Multicomponent Polymerization of Alkynes, Sulfonyl Azide, and Iminophosphorane at Room Temperature for the Synthesis of Hyperbranched Poly(phosphorus amidine)s

Liguo Xu; Kou Yang; Rongrong Hu; Ben Zhong Tang

doi:10.1055/s-0037-1610275

Synlett, Table of Contents

Synlett 2018; 29(19): 2523-2528
DOI: 10.1055/s-0037-1610275

cluster

Multicomponent Polymerization of Alkynes, Sulfonyl Azide, and Iminophosphorane at Room Temperature for the Synthesis of Hyperbranched Poly(phosphorus amidine)s

Liguo Xu

^aState Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, P. R. of China Email: msrrhu@scut.edu.cn

,

Kou Yang

^aState Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, P. R. of China Email: msrrhu@scut.edu.cn

,

Rongrong Hu*

^aState Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, P. R. of China Email: msrrhu@scut.edu.cn

,

Ben Zhong Tang*

^aState Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, P. R. of China Email: msrrhu@scut.edu.cn

^bDepartment of Chemistry, Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration and Reconstruction, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong Email: tangbenz@ust.hk

› Author Affiliations

Abstract

All articles of this category

Published as part of the Cluster Synthesis of Materials

Abstract

The construction of functional hyperbranched polymers with unique topological structures and distinct properties remains a great challenge. Multicomponent polymerization, as a fascinating polymer synthetic approach, has proved to be a powerful tool for the synthesis of polymers with diverse structures and multifunctionalities, which is a great advantage for the preparation of hyperbranched polymers. In this work, a multicomponent polymerization of alkynes, sulfonyl azide, and iminophosphorane is utilized for the construction of heteroatom-rich hyperbranched poly(phosphorus amidine)s with different topological structures and fluorescence response toward platinum group metal ions.

Key words

hyperbranched polymer - multicomponent polymerization - alkynes - poly(phosphorus amidine)s - luminescence

Full Text

References

References and Notes

1a Gao C. Yan D. Prog. Polym. Sci. 2004; 29: 183
1b Hutchings L. Dodds J. Roberts S. Macromolecules 2005; 38: 5970
1c Zheng Y. Li S. Weng Z. Gao C. Chem. Soc. Rev. 2015; 44: 4091

2a Wooley K. Hawker C. Frechet J. 1991; 113: 4252
2b Khandare J. Calderon M. Dagia NM. Haag R. Chem. Soc. Rev. 2012; 41: 2824
2c Gao H. Yorifuji D. Wakita J. Jiang Z. Ando S. Polymer 2010; 51: 3173
2d Zhou YF. Huang W. Liu JY. Zhu XY. Yan DY. Adv. Mater. 2010; 22: 4567
2e Voit BI. Lederer A. Chem. Rev. 2009; 109: 5924

3a Pu KY. Li K. Shi JB. Liu B. Chem. Mater. 2009; 21: 3816
3b Li N. Jin Y. Xue L. Li P. Yan D. Zhu X. Chinese J. Polym. Sci. 2013; 31: 530

4 Wu Y. Hao X. Wu J. Jin J. Ba X. Macromolecules 2010; 43: 731
5 Imbesi P. Fidge C. Raymond J. Cauet S. Wooley K. ACS Macro Lett. 2012; 1: 473
6 Liu J. Lam JW. Y. Tang BZ. Chem. Rev. 2009; 109: 5799
7 Yates C. Hayes W. Eur. Polym. J. 2004; 40: 1257
8 Hu Y. Chen L. Guo Z. Nagai A. Jiang D. J. Am. Chem. Soc. 2011; 133: 17622
9 Hu R. Lam JW. Y. Liu J. Sung H. Williams ID. Yue Z. Wong K. Yuen MM. F. Tang BZ. Polym. Chem. 2012; 3: 1481

10a Zhao T. Zheng Y. Poly J. Wang WX. Nat. Commun. 2013; 4: 1873
10b Nuhn L. Schull C. Frey H. Zentel R. Macromolecules 2013; 46: 2892

11a Hu R. Li W. Tang BZ. Macromol. Chem. Phys. 2016; 217: 213
11b Rotstein BH. Zaretsky S. Rai V. Yudin AK. Chem. Rev. 2014; 114: 8323
11c Estevez V. Villacampa M. Menendez JC. Chem. Soc. Rev. 2014; 43: 4633

12a Kreye O. Toth T. Meier MA. J. Am. Chem. Soc. 2011; 133: 1790
12b Deng X. Li L. Li Z. Lv A. Du F. Li Z. ACS Macro Lett. 2012; 1: 1300
12c Sehlinger A. Dannecker P.-K. Kreye O. Meier MA. R. Macromolecules 2014; 47: 2774
12d Xue H. Zhao Y. Wu H. Wang Z. Yang B. Wei Y. Wang Z. Tao L. J. Am. Chem. Soc. 2016; 138: 8690
12e Li W. Wu X. Zhao Z. Qin A. Hu R. Tang BZ. Macromolecules 2015; 48: 7747
12f Wei B. Li W. Zhao Z. Qin A. Hu R. Tang BZ. J. Am. Chem. Soc. 2017; 139: 5075
12g Tian T. Hu R. Tang BZ. J. Am. Chem. Soc. 2018; 140: 6156
12h Xu L. Zhou F. Liao M. Hu R. Tang BZ. Polym. Chem. 2018; 9: 1674
12i Zhao Y. Wu H. Wang Z. Wei Y. Wang Z. Tao L. Sci. China Chem. 2016; 12: 1541
12j Jia T. Zheng N. Cai W. Zhang J. Ying L. Huang F. Cao Y. Chinese J. Polym. Sci. 2017; 2: 269

13 Deng X. Cui Y. Du F. Li Z. Polym. Chem. 2014; 5: 3316
14 Zhang Z. Tan Z. Hong C. Wu D. You Y. Polym. Chem. 2016; 7: 1468
15 Kim H. Bang KT. Choi I. Lee JK. Choi TL. J. Am. Chem. Soc. 2016; 138: 8612

16a Cui S. Wang J. Wang Y. Org. Lett. 2008; 10: 1267
16b Bae I. Han H. Chang S. J. Am. Chem. Soc. 2005; 127: 2038
16c Choi W. Kim J. Ryu T. Kim KB. Lee PH. Org. Lett. 2015; 17: 3330

17 Xu L. Hu R. Tang BZ. Macromolecules 2017; 50: 6043

18a Musina A. Bocokic V. Lavric V. van Zutphen S. Ind. Eng. Chem. Res. 2014; 53: 13362
18b Salzinger S. Seemann U. Plikhta A. Rieger B. Macromolecules 2011; 44: 5920
18c Steinmann M. Wagner M. Wurm F. Chem. Eur. J. 2016; 22: 17329

19 Synthesis of Model Compound 6 To a solution of sulfonyl azide 5 (219 mg, 1.2 mmol), alkyne 4 (122 mg, 1.2 mmol), iminophosphorane 3 (353 mg, 1.0 mmol), and CuI (38 mg, 0.2 mmol) in CH₂Cl₂ (8 mL) was added Et₃N (282 μL, 2.0 mmol) with a syringe under a nitrogen atmosphere. The resulting mixture was stirred at r.t. for 8 h. The reaction mixture was concentrated and the residue was subject to silica gel column chromatography (EtOAc/petroleum v/v, 1:1) to give product 6, which was further recrystallized from EtOAc/petroleum to afford a white solid with 84% (513 mg) yield. IR (KBr thin film): 3307, 3056, 2923, 1590, 1544, 1495, 1460, 1342, 1277, 1133 cm⁻¹. ¹H NMR (500 MHz, DMSO-d ₆): δ = 8.31 (d, J = 5.2 Hz, 1 H), 7.57 (m, 3 H), 7.47 (m, 12 H), 7.28 (t, J = 7.4 Hz, 1 H), 7.08 (t, J = 7.8 Hz, 2 H), 6.79 (m, 4 H), 6.67–6.56 (m, 8 H) ppm. HRMS: m/z [M + H]⁺ calcd for C38H32N2O2PS: 611.1922; found: 611.1929, m/z [M + Na]⁺ calcd for C38H32N2NaO2PS: 633.1742; found: 633.1743.
20 Multicomponent polymerizations were conducted under nitrogen by using the standard Schlenk technique. A typical procedure for the polymerization of 1a, 2, and 3 is given below as an example (see Table 1, entry 4). Alkyne monomer 1a (32 mg, 0.10 mmol), disulfonyl azides 2 (38 mg, 0.10 mmol), iminophosphorane 3 (88 mg, 0.25 mmol), and CuI (4 mg, 0.02 mmol) were added to a 10 mL Schlenk tube equipped with a magnetic stirrer. After purging with dry nitrogen for 3 times, DMF (1.3 mL) and Et₃N (28 μL, 0.20 mmol) were then added. After stirring at r.t. for 1 h, the reaction mixture was diluted with DMF (2 mL) and then precipitated in diethyl ether (200 mL) through a cotton-filled dropper. The precipitates were then collected by filtration and dried under vacuum to constant weight to afford the polymer product. hb-P1: Yellow powder; 79% (107 mg) yield. M _w = 133 100 g/mol, M _w/M _n = 6.90. IR (KBr): 3284, 3053, 3030, 2098, 1588, 1538, 1499, 1436, 1339, 1236, 1132 cm⁻¹. ¹H NMR (500 MHz, DMSO-d ₆): δ = 8.31, 7.48, 7.28, 6.81, 6.62, 6.29, 6.01, 4.06 ppm. hb-P2: Yellow powder; 81% (117 mg) yield. M _w = 441 700 g/mol, M _w/M _n = 9.37. IR (KBr): 3290, 3060, 3022, 2104, 1581, 1537, 1484, 1434, 1342, 1234, 1133 cm⁻¹. ¹H NMR (500 MHz, DMSO-d ₆): δ = 8.19, 7.45, 7.17, 6.87, 6.76, 6.55, 6.01, 4.14 ppm.

Supplementary Material

Supporting Information