果胶负载钯催化剂的制备及Suzuki反应催化性能

doi:10.7503/cjcu20150799

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (4): 669.doi: 10.7503/cjcu20150799

果胶负载钯催化剂的制备及Suzuki反应催化性能

周文俊, 周宇, 张霞忠(), 曾彬

内江师范学院化学化工学院, 内江 641112

收稿日期:2015-10-19 出版日期:2016-04-10 发布日期:2016-03-04
基金资助:
四川省教育厅重大成果转化项目(批准号: 12ZZ012)、四川省教育厅自然科学青年基金项目(批准号: 12ZB074,13ZB0002)和内江师范学院博士科研启动费项目(批准号: 2012B05)资助

Preparation and Suzuki Reaction Performance of Pectin-supported Palladium Catalyst^†

ZHOU Wenjun, ZHOU Yu, ZHANG Xiazhong^*(), ZENG Bin

College of Chemistry and Chemical Engineering, Neijiang Normal University, Neijiang 641112, China

Received:2015-10-19 Online:2016-04-10 Published:2016-03-04
Contact: ZHANG Xiazhong E-mail:zhangxiazhong@163.com
Supported by:
† Supported by the Sichuan Province Education Office Fostering Projects, China(No.12ZZ012), the Youth Found of Sichuan Province Education Office, China(Nos.12ZB074, 13ZB0002) and the Startup Foundation of Ph.D.Scientific Research of Neijiang Normal University, China(No.2012B05)

摘要/Abstract

摘要：

以柑橘皮果胶为载体, 采用吸附法制备了果胶负载钯催化剂, 并将其应用于四苯硼钠与溴代芳烃的交叉偶联反应中. 该反应体系以聚乙二醇400(PEG 400)/H₂O为反应溶剂, 三乙胺为碱, 在空气中于110 ℃反应15~60 min, 四苯硼钠中4个苯基均可顺利参与反应, 高产率地获得相应的目标化合物. 该方法具有条件温和、反应时间短、收率高且催化剂可循环利用等优点.

关键词: 果胶负载钯, Suzuki反应, 四苯硼钠, 溴代芳烃

Abstract:

To discover new heterogeneous palladium catalyst in organic synthesis, pectin, which was extracted form citrus peel, was used as supporter for the preparation of pectin-supported palladium catalyst. The pectin-supported palladium catalyst was applied to Suzuki cross-coupling reaction between sodium tetraphenylborate and aryl bromides. The results revealed that all four aryl groups of sodium tetraryylborate could be efficiently utilized in the Suzuki cross-coupling reactions in an atom-efficient way in the presence of Et₃N as base in PEG 400/H₂O at 110 ℃ in open air, providing excellent yields of the corresponding functionalized biaryls within 1 h. The present protocol has the advantages highly efficient, high yield, mild condition, short reaction time, as well as the catalyst can be recycled and reused.

Key words: Pectin supported-Pd, Suzuki reaction, Sodium tetraphenylborate, Aryl bromide

中图分类号:

O621.25

TrendMD:

周文俊, 周宇, 张霞忠, 曾彬. 果胶负载钯催化剂的制备及Suzuki反应催化性能. 高等学校化学学报, 2016, 37(4): 669.

ZHOU Wenjun, ZHOU Yu, ZHANG Xiazhong, ZENG Bin. Preparation and Suzuki Reaction Performance of Pectin-supported Palladium Catalyst^†. Chem. J. Chinese Universities, 2016, 37(4): 669.

图/表 7

参考文献 27

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果胶负载钯催化剂的制备及Suzuki反应催化性能

Preparation and Suzuki Reaction Performance of Pectin-supported Palladium Catalyst^†

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Entry	Base	n(Base)/ mmol	Molar fraction of Pd(%)	T/℃	t/min	Yield^b (%)	Entry	Base	n(Base)/ mmol	Molar fraction of Pd(%)	T/℃	t/min	Yield^b (%)
1	Et₃N	3.0	1.6	80	20	65	12	NaHCO₃	3.0	1.6	110	60	65
2	Et₃N	3.0	1.6	85	20	70	13	Py	3.0	1.6	110	60	40
3	Et₃N	3.0	1.6	90	20	72	14	NaH₂PO₄	3.0	1.6	110	120	50
4	Et₃N	3.0	1.6	95	20	72	15	AcONa	3.0	1.6	110	120	45
5	Et₃N	3.0	1.6	100	20	76	16	KH₂PO₄	3.0	1.6	110	120	44
6	Et₃N	3.0	1.6	105	20	80	17	Et₂NH	3.0	1.6	110	40	70
7	Et₃N	3.0	1.6	110	20	88	18	Et₃N	2.5	1.6	110	20	80
8	Et₃N	3.0	1.6	115	20	87	19	Et₃N	3.5	1.6	110	20	86
9	Et₃N	3.0	1.6	120	20	87	20	Et₃N	4.0	1.6	110	20	87
10	K₂CO₃	3.0	1.6	110	60	65	21	Et₃N	3.0	2.0	110	20	88
11	Na₂CO₃	3.0	1.6	110	60	67	22	Et₃N	3.0	2.4	110	20	88

Entry	R'	R	t/min	Yield^b(%)	Entry	R'	R	t/min	Yield^b(%)
1	H	H	20	88	10	4-NH₂	H	25	86
2	4-Cl	H	25	93	11	4-CH₃	H	30	76
3	4-CN	H	20	96	12	4-OCH₃	H	30	94
4	4-NO₂	H	15	96	13	4-CN	4-CH₃	50	60
5	4-CH₂CN	H	30	95	14	4-CH₃	4-CH₃	25	70
6	4-Ac	H	30	97	15	4-NO₂	4-CH₃	30	80
7	4-CHO	H	20	96	16	4-Ac	4-CH₃	35	72
8	4-COOCH₃	H	30	91	17	4-OCH₃	4-CH₃	60	71
9	4-Ph	H	40	78	18	H	4-CH₃	45	61

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No.	Cycle	t/min	Yield^b(%)
1	1st	20	88
2	2nd	20	70
3	3rd	40	65
4	4th	60	55

No.	Cycle	t/min	Yield^b(%)
1	1st	20	88
2	2nd	20	70
3	3rd	40	65
4	4th	60	55

果胶负载钯催化剂的制备及Suzuki反应催化性能

Preparation and Suzuki Reaction Performance of Pectin-supported Palladium Catalyst†

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Preparation and Suzuki Reaction Performance of Pectin-supported Palladium Catalyst^†