu] ₂• C ₆H ₅CH ₃	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	82
38	Ba(NO ₃) ₂	Cu ₂O	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	73
39	Ba(NO ₃) ₂	CuCl	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	76
40	Ba(NO ₃) ₂	CuBr ₂	L ₁	(NH ₄) ₂S ₂O ₈	CF ₃COOAg	CF ₃SO ₃H	DMF	77

利用芳基乙烷的脱氢硝化合成硝基芳香烯烃的新方法