双活性中心催化剂的制备及催化合成炔丙基胺

doi:10.7503/cjcu20170721

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (3): 482.doi: 10.7503/cjcu20170721

双活性中心催化剂的制备及催化合成炔丙基胺

刘丽丽¹(), 台夕市¹(), 刘均波², 李丹¹, 周小晶¹, 张丽君¹, 危潇飞¹

1. 潍坊学院化学化工与环境工程学院, 潍坊 261061
2. 机电与车辆工程学院, 潍坊 261061

收稿日期:2017-11-10 出版日期:2018-03-10 发布日期:2018-01-23
作者简介:联系人简介: 刘丽丽, 女, 博士, 讲师, 主要从事多相催化方面的研究. E-mail:liulili122@126.com; 台夕市, 男, 博士, 教授, 主要从事新材料合成及性能方面的研究. E-mail:taixs@wfu.edu.cn
基金资助:
山东省自然科学基金(批准号: ZR2017MB056, BS2014CL021, ZR2016BQ40)、潍坊市科技发展计划项目(批准号: 2014GX030)和大学生国家创新创业训练计划项目(批准号: 20171106141)资助

Preparation of Propargylamines Catalyzed by Heterogeneous Catalysts with Double Catalytic Sites^†

LIU Lili^1,^*(), TAI Xishi^1,^*(), LIU Junbo², LI Dan¹, ZHOU Xiaojing¹, ZHANG Lijun¹, WEI Xiaofei¹

1. School of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, China
2. School of Mechanical-Electronic and Vehicle Engineering, Weifang University, Weifang 261061, China

Received:2017-11-10 Online:2018-03-10 Published:2018-01-23
Contact: LIU Lili,TAI Xishi E-mail:liulili122@126.com;taixs@wfu.edu.cn
Supported by:
† Supported by the Natural Science Foundation of Shandong Province of China(Nos.ZR2017MB056, BS2014CL021, ZR2016BQ40), the Technology Research and Development Program of Weifang, China(No.2014GX030) and the National Undergraduate Training Program for Innovation and Entrepreneurship, China(No.20171106141)

摘要/Abstract

摘要：

以2,6-吡啶二甲酸和醋酸镍为原料, 采用水热法合成了超分子配位聚合物Ni₂(2,6-NDC)₂(H₂O)₅·2H₂O(CP-Ni-NDC); 然后分别以HAuCl₄和AgNO₃为前体, 采用浸渍法制备了具有双活性中心的催化剂Au@CP-Ni-NDC和Ag@CP-Ni-NDC. 采用X射线衍射、红外光谱、热重分析、透射电子显微镜、 X射线光电子能谱、电感耦合等离子体原子发射光谱和NH₃程序升温脱附等方法对这2种催化剂进行表征, 并考察了其在醛、炔和胺三组分偶联(A³)反应合成炔丙基胺类化合物过程中的催化活性. 实验结果表明, CP-Ni-NDC中的Ni与2,6-吡啶二甲酸络合形成了聚合物, 层与层之间由氢键和π-π键作用形成三维超分子结构; 催化剂4.49%Au@CP-Ni-NDC和3.43%Ag@CP-Ni-NDC存在路易斯酸-Au(或路易斯酸-Ag)双活性中心, 有较高的催化合成炔丙基胺的活性, 在120 ℃反应 10 h, 苯甲醛、苯乙炔和六氢吡啶发生A³反应制备 1-(1,3-二苯基-2-丙炔基)-哌啶的产率分别为63%和43%, 转化数(Turnover number, TON)分别为9.9和4.8(基于总Au或总Ag含量). 催化剂4.49%Au@CP-Ni-NDC和3.43%Ag@CP-Ni-NDC对于带有不同官能团的芳香醛和脂肪醛均具有较好的适应性, 且可以重复使用4次.

关键词: 配位聚合物, 双活性中心, 催化剂, 炔丙基胺

Abstract:

The supramolecular coordination polymer Ni₂(2,6-NDC)₂(H₂O)₅∙2H₂O(CP-Ni-NDC) was synthesized by hydrothermal method from 2,6-pyridinedicarboxylic acid and nickelous acetate. Then, Au@CP-Ni-NDC and Ag@CP-Ni-NDC catalysts with double catalytic sites were prepared with HAuCl₄ and AgNO₃ as precursors by impregnation method. The two catalysts were characterized by single crystal X-ray diffraction, powder X-ray diffraction(XRD), infrared spectroscopy(IR), thermogravimetric analysis(TG), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), inductivity coupled plasma-atomic emiss ions spectrometry(ICP-AES) and temperature-programmed desorption(NH₃-TPD). X-Ray crystallographic results reveal that CP-Ni-NDC is a one-dimensional chain, which further assembles into a three-dimensional supramolecular network via the π-π stacking interaction and hydrogen bonds. IR spectra, NH₃-TPD and XPS results indicated that 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC contains Lewis acid-Au(Ag) double catalytic sites. The catalytic performance of the catalysts were examined in one-pot synthesis of structurally divergent propargylamines by three component coupling of aldehyde, alkyne and amine(A³) in 1,4-dioxane. The substrate scope, catalyst reusability and possible mechanism were investigated. The results indicated that 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC displyed good catalytic activity. The yields of propargylamines were 63% and 43% over 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC at 120 ℃ within 10 h, respectively. Taking into account the total metal content of the catalyst, the TON numbers calculated were 9.9 and 4.8, respectively. 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC have good catalytic activities for aromatic aldehydes and aliphatic aldehydes. And the catalysts of 4.49%Au@CP-Ni-NDC and 3.43%Ag@CP-Ni-NDC could be recovered easily by centrifugation and reused four times.

Key words: Coordination polymer, Double catalytic sites, Catalyst, Propargylamine

中图分类号:

O643

TrendMD:

刘丽丽, 台夕市, 刘均波, 李丹, 周小晶, 张丽君, 危潇飞. 双活性中心催化剂的制备及催化合成炔丙基胺. 高等学校化学学报, 2018, 39(3): 482.

LIU Lili, TAI Xishi, LIU Junbo, LI Dan, ZHOU Xiaojing, ZHANG Lijun, WEI Xiaofei. Preparation of Propargylamines Catalyzed by Heterogeneous Catalysts with Double Catalytic Sites^†. Chem. J. Chinese Universities, 2018, 39(3): 482.

图/表 13

参考文献 30

[1]	Liu L. L., Zhang X., Gao J. S., Xu C. M., Green Chem., 2012, 14(6), 1710—1720
[2]	Li P., Wang L., Tetrahedron, 2007, 38(40), 5455—5459
[3]	Liu L. L., Tai X. S., Zhou X. J., Xin C. L., Yan Y. M., Scientific Reports, 2017, 7(1), 12709—12717
[4]	Cheng M., Li B.G., Chinese Journal of Synthetic Chemistry, 2012,20(1), 1—6
	(成明, 李伯刚.合成化学,2012, 20(1), 1—6)
[5]	Wei C. M., Li Z. G., Li C. J., Synlett., 2004, 35(9), 1472—1483
[6]	Xiao F. P., Chen Y. L., Liu Y., Wang J., Tetrahedron, 2008, 64(12), 2755—2761
[7]	Liu L. L., Tai X. S., Zhang N. N., Meng Q. G., Xin C. L., Reac. Kinet. Mech. Cat., 2016, 119(1), 335—348
[8]	Liu L. L., Tai X. S., Zhou X. J., Liu L. J., Chem. Res. Chinese Universities, 2017, 33(2), 231—238
[9]	Lo V. K., Liu Y., Wong M. K., Che C. M., Org. Lett., 2006, 8(8), 1529—1532
[10]	Wei C., Li Z., Li C. J., Org. Lett., 2003, 5(23), 4473—4475
[11]	Gholinejad M., Saadati F., Shaybanizade S., Pullithadathil B., RSC Adv., 2016, 6(6), 4983—4991
[12]	Gommermann N., Koradin C., Polborn K., Knochel P., Angew. Chem. Int. Ed., 2003, 42(46), 5763—5766
[13]	Chen W. W., Nguyen R. V., Li C. J., Tetrahedron Lett., 2009, 50(24), 2895—2898
[14]	Zani L., Alesi S., Cozzi P. G., Bolm C., J. Org. Chem., 2006, 71(4), 1558—1562
[15]	Li P. H., Wang L., Chin. J. Chem., 2010, 36(50), 1076—1080
[16]	Zhang Y., Li P., Wang M., Wang L., J. Org. Chem., 2009, 74(11), 4364—4367
[17]	Wang X. X., Quan Z. J., Wang X. C., Asian J. Org. Chem., 2015, 4(1), 54—61
[18]	Berrichi A., Bachir R., Benabdallah M., Choukchou-Braham N., Tetrahedron Lett., 2015, 56(11), 1302—1306
[19]	Huang B., Yao X., Li C., Adv. Synth. Catal., 2006, 348(12/13), 1528—1532
[20]	Li W., Zou H. Y., Wang N., Qi Y. J., Journal of Changchun Normal University(Natural Science), 2013, 32(1), 65—70
	(李伟, 邹恒野, 王楠, 齐艳娟. 长春师范学院学报(自然科学版), 2013, 32(1), 65—70)
[21]	Liu L. L., Zhang X., Rang S. M., Yang Y., Dai X. P., Gao J. S., Xu C. M., He J., RSC Adv., 2014, 4(25), 13093—13107
[22]	Liu L. L., Tai X. S., Liu M. F., Li Y. F, Feng Y. M., Sun X. R., CIESC Journal, 2015, 66(5), 1738—1747
	(刘丽丽, 台夕市, 刘美芳, 李玉峰, 冯一民, 孙晓日.化工学报,2015, 66(5), 1738—1747)
[23]	Yong G. P., Tian D., Tong H. W., Liu S. M., J. Mol. Catal. A: Chem., 2010, 323(1/2), 40—44
[24]	Hareesh K., Joshi R. P., Dahiwale S. S., Bhoraskar V. N., Dhole S. D., Vacuum, 2016, 124, 40—45
[25]	Liu L. L., Tai X. S., Yu G. L., Guo H. M., Meng Q. G., Chem. Res. Chinese Universities, 2016, 32(3), 443—450
[26]	Zhang X., Shi H., Xu B. Q., Catal. Today, 2007, 122(3/4), 330—337
[27]	Liu L. L., Tai X. S., Zhou X. J., Materials, 2017, 10, 99—111
[28]	Kidwai M., Bansal V., Kumar A., Mozumdar S., Green Chem., 2007, 9, 742—745
[29]	Yan W. J., Wang R, Xu Z. Q., Xu J. K., Lin L., Shen Z. Q., Zhou Y. F., J. Mol. Catal. A: Chem., 2006, 255(1/2), 81—85
[30]	Zhang X., Corma A., Angew. Chem. Int. Ed., 2008, 47(23), 4358—4361

Entry	Catalyst	Aldehyde	Alkyne	t/h	Yield(%)	TON^b
1		Benzaldehyde	Phenylacetylene	10	2
2	CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	4
3	0.81%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	9	7.7
4	2.03%Au@CP--Ni-NDC	Benzaldehyde	Phenylacetylene	1	22	7.5
5	4.49%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	50	7.8
6	4.49%Au@CP-Ni-NDC-Py	Benzaldehyde	Phenylacetylene	1	35	5.5
7	4.49%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	63	9.9
8	3.43%Ag@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	28	3.1
9	3.43%Ag@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	43	4.8

Entry	Catalyst	Aldehyde	Alkyne	t/h	Yield(%)	TON^b
1		Benzaldehyde	Phenylacetylene	10	2
2	CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	4
3	0.81%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	9	7.7
4	2.03%Au@CP--Ni-NDC	Benzaldehyde	Phenylacetylene	1	22	7.5
5	4.49%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	50	7.8
6	4.49%Au@CP-Ni-NDC-Py	Benzaldehyde	Phenylacetylene	1	35	5.5
7	4.49%Au@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	63	9.9
8	3.43%Ag@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	1	28	3.1
9	3.43%Ag@CP-Ni-NDC	Benzaldehyde	Phenylacetylene	10	43	4.8

Entry	Catalyst	Aldehyde	Alkyne	t/h	Yield(%)	TON^b
1	4.49%Au@CP-Ni-NDC	4-Chlorobenzaldehyde	Phenylacetylene	10	44	6.9
2		4-Methylbenzaldehyde	Phenylacetylene	10	97	15.2
3		4-Methoxybenzaldehyde	Phenylacetylene	10	80	12.5
4		Cyclohexylaldehyde	Phenylacetylene	10	93	14.6
5		n-Octanaldehyde	Phenylacetylene	10	99	15.5
6		n-Heptaldehyde	Phenylacetylene	10	99	15.5
7		Benzaldehyde	4-Ethylphenylacetylene	10	36	5.6
8		Benzaldehyde	4-Butylphenylacetylene	10	32	5.0
9		Benzaldehyde	1-Octyne	10	22	3.4
10	3.43%Ag@CP-Ni-NDC	4-Chlorobenzaldehyde	Phenylacetylene	10	31	3.5
11		4-Methylbenzaldehyde	Phenylacetylene	10	75	8.4
12		4-Methoxybenzaldehyde	Phenylacetylene	10	71	8.0
13		Cyclohexylaldehyde	Phenylacetylene	10	70	7.9
14		n-Octanaldehyde	Phenylacetylene	10	81	9.1
15		n-Heptaldehyde	Phenylacetylene	10	99	11.1
16		Benzaldehyde	4-Ethylphenylacetylene	10	27	3.0
17		Benzaldehyde	4-Butylphenylacetylene	10	32	3.6
18		Benzaldehyde	1-Octyne	10	19	2.1

Entry	Catalyst	Aldehyde	Alkyne	t/h	Yield(%)	TON^b
1	4.49%Au@CP-Ni-NDC	4-Chlorobenzaldehyde	Phenylacetylene	10	44	6.9
2		4-Methylbenzaldehyde	Phenylacetylene	10	97	15.2
3		4-Methoxybenzaldehyde	Phenylacetylene	10	80	12.5
4		Cyclohexylaldehyde	Phenylacetylene	10	93	14.6
5		n-Octanaldehyde	Phenylacetylene	10	99	15.5
6		n-Heptaldehyde	Phenylacetylene	10	99	15.5
7		Benzaldehyde	4-Ethylphenylacetylene	10	36	5.6
8		Benzaldehyde	4-Butylphenylacetylene	10	32	5.0
9		Benzaldehyde	1-Octyne	10	22	3.4
10	3.43%Ag@CP-Ni-NDC	4-Chlorobenzaldehyde	Phenylacetylene	10	31	3.5
11		4-Methylbenzaldehyde	Phenylacetylene	10	75	8.4
12		4-Methoxybenzaldehyde	Phenylacetylene	10	71	8.0
13		Cyclohexylaldehyde	Phenylacetylene	10	70	7.9
14		n-Octanaldehyde	Phenylacetylene	10	81	9.1
15		n-Heptaldehyde	Phenylacetylene	10	99	11.1
16		Benzaldehyde	4-Ethylphenylacetylene	10	27	3.0
17		Benzaldehyde	4-Butylphenylacetylene	10	32	3.6
18		Benzaldehyde	1-Octyne	10	19	2.1

双活性中心催化剂的制备及催化合成炔丙基胺

Preparation of Propargylamines Catalyzed by Heterogeneous Catalysts with Double Catalytic Sites^†

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Entry	Catalyst	Yield(%)	Entry	Catalyst	Yield(%)
Fresh	4.49%Au@CP-Ni-NDC	63	Fresh	3.43%Ag@CP-Ni-NDC	43
Run 1	4.49%Au@CP-Ni-NDC	44	Run 1	3.43%Ag@CP-Ni-NDC	39
Run 2	4.49%Au@CP-Ni-NDC	35	Run 2	3.43%Ag@CP-Ni-NDC	34
Run 3	4.49%Au@CP-Ni-NDC	30	Run 3	3.43%Ag@CP-Ni-NDC	30

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双活性中心催化剂的制备及催化合成炔丙基胺

Preparation of Propargylamines Catalyzed by Heterogeneous Catalysts with Double Catalytic Sites†

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Preparation of Propargylamines Catalyzed by Heterogeneous Catalysts with Double Catalytic Sites^†