醋酸碘苯促进的脱氢氧化反应合成2-硫芳(烷)基苯酚及10H-吩噻嗪

doi:10.6023/cjoc202201039

摘要/Abstract

报道了一种醋酸碘苯促进苯酚邻位C(sp²)—H与硫酚S—H之间通过氧化脱氢直接构建C—S键合成2-硫芳(烷)基苯酚衍生物的新方法. 当底物为2-氨基苯硫酚时, 则实现了缩合环化产物10H-吩噻嗪的高效合成. 未见文献报道的新化合物均通过了¹H NMR、¹³C NMR、IR和HRMS的表征, 其中2-((4-溴苯基)硫代)-1,4-苯二酚(3i)的结构还通过了X-ray单晶衍射的证实. 该方法原料易得、条件温和、操作简便, 同时具有良好的原子经济性.

关键词: 2-硫芳(烷)基苯酚, 10H-吩噻嗪, 脱氢氧化, C—S键形成

A PhI(OAc)₂-promoted reaction for the synthesis of 2-(aryl/alkylthio)phenol derivatives has been developed, which was realized via dehydrogenation oxidation between ortho-C(sp²)—H of phenols and S—H of thiophenols for direct formation of C—S bonds. Particularly, this method was also successfully applied for the efficient construction of tricyclic 10H-phenothiazines using 2-aminothiophenols as the substrates. All the newly synthesized products were identified by means of ¹H NMR, ¹³C NMR, IR and HRMS. Besides, 2-((4-bromophenyl)thio)benzene-1,4-diol (3i) was further confirmed by X-ray single crystal diffraction analysis. The method has the advantages of simple and easily available starting materials, mild reaction conditions, simple operation, as well as high atom economy.

Key words: 2-(aryl/alkylthio)phenols, 10H-phenothiazines, dehydrogenation oxidation, C—S bond formation

引用此文

曹廷舒, 魏向阳, 罗敏, 汪逸飞, 潘子俊, 徐程, 殷国栋. 醋酸碘苯促进的脱氢氧化反应合成2-硫芳(烷)基苯酚及10H-吩噻嗪[J]. 有机化学, 2022, 42(7): 2079-2088.

Tingshu Cao, Xiangyang Wei, Min Luo, Yifei Wang, Zijun Pan, Cheng Xu, Guodong Yin. PhI(OAc)₂-Promoted Dehydrogenation Oxidation for the Synthesis of 2-(Aryl/alkylthio)phenols and 10H-Phenothiazines[J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2079-2088.

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参考文献 20

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Entry	Additive (equiv.)	Solvent	Temp./℃	Yield/%
1	None	MeCN/H₂O (V∶V=1∶1)	r.t.	70
2	HCOOH (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	64
3	HCl (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	68
4	CF₃COOH (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	92
5	FeCl₃ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	86
6	ZnCl₂ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	67
7	ZrCl₄ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	75
8	AgOTf (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	83
9	Cu(OTf)₂ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	80
10	I₂ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	42
11	CF₃COOH (0.3)	MeCN/H₂O (V∶V=1∶1)	r.t.	89
12	CF₃COOH (0.1)	MeCN/H₂O (V∶V=1∶1)	r.t.	76
13	CF₃COOH (0.2)	MeCN/H₂O (V∶V=1∶2)	r.t.	64
14	CF₃COOH (0.2)	MeCN/H₂O (V∶V=2∶1)	r.t.	62
15	CF₃COOH (0.2)	MeCN/H₂O (V∶V=5∶1)	r.t.	51
16	CF₃COOH (0.2)	MeCN/H₂O (V∶V=1∶1)	40	82
17	CF₃COOH (0.2)	MeCN/H₂O (V∶V=1∶1)	60	65

Entry	Additive (equiv.)	Solvent	Temp./℃	Yield/%
1	None	MeCN/H₂O (V∶V=1∶1)	r.t.	70
2	HCOOH (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	64
3	HCl (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	68
4	CF₃COOH (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	92
5	FeCl₃ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	86
6	ZnCl₂ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	67
7	ZrCl₄ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	75
8	AgOTf (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	83
9	Cu(OTf)₂ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	80
10	I₂ (0.2)	MeCN/H₂O (V∶V=1∶1)	r.t.	42
11	CF₃COOH (0.3)	MeCN/H₂O (V∶V=1∶1)	r.t.	89
12	CF₃COOH (0.1)	MeCN/H₂O (V∶V=1∶1)	r.t.	76
13	CF₃COOH (0.2)	MeCN/H₂O (V∶V=1∶2)	r.t.	64
14	CF₃COOH (0.2)	MeCN/H₂O (V∶V=2∶1)	r.t.	62
15	CF₃COOH (0.2)	MeCN/H₂O (V∶V=5∶1)	r.t.	51
16	CF₃COOH (0.2)	MeCN/H₂O (V∶V=1∶1)	40	82
17	CF₃COOH (0.2)	MeCN/H₂O (V∶V=1∶1)	60	65