Synthesis, Inhaltsverzeichnis Synthesis 2023; 55(02): 354-358DOI: 10.1055/s-0041-1737327 paper Special Issue dedicated to Prof. Alain Krief Elucidation of the Nucleophilic Potential of Diazocyclopentadiene Autoren Manfred Hartnagel Armin R. Ofial Herbert Mayr ∗ Artikel empfehlen Abstract Artikel einzeln kaufen(opens in new window) Alle Artikel dieser Rubrik(opens in new window) Dedicated to Professor Alain Krief on the occasion of his 80th birthday Abstract Diazocyclopentadiene reacts with benzhydrylium ions (Ar2CH+) to give 2,5-dibenzhydryl-substituted diazocyclopentadienes. The kinetics have been determined photometrically in dichloromethane under pseudo-first-order conditions using diazocyclopentadiene in excess. Plots of the second-order rate constants (log k 2) versus the electrophilicity parameters E of the benzhydrylium ions gave the nucleophilicity parameter N = 4.84 and susceptibility s N = 1.06 for diazocyclopentadiene according to the correlation log k(20 °C) = s N(E + N). Diazocyclopentadiene thus has a similar nucleophilic reactivity as pyrrole. Previously reported electrophilic substitutions of diazocyclopentadiene are rationalized by these parameters and new reaction possibilities are predicted. Key words Key wordsdiazo compounds - kinetics - linear free energy relationships - nucleophilicity - reactivity scales Volltext Referenzen References 1 Doering W. vE, DePuy CH. J. Am. Chem. Soc. 1953; 75: 5955 2 Najafian K, Schleyer P. vR, Tidwell TT. Org. Biomol. Chem. 2003; 1: 3410 3 Williams CI, Whitehead MA, Bertrand JJ.-C. J. Mol. Struct. (Theochem) 1997; 389: 13 4 McAllister MA, Tidwell TT. J. Am. Chem. Soc. 1992; 114: 5362 5 Clark DT, Adams DB, Scanlan IW, Woolsey IS. Chem. Phys. Lett. 1974; 25: 263 6 Aarons LJ, Connor JA, Hillier IH, Schwarz M, Lloyd DR. J. Chem. Soc., Faraday Trans. 2 1974; 8: 1106 7 Yoshida Z.-i, Kobayashi T. Bull. Chem. Soc. Jpn. 1972; 45: 742 8 Schuster P, Polansky OE. Monatsh. Chem. 1965; 96: 396 9 Sakaizumi T, Fukuda S, Ohashi O, Yamaguchi I. J. Mol. Spectrosc. 1990; 141: 325 10 Jacobsen JP, Schaumburg K, Nielsen JT. J. Magn. Res. 1974; 13: 372 11 Cataliotti R, Poletti A, Paliani G, Foffani A. Z. Naturforsch., B 1972; 27: 875 12 Duthaler RO, Förster HG, Roberts JD. J. Am. Chem. Soc. 1978; 100: 4974 13 Cram DJ, Partos RD. J. Am. Chem. Soc. 1963; 85: 1273 14 Selective 2,5-dibrominations have later been reported: Dinh LV, Hampel F, Gladysz JA. J. Organomet. Chem. 2005; 690: 493 15 Maier G, Endres J. J. Mol. Struct. 2000; 556: 179 16 Platz MS, Olson DR. J. Phys. Org. Chem. 1996; 9: 689 17 Ando W, Suzuki J, Saiki Y, Migita T. J. Chem. Soc., Chem. Commun. 1973; 365 18 Ando W, Saiki Y, Migita T. Tetrahedron 1973; 29: 3511 19 Moss RA. J. Org. Chem. 1966; 31: 3296 20 Merino P. In Monocyclic Arenes, Quasiarenes, and Annulenes, Science of Synthesis, Vol. 45a. Siegel JS, Tobe Y. Thieme; Stuttgart: 2009: 143-156 21 Reimer KJ, Shaver A. J. Organomet. Chem. 1975; 93: 239 22 Sisler EC, Serek M. Plant Biol. 2003; 5: 473 23 Sisler EC. Biotechnol. Adv. 2006; 24: 357 24 Mayr H, Ofial AR. J. Phys. Org. Chem. 2008; 21: 584 25 Mayr H, Ofial AR. Pure Appl. Chem. 2005; 77: 1807 26 Mayr H, Kempf B, Ofial AR. Acc. Chem. Res. 2003; 36: 66 27 Mayr H, Bug T, Gotta MF, Hering N, Irrgang B, Janker B, Kempf B, Loos R, Ofial AR, Remennikov G, Schimmel H. J. Am. Chem. Soc. 2001; 123: 9500 28 Mayr H. Tetrahedron 2015; 71: 5095 29 Bug T, Hartnagel M, Schlierf C, Mayr H. Chem. Eur. J. 2003; 9: 4068 30 Nigst TA, Westermaier M, Ofial AR, Mayr H. Eur. J. Org. Chem. 2008; 2369 31 For a freely accessible database of reactivity parameters E, N, and s N, see (accessed on November 19th, 2021): www.cup.lmu.de/oc/mayr/DBintro.html 32 Eitel A, Wessely F. Monatsh. Chem. 1964; 95: 1382 33 Kaumanns O, Mayr H. J. Org. Chem. 2008; 73: 2738 34 Dürr H, Sergio R. Chem. Ber. 1974; 107: 2027 35 Mackert PJ, Hafner K, Nimmerfroh N, Banert K. Chem. Ber. 1994; 127: 1479 36 Lakhdar S, Ammer J, Mayr H. Angew. Chem. Int. Ed. 2011; 50: 9953 ; Angew. Chem. 2011, 123, 10127 37 Lakhdar S, Tokuyasu T, Mayr H. Angew. Chem. Int. Ed. 2008; 47: 8723 ; Angew. Chem. 2008, 120, 8851 38 Mayr H, Lakhdar S, Maji B, Ofial AR. Beilstein J. Org. Chem. 2012; 8: 1458 39 Paras NA, MacMillan DW. C. J. Am. Chem. Soc. 2001; 123: 4370 40 Regitz M, Liedhegener A. Tetrahedron 1967; 23: 2701 41 Rau D, Mayr H. Chem. Ber. 1994; 127: 2493 42a Mayr H, Striepe W. J. Org. Chem. 1985; 50: 2995 42b Mayr H, Hagen-Bartl G. Encyclopedia of Reagents for Organic Synthesis, Vol. 8 . Paquette LA. Wiley; Hoboken: 1995. 43 Mayr H, Schneider R, Schade C, Bartl J, Bederke R. J. Am. Chem. Soc. 1990; 112: 4446 Zusatzmaterial Zusatzmaterial Supporting Information (PDF) (opens in new window)
