Alternating Copolymerization of Aryl Aldehyde Imines and Carbon Monoxide†

doi:10.7503/cjcu20150421

Abstract

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:

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

Figures/Tables 8

References 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