Nukleofilowe podstawienie wodoru w nitroarenach. Proces analogiczny i komplementarny do podstawienia elektrofilowego

• Autorzy: Mąkosza M.

Warianty tytułu

EN

Nucleophilic substitution of hydrogen in nitroarenes. An alogous and complementary process to electrophilic substitution

• Języki publikacji: PL

Abstrakty

EN

Nucleophiles add to electron-deficient arenes, also those containing halogens, initially in positions occupied by hydrogen to form óH adducts. This addition is faster than addition in similarly activated positions occupied by halogens. Formation of the óH adducts is a reversible process, thus they dissociate and slower addition in positions occupied by halogens results in formation of óH adducts followed by fast departure of X– to form products of nucleophilic substitution of halogen, SNAr. In the review it is shown that there are a few ways for fast further conversion of initially formed óH adducts into products of nucleopilic substitution of hydrogen such as oxidative substitution, vicarious substitution, etc. Since formation of óH adducts is faster than óH adducts and the former undergo fast transformations into products of nucleophilic substitution of hydrogen we should accept than this is the major, primary reaction whereas conventional nucleophilic substitution of halogens, SNAr reaction “ipso” substitution is just a secondary process. In modern textbooks only SNAr reactions are discussed whereas nucleophilic substitution of hydrogen is not mentioned, thus it is necessary to introduce proper corrections in textbooks and teaching of this chapter of chemistry of arenes.

Słowa kluczowe

PL

podstawienie elektrofilowe; podstawienie nukleofilowe; pierścienie aromatyczne

EN

nitroarenes; nucleophilic substitution; oxidation; vicarious substitution

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Wiadomości Chemiczne
• Rocznik: 2011
• Tom: [Z] 65, 9-10
• Strony: 795--819
• Opis fizyczny: Bibliogr. 59 poz., schem

Twórcy

autor

Mąkosza M.

• Instytut Chemii Organicznej Polskiej Akademii Nauk ul. Kasprzaka 44/52, 01-224 Warszawa

Bibliografia

• [1] R . Taylor, Electrophilic Aromatic Substitution, J. Wiley, NY 1990.
• [2] G.A. Olah, R. Malhorta, S.C. Narang, Nitration: Methods and Mechanisms, VCH, NY 1989.
• [3] H. Pellissier, M. Santelli, Tetrahedron, 2003, 59, 701.
• [4] J.F. Bunnett, Acc. Chem. Res., 1978, 11, 413.
• [5] F. Bellina, R. Rossi, Chem. Rev., 2010, 110, 1082.
• [6] J.F. Bunnett, R.E. Zahler, Chem. Rev., 1951, 49, 273.
• [7] J. Miller, Aromatic Nucleophilic Substitution, Elsevier, Amsterdam 1968.
• [8] F. Terrier, Nucleophilic Aromatic Displacement, Verlag Chemie, Weinheim 1991.
• [9] a) V. von Richter, Chem. Ber., 1871, 4, 21; b) M.J. Rosenblum, J. Am. Chem. Soc., 1960, 82, 3796.
• [10] R .B. Davis, L.C. Pizzini, J. Org. Chem., 1960, 25, 1884.
• [11] J. Goliński, M. Mąkosza, Tetrahedron Lett., 1978, 19, 3495.
• [12] M. Mąkosza, J. Winiarski, Acc. Chem. Res., 1987, 20, 282.
• [13] M. Mąkosza, Russ. Chem. Bull., 1996, 45, 491.
• [14] E .V. Malykhin, G.A. Kolesnichenko, V.D. Shteingarts, Zh. Org. Khim., 1985, 21, 1150.
• [15] H.C. van der Plas, M. Woźniak, Croat. Chem. Acta, 1986, 59, 33.
• [16] B. Szpakiewicz, M. Grzegorzek, Zh. Org. Khim., 2004, 40, 869.
• [17] M. Mąkosza, K. Staliński, Chem. Eur. J., 1997, 3, 2025.
• [18] W. Adam, M. Mąkosza, K. Staliński, C.G. Zhao, J. Org. Chem., 1998, 63, 4390.
• [19] M. Mąkosza, Tetrahedron Lett., 1969, 673.
• [20] M. Mąkosza, K. Kamieńska-Trela, M. Paszewski, M. Bechcicka, Tetrahedron, 2005, 4, 11952.
• [21] a) M. Mąkosza, M. Surowiec, A. Szczepańska, D. Sulikowski, O. Maltsev, Synlett, 2007, 470; b) D. Sulikowski, M. Mąkosza, Eur. J. Org. Chem., 2010, 4218.
• [22] M. Mąkosza, D. Sulikowski, J. Org. Chem., 2009, 74, 3827.
• [23] M. Mąkosza, M. Paszewski, D. Sulikowski, Synlett, 2008, 2938.
• [24] G. Bartoli, Acc. Chem. Res., 1984, 17, 109.
• [25] M. Mąkosza, M. Surowiec, J. Organomet. Chem., 2001, 624, 167.
• [26] O .N. Chupakhin, V.N. Charushin, H.C. van der Plas Nucleophilic Aromatic Substitution of Hydrogen, Academic Press, San Diego CA 1994.
• [27] a) M. Mąkosza, K. Staliński, Polish J. Chem., 1999, 73, 151; b) M. Mąkosza, M. Paszewski, Polish J. Chem., 2005, 79, 163.
• [28] M. Mąkosza, Chem. Soc. Rev., 2010, 39, 2855.
• [29] M. Mąkosza, J. Goliński, J. Baran, J. Org. Chem., 1984, 49, 1488.
• [30] M. Mąkosza, T. Glinka, J. Org. Chem., 1983, 48, 3860.
• [31] M. Mąkosza, S. Ludwiczak, J. Org. Chem., 1984, 49, 4562.
• [32] M. Mąkosza, A. Rydz, Z. Wróbel, Polish J. Chem., 1995, 69, 918.
• [33] M. Mąkosza, J. Stalewski, Liebigs Ann. Chem., 1991, 605.
• [34] M. Mąkosza, K. Wojciechowski, Liebigs Ann. Rec., 1997, 1805.
• [35] a) M. Mąkosza, Z. Owczarczyk, J. Org. Chem., 1989, 54, 5094; b) M.D. Crozet, C. Suspene, M. Kaafarani, M.P. Crozet, P. Vanelle, Heterocycles, 2004, 63, 1629.
• [36] M. Mąkosza, A. Kwast, Eur. J. Org. Chem., 2004, 2125.
• [37] M. Mąkosza, T. Lemek, A. Kwast, F. Terrier, J. Org. Chem., 2002, 67, 394.
• [38] M. Mąkosza, A. Kwast, J. Phys. Org. Chem., 1998, 11, 341.
• [39] M. Mąkosza, T. GIinka, J. Kinowski, Tetrahedron, 1984, 40, 1863.
• [40] a) A. Angeli, F. Angelico, Gazz. Chim. Ital., 1901, 31, 27; b) C.C. Price, S.-T. Voong, Org. Synth., 1955, 28, 86.
• [41] S . Seko, K. Miyake, J. Chem. Soc., Chem. Commun., 1998, 1519.
• [42] M. Mąkosza, M. Białecki, J. Org. Chem., 1998, 63, 4878.
• [43] A .R. Katritzky, K.S. Laurenzo, J. Org. Chem., 1986, 51, 5039.
• [44] P.F. Pagoria, A.R.R. Mitchell, D. Schmidt, J. Org. Chem., 1996, 61, 2934.
• [45] M. Mąkosza, K. Sienkiewicz, J. Org. Chem., 1998, 63, 4199.
• [46] J. Suwiński, K. Świerczek, Tetrahedron, 2001, 57, 1639.
• [47] S . Błażej, A. Kwast, M. Mąkosza, Tetrahedron Lett., 2004, 45, 5413.
• [48] M. Mąkosza, G. Varvounis, M. Surowiec, T. Giannopoulos, Eur. J. Org. Chem., 2003, 3791.
• [49] H.C. van der Plas, Acc. Chem. Res., 1978, 11, 462.
• [50] M. Mąkosza, D. Sulikowski, Eur. J. Org. Chem., w druku.
• [51] M. Mąkosza, S. Nizamov, Tetrahedron, 2001, 57, 9615.
• [52] M. Mąkosza, Synthesis, 2011, 2341.
• [53] M. Mąkosza, K. Wojciechowski, Chem. Rev., 2004, 104, 2631.
• [54] M. Mąkosza, K. Wojciechowski, [w:] Targets in Heterocyclic Systems, Vol. 14, O.A Attanasi, W. Spinelli Eds., Societa Chimica Italiana, Roma, 2010, str. 19.
• [55] a) J. Clayden, N. Greeves, S. Warren, P. Wothers, Organic Chemistry, Oxford University Press Inc., New York 2001; b) E.V. Anslyn, W.A. Daugherty, Modern Physical Organic Chemistry, University Science Books, Sausalito 2006; c) M.G. Moloney, Structure and Reactivity in Organic Chemistry, Blackwell 2008.
• [56] a) F.A. Carey, R.J. Sundberg, Advanced Organic Chemistry, Part A and B, 5th Edition, Springer 2007; b) J. March, M.B. Smith, March's Advanced Organic Chemistry, Reactions, Mechanisms and Structure, 6th Edition, J. Wiley 2007.
• [57] a) H. Mayr, M. Patz, Angew. Chem. Int. Ed. Engl. 1994, 33, 938; b) H. Mayr, A.R. Ofial, Pure Appl. Chem., 2005, 77, 1808.
• [58] M. Mąkosza, S. Błażej, Chem. Eur. J., 2008, 14, 11113; b) F. Seelinger, S. Błazej, S. Bernhardt, M. Mąkosza, H. Mayr, Chem. Eur. J., 2008, 14, 6108.
• [59] M. Schlosser, R. Ruzziconi, Synthesis, 2010, 2111.