Highly Chemoselective Solvent-Free Synthesis of 1,3,5-Triaryl-1,5-diketones: Crystallographic Investigation and Intramolecular Weak Bifurcated H Bonds Involving Aliphatic C–H Group

Abstract

Several 1,3,5-triaryl-1,5-diketones have been chemoselectively synthesized under solvent-free conditions. It was found that intramolecular weak bifurcated H-bonds interaction of aliphatic C–H group plays a decisive role in the structural arrangement of 3-(2,6-dichlorophenyl)-1,5-diphenylpentane-1,5-dione in a solid state resulting in significant impact on the corresponding bond lengths and dihedral angles.

Key words

solvent-free reaction - intramolecular bifurcated weak bonds - X-ray crystallographic analysis - highly chemoselective synthesis - 1,5-diketones

• References and Notes

• 1 Desiraju G, Steiner T. The Weak Hydrogen Bond: In Structural Chemistry and Biology . Oxford University Press; Oxford/New York: 2001
• 2 Butcher SE, Pyle AM. Acc. Chem. Res. 2011; 44: 130
• 3 Sutor DJ. Nature 1962; 195: 68
• 4 Taylor R, Kennard O. J. Am. Chem. Soc. 1982; 104: 5063
• 5 Bondi AJ. Phys. Chem. 1964; 68: 441
• 6 Joseph S, Sathishkumar R, Mahapatra S, Desiraju GR. Acta Crystallogr., Sect. B: Struct. Sci. 2011; 67: 525
• 7 Teyssandier J, De Feyter S, Mali KS. Chem. Commun. 2016; 52: 11465
• 8 Hembury GA, Borovkov VV, Inoue Y. Chem. Rev. 2008; 108: 1
• 9 Ajitha MJ, Huan KW. Synthesis 2016; 48: 3449
• 10 Chen D, Oezguen N, Urvil P, Ferguson C, Dann SM, Savidge TC. Sci. Adv. 2016; 2: e1501240
• 11 Rozas I, Alkorta I, Elguero J. J. Phys. Chem. A 1998; 102: 9925
• 12 Albrecht G, Corey RB. J. Am. Chem. Soc. 1939; 61: 1087
• 13 Feldblum ES, Arkin IT. Proc. Natl. Acad. Sci. U.S.A. 2014; 111: 4085
• 14a Tzeli D, Tsoungas PG, Petsalakis ID, Kozielewicz P. Struct. Chem. 2017; 28: 925
• 14b Thomas J, Liu X, Jäger W, Xu Y. Angew. Chem. Int. Ed. 2015; 54: 11711
• 14c Preimesberger MR, Majumdar A, Aksel T, Sforza K, Lectka T, Barrick D, Lecomte JT. J. Am. Chem. Soc. 2015; 137: 1008
• 15 Caccamese S, McMillan JA, Montaudo G. J. Org. Chem. 1978; 43: 2703
• 16a Hu XY, Shan ZX, Soloshonok VA. Cryst. Growth Des. 2012; 12: 33
• 16b Hu XY, Guo JX, Yin ZY, Shan ZX. ChemistrySelect 2018; 3: 3309
• 17 Rojas J, Domínguez JN, Charris JE, Lobo G, Payá M, Ferrándiz ML. Eur. J. Med. Chem. 2002; 37: 699
• 18a Tanaka K, Toda F. Chem. Rev. 2000; 100: 1025
• 18b Jörres M, Chen X, Aceña JL, Merkens C, Bolm C, Liu H, Soloshonok VA. Adv. Synth. Catal. 2014; 356: 2203
• 18c Jörres M, Aceña JL, Soloshonok VA, Bolm C. ChemCatChem. 2015; 7: 1265
• 19 Pauling L. The Nature of the Chemical Bond . Cornell University Press; Ithaca NY: 1960
• 20 Shan ZX, Luo XX, Hu L, Hu XY. Sci. China: Chem. 2010; 53: 1095
• 21 Shan ZX, Hu XY, Hu L, Peng XT. Helv. Chim. Acta 2009; 92: 1102
• 22 Luo XX, Shan ZX. Tetrahedron Lett. 2006; 47: 5623
• 23 General Procedure To a mixture of aromatic aldehydes (5 mmol) and acetophenone (11 mmol) a fine powder of NaOH (5 mmol) and K₂CO₃ (5 mmol) was added. The reaction mixture was ground at room temperature until it became incompact solid (generally 20–30 min). After the solid was treated with water, the water-insoluble solid was recrystallized in ethanol. 3-(2,6-Dichlorophenyl)-1,5-diphenylpentane-1,5-dione (4a) Mp 125–128 °C, 86% yield, white solid. ¹H NMR (400 MHz, CDCl₃): δ = 8.03–7.93 (m, 4 H), 7.54 (d, J = 7.4 Hz, 2 H), 7.45 (t, J = 7.6 Hz, 4 H), 7.33 (d, J = 7.9 Hz, 1 H), 7.23 (d, J = 7.9 Hz, 1 H), 7.06 (t, J = 8.0 Hz, 1 H), 5.07 (p, J = 7.1 Hz, 1 H), 3.84–3.65 (m, 4 H). ¹³C NMR (100 MHz, CDCl₃): δ = 198.3, 138.3, 136.9, 136.7, 134.5, 133.2, 129.9, 128.9, 128.6, 128.3, 128.2, 41.1, 33.3. Crystal Structure of Compound 4a C₂₃H₁₈Cl₂O₂, MW = 397.27, D _calc = 1.342 g/cm³; V = 983.0(2) ų, triclinic; Z = 2; space group P-1, a = 9.4157(12), b = 10.3008(14), c = 10.9517(15), μ (Mo Kα) = 0.345 mm^–1, –11 ≤ h ≤ 12, –13 ≤ k ≤ 13, –14 ≤ l ≤ 14, F(000) = 412, GOF = 1.059, T = 296 (2) K; CCDC 1904249.