Convenient Method for Preparingα-Ketoarylthioamide by Air Oxidation under Base Conditions

doi:10.6023/cjoc202002011

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (1): 370-375.DOI: 10.6023/cjoc202002011 Previous Articles Next Articles

Article

碱促进下空气氧化制备 α-芳甲酰基硫代酰胺的便捷方法

王聪^a^,^b, 姚瑶瑶^a, 谢珺^a, 王建塔^a, 王飞清^c, 张吉泉^a, 汤磊^a^,^b^,^d^,^*()

a 贵州医科大学药学院贵阳 550025
b 贵州医科大学药用植物功效与利用国家重点实验室贵阳 550014
c 贵州中医药大学第一附属医院贵阳 550001
d 贵州省化学合成药物研发利用工程技术研究中心贵阳 550004

收稿日期:2020-06-04 修回日期:2020-07-30 发布日期:2020-08-19
通讯作者: 汤磊
作者简介:
* Corresponding authors. E-mail: kingland1@163.com, tlei1974@hotmail.com
共同第一作者(These authors contributed equally to this work).
基金资助:
国家自然科学基金(81560559); 国家自然科学基金(81703356); 贵州省教育厅自然科学基金(黔教合KY字[2021]161); 贵州省科技厅社发公关(黔科合SY[2015]3030); 贵州省卫健委科学技术基金(gzwjk2019-1-179); 贵州医科大学博士后流动站资助项目.

Convenient Method for Preparingα-Ketoarylthioamide by Air Oxidation under Base Conditions

Cong Wang^a^,^b, Yaoyao Yao^a, Jun Xie^a, Jianta Wang^a, Feiqing Wang^c, Jiquan Zhang^a, Lei Tang^a^,^b^,^d^,^*()

a College of Pharmacy, Guizhou Medical University, Guiyang 550025
b State Key Laboratory of Functions and Applications of Medicinal Plants, Guizhou Medical University, Guiyang 550014
c The First Affiliated Hospital of Guizhou University of Traditional Chinese Medicine, Guiyang 550001
d Guizhou Provincial Engineering Technology Research Center for Chemical Drug R & D, Guizhou Medical University, Guiyang 550004

Received:2020-06-04 Revised:2020-07-30 Published:2020-08-19
Contact: Lei Tang
Supported by:
the National Natural Science Foundation of China(81560559); the National Natural Science Foundation of China(81703356); the Natural Science Research Fund of Guizhou Education Department(黔教合KY字[2021]161); the Scientific and Technological Foundation of Guizhou Health Committee(gzwjk2019-1-179); the Mobile Postdoctoral Center of Guizhou Medical University

1. cjoc202002011辅助材料.pdf(333KB)

Abstract

A practical method for preparing α-ketoaryl thioamide by air oxidation has been developed. Under air atmosphere, in the presence of K₂CO₃ as base and dimethyl sulfoxide (DMSO) as solvent at 120 ℃, a variety of α-ketoarylthioamides were obtained from aryl thioamide in yields of 42%~85%. This reaction has good substrate applicability, metal-free and atomic economy, and provides an efficient, economical, green and convenient method for the synthesis of α-ketoaryl thioamide.

Key words: air, dimethyl sulfoxide (DMSO), K2CO3, green oxidation, α-ketoaryl thioamide

Cite this article

Cong Wang, Yaoyao Yao, Jun Xie, Jianta Wang, Feiqing Wang, Jiquan Zhang, Lei Tang. Convenient Method for Preparingα-Ketoarylthioamide by Air Oxidation under Base Conditions[J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 370-375.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 8

References 25

[1]	(a) Franz G.; Sheldon R.A. Oxidation, InUllmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2000.
	(b) Backvall J.E. Modern Oxidation Methods, Wiley-VCH, Weinheim, 2010.
[2]	(a) Shilov A.E.; Shul'Pin G.B. Chem. Rev. 1997, 97, 2879.
	Sheldon R.; Kochi J.K. Metal-Catalyzed Oxidations of Organic Compounds, Academic Press, New York, 1981.
[3]	Muzart J. Chem. Rev. 1992, 92, 113.
[4]	Shul'pin G.B.; Vinogradov M.M.; Shul'pina L.S. Catal. Sci. Technol. 2018, 8, 4287.
[5]	Kim H.S.; Kim Y.J.; Lee H.; Park K.Y.; Chin C.S. Angew. Chem., Int. Ed. 2002, 41, 4300.
[6]	(a) Hill C.L. Nature 1999, 401, 436.
	(b) Noyori R.; Aoki M.; Sato K. Chem. Commun. 2003, 1977.
	(c) Alfonsi K.; Colberg J.; Dunn P.J.; Fevig T.; Jennings S.; Johnson T.A.; Kleine H.P.; Knight C.; Nagy M.A.; Perry D. A.; Stefaniak M. Green Chem. 2008, 10, 31.
	(d) Oller I.; Malato S.; Sánchez-Pérez J.A. Sci. Total Environ. 2011, 409, 4141.
[7]	(a) Creary X.; Zhu C. J. Am. Chem. Soc. 1995, 117, 5859.
	(b) Coleman C.; MacElroy J.M.D.; Gallagher J.F.; O'Shea D.F. J. Comb. Chem. 2002, 4, 87.
	(c) Zou J.P.; Wang X.S.; Wang Z.T.; Lu Z.E. Org. Prep. Proced. Int. 2002, 34, 208.
	(d) Guinchard X.; Vallée Y.; Denis J.N. J. Org. Chem. 2007, 72, 3972.
	(e) Li M.; Cao G.-R.; Zhao J.-W.; Wen L.-L.; Liu Y.-J.; Xia Y.-M.; Zhu S.-Z. Tetrahedron Lett. 2009, 50, 6247.
	(f) Poor M.A.; Darehkordi A.; Anary-Abbasinejad M.; Sodkouieh S.M. J. Heterocycl. Chem. 2017, 54, 2781.
	(g) Ravez S.; Corbet C.; Spillier Q.; Robin A.D.; Mullarky E.; Cantley L.C.; Feron O.; Frederick R. J. Med. Chem. 2017, 60, 1591.
[8]	Nguyen T.B.; Retailleau P. Green Chem. 2017, 19, 5371.
[9]	Ravez S.; Corbet C.; Spillier Q.; Dutu A.; Robin A.D.; Mullarky E.; Cantley L.C.; Feron O.; Frédérick R. J. Med. Chem. 2017, 60, 1591.
[10]	Yu P.; Wang Y.W.; Zeng Z.G.; Chen Y.F. J. Org. Chem. 2019, 84, 14883.
[11]	Paul N.; Sathishkumar R.; Anuba C.; Muthusubramanian S. RSC Adv. 2013, 3, 7445.
[12]	(a) Eftekhari-Sis B.; Khajeh S.V.; Büyükgüngör O. Synlett 2013, 24, 977.
	(b) Saeidian H.; Vahdati-Khajehi S.; Bazghosha H.; Mirjafary Z. J. Sulfur Chem. 2014, 35, 700.
	(c) Saeidian H.; Vahdati-Khajehi S.; Amini S.M.; Zirak M.; Saraei M.J. Sulfur Chem. 2013, 34, 464.
[13]	(a) Asinger F.; Gentz F. Angew. Chem., Int. Ed. 1963, 2, 397.
	(b) Creary X.; Zhu C. J. Am. Chem. Soc. 1995, 117, 5859.
[14]	Gan L.; Gao Y.; Wei L.; Wan J.P. J. Org. Chem. 2019, 2, 1064.
[15]	Li H.Z.; Xue W.J.; Wu A.X. Tetrahedron 2014, 70, 4645.
[16]	Liu W.; Chen C.; Zhou P. ChemistrySelect 2017, 2, 5532.
[17]	Darabi H.R.; Aghapoor K.; Tabar-Heydar K.; Nooshabadi M. Phosphorus, Sulfur Silicon Relat. Elem. 2002, 177, 1189.
[18]	(a) Nguyen T.B.; Tran M.Q.; Ermolenko L.; Al-Mourabit A. Org, Lett. 2014, 16, 310.
	(b) Xu H.L.; Deng H.; Li Z.K.; Xiang H.F.; Zhou X.G. Eur. J. Org. Chem. 2013, 31, 7054.
[19]	(a) Coats S.J.; Link J.S.; Hlasta D.J. Org. Lett. 2003, 5, 721.
	(b) Kaleta Z.; Makowski B.T.; Soós T.; Dembinski R. Org. Lett. 2006, 8, 1625.
	(c) Curphey T.J. J. Org. Chem. 2002, 67, 6461.
[20]	Valdez-Rojas J.E.; Rios-Guerra H.; Ramirez-Sanchez A.L.; Garcia-Gonzalez G.; Alvarez-Toledano C.; Lopez-Cortes J.G.; Toscano R. A.; Penieres-Carrillo J.G. Can. J. Chem. 2012, 90, 567.
[21]	Moghaddam F.M.; Mirjafary Z.; Saeidian H.; Javan M.J. Synlett 2008, 892.
[22]	(a) Chebolu R.; Bahuguna A.; Sharma R.; Mishra V.K.; Ravikumar P.C. Chem. Commun. 2015, 51, 15438.
	(b) Shen W.G.; Wu Q.Y.; Gong X.Y.; Liu F.; Ao G. Green Chem. 2019, 21, 2983.
[23]	(a) Hu M.; Wu W.Q.; Jiang H.F. ChemSusChem 2019, 12, 2911.
	(b) Ye R.; Cao Y.; Xi X.; Liu L.; Chen T. Org. Biomol. Chem. 2019, 17, 4220.
[24]	(a) Zhang X.M.; Guo Y.J.; Tao G.D.; Zhang W. Chin. J. Org. Chem. 2017, 37, 2993. (in Chinese)
	( 张新明, 郭玉军, 陶贵德, 张武, 有机化学, 2017, 37, 2993.).
	Park K.K.; Tsou L.K.; Hamilton A.D. Synthesis 2006, 3617.
[25]	Ravez S.; Corbet C.; Spillier Q.; Feron O.; Frédérick R. WO 2017/157882, 2017.

Entry			2	Yield ^b /%
1	C ₆H ₅	2a		79
2	2-MeOC ₆H ₄	2b		79
3	2-MeC ₆H ₄	2c		66
4	2-FC ₆H ₄	2d		42
5	2-ClC ₆H ₄	2e		46
6	2-BrC ₆H ₄	2f		65
7	2-HOC ₆H ₄	—		—
8	3-ClC ₆H ₄	2g		48
9	3-BrC ₆H ₄	2h		70
10	3-MeC ₆H ₄	2i		64
11	3-MeOC ₆H ₄	2j		42
12	4-MeOC ₆H ₄	2k		77
13	4-MeC ₆H ₄	2l		74
14	4-ClC ₆H ₄	2m		74
15	α-Naphthyl	2n		79
16			2o	78

Entry			2	Yield ^b /%
1	C ₆H ₅	2a		79
2	2-MeOC ₆H ₄	2b		79
3	2-MeC ₆H ₄	2c		66
4	2-FC ₆H ₄	2d		42
5	2-ClC ₆H ₄	2e		46
6	2-BrC ₆H ₄	2f		65
7	2-HOC ₆H ₄	—		—
8	3-ClC ₆H ₄	2g		48
9	3-BrC ₆H ₄	2h		70
10	3-MeC ₆H ₄	2i		64
11	3-MeOC ₆H ₄	2j		42
12	4-MeOC ₆H ₄	2k		77
13	4-MeC ₆H ₄	2l		74
14	4-ClC ₆H ₄	2m		74
15	α-Naphthyl	2n		79
16			2o	78

Entry	R ²	R ³	2	Yield ^b /%
1	CH ₃	CH ₃	2p	85
2	C ₂H ₅	C ₂H ₅	2q	72
3 ^c	C ₄H ₉	C ₄H ₉	2r	45

Entry	R ²	R ³	2	Yield ^b /%
1	CH ₃	CH ₃	2p	85
2	C ₂H ₅	C ₂H ₅	2q	72
3 ^c	C ₄H ₉	C ₄H ₉	2r	45

碱促进下空气氧化制备 α-芳甲酰基硫代酰胺的便捷方法

Convenient Method for Preparingα-Ketoarylthioamide by Air Oxidation under Base Conditions

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 8

References 25

Related Articles 15

Recommended Articles

Metrics

Comments

Entry	Base (equiv.)	Solvent	Temp./℃	Time/h	Yield ^b /%
1	None	DMSO	120	24	No product
2	K ₂ CO ₃ (2)	DMSO	120	12	79
3	NaCO ₃ (2)	DMSO	120	12	75
4	NaHCO ₃ (2)	DMSO	120	16	76
5	KOH (2)	DMSO	120	24	Trace
6	K ₂CO ₃ (2)	CH ₃CN	Reflux	24	No reaction
7	K ₂CO ₃ (2)	Acetone	Reflux	24	No reaction
8	K ₂CO ₃ (2)	DMF	120	12	Trace
9	K ₂CO ₃ (2)	DMSO	80	24	No reaction
10	K ₂CO ₃ (2)	DMSO	100	24	Trace
11	K ₂CO ₃ (2)	DMSO	110	16	76
12	K ₂CO ₃ (2)	DMSO	130	10	65
13	K ₂CO ₃ (2)	DMSO	140	9	34
14	K ₂CO ₃ (1.5)	DMSO	120	12	70
15	K ₂CO ₃ (3)	DMSO	120	12	79
16	K ₂CO ₃ (4)	DMSO	120	12	78

[1]	Yu Tian, Juan Zhang, Wenchao Gao, Honghong Chang. Application of Dimethyl Sulfoxide as Methylating Reagent in Organic Synthesis [J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2391-2406.
[2]	Lijuan Xiao, Yanping Zhang, Miao Hong. Research Progress of Lewis Acid and Base Pairs Applied in Materials Chemistry [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 949-960.
[3]	Zehui Li, Haoyu Zou, Lincai Li, Yiling Zhao, Hongping Zhu. Synthesis and Propylene Oxide Carbonylation Hydroesterification Catalytic Property of N,O-Ligand Coordination Cobalt Compounds [J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3907-3915.
[4]	Yiling Zhao, Zhikang Chen, Lei Li, Conglei Liu, Hongping Zhu. Silylene/Organoaluminum Lewis Pair System and the Initiation Property for Polymerization of (Meth)acrylates [J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3590-3597.
[5]	Yiwen Guan, Kejian Chang, Qianlin Sun, Xin Xu. Progress in Rare-Earth Metal-Based Lewis Pair Chemistry [J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1326-1335.
[6]	Jiejun Huang, Rongrong Qian, Shuang Wang, Hong'en Cao. Polyselenide-Catalyzed Cyclohexene Oxidation to Produce 1,2-Cyclohexanediol [J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1639-1645.
[7]	Hao Tang, Beibei Zhang, Weidong Chen, Junfei Luo. A Mild and Efficient Catalytic Aerobic Oxidative Dehydrogenation of N-Pyridylindolines [J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 1131-1137.
[8]	Peng Zhou, Shangwei Feng, Huihua Qiu, Jiantao Zhang. Sodiump-Toluenesulfinate/KI-Mediated Aerobic Oxidative Iodination of Terminal Alkynes for Synthesis of 1-Iodoalkynes and 1,3-Diynes [J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 394-399.
[9]	Cao Zhicheng, Liu Jianchao, Chu Youqun, Zhao Fengming, Zhu Yinghong, She Yuanbin. Paired Electro-synthesis of Aryl Nitriles [J]. Chin. J. Org. Chem., 2019, 39(9): 2499-2506.
[10]	Wang Qiaotian, Han Caifang, Feng Xiangqing, Du Haifeng. Chiral Spiro Dienes Derived Boranes for Asymmetric Hydrosilylation of Ketones [J]. Chin. J. Org. Chem., 2019, 39(8): 2257-2263.
[11]	Zhang Zhenbei, Sun Wei, Cao Zhishan. Progress in Activation of Small Molecules Promoted by Frustrated Lewis Pairs [J]. Chin. J. Org. Chem., 2018, 38(6): 1292-1318.
[12]	Wang Hui, Zheng Yi, Pan Zhentao, Fu Hongliang, Ling Fei, Zhong Weihui. Progress of Frustrated Lewis Pairs in Catalytic Hydrogenation [J]. Chin. J. Org. Chem., 2017, 37(2): 301-313.
[13]	Chen Huajie. Recent Advances in High-Mobility Polymeric Semiconductor Materials [J]. Chin. J. Org. Chem., 2016, 36(3): 460-479.
[14]	Guo Shengmei, Gong Jiuhan, Lu Lin, Zhu Zheng, Cai Hu. Synthesis of Methylene-Bridged Bis-1,3-dicarbonyl Compounds under Aerobic Condition [J]. Chin. J. Org. Chem., 2015, 35(6): 1348-1352.
[15]	Chen Pingliang, Lu Shijie, Hu Xingen, Xu Qing. CsOH/DMSO Promoted Reactions of Aryl Halides with Phenols: A Convenient Method for the Synthesis of Diaryl Ethers [J]. Chin. J. Org. Chem., 2014, 34(1): 112-117.