Highly efficient synthesis and solid-state characterization of 1,2,4,5-tetrakis(alkyl- and arylamino)benzenes and cyclization to their respective benzobis(imidazolium) salts

Organic Letters

Volumn 8, Issue 9, 2006, Pages 1831-1834

  Khramov, Dimitri M ^a   Boydston, Andrew J ^a   Bielawski, Christopher W ^a  

^a UNIVERSITY OF TEXAS AT AUSTIN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE DERIVATIVE; IMIDAZOLE DERIVATIVE; INORGANIC SALT;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; CONFORMATION; CYCLIZATION; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

BENZENE DERIVATIVES; CATALYSIS; CRYSTALLOGRAPHY, X-RAY; CYCLIZATION; IMIDAZOLES; MOLECULAR CONFORMATION; MOLECULAR STRUCTURE; SALTS;

EID: 33646455324     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol060349c     Document Type: Article

References (56)

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33. In a related example, Pd-catalyzed aryl animation was used to synthesize 1,2,4,5-tetra(morpholino)benzene in 76% yield via coupling of 1,2,4,5-tetrabromobenzene with morpholine, see: Witulski, B.; Senft, S.; Thum, A. Synlett 1998, 504.
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35. 2IPr·HCl) in lieu of IPr· HCl afforded comparable results.
36. 2.
37. 3) and imidazolylidenes (1,3-bis(2,6-di-tert-butyl)imidazolylidene, 1,3-bis(2,6-dimesityl)imidazolylidene) were screened, but did not afford appreciable yields of product.
38. Residual inorganic salts were removed by filtering chloroform solutions of the tetraaminobenzenes followed by evaporation.
39. Use of an oxygen atmosphere effects azophenine formation more rapidly than use of aerated solvents.
40. Selected bond lengths (Å) and angles (deg): For 4: N1-C1, 1.429(2); N2-C2, 1.441(2); C1-C2, 1.411(2); C2-C3, 1.394(2); C1-C3A, 1.394(2); C2-C1-N1, 121.1(1); C1-C2-N2, 119.6(1); C2-C1-N1-C4, 109.8(1); C1-C2-N2-C8, 99.8(2). For 5: N1-C1, 1.349(1); N2-C2, 1.294(1); C1-C2, 1.513(1); C1-C3A, 1.367(1); C2-C3, 1.437(1); N1-C1-C2, 113.0(1); N2-C2-C1, 113.9(1); C4-N1-C1-C2, 175.1(1); C1-C2-N2-C8, 179.3(1).
41. A solution to the crystal structure of 1,2,4,5-tetrakis(mesitylamino) benzene (8) was also determined; key bond distances (Å) and angles (deg): N1-C1, 1.413(2); N2-C3, 1.424(2); C1-C2, 1.391(2); C2-C3, 1.398(2); C1-C3A, 1.404(2); C3A-C1-N1, 118.9(1); C1A-C3-N2, 118.5(1); C4-N1-C1-C3A, 173.9(2); C1A-C3-N2-C13, 172.9(2). Using the procedure described in the text, the corresponding azophenine (9) was synthesized and a solution to its corresponding crystal structure was determined; key bond lengths (Å) and angles (deg); N1-C1, 1.293(2); N2-C3, 1.357(2); C1-C2, 1.440(2); C2-C3, 1.356(2); C1-C3A, 1.494(2); N1-C1-C3A, 115.6(1); N2-C3-C1A, 114.2(1); C3A-C1-N1-C4, 176.9(1); C1A-C3-N2-C13, 171.3(1). See the Supporting Information for additional details.
42. Efforts toward optimizing these reactions are underway.
43. Oxidative susceptibilities of the 1,2,4,5-tetraminobenzenes can be greatly reduced through protonation with HCl prior to isolation.
44. For discussions comparing relative stabilites of electron deficient arylamines, see: (a) Li, Z.; Cheng, J.-P. J. Org. Chem. 2002, 68, 7350.
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47. The mechanistic implications of these findings are currently under investigation in our laboratories.
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49. 1H NMR spectroscopy; however, the isolation of 13 was challenged by its high solubility in common solvents.
50. A similar approach utilizing aryl animation of 1,2-dibromobenzene followed by cyclization has been reported: Rivas, R. M.; Riaz, U.; Giessart, A.; Smulik, J. A.; Diver, S. T. Org. Lett. 2001, 3, 2673.
51. For syntheses of related benzimidazolium and benzimidazolylidene compounds, see: (a) Huynh, H. V.; Holtgrewe, C.; Pape, T.; Koh, L. L.; Hahn, F. E. Organometallics 2006, 25, 245.
52. (b) Hahn, F. E.; Jahnke, M. C.; Gomez-Benitez, V.; Morales-Morales, D.; Pape, T. Organometallics 2005, 24, 6458.
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54. 4, which may be related to the higher solubilities of bis(benzobisimidazolium) tetrafluoroborate salts as compared to their analogous chloride salts.
55. The overall yield of 16 from 1,2,4,5-tetrabromobenzene was improved to 84% by using a one-pot, two-step procedure. See the Supporting Information for additional details.
56. Khramov, D. M.; Boydston, A. J.; Bielawski, C. W. Manuscript in preparation.