芳香醛亚胺与一氧化碳的交替共聚反应

doi:10.7503/cjcu20150421

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (1): 59.doi: 10.7503/cjcu20150421

芳香醛亚胺与一氧化碳的交替共聚反应

吕浩挺, 苗群, 孙怀林()

南开大学化学系, 元素有机化学国家重点实验室, 化学与工程协同创新中心, 天津 300071

收稿日期:2015-05-22 出版日期:2016-01-10 发布日期:2015-12-20
基金资助:
国家自然科学基金(批准号: 20834002)、天津市自然科学基金(批准号: 08JCZDJC21600)和高等学校博士学科点专项科研基金(批准号: 20090031110012)资助

Alternating Copolymerization of Aryl Aldehyde Imines and Carbon Monoxide^†

LÜ Haoting, MIAO Qun, SUN Huailin^*()

State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Department of Chemistry, Nankai University, Tianjin 300071, China

Received:2015-05-22 Online:2016-01-10 Published:2015-12-20
Contact: SUN Huailin E-mail:sunhl@nankai.edu.cn
Supported by:
† Supported by the National Natural Sciences Foundation of China(No.20834002), the Natural Sciences Foundation of Tianjin, China(No.08JCZDJC21600) and the Research Fund for the Doctoral Program of Higher Education, China(No.20090031110012)

摘要/Abstract

摘要：

以苯乙酰基四羰基钴作为催化剂, 研究了对芳香醛亚胺与一氧化碳(CO)的交替共聚反应. 采用6种芳香醛亚胺单体, 分别与CO进行交替共聚反应, 得到了6种新的多肽类聚合物.利用核磁共振谱、红外光谱、凝胶渗透色谱(GPC)及MALDI-TOF质谱等对聚合物的结构进行了表征. 探讨了芳香醛亚胺苯环上取代基的位阻效应和电子效应对聚合反应的影响. 结果表明, 聚合物链终止端存在3种不同类型的端基, 分别具有慕尼黑酮类结构、咪唑啉类结构以及酰胺类结构, 对这些端基的形成机理进行了讨论.

关键词: 酰基钴, 亚胺, 多肽, 催化, 共聚

Abstract:

Alternating copolymerization of aryl aldehyde imines and CO, using phenylacetyl tetracarbonyl cobalt as catalyst, was investigated in details. The reactions were carried in dioxane at 50 ℃ under 6 MPa of CO pressure, and six new polypeptide products were obtained from copolymerization of the corresponding aryl imines and CO. The steric and electronic effects of substituents at the phenyl rings were examined, which showed obvious influences on the molecular weight of the polymerization products as well as the copolymerization. The structures of the polypeptide products were characterized by naclear magnetic resonance(NMR), Infrared(IR), gel permeation chromatography(GPC) as well as matrix-assisted laser desorption/ionization time of flight mass spectrometry(MALDI-TOF MS) methods. According to the MS results, there existed three kinds of new end group structures at the terminal ends of the polymerization products, which should correspond to münchnone, imidazoline and amide structures, respectively. Possible mechanisms for the formation of the three kinds of end groups were discussed.

Key words: Acylcobalt, Imine, Polypeptide, Catalysis, Copolymerization

TrendMD:

吕浩挺, 苗群, 孙怀林. 芳香醛亚胺与一氧化碳的交替共聚反应. 高等学校化学学报, 2016, 37(1): 59.

LÜ Haoting, MIAO Qun, SUN Huailin. Alternating Copolymerization of Aryl Aldehyde Imines and Carbon Monoxide^†. Chem. J. Chinese Universities, 2016, 37(1): 59.

图/表 8

参考文献 27

[1]	Bodanszky M., Bodanszky A., Principles of Peptide Synthesis, 2nd Ed., Springer, New York, 1994, 215—318
[2]	Sewald N., Jakubke H.D., Peptides: Chemistry and Biology, Wiley-VCH, Weinheim, 2002, 61—130
[3]	Luxenhofer R., Fetsch C., Grossmann A., J. Polym. Sci. Pol. Chem., 2013, 51, 2731—2752
[4]	Sun J., Zuckermann R. N., ACS Nano, 2013, 7, 4715—4732
[5]	Xin J., Zhang Y., Zhang L., Lin Y., Zhou Q., Chem. Res. Chinese Universities, 2013, 29(5), 924—928
[6]	Fetsch C., Grossmann A., Holz L., Nawroth J. F., Luxenhofer R., Macromolecules,2011, 44, 6746—6758
[7]	Kricheldorf H. R., Angew. Chem. Int. Ed., 2006, 45, 5752—5784
[8]	Pattabiraman V. R., Bode J. W., Nature,2011, 480, 471—479
[9]	Deming T. J., Adv. Mater., 1997, 9, 299—311
[10]	Sen A., Acc. Chem. Res., 1993, 26, 303—310
[11]	Drent E., Budzelaar P. H. M., Chem. Rev., 1996, 96, 663—681
[12]	Kacker S., Kim J. S., Sen A., Angew. Chem. Int. Ed., 1998, 37, 1251—1253
[13]	Dghaym R. D., Yaccato K. J., Arndtsen B. A., Organomeallics,1998, 17, 4—6
[14]	Cavallo L., J. Am. Chem. Soc., 1999, 121, 4238—4241
[15]	Davis J. L., Arndtsen B. A., Organometallics,2000, 19, 4657—4659
[16]	Lafrance D. , Davis J. L., Dhawan R., Arndtsen B. A., Organometallics,2001, 20, 1128—1136
[17]	Sun H., Zhang J., Liu Q., Zhao J., Yu L., Angew. Chem. Int. Ed., 2007, 46, 6068—6072
[18]	Zhang Y. P., Sun H. L., Chem. J. Chinese Universities, 2014, 35(1), 54—57
	(张永坡, 孙怀林. 高等学校化学学报, 2014, 35(1), 54—57)
[19]	Jia L., Sun H., Shay J. T., Allgeier A. M., Hanton S. D., J. Am. Chem. Soc., 2002, 124, 7282—7283
[20]	Yoshida H., Fukushima H., Ohshita J., Kunai A., J. Am. Chem. Soc., 2006, 128, 11040—11041
[21]	Karabatsos G. J., Lande S. S., Tetrahedron,1968, 24, 3907—3922
[22]	Joly G. D., Jacobsen E. N., J. Am. Chem. Soc., 2004, 126, 4102—4103
[23]	Baldridge A., Kowalik J., Tolbert L. M., Synthesis,2010, 14, 2424—2436
[24]	Yudin L. G., Zh. Org. Khim., 1983, 11, 2361—2366
[25]	Moffett R. B., Hoehn W. M., J. Am. Chem. Soc., 1947, 69, 1792—1794
[26]	Dghaym R. D., Dhawan R., Arndtsen B. A., Angew. Chem. Int. Ed., 2001, 40, 3228—3230
[27]	Speckampa W. N., Hiemstra H., Tetrahedron,1985, 41, 4367—4416

Imine	Appearance	Yield(%)	b.p./℃	IR(KBr), /cm^-1	HRMS(ESI), [M+H]⁺(cacld.), m/z
1	Colourless liquid	88	54—56(66.7 Pa)	1642	148.1125(148.1121)
2	Colourless liquid	92	80—82(13.3 Pa)	1650	192.1387(192.1383)
3	Colourless liquid	94	56—58(533.3 Pa)	1651	134.0968(134.0964)
4	Colourless liquid	92	80—82(66.7 Pa)	1651	164.1072(164.1070)
5	White solid	98	56—58(13.3 Pa)	1645	180.1021(180.1019)
6	White solid	89	64—66(26.7 Pa)	1637	164.1075(164.1070)

Imine	Appearance	Yield(%)	b.p./℃	IR(KBr), /cm^-1	HRMS(ESI), [M+H]⁺(cacld.), m/z
1	Colourless liquid	88	54—56(66.7 Pa)	1642	148.1125(148.1121)
2	Colourless liquid	92	80—82(13.3 Pa)	1650	192.1387(192.1383)
3	Colourless liquid	94	56—58(533.3 Pa)	1651	134.0968(134.0964)
4	Colourless liquid	92	80—82(66.7 Pa)	1651	164.1072(164.1070)
5	White solid	98	56—58(13.3 Pa)	1645	180.1021(180.1019)
6	White solid	89	64—66(26.7 Pa)	1637	164.1075(164.1070)

Entry	Imine	n(M)/n(C)^b	t/h	Yield(%)	Polypeptide	10^-3	PDI^d
1	1	10∶1	12	100	7	1.8
2	1	20∶1	24	100	7	5.3	1.33
3	1	30∶1	30	100	7	6.8	1.43
4	2	10∶1	24	100	8	5.9	1.39
5	2	20∶1	24	45	8	7.4	1.43
6	3	10∶1	12	100	9	3.0	1.42
7	3	20∶1	24	43	9	2.9	1.49
8	4	10∶1	10	100	10	5.3	1.28
9	4	20∶1	24	60	10	5.3	1.67
10	5	10∶1	16	100	11	3.6	1.44
11	5	20∶1	24	37	11	3.2	1.35
12	6	20∶1	24	100	12	3.8	1.66
13	6	30∶1	36	52	12	5.1	1.69

Entry	Imine	n(M)/n(C)^b	t/h	Yield(%)	Polypeptide	10^-3	PDI^d
1	1	10∶1	12	100	7	1.8
2	1	20∶1	24	100	7	5.3	1.33
3	1	30∶1	30	100	7	6.8	1.43
4	2	10∶1	24	100	8	5.9	1.39
5	2	20∶1	24	45	8	7.4	1.43
6	3	10∶1	12	100	9	3.0	1.42
7	3	20∶1	24	43	9	2.9	1.49
8	4	10∶1	10	100	10	5.3	1.28
9	4	20∶1	24	60	10	5.3	1.67
10	5	10∶1	16	100	11	3.6	1.44
11	5	20∶1	24	37	11	3.2	1.35
12	6	20∶1	24	100	12	3.8	1.66
13	6	30∶1	36	52	12	5.1	1.69

芳香醛亚胺与一氧化碳的交替共聚反应

Alternating Copolymerization of Aryl Aldehyde Imines and Carbon Monoxide^†

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芳香醛亚胺与一氧化碳的交替共聚反应

Alternating Copolymerization of Aryl Aldehyde Imines and Carbon Monoxide†

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Alternating Copolymerization of Aryl Aldehyde Imines and Carbon Monoxide^†