Environmental and safety aspects of tertiary amino-functionalized ILs’ use as efficient recyclable catalysts for direct a-bromination of cyclic conjugated enones

Patrizia Primerano; Maria Francesca Milazzo; Francesco Risitano; Massimiliano Cordaro; Angela Scala

Journal of Industrial and Engineering Chemistry, Vol.43, 20-27, November, 2016

DOI10.1016/j.jiec.2016.07.042 Export Citation

Environmental and safety aspects of tertiary amino-functionalized ILs’ use as efficient recyclable catalysts for direct a-bromination of cyclic conjugated enones

Patrizia Primerano^†, Maria Francesca Milazzo^†, Francesco Risitano¹, Massimiliano Cordaro¹, and Angela Scala¹

Dipartimento di Ingegneria, University of Messina, Contrada Di Dio, 98166 Messina, Italy
¹Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, University of Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166 Messina, Italy

E-mail:,

To develop chemical processes, according to Green Chemistry and Engineering principles, the use of solvents must be greatly reduced or eliminated. This paper focuses on the use of a new generation of amino-functionalised ionic liquids, which enclose both solvent and catalytic properties for the bromination of cycloenones characterised by a conjugative endo-cyclic C=C bond of various nature. These procedures represent an interesting approach to the environmental sustainability of bromination reactions, even if liquid Br2 is toxic and awkward. Given the large uses of brominated compounds in chemical industry, this procedure could be specially appreciated.

Keywords:Amino ionic liquid;Brominated compound;Environmentally friendly synthesis;Sustainability;Safety

[References]

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Anastas PT, Zimmerman J, Environ. Sci. Technol., 37(5), 94A (2003)
Kumar L, Mahajan T, Agarwal DD, Ind. Eng. Chem. Res., 51(5), 2227 (2012)
Kumar L, Mahajan T, Sharma V, Agarwal DD, Ind. Eng. Chem. Res., 50(2), 705 (2011)
Tanaka K, Shiraishi R, Toda F, J. Chem. Soc.-Perkin Trans. 1, 1, 3069 (1999)
Salazar J, Dorta R, Synlett, 1318 (2004)
Kavala V, Naik S, Patel BK, J. Org. Chem., 70(11), 4267 (2005)
Kaushik MP, Polshettiwar V, Indian J. Chem., 45B, 2542 (2006)
Kabalka GW, Yang K, Reddy NK, Narayana C, Synth. Commun., 28, 925 (1998)
Muathen HA, Synth. Commun., 34, 3545 (2004)
Dewkar GK, Narina SV, Sudalai A, Org. Lett., 5(23), 4501 (2003)
Ye C, Shreeve JM, J. Org. Chem., 69(24), 8561 (2004)
Braddock DC, Cansell G, Hermitage SA, Synlett, 3, 461 (2004)
Ying TK, Bao WL, Zhang YM, J. Chem. Res., 12, 806 (2004)
Kim KM, Park IH, Synthesis, 2641 (2004)
Moriuchi T, Yamaguchi M, Kikushima K, Hirao T, Tetrahedron Lett., 48, 2667 (2007)
Eissen M, Lenoir D, Chem.-Eur. J., 14, 9830 (2008)
Kenzie LCM, Huffman LM, Hutchison JE, J. Chem. Educ., 82(2), 306 (2005)
Primerano P, Cordaro M, Scala A, Tetrahedron Lett., 54, 4061 (2013)
Primerano P, Milazzo MF, Risitano F, Matarazzo A, J. Chem. Technol. Biotechnol., 91(5), 1274 (2016)
Primerano P, Milazzo MF, Risitano F, Chem. Eng. Trans., doi:http://dx.doi.org/10.3303/CET1543380., 43, 2275 (2015)
Seevers RH, Counsell RE, Chem. Rev., 82(6), 575 (1982)
Butler A, Walker JV, Chem. Rev., 93(5), 1937 (1993)
Gribble GW, Chem. Soc. Rev., 28, 335 (1999)
Kuroboshi M, Waki Y, Tanaka H, J. Org. Chem., 68(10), 3938 (2003)
Yao Q, Kinney EP, Yang Z, J. Org. Chem., 68(19), 7528 (2003)
Gao C, Tao X, Qiana Y, Huang J, Chem. Commun., 1444 (2003)
Euzenat L, Horhant D, Ribourdouille Y, Duriez C, Alcaraz G, Vaultier M, Chem. Commun., 2280 (2003)
Heravi MM, Abdolhosseini N, Oskooie HA, Tetrahedron Lett., 46(51), 8959 (2005)
Verdelet T, Merceya G, Correa N, Jean L, Renard PY, Tetrahedron, 67(45), 8757 (2011)
Alaee M, Ariasb P, Sjodinc A, Bergman A, Environ. Int., 29, 683 (2003)
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Covaci A, Harra S, Abdallah MAE, Ali N, Law RJ, Herzke D, de Wit CA, Environ. Int., 37, 532 (2011)
Andersson PL, Oberg K, Orn U, Environ. Toxicol. Chem., 25, 1275 (2006)
Belmont DT, Paquette LA, J. Org. Chem., 50(21), 4102 (1985)
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Sheldon R, in: Dunn PJ, Wells AS, Williams MT (Eds.), Green Chemistry in Pharmaceutical Industry, Wiley, Weinheim, Germany, 2010 p. 1.
Bose G, Barua PMB, Chaudhuri MK, Kalita D, Khan AT, Chem. Lett., 30(4), 290 (2001)
Jyothi D, HariPrasad S, Synth. Commun., 39(5), 875 (2009)
Ponaras AA, Zaim O, J. Org. Chem., 51(24), 4741 (1986)
Dunn GL, De Pasquo VJ, Hoover JRE, J. Org. Chem., 33(4), 1454 (1968)
Janssen CGM, Simons LHJG, Godefroi EF, Synthesis, 5, 389 (1982)
Kim KM, Park IH, Synthesis, 16, 2641 (2004)
Shih C, Fritzen EL, Swenton JS, J. Org. Chem., 45, 4462 (1980)
Li W, Li J, Wan ZK, Wu J, Massefski W, Org. Lett., 9, 4607 (2007)
Ramanarayanan GV, Vidyanand GS, Akamanchi KG, Synlett, 12, 2059 (2002)
Corey EJ, J. Am. Chem. Soc., 76(1), 175 (1954)
Leard RE, Bedenbaugh JH, Bedenbaugh AO, J. Heterocycl. Chem., 20, 1363 (1983)
Harris TM, Harris CM, Brush CK, J. Org. Chem., 35, 1329 (1970)
Chia M, Haider MA, Pollock G, Kraus GA, Neurock M, Dumesic JA, J. Am. Chem. Soc., 135(15), 5699 (2013)
Maji T, Karmakar A, Reiser O, J. Org. Chem., 76(2), 736 (2011)
Merle A, Descotes G, J. Heterocycl. Chem., 12(5), 981 (1975)
Zaragoza F, Stephensen H, Peschke B, Rimvall K, J. Med. Chem., 48(1), 306 (2005)
Balli H, Schelz D, Helv. Chim. Acta, 53(7), 1903 (1970)
Smith MB, March J, Advanced Organic Chemistry, Reactions, Reactions, Mechanisms, and Structure, 5th ed., Wiley Interscience, New York, 2001 (Chapter 12).
Chaudhuri MK, Khan AT, Patel BK, Dey D, Kharmawophlang W, Lakshmiprabha TR, Mandal GC, Tetrahedron Lett., 39, 8163 (1998)
Grignon-Dubois M, Meola A, Synth. Commun., 25(19), 2999 (1995)
Cook DJ, Bowen RE, Soster P, Daniels EJ, Org. Chem., 26, 4949 (1961)
Calvin SJ, Mangan D, Miskelly I, Moody TS, Stevenson PJ, Org. Process Res. Dev., 16, 82 (2012)
Jyothi D, HariPrasad S, Synlett, 14, 2309 (2009)
Eder E, Hoffman C, Bastian H, Deininger C, Scheckenbach S, Environ. Health Perspect., 88, 99 (1990)
Lutz D, Eder E, Neudecker T, Henschler D, Mutat. Res., 93, 305 (1982)
Basu AK, Marnett LJ, Cancer Res., 44, 2848 (1984)
Marnett L, Hurd HK, Hollstein MC, Levin DE, Esterbauer H, Ames BN, Mutat. Res., 148, 25 (1985)
Brennecke JF, Maginn EJ, AIChE J., 47(11), 2384 (2001)
Allen DT, Shonnard DR, Green Engineering, Prentice Hall, Upper Saddle River, NJ, 2002.
Docherty KM, Kulpa CF, Green Chem., 7, 185 (2005)
Olson KR, Poisoning & Drug Overdose, 4th ed., Appleton & Lange, 2003 p. 140.
Patel SJ, Ng D, Mannan MS, J. Loss Prev. Process Ind., 23(4), 483 (2010)
De Rademaeker E, Suter G, Pasman HJ, Fabiano B, Process Saf. Environ. Protect., 92(4), 280 (2014)

[1] Anastas PT, Warner JC, Green Chemistry Theory and Practice, Oxford University Press, Oxford, 1998.

[2] Anastas PT, Zimmerman J, Environ. Sci. Technol., 37(5), 94A (2003)

[3] Kumar L, Mahajan T, Agarwal DD, Ind. Eng. Chem. Res., 51(5), 2227 (2012)

[4] Kumar L, Mahajan T, Sharma V, Agarwal DD, Ind. Eng. Chem. Res., 50(2), 705 (2011)

[5] Tanaka K, Shiraishi R, Toda F, J. Chem. Soc.-Perkin Trans. 1, 1, 3069 (1999)

[6] Salazar J, Dorta R, Synlett, 1318 (2004)

[7] Kavala V, Naik S, Patel BK, J. Org. Chem., 70(11), 4267 (2005)

[8] Kaushik MP, Polshettiwar V, Indian J. Chem., 45B, 2542 (2006)

[9] Kabalka GW, Yang K, Reddy NK, Narayana C, Synth. Commun., 28, 925 (1998)

[10] Muathen HA, Synth. Commun., 34, 3545 (2004)

[11] Dewkar GK, Narina SV, Sudalai A, Org. Lett., 5(23), 4501 (2003)

[12] Ye C, Shreeve JM, J. Org. Chem., 69(24), 8561 (2004)

[13] Braddock DC, Cansell G, Hermitage SA, Synlett, 3, 461 (2004)

[14] Ying TK, Bao WL, Zhang YM, J. Chem. Res., 12, 806 (2004)

[15] Kim KM, Park IH, Synthesis, 2641 (2004)

[16] Moriuchi T, Yamaguchi M, Kikushima K, Hirao T, Tetrahedron Lett., 48, 2667 (2007)

[17] Eissen M, Lenoir D, Chem.-Eur. J., 14, 9830 (2008)

[18] Kenzie LCM, Huffman LM, Hutchison JE, J. Chem. Educ., 82(2), 306 (2005)

[19] Primerano P, Cordaro M, Scala A, Tetrahedron Lett., 54, 4061 (2013)

[20] Primerano P, Milazzo MF, Risitano F, Matarazzo A, J. Chem. Technol. Biotechnol., 91(5), 1274 (2016)

[21] Primerano P, Milazzo MF, Risitano F, Chem. Eng. Trans., doi:http://dx.doi.org/10.3303/CET1543380., 43, 2275 (2015)

[22] Seevers RH, Counsell RE, Chem. Rev., 82(6), 575 (1982)

[23] Butler A, Walker JV, Chem. Rev., 93(5), 1937 (1993)

[24] Gribble GW, Chem. Soc. Rev., 28, 335 (1999)

[25] Kuroboshi M, Waki Y, Tanaka H, J. Org. Chem., 68(10), 3938 (2003)

[26] Yao Q, Kinney EP, Yang Z, J. Org. Chem., 68(19), 7528 (2003)

[27] Gao C, Tao X, Qiana Y, Huang J, Chem. Commun., 1444 (2003)

[28] Euzenat L, Horhant D, Ribourdouille Y, Duriez C, Alcaraz G, Vaultier M, Chem. Commun., 2280 (2003)

[29] Heravi MM, Abdolhosseini N, Oskooie HA, Tetrahedron Lett., 46(51), 8959 (2005)

[30] Verdelet T, Merceya G, Correa N, Jean L, Renard PY, Tetrahedron, 67(45), 8757 (2011)

[31] Alaee M, Ariasb P, Sjodinc A, Bergman A, Environ. Int., 29, 683 (2003)

[32] Arsenault G, Lough A, Marvin C, McAlees A, McCrindle R, MacInnis G, Pleskach K, Potter D, Riddell N, Sverko E, Tittlemier S, Tomy G, Chemosphere, 72, 1163 (2008)

[33] Covaci A, Harra S, Abdallah MAE, Ali N, Law RJ, Herzke D, de Wit CA, Environ. Int., 37, 532 (2011)

[34] Andersson PL, Oberg K, Orn U, Environ. Toxicol. Chem., 25, 1275 (2006)

[35] Belmont DT, Paquette LA, J. Org. Chem., 50(21), 4102 (1985)

[36] Dicks A, Hent A, Green chemistry metrics, A Guide to Determining and Evaluating Process Greenness, Springer International Publishing AG, Switzerland, 2014.

[37] Sheldon R, in: Dunn PJ, Wells AS, Williams MT (Eds.), Green Chemistry in Pharmaceutical Industry, Wiley, Weinheim, Germany, 2010 p. 1.

[38] Bose G, Barua PMB, Chaudhuri MK, Kalita D, Khan AT, Chem. Lett., 30(4), 290 (2001)

[39] Jyothi D, HariPrasad S, Synth. Commun., 39(5), 875 (2009)

[40] Ponaras AA, Zaim O, J. Org. Chem., 51(24), 4741 (1986)

[41] Dunn GL, De Pasquo VJ, Hoover JRE, J. Org. Chem., 33(4), 1454 (1968)

[42] Janssen CGM, Simons LHJG, Godefroi EF, Synthesis, 5, 389 (1982)

[43] Kim KM, Park IH, Synthesis, 16, 2641 (2004)

[44] Shih C, Fritzen EL, Swenton JS, J. Org. Chem., 45, 4462 (1980)

[45] Li W, Li J, Wan ZK, Wu J, Massefski W, Org. Lett., 9, 4607 (2007)

[46] Ramanarayanan GV, Vidyanand GS, Akamanchi KG, Synlett, 12, 2059 (2002)

[47] Corey EJ, J. Am. Chem. Soc., 76(1), 175 (1954)

[48] Leard RE, Bedenbaugh JH, Bedenbaugh AO, J. Heterocycl. Chem., 20, 1363 (1983)

[49] Harris TM, Harris CM, Brush CK, J. Org. Chem., 35, 1329 (1970)

[50] Chia M, Haider MA, Pollock G, Kraus GA, Neurock M, Dumesic JA, J. Am. Chem. Soc., 135(15), 5699 (2013)

[51] Maji T, Karmakar A, Reiser O, J. Org. Chem., 76(2), 736 (2011)

[52] Merle A, Descotes G, J. Heterocycl. Chem., 12(5), 981 (1975)

[53] Zaragoza F, Stephensen H, Peschke B, Rimvall K, J. Med. Chem., 48(1), 306 (2005)

[54] Balli H, Schelz D, Helv. Chim. Acta, 53(7), 1903 (1970)

[55] Smith MB, March J, Advanced Organic Chemistry, Reactions, Reactions, Mechanisms, and Structure, 5th ed., Wiley Interscience, New York, 2001 (Chapter 12).

[56] Chaudhuri MK, Khan AT, Patel BK, Dey D, Kharmawophlang W, Lakshmiprabha TR, Mandal GC, Tetrahedron Lett., 39, 8163 (1998)

[57] Grignon-Dubois M, Meola A, Synth. Commun., 25(19), 2999 (1995)

[58] Cook DJ, Bowen RE, Soster P, Daniels EJ, Org. Chem., 26, 4949 (1961)

[59] Calvin SJ, Mangan D, Miskelly I, Moody TS, Stevenson PJ, Org. Process Res. Dev., 16, 82 (2012)

[60] Jyothi D, HariPrasad S, Synlett, 14, 2309 (2009)

[61] Eder E, Hoffman C, Bastian H, Deininger C, Scheckenbach S, Environ. Health Perspect., 88, 99 (1990)

[62] Lutz D, Eder E, Neudecker T, Henschler D, Mutat. Res., 93, 305 (1982)

[63] Basu AK, Marnett LJ, Cancer Res., 44, 2848 (1984)

[64] Marnett L, Hurd HK, Hollstein MC, Levin DE, Esterbauer H, Ames BN, Mutat. Res., 148, 25 (1985)

[65] Brennecke JF, Maginn EJ, AIChE J., 47(11), 2384 (2001)

[66] Allen DT, Shonnard DR, Green Engineering, Prentice Hall, Upper Saddle River, NJ, 2002.

[67] Docherty KM, Kulpa CF, Green Chem., 7, 185 (2005)

[68] Olson KR, Poisoning & Drug Overdose, 4th ed., Appleton & Lange, 2003 p. 140.

[69] Patel SJ, Ng D, Mannan MS, J. Loss Prev. Process Ind., 23(4), 483 (2010)

[70] De Rademaeker E, Suter G, Pasman HJ, Fabiano B, Process Saf. Environ. Protect., 92(4), 280 (2014)