Highly regioselective, Lewis acid-free electrophilic aromatic substitution

Journal of Chemical Technology and Biotechnology

Volumn 68, Issue 4, 1997, Pages 432-436

  Smith, Keith ^a  

^a SWANSEA UNIVERSITY   (United Kingdom)

Author keywords

Acylation; Aromatic substitution; Bromination; Catalysis; Chlorination; Nitration; Regioselectivity; Zeolites

Indexed keywords

ACYLATION; CHLORINATION; NITRATION; STOICHIOMETRY; SUBSTITUTION REACTIONS; ZEOLITES;

BROMINATION; LEWIS ACID FREE ELECTROPHILIC AROMATIC SUBSTITUTION; REGIOSELECTIVITY;

CATALYST SELECTIVITY;

ALUMINUM CHLORIDE; AROMATIC COMPOUND; ZEOLITE;

ACYLATION; BROMINATION; CATALYSIS; CHLORINATION; CONFERENCE PAPER; NITRATION; STOICHIOMETRY;

EID: 0031127661     PISSN: 02682575     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1097-4660(199704)68:4<432::AID-JCTB617>3.0.CO;2-X     Document Type: Conference Paper

References (28)

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4. Dyer, A., An Introduction to Zeolite Molecular Sieves. Wiley, Chichester, 1988.
5. Smith, K., Butters, M. & Nay, B., Highly para-selective mono-chlorination of aromatic compounds under mild conditions by t-butyl hypochlorite in the presence of zeolites. Synthesis, (1985) 1157.
6. De La Vega, F. & Sasson, Y., Selective para-bromination of toluene catalysed by Na-Y zeolite in the presence of an epoxide. J. Chem. Soc., Chem. Commun., (1989) 653; see also, Zeolites, 9 (1989) 418; 11 (1991) 617; 13 (1991) 341.
7. De La Vega, F. & Sasson, Y., Selective para-bromination of toluene catalysed by Na-Y zeolite in the presence of an epoxide. J. Chem. Soc., Chem. Commun., (1989) 653; see also, Zeolites, 9 (1989) 418; 11 (1991) 617; 13 (1991) 341.
8. De La Vega, F. & Sasson, Y., Selective para-bromination of toluene catalysed by Na-Y zeolite in the presence of an epoxide. J. Chem. Soc., Chem. Commun., (1989) 653; see also, Zeolites, 9 (1989) 418; 11 (1991) 617; 13 (1991) 341.
9. De La Vega, F. & Sasson, Y., Selective para-bromination of toluene catalysed by Na-Y zeolite in the presence of an epoxide. J. Chem. Soc., Chem. Commun., (1989) 653; see also, Zeolites, 9 (1989) 418; 11 (1991) 617; 13 (1991) 341.
10. Smith, K. & Bahzad, D., Highly efficient para-selective bromination of simple aromatic substrates by means of bromine and a reusable zeolite. J. Chem. Soc., Chem. Commun., (1996) 467.
11. Mistry, A. G., Smith, K. & Bye, M. R., Solid supported halogenations: a novel method for bromination of heterocycles. In Bromine Compounds: Chemistry and Applications, eds D. Price, B. Iddon & B. J. Wakefield. Elsevier, Amsterdam, 1988, p. 277.
12. Konishi, H., Aritoni, K., Okano, T. & Kiji, K., A mild, selective monobromination reagent for alkoxybenzenes; N-bromosuccinimide-silica gel. Bull. Chem. Soc. Japan 62 (1989) 591.
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14. Smith, K., James, D. M., Mistry, A. G., Bye, M. R. & Faulkner, D. J., A new method for bromination and polybromination of carbazoles, β-carbolines and iminodibenzyls by using N-bromosuccinimide and silica gel. Tetrahedron, 48 (1992) 7479.
15. Smith, K., James, D. M., Matthews, I. & Bye, M. R., Selective para-bromination of phenols via a regenerable polymer-bound tetralkylammonium tribromide. J. Chem. Soc., Perkin Trans. 1, (1992) 1877.
16. Olah, G. A., Malhotra, R. & Narang, S. C., Nitration: Methods and Mechanisms. VCH, New York, 1989, pp. 5-7; Schofield, K., Aromatic Nitration. Cambridge University Press, Cambridge, 1980; Taylor, R., Electrophilic Aromatic Substitution. John Wiley and Sons, Chichester, 1990.
17. Olah, G. A., Malhotra, R. & Narang, S. C., Nitration: Methods and Mechanisms. VCH, New York, 1989, pp. 5-7; Schofield, K., Aromatic Nitration. Cambridge University Press, Cambridge, 1980; Taylor, R., Electrophilic Aromatic Substitution. John Wiley and Sons, Chichester, 1990.
18. Olah, G. A., Malhotra, R. & Narang, S. C., Nitration: Methods and Mechanisms. VCH, New York, 1989, pp. 5-7; Schofield, K., Aromatic Nitration. Cambridge University Press, Cambridge, 1980; Taylor, R., Electrophilic Aromatic Substitution. John Wiley and Sons, Chichester, 1990.
19. Smith, K., Fry, K., Butters, M. & Nay, B., para-Selective mononitration of alkylbenzenes under mild conditions by use of benzoyl nitrate in the presence of a zeolite catalyst. Tetrahedron Lett., 30 (1989) 5333.
20. Smith, K., Musson, A. & DeBoos, G. A., Superior methodology for the nitration of simple aromatic compounds J. Chem. Soc., Chem. Commun., (1996) 469; UK Patent Application Number 9510166.3 (19 May 1995).
21. Smith, K. & Pollaud, G., Syntheses of 1-arylalkenes and 1-arylalkanes via Friedel-Crafts alkylation reactions of allylic alcohols. J. Chem. Soc., Perkin Trans. 1, (1994) 3519.
22. Smith, K. & Fry, K. B., Selective bromination of alkenes using bromine and zeolite molecular sieves. J. Chem. Soc., Chem. Commun., (1992) 187.
23. See, for example, Smith, K., Selective catalysts and new reagents for control in organic synthesis. In New Aspects of Organic Synthesis II, eds Z. Yoshida and Y. Ohshiro. Kadansha, Tokyo and VCH, Weinheim, 1992, p. 43; Smith, K., Lindsay, C. M. & Pritchard, G. J., Directed lithiation of arenethiols. J. Am. Chem. Soc., 111 (1989) 665; Smith, K., Lindsay, C. M., Morris, I. K., Matthews, I. & Pritchard, G. J., The synthesis of 2-substituted thiazolo[5,4-c]pyridines via directed metalation. Sulfur Letters, 17 (1994) 197; Smith, K., Anderson, D. & Matthews, I., A convenient synthesis of 2-substituted thiazolo[4,5-b]pyridines via directed metalation. Sulfur Letters, 18 (1995) 79; Smith, K., Anderson, D. & Matthews, I., First synthesis of 3-mercapto-2(1H)-pyridinone, a simple disubstituted pyridine useful for synthesis of the 4-azaphenoxathiin ring system and its novel diazaphenoxathiin analogs: 1,6-dia-zaphenoxathiin and 2,6-diazaphenoxathiin. J. Org. Chem., 61 (1996) 662; Smith, K., El-Hiti, G. A., Abdel-Megeed, M. F. & Abdo, M. A., Lithiation of 3-(acylamino)-2-unsubstituted-, 3-(acylamino)-2-ethyl-and 3-(acylamino)-2-propyl-4(3H)-quinazolinones: convenient syntheses of more complex quinazolinones. J. Org. Chem., 61 (1996) 647.
24. See, for example, Smith, K., Selective catalysts and new reagents for control in organic synthesis. In New Aspects of Organic Synthesis II, eds Z. Yoshida and Y. Ohshiro. Kadansha, Tokyo and VCH, Weinheim, 1992, p. 43; Smith, K., Lindsay, C. M. & Pritchard, G. J., Directed lithiation of arenethiols. J. Am. Chem. Soc., 111 (1989) 665; Smith, K., Lindsay, C. M., Morris, I. K., Matthews, I. & Pritchard, G. J., The synthesis of 2-substituted thiazolo[5,4-c]pyridines via directed metalation. Sulfur Letters, 17 (1994) 197; Smith, K., Anderson, D. & Matthews, I., A convenient synthesis of 2-substituted thiazolo[4,5-b]pyridines via directed metalation. Sulfur Letters, 18 (1995) 79; Smith, K., Anderson, D. & Matthews, I., First synthesis of 3-mercapto-2(1H)-pyridinone, a simple disubstituted pyridine useful for synthesis of the 4-azaphenoxathiin ring system and its novel diazaphenoxathiin analogs: 1,6-dia-zaphenoxathiin and 2,6-diazaphenoxathiin. J. Org. Chem., 61 (1996) 662; Smith, K., El-Hiti, G. A., Abdel-Megeed, M. F. & Abdo, M. A., Lithiation of 3-(acylamino)-2-unsubstituted-, 3-(acylamino)-2-ethyl-and 3-(acylamino)-2-propyl-4(3H)-quinazolinones: convenient syntheses of more complex quinazolinones. J. Org. Chem., 61 (1996) 647.
25. See, for example, Smith, K., Selective catalysts and new reagents for control in organic synthesis. In New Aspects of Organic Synthesis II, eds Z. Yoshida and Y. Ohshiro. Kadansha, Tokyo and VCH, Weinheim, 1992, p. 43; Smith, K., Lindsay, C. M. & Pritchard, G. J., Directed lithiation of arenethiols. J. Am. Chem. Soc., 111 (1989) 665; Smith, K., Lindsay, C. M., Morris, I. K., Matthews, I. & Pritchard, G. J., The synthesis of 2-substituted thiazolo[5,4-c]pyridines via directed metalation. Sulfur Letters, 17 (1994) 197; Smith, K., Anderson, D. & Matthews, I., A convenient synthesis of 2-substituted thiazolo[4,5-b]pyridines via directed metalation. Sulfur Letters, 18 (1995) 79; Smith, K., Anderson, D. & Matthews, I., First synthesis of 3-mercapto-2(1H)-pyridinone, a simple disubstituted pyridine useful for synthesis of the 4-azaphenoxathiin ring system and its novel diazaphenoxathiin analogs: 1,6-dia-zaphenoxathiin and 2,6-diazaphenoxathiin. J. Org. Chem., 61 (1996) 662; Smith, K., El-Hiti, G. A., Abdel-Megeed, M. F. & Abdo, M. A., Lithiation of 3-(acylamino)-2-unsubstituted-, 3-(acylamino)-2-ethyl-and 3-(acylamino)-2-propyl-4(3H)-quinazolinones: convenient syntheses of more complex quinazolinones. J. Org. Chem., 61 (1996) 647.
26. See, for example, Smith, K., Selective catalysts and new reagents for control in organic synthesis. In New Aspects of Organic Synthesis II, eds Z. Yoshida and Y. Ohshiro. Kadansha, Tokyo and VCH, Weinheim, 1992, p. 43; Smith, K., Lindsay, C. M. & Pritchard, G. J., Directed lithiation of arenethiols. J. Am. Chem. Soc., 111 (1989) 665; Smith, K., Lindsay, C. M., Morris, I. K., Matthews, I. & Pritchard, G. J., The synthesis of 2-substituted thiazolo[5,4-c]pyridines via directed metalation. Sulfur Letters, 17 (1994) 197; Smith, K., Anderson, D. & Matthews, I., A convenient synthesis of 2-substituted thiazolo[4,5-b]pyridines via directed metalation. Sulfur Letters, 18 (1995) 79; Smith, K., Anderson, D. & Matthews, I., First synthesis of 3-mercapto-2(1H)-pyridinone, a simple disubstituted pyridine useful for synthesis of the 4-azaphenoxathiin ring system and its novel diazaphenoxathiin analogs: 1,6-dia-zaphenoxathiin and 2,6-diazaphenoxathiin. J. Org. Chem., 61 (1996) 662; Smith, K., El-Hiti, G. A., Abdel-Megeed, M. F. & Abdo, M. A., Lithiation of 3-(acylamino)-2-unsubstituted-, 3-(acylamino)-2-ethyl-and 3-(acylamino)-2-propyl-4(3H)-quinazolinones: convenient syntheses of more complex quinazolinones. J. Org. Chem., 61 (1996) 647.
27. See, for example, Smith, K., Selective catalysts and new reagents for control in organic synthesis. In New Aspects of Organic Synthesis II, eds Z. Yoshida and Y. Ohshiro. Kadansha, Tokyo and VCH, Weinheim, 1992, p. 43; Smith, K., Lindsay, C. M. & Pritchard, G. J., Directed lithiation of arenethiols. J. Am. Chem. Soc., 111 (1989) 665; Smith, K., Lindsay, C. M., Morris, I. K., Matthews, I. & Pritchard, G. J., The synthesis of 2-substituted thiazolo[5,4-c]pyridines via directed metalation. Sulfur Letters, 17 (1994) 197; Smith, K., Anderson, D. & Matthews, I., A convenient synthesis of 2-substituted thiazolo[4,5-b]pyridines via directed metalation. Sulfur Letters, 18 (1995) 79; Smith, K., Anderson, D. & Matthews, I., First synthesis of 3-mercapto-2(1H)-pyridinone, a simple disubstituted pyridine useful for synthesis of the 4-azaphenoxathiin ring system and its novel diazaphenoxathiin analogs: 1,6-dia-zaphenoxathiin and 2,6-diazaphenoxathiin. J. Org. Chem., 61 (1996) 662; Smith, K., El-Hiti, G. A., Abdel-Megeed, M. F. & Abdo, M. A., Lithiation of 3-(acylamino)-2-unsubstituted-, 3-(acylamino)-2-ethyl-and 3-(acylamino)-2-propyl-4(3H)-quinazolinones: convenient syntheses of more complex quinazolinones. J. Org. Chem., 61 (1996) 647.
28. See, for example, Smith, K., Selective catalysts and new reagents for control in organic synthesis. In New Aspects of Organic Synthesis II, eds Z. Yoshida and Y. Ohshiro. Kadansha, Tokyo and VCH, Weinheim, 1992, p. 43; Smith, K., Lindsay, C. M. & Pritchard, G. J., Directed lithiation of arenethiols. J. Am. Chem. Soc., 111 (1989) 665; Smith, K., Lindsay, C. M., Morris, I. K., Matthews, I. & Pritchard, G. J., The synthesis of 2-substituted thiazolo[5,4-c]pyridines via directed metalation. Sulfur Letters, 17 (1994) 197; Smith, K., Anderson, D. & Matthews, I., A convenient synthesis of 2-substituted thiazolo[4,5-b]pyridines via directed metalation. Sulfur Letters, 18 (1995) 79; Smith, K., Anderson, D. & Matthews, I., First synthesis of 3-mercapto-2(1H)-pyridinone, a simple disubstituted pyridine useful for synthesis of the 4-azaphenoxathiin ring system and its novel diazaphenoxathiin analogs: 1,6-dia-zaphenoxathiin and 2,6-diazaphenoxathiin. J. Org. Chem., 61 (1996) 662; Smith, K., El-Hiti, G. A., Abdel-Megeed, M. F. & Abdo, M. A., Lithiation of 3-(acylamino)-2-unsubstituted-, 3-(acylamino)-2-ethyl-and 3-(acylamino)-2-propyl-4(3H)-quinazolinones: convenient syntheses of more complex quinazolinones. J. Org. Chem., 61 (1996) 647.