Diacetylene-Based C _2h-Symmetric Monomers for Two-Dimensional-Polymer Synthesis

Abstract

Two linear monomers with two terminal photoreactive groups (anthracene or maleimide) embedded in a diacetylene skeleton were synthesized for two-dimensional-polymer synthesis. Both of them were crystallized and their single-crystal structures were solved. It was found that the size of terminal groups can be critical for diacetylene’s arrangement. The crystal structure of dimaleimide monomer revealed that maleimide groups strongly stacking in antiparallel and the photo-induced [2+2] cycloaddition of stacked maleimides was preliminary studied.

Key words

two-dimensional polymer - single crystal - topochemistry - diacetylene - maleimide

• References and Notes

• 1 Sakamoto J, Heijst van J, Lukin O, Schlüter AD. Angew. Chem. Int. Ed. 2009; 48: 1030
• 2 Servalli M, Trapp N, Wörle M, Klärner F.-G. J. Org. Chem. 2016; 81: 2572
• 3 Kissel P, Schlüter AD, Sakamoto J. Chem. Eur. J. 2009; 15: 8955
• 4 Kissel P, Erni R, Schweizer WB, Rossell MD, King BT, Bauer T, Götzinger S, Schlüter AD, Sakamoto J. Nat. Chem. 2012; 4: 287
• 5 Kissel P, Murray DJ, Wulftange WJ, Catalano VJ, King BT. Nat. Chem. 2014; 6: 774
• 6 Kory MJ, Wörle M, Weber T, Payamyar P, van de PollStan W, Dshemuchadse J, Trapp N, Schlüter AD. Nat. Chem. 2014; 6: 779
• 7 Wegner G. Z. Naturforsch. 1969; 24: 824
• 8 Wegner G. Pure Appl. Chem. 1977; 49: 443
• 9 Yee KC, Chance RR. J. Polym. Sci., Polym. Phys. Ed. 1978; 16: 431
• 10 Galiotis C, Read RT, Yeung PH. J, Young RJ, Chalmers IF, Bloor D. J. Polym. Sci., Polym. Phys. Ed. 1984; 22: 1589
• 11 Li M, Schlüter AD, Sakamoto J. J. Am. Chem. Soc. 2012; 134: 11721
• 12 Matsumoto T. Macromolecules 1999; 32: 4933
• 13 Li Q, Horie K, Yokota R. Polym. J. 1998; 30: 805
• 14 Schmidt GM. J. Pure Appl. Chem. 1971; 27: 647
• 15 Schmidt GM. J. J. Chem. Soc. 1964; 2014
• 16 Tedaldi LM, Aliev AE, Baker JR. Chem. Commun. 2012; 48: 4725
• 17 Laurenti D, Santelli-Rouvier C, Pèpe G, Santelli M. J. Org. Chem. 2000; 65: 6418
• 18 DeCicco RC, Black A, Li L, Goroff NS. Eur. J. Org. Chem. 2012; 4699
• 19 Neises B, Steglich W. Angew. Chem., Int. Ed. Engl. 1978; 17: 522
• 20 Synthesis of Monomer 1 A sealed tube was charged with compound 3 (221 mg, 2 mmol), 9-anthracene carboxylic acid (1115 mg, 5 mmol), N,N-dicyclohexylcarbodimide (1128 mg, 5 mmol), and 4-dimethylaminopyridine (28 mg, 0.2 mmol) in 1-methyl-2-pyrrolidone (10 mL) under argon atmosphere. The mixture was stirred at 40 °C for 5 d. The yellow mixture was washed with water and passed a silicon chromatographic column affording monomer 1 as a yellow solid (820 mg, 1.6 mmol, 79%); mp >250 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.56 (s, 2 H, H-6), 8.08 (d, J = 8 Hz, 4 H, H-2 or H-5), 8.03 (d, J = 8 Hz, 4 H, H-2 or H-5), 7.57 (m, 4 H, H-3 or H-4), 7.48 (m, 4 H, H-3 or H-4), 5.29 (s, 4 H, H-1) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 168.81, 131.03, 130.16, 128.78, 127.49, 126.24, 125.69, 124.91, 73.86, 71.17, 53.36 ppm. HRMS (LC-MS TOF, formic acid): m/z calcd for C₃₆H₂₂O₄ [MH]⁺: 519.1591; found: 519.1587.
• 21 Grigoras M, Sava M, Colotin G, Simionescu CI. J. Appl. Polym. Sci. 2008; 107: 846

Synthesis of Monomer 2
• 22a A solution of compound 4 (0.383 g, 0.95 mmol) in xylene (200 mL) was refluxed for 3 h under an argon atmosphere. After reaction, the hot solution was quickly filtered to remove insoluble byproducts and then concentrated by rotary vacuum. Monomer 2 was obtained as white solid from the cooling solution (0.168 g, 0.63 mmol, 66.3%).
• 22b An open beak was charged with CuCl (0.102 g, 1 mmol) and TMEDA (0.121 g, 1 mmol) in acetone (2 mL). After stirring for 3 min, compound 8 (0.654 g, 4.80 mmol) was added, and the reaction continued for 16 h at 40 °C. By extraction from the product mixture with EtOAc and concentration, monomer 2 was obtained as a pale yellow solid (0.131 g, 0.49 mmol, 20.4%); mp 147 °C. ¹H NMR (400 MHz, CDCl₃): δ = 6.75 (s, 2 H, CH), 4.33 (s, 2 H, CH₂) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 169.18, 134.72, 72.13, 67.52, 27.58 ppm. HRMS (LC-MS TOF, formic acid): m/z calcd for C₁₄H₈N₂O₄ [MH]⁺: 269.0562; found: 269.0567.
• 23 Kötteritzsch J, Stumpf S, Hoeppener SJ, Vitz MD, Hager U, Schubert S. Macromol. Chem. Phys. 2013; 214: 1636
• 24 Stolz RM, Northrop BH. J. Org. Chem. 2013; 78: 8105
• 25 Rao V, Navath S, Kottur M, McElhanon JR, McGrath DV. Tetrahedron Lett. 2013; 54: 5011
• 26 Link M, Li X, Kleim J, Wolfbeis OS. Eur. J. Org. Chem. 2010; 6922
• 27 Xu R, Gramlich V, Frauenrath H. J. Am. Chem. Soc. 2006; 128: 5541