1,2,4-Triphenylpyrroles: Synthesis, Structure and Luminescence Properties

Joana R. M. Ferreira; Raquel Nunes da Silva; João Rocha; Artur M. S. Silva; Samuel Guieu

doi:10.1055/s-0039-1690828

Synlett, Table of Contents

Synlett 2020; 31(06): 632-634
DOI: 10.1055/s-0039-1690828

cluster

1,2,4-Triphenylpyrroles: Synthesis, Structure and Luminescence Properties

Joana R. M. Ferreira

^aQOPNA, LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal Email: sguieu@ua.pt

,

Raquel Nunes da Silva

^aQOPNA, LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal Email: sguieu@ua.pt

^bInstitute of Biomedicine (iBiMED), Department of Medical Sciences, University of Aveiro, 3810-193 Aveiro, Portugal

,

João Rocha

^cCICECO, Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

,

Artur M. S. Silva

^aQOPNA, LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal Email: sguieu@ua.pt

,

Samuel Guieu∗

^aQOPNA, LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal Email: sguieu@ua.pt

^cCICECO, Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

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Abstract

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Abstract

Pyrroles are widely found in natural products and play an important role in biological processes. Certain pyrrole derivatives are fluorescent and may be used as molecular probes or biomarkers in the diagnosis of diseases, such as Alzheimer’s or Parkinson’s. Herein is reported the synthesis of five new pyrrole derivatives bearing phenyl rings on positions 1, 2, and 4, with electron-donating groups at the periphery. The introduction of more or stronger electron-donating groups red-shifts and increases the efficiency of the fluorescence emission.

Key words

triphenylpyrroles - Nef reaction - Paal–Knorr reaction - fluorescence - crystal structure

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References

References and Notes
1 Gholap SS. Eur. J. Med. Chem. 2016; 110: 13
2 Kaur R, Rani V, Abbot V, Kapoor Y, Konar D, Kumar K. J. Pharm. Chem. Chem. Sci. 2017; 1: 17
3 Fleming CL, Ashton TD, Gaur V, McGee SL, Pfeffer FM. J. Med. Chem. 2014; 57: 1132
4 Idhayadhulla A, Surendra Kumar R, Jamal A, Nasser A. J. Mex. Chem. Soc. 2011; 55: 218
5 Eakin AE, Green O, Hales N, Walkup GK, Bist S, Singh A, Mullen G, Bryant J, Embrey K, Gao N, Breeze A, Timms D, Andrews B, Uria-Nickelsen M, Demeritt J, Loch JT. III, Hull K, Blodgett A, Illingworth RN, Prince B, Boriack-Sjodin PA, Hauck S, MacPherson LJ, Ni H, Sherer B. Antimicrob. Agents Chemother. 2012; 56: 1240
6 Pagadala LR, Mukkara LD, Singireddi S, Singh A, Thummaluru VR, Jagarlamudi PS, Guttala RS, Perumal Y, Dharmarajan S, Upadhyayula SM, Ummanni R, Basireddy VS. R, Ravirala N. Eur. J. Med. Chem. 2014; 84: 118
7 Rane RA, Naphade SS, Bangalore PK, Palkar MB, Shaikh MS, Karpoormath R. Bioorg. Med. Chem. Lett. 2014; 24: 3079
8 He X.-Y, Lu L, Qiu J, Zou P, Yu F, Jiang X.-K, Li L, Jiang S, Liu S, Xie L. Bioorg. Med. Chem. 2013; 21: 7539
9 Lee H, Lee J, Lee S, Shin Y, Jung W, Kim J.-H, Park K, Kim K, Cho HS, Ro S, Lee S, Jeong SW, Choi T, Chung H.-H, Koh JS. Bioorg. Med. Chem. Lett. 2001; 11: 3069
10 Hall MJ, McDonnell SO, Killoran J, O’Shea DF. J. Org. Chem. 2005; 70: 5571
11 Kikuchi K, Hibi S, Yoshimura H, Tokuhara N, Tai K, Hida T, Yamauchi T, Nagai M. J. Med. Chem. 2000; 43: 409
12 Cardona F, Rocha J, Silva AM. S, Guieu S. Dyes Pigm. 2014; 111: 16
13 Guieu S, Cardona F, Rocha J, Silva AM. S. New J. Chem. 2014; 38: 5411
14 Hong Y, Lam JW. Y, Tang BZ. Chem. Soc. Rev. 2011; 40: 5361
15 Luo J, Xie Z, Lam JW. Y, Cheng L, Chen H, Qiu C, Kwok HS, Zhan X, Liu Y, Zhu D, Tang BZ. Chem. Commun. 2001; 1740
16 Guieu S, Rocha J, Silva AM. S. Tetrahedron 2013; 69: 9329
17 Vaz PA. A. M, Rocha J, Silva AM. S, Guieu S. New J. Chem. 2016; 40: 8198
18 Guieu S. Quimica (Lisboa, Port.) 2018; 42: 97
19 Guieu S, Cardona F, Rocha J, Silva AM. S. Chem. Eur. J. 2018; 24: 17262
20 Guieu S, Rocha J, Silva AM. S. Tetrahedron Lett. 2013; 54: 2870
21 Guieu S, Pinto J, Silva VL. M, Rocha J, Silva AM. S. Eur. J. Org. Chem. 2015; 3423
22 Würthner F, Kaiser TE, Saha-Möller CR. Angew. Chem. Int. Ed. 2011; 50: 3376
23 Kim E, Lee Y, Lee S, Park SB. Acc. Chem. Res. 2015; 48: 538
24 Feng X, Tong B, Shen J, Shi J, Han T, Chen L, Zhi J, Lu P, Ma Y, Dong Y. J. Phys. Chem. B 2010; 114: 16731
25 Lei Y, Liu Q, Dong L, Cai Z, Shi J, Zhi J, Tong B, Dong Y. Chem. Eur. J. 2018; 24: 14269
26 1,2,4-Triphenylpyrroles 4a–e; General Procedure The appropriate nitro ketone 2a–c (1 equiv) was dissolved in a mixture of MeOH (8 mL) and THF (12 mL) then KOH (1 equiv) was added. The mixture was stirred for 2 h. The solution, cooled in ice, was added dropwise to an ice-cold solution of concd H₂SO₄ (4 mL ) in MeOH (10 mL), and the mixture was stirred for ~1 h at rt. Half of the solvent was removed under reduced pressure and the mixture was poured in ice–water. The product was extracted with CH₂Cl₂ and the organic layer was dried (Na₂SO₄) and concentrated to dryness to give compound 3a–c, which was used in the following step without purification. The appropriate amine (1 equiv) was added to a solution of the acetal 3a–c (1 equiv) in MeOH (5 mL), and the resulting solution was stirred for 24 h at rt. During this time a precipitate formed. H₂O was then added, and the product was extracted with CH₂Cl₂. The organic phase was dried (Na₂SO₄) and concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel).
27 1,2,4-Tris(4-methoxyphenyl)-1H-pyrrole (4c)Yellow–brown oil; yield: 23 mg (0.06 mmol, 11%). ¹H NMR (300 MHz, CDCl₃): δ = 7.50 (d, J = 8.8 Hz, 2 H), 7.15–7.08 (m, 4 H), 7.07 (d, J = 2.0 Hz, 1 H), 6.91 (d, J = 8.8 Hz, 2 H), 6.85 (d, J = 9.0 Hz, 2 H), 6.77 (d, J = 8.9 Hz, 2 H), 6.58 (d, J = 2.0 Hz, 1 H), 3.82 (s, 3 H), 3.81 (s, 3 H), 3.77 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 158.4, 158.3, 158.0, 134.7, 133.8, 129.7, 128.3, 127.1, 126.3, 125.6, 124.9, 119.8, 114.3, 114.3, 113.7, 107.3, 55.6, 55.4, 55.3. ESI(+)–HRMS: m/z [M + H]⁺ calcd for C₂₅H₂₄NO₃: 386.1751; found: 386.1743 (–1.99 ppm).
28 CCDC 1879235 contains the supplementary crystallographic data for compound 4b. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
29 Allen FH, Kennard O, Watson DG, Brammer L, Orpen AG, Taylor R. J. Chem. Soc., Perkin Trans. 2 1987; S1

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