Supplementary Information Synthesis, characterization and application of poly (N, N'-dibromo-Nethylnaphthyl-2, 7-disulfonamide) as an efficient catalyst for the synthesis of 2-arylbenzimidazole and 2-aryl-1-arylmethyl-1 H-1, 3-benzimidazole derivatives Vida Saleh 1,*, Ardeshir Khazaei 1,*, Hamid Abizadeh 1, Shahnaz Saednia 1 2 Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683, Iran 2 Young Researchers & Elites Club, Toyserkan Branch, Islamic Azad university, Toyserkan, Iran. *Corresponding authors (email: Khazaei_1326@yahoo.com, Vida.saleh@yahoo.com) Table of Contents Page Figure S1. IR spectrum of naphthalene-2, 7-disufonyl chloride (nujol) ……………….. S4 Figure S2. 1H NMR (90 MHz, CDCl3) spectrum of naphthalene-2, 7-disufonyl chloride S4 Figure S3. IR spectrum of poly (N-ethylnaphthyl-2, 7-disulfonamide) (KBr) ………… S5 Figure S4. 1H NMR (400 MHz, DMSO-d6) spectrum of poly (N-ethylnaphthyl-2, 7disulfonamide) ……………………………………………………………………………. S5 Figure S5. 13C NMR (100.6 MHz, DMSO-d6) spectrum of poly (N- ethylnaphthyl-2, 7disulfonamide) ……………………………………………………………………………. S6 Figure S6. Gel permeation chromatography (GPC) diagram for poly (N-ethylnaphthyl2, 7-disulfonamide) ………………………………………………………………………. S6 Figure S7. IR spectrum of PBNS (KBr) …………………………………………………. S7 Figure S8. 1H NMR (400 MHz, DMSO-d6) spectrum of PBNS ………………………… S7 Figure S9. 13C NMR (100.6 MHz, DMSO-d6) spectrum of PBNS ……………………… S8 Figure S10. TGA/DTG thermogram of poly (N-ethylnaphthyl-2, 7-disulfonamide) ……. S8 Figure S11. TGA/DTG thermogram of PBNS …………………………………………... S9 Figure S12. IR spectrum of 2-phenyl-1 H-benzoimidazole(KBr) ……………………… S9 Figure S13. 1H NMR (90 MHz, CDCl3) spectrum of 2-phenyl-1 H-benzoimidazole….. S10 Figure S14. IR spectrum of [4-(1 H-Benzoimidazol-2-yl)-phenyl]-dimethyl-amine (KBr) ……………………………………………………………………………………... S10 Figure S15. 1H NMR (90 MHz, CDCl3) spectrum of [4-(1H-Benzoimidazol-2-yl)phenyl]-dimethyl-amine ………………………………………………………………….. S11 Figure S16. IR spectrum of 2-(1 H-Benzoimidazol-2-yl)-phenol (KBr) ………………... S11 Figure S17. 1H NMR (90 MHz, CDCl3) spectrum of 2-(1 H-Benzoimidazol-2-yl)phenol …………………………………………………………………………………….. S12 Figure S18. IR spectrum of 2-p-Tolyl-1 H-benzoimidazole (KBr) ……………………… S12 Figure S19. 1H NMR (90 MHz, CDCl3) spectrum of 2-p-Tolyl-1 H-benzoimidazole ….. S13 Figure S20. IR spectrum of 2-(2-methoxy-phenyl)-1 H-benzoimidazole (KBr) ………... S13 Figure S21. 1H NMR (90 MHz, CDCl3) spectrum of 2-(2-methoxy-phenyl)-1 Hbenzoimidazole …………………………………………………………………………... S14 Figure S22. IR spectrum of 2-(3-nitro-phenyl)-1 H-benzoimidazole (KBr) …………….. S14 Table of Contents 1 Figure S23. Page H NMR (90 MHz, CDCl3) spectrum of 2-(3-nitro-phenyl)-1 H- benzoimidazole …………………………………………………………………………... 1 Figure S24. S15 H NMR (90 MHz, CDCl3) spectrum of 2-(4-chloro-phenyl)-1 H- benzoimidazole …………………………………………………………………………... S15 Figure S25. IR spectrum of 2-furan-2-yl-1 H-benzoimidazole (KBr) ..………………... S16 Figure S26. 1H NMR (90 MHz, CDCl3) spectrum of 2-furan-2-yl-1 H-benzoimidazole S16 Figure S27. IR spectrum of 1-benzyl-2-phenyl-1 H-benzoimidazole (KBr) ……….…. S17 1 Figure S28. H NMR (90 MHz, CDCl3) spectrum of 1-benzyl-2-phenyl-1 H- benzoimidazole …………………………………………………………………………... S17 Figure S29. IR spectrum of 1-(4-nitro-benzyl)-2-(4-nitro-phenyl)-1 H-benzoimidazole (KBr) ……………………………………………………………………………………... S18 Figure S30. 1H NMR (90 MHz, CDCl3) spectrum of 1-(4-nitro-benzyl)-2-(4-nitrophenyl)-1 H-benzoimidazole ………………………………………………………..……. S18 Figure S31. IR spectrum of 1-(3-nitro-benzyl)-2-(3-nitro-phenyl)-1 H-benzoimidazole (KBr) ……………………………………………………………………………………... S19 Figure S32. 1H NMR (90 MHz, CDCl3) spectrum of 1-(3-nitro-benzyl)-2-(3-nitrophenyl)-1 H-benzoimidazole ……………………………...……………………………… S19 Figure S33. IR spectrum of 1-(4-chloro-benzyl)-2-(4-chloro-phenyl)-1 H- benzoimidazole (KBr) ……………………………………………………………………. S20 Figure S34. 1H NMR (90 MHz, CDCl3) spectrum of 1-(4-chloro-benzyl)-2-(4-chlorophenyl)-1 H-benzoimidazole ……………………………………………………………... S20 Figure S35. IR spectrum of 1-(4-cyano-benzyl)-2-(4-cyano-phenyl)-1 H- benzoimidazole (KBr) ……………………………………………………………………. S21 Figure S36. 1H NMR (90 MHz, CDCl3) spectrum of 1-(4-cyano-benzyl)-2-(4-cyanophenyl)-1 H-benzoimidazole ...…………………………………………………………… S21 Figure S37. IR spectrum of 1-(4-methoxy-benzyl)-2-(4-methoxy-phenyl)-1 Hbenzoimidazole (KBr) ……………………………………………………………………. Figure S38. 13 S22 C NMR spectrum (90 MHz, CDCl3) of 1-(4-methoxy-benzyl)-2-(4- methoxy-phenyl)-1 H-benzoimidazole …………………………………………………... S22 ClO2S SO2Cl Figure S1.IR spectrum of naphthalene-2, 7-disufonyl chloride ClO2S SO2Cl Figure S2.1H NMR spectrum (90 MHz,CDCl3) of naphthalene-2, 7-disufonyl chloride. S4 O O S N H O S N O H n Figure S3.IR spectrum of poly (N-ethylnaphthyl-2, 7-disulfonamide) (KBr). O O S N H O S N O H n Figure S4.1H NMR(400 MHz,DMSO-d6) spectrum ofpoly (N-ethylnaphthyl-2, 7disulfonamide). S5 O O S N H O S N O H n Figure S5.13C NMR(100.6 MHz,DMSO-d6) spectrum ofpoly (N-ethylnaphthyl-2, 7disulfonamide). Figure S6.Gel permeation chromatography (GPC) diagram for poly (N-ethylnaphthyl-2, 7disulfonamide). S6 O O S S O O N N Br n Br Figure S7. IR spectrum of PBNS (KBr). O O S S O O N N Br Figure S8. 1H NMR(400 MHz, DMSO-d6) spectrum ofPBNS. S7 Br n O O S S O O N Br N n Br Figure S9.13C NMR(100.6 MHz, DMSO-d6) spectrum ofPBNS. O O S N H O S N O H Figure S10. TGA/DTG thermogram ofpoly (N-ethylnaphthyl-2, 7-disulfonamide). S8 n O O S S O O N N Br n Br Figure S11. TGA/DTG thermogram of PBNS. N N H Figure S12. IR spectrum of 2-phenyl-1H-benzoimidazole (KBr). S9 N N H Figure S13.1H NMR(90 MHz, CDCl3) spectrum of2-phenyl-1H-benzoimidazole. N N(CH3)2 N H Figure S14.IR spectrum of [4-(1 H-Benzoimidazol-2-yl)-phenyl]-dimethyl-amine (KBr). S10 N N(CH3)2 N H Figure S15.1H NMR(90 MHz, CDCl3)spectrum of [4-(1H-Benzoimidazol-2-yl)-phenyl]dimethyl-amine. N N H HO Figure S16.IR spectrum of 2-(1 H-Benzoimidazol-2-yl)-phenol (KBr). S11 N N H HO Figure S17.1H NMR(90 MHz, CDCl3)spectrumof 2-(1H-Benzoimidazol-2-yl)-phenol. N CH3 N H Figure S18.IR spectrum of 2-p-Tolyl-1H-benzoimidazole (KBr). S12 N CH3 N H Figure S19.1H NMR(90 MHz, CDCl3)spectrumof 2-p-Tolyl-1H-benzoimidazole. N N H H 3C O Figure S20.IR spectrum of 2-(2-methoxy-phenyl)-1H-benzoimidazole (KBr). S13 N N H H3CO Figure S21.1H NMR(90 MHz, CDCl3)spectrumof 2-(2-methoxy-phenyl)-1 H-benzoimidazole. N N H NO2 Figure S22.IR spectrum of 2-(3-nitro-phenyl)-1H-benzoimidazole (KBr). S14 N N H NO2 Figure S23.1H NMR (90 MHz, CDCl3)spectrum of 2-(3-nitro-phenyl)-1H-benzoimidazole. N Cl N H Figure S24.1H NMR(90 MHz, CDCl3)spectrum of 2-(4-chloro-phenyl)-1H-benzoimidazole. S15 N N H O Figure S25.IR spectrum of 2-furan-2-yl-1H-benzoimidazole (KBr). N N H O Figure S26.1H NMR(90 MHz, CDCl3)spectrum of 2-furan-2-yl-1H-benzoimidazole. S16 N N Figure S27.IR spectrum of 1-benzyl-2-phenyl-1H-benzoimidazole (KBr). N N Figure S28.1H NMR(90 MHz, CDCl3)spectrum of 1-benzyl-2-phenyl-1H-benzoimidazole. S17 NO2 N NO2 N Figure S29.IR spectrum of 1-(4-nitro-benzyl)-2-(4-nitro-phenyl)-1H-benzoimidazole (KBr). NO 2 N N O2 N Figure S30.1H NMR(90 MHz, CDCl3)spectrum of 1-(4-nitro-benzyl)-2-(4-nitro-phenyl)-1Hbenzoimidazole. S18 N O2 N N NO2 Figure S31.IR spectrum of 1-(3-nitro-benzyl)-2-(3-nitro-phenyl)-1H-benzoimidazole (KBr). NO2 N N NO2 Figure S32.1H NMR(90 MHz, CDCl3)spectrum of 1-(3-nitro-benzyl)-2-(3-nitro-phenyl)-1Hbenzoimidazole. S19 Cl N Cl N Figure S33.IR spectrum of 1-(4-chloro-benzyl)-2-(4-chloro-phenyl)-1H-benzoimidazole (KBr). Cl N Cl N Figure S34.1H NMR(90 MHz, CDCl3)spectrumof 1-(4-chloro-benzyl)-2-(4-chloro-phenyl)-1Hbenzoimidazole. S20 CN N CN N Figure S35.IR spectrum of 1-(4-cyano-benzyl)-2-(4-cyano-phenyl)-1H-benzoimidazole (KBr). CN N CN N Figure S36.1H NMR(90 MHz, CDCl3)spectrum of 1-(4-cyano-benzyl)-2-(4-cyano-phenyl)-1Hbenzoimidazole. S21 OC H3 N OC H 3 N Figure S37.IR spectrum of 1-(4-methoxy-benzyl)-2-(4-methoxy-phenyl)-1H-benzoimidazole (KBr). OC H 3 N OC H3 N Figure S38.13C NMRspectrum (90 MHz, CDCl3) of 1-(4-methoxy-benzyl)-2-(4-methoxyphenyl)-1H-benzoimidazole. S22