Skip to main content
SpringerLink
Log in

Methods for the Catalytic Synthesis of Piperazine

  • CATALYSIS IN CHEMICAL AND PETROCHEMICAL INDUSTRY
  • Published:
Catalysis in Industry Aims and scope Submit manuscript

Abstract

Piperazine synthesis methods on intermolecular and intramolecular cyclization catalytic processes are compared and reviewed analytically. The advantages and disadvantages of current ways of synthesizing piperazine are described while focusing on the preferred and highly selective processes of intramolecular cyclization using aminoethylethanolamine and diethylenetriamine, and one-step intermolecular cyclization using ethylenediamine, mono-, and diethanolamine.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Fig. 6.
Fig. 7.
Fig. 8.
Fig. 9.
Fig. 10.

Similar content being viewed by others

REFERENCES

  1. Piperazin: Sbornik statei/AN Latviiskoi SSR (Piperazine: Collection of Papers/AN Latvian SSR), Giller, S.A. and Shimanska, M.V., Eds., Riga: Zinatne, 1965.

    Google Scholar 

  2. GNITIVE Marker Research. Global Piperazine–PIP Market Report 2022. https://www.cognitivemarketresearch.com/chemical-%26-materials/piperazine-%28 pip%29-market-report. Cited April 17, 2022.

  3. Sridhar, S. and Carter, R.G., in: Kirk-Othmer Encyclopedia of Chemical Technology, New York: Wiley, 2001. https://doi.org/10.1002/0471238961.0409011303011820.a01.pub

  4. Roose, P., Eller, K., Henkes, E., Rossbacher, R., and Höke, H., in: Ullmann’s Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH, 2015. https://doi.org/10.1002/14356007.a02_001.pub2

  5. Shimanskaya, M.V., Oshis, Ya.F., and Anderson, A.A., Chem. Heterocycl. Compd., 1983, vol. 19, no. 12, pp. 1249–1262.

    Article  Google Scholar 

  6. KR Patent 20170041077, 2017.

  7. Lei, M., Li, Y., An-Hui, L., and Yunjie, D., RSC Adv., 2018, vol. 8, no. 15, pp. 8152−8163. https://doi.org/10.1039/c7ra12891f

    Article  CAS  Google Scholar 

  8. Borisenko, V.S., Bobylev, V.A., and Tereshchenko, G.F., Zh. Obshch. Khim., 1985, vol. 55, no. 5, pp. 1141–1146.

    CAS  Google Scholar 

  9. Borisenko, V.S., Bobylev, V.A., Selivanov, S.I., Utsal’, V.A., and Tereshchenko, G.F., Zh. Obshch. Khim., 1986, vol. 56, no. 10, pp. 2339–2345.

    CAS  Google Scholar 

  10. Jpn. Patent 6301695, 2018.

  11. Clapp, L.B., J. Am. Chem. Soc., 1948, vol. 70, no. 1, pp. 184–186. https://doi.org/10.1021/ja01181a053

    Article  CAS  PubMed  Google Scholar 

  12. Ishiguro, T., Kitamura, E., and Matsumura, M., J. Pharm. Soc. Jpn., 1957, vol. 77, no. 10, pp. 1051–1054. https://doi.org/10.1248/yakushi1947.77.10_1051

    Article  CAS  Google Scholar 

  13. USSR Inventor’s Certificate no. 166033, Byull. Izobret., 1964.

  14. Ishiguro, T., Kitamura, E., Matsumura, M., and Ogawa, H., J. Pharm. Soc. Jpn., 1955, vol. 75, no. 11, pp. 1318–1321. https://doi.org/10.1248/yakushi1947.75.11_1318

    Article  CAS  Google Scholar 

  15. Sasaki, T., J. Synt. Org. Chem., Jpn. 1958, vol. 16, no. 11, pp. 614–620. https://doi.org/10.5059/yukigoseikyokaishi.16.614

    Article  CAS  Google Scholar 

  16. Balandin, A.A., Karpeiskaya, E.I., Ferapontov, V.A., and Tolstopyatova, A.A., Dokl. Akad. Nauk SSSR, 1965, vol. 165, no. 1, pp. 99–102.

    CAS  Google Scholar 

  17. Balandin, A.A., Ferapontov, V.A., Karpeiskaya, E.I., Gorshkova, L.S., and Tolstopyatova, A.A., Dokl. Akad. Nauk SSSR, 1966, vol. 168, no. 5, pp. 1061–1064.

    CAS  Google Scholar 

  18. Sun, Y., J. Chem. Eng. Chin. Univ., 1999, vol. 13, no. 2, pp. 178–181.

    CAS  Google Scholar 

  19. US Patent 4234730, 1980.

  20. Jiangang, L., Jiansheng, L., Xiuyun, S., and Lianjun, W., Petrochem. Technol. (China), 2004, vol. 33, no. 9, pp. 861–864.

    Google Scholar 

  21. Zhang, Y., Bai, G., Yan, X., Li, Y., Zeng, T., Wang, J., Wang, H., Xing, J., Luan, D., Tang, X., and Chen, L., Catal. Commun., 2007, vol. 8, no. 7, pp. 1102–1106. https://doi.org/10.1016/j.catcom.2006.10.018

    Article  CAS  Google Scholar 

  22. Shang, H., Wang, L., Wang, S., Gao, P., and Zheng, X., Chem. React. Eng. Technol. (China), 2012, vol. 28, no. 2, pp. 188–192.

    CAS  Google Scholar 

  23. Jpn. Patent 5803619, 2013.

  24. Corma, A., Ródenas, T., and Sabater, M.J., Chem.—Eur. J., 2010, vol. 16, no. 1, pp. 254–260. https://doi.org/10.1002/chem.200901501

    Article  CAS  PubMed  Google Scholar 

  25. Jenner, G. and Bitsi, G., J. Mol. Catal., 1988, vol. 45, no. 2, pp. 165–168. https://doi.org/10.1016/0304-5102(88)80005-1

    Article  CAS  Google Scholar 

  26. US Patent 3068232, 1962.

  27. Yang, Z., Gong, F., and Qi, Y., Chem. React. Eng. Technol. (China), 2016, vol. 32, no. 6, pp. 570–575.

    CAS  Google Scholar 

  28. Weitkamp, J., Ernst, S., Buysch, H.-J., and Lindner, D., Stud. Surf. Sci. Catal., 1991, vol. 65, pp. 297–304. https://doi.org/10.1016/S0167-2991(08)62914-6

    Article  CAS  Google Scholar 

  29. Sun, S.-H., Shen, W., Xu, H.-L., Zhou, Y.-M., Xiang, Y., and Liu, J.-X., Chin. J. Catal., 1998, vol. 19, no. 5, pp. 432–435.

    CAS  Google Scholar 

  30. Liu, R.-J., Bao, J.-Y., Zhang, Y., Tian, Z., and Wei, Z.-X., Chem. Eng. (China), 2006, vol. 34, no. 6, pp. 68–71.

    Article  CAS  Google Scholar 

  31. Wei, X.-X., Tian, Z.-S., Liang, J.-G., Liu, R.-J., Hao, H., and Wei, N.-N., Chem. Eng. (China), 2012, vol. 40, no. 1, pp. 56–58.

    Google Scholar 

  32. Gen-zhi, G., Yan-xin, L., Bin, Z., and Xiao-feng, Z., J. Petrochem. Univ. (China), 2006, vol. 19, no. 3, pp. 48–50.

    Google Scholar 

  33. Ishiguro, T., Kitamura, E., and Matsumura, M., J. Pharm. Soc. Jpn., 1953, vol. 73, no. 10, pp. 1110–1114. https://doi.org/10.1248/yakushi1947.73.10_1110

    Article  CAS  Google Scholar 

  34. Sasaki, T., J. Synt. Org. Chem., Jpn., 1959, vol. 17, no. 1, pp. 17–28. https://doi.org/10.5059/yukigoseikyokaishi.17.17

    Article  CAS  Google Scholar 

  35. Kliger, G.A., Fidler, Kh., Lesik, O.A., Khabish, D., Khlebov, L.S., Zaikin, V.G., Khaage, K., and Loktev, S.M., Neftekhimiya, 1988, vol. 28, no. 5, pp. 684–694.

    CAS  Google Scholar 

  36. US Patent 8981093, 2015.

  37. Ishiguro, T., Kitamura, E., Matsumura, M., and Ogawa, H., J. Pharm. Soc. Jpn., 1955, vol. 75, no. 11, pp. 1367–1369. https://doi.org/10.1248/yakushi1947.75.11_1367

    Article  CAS  Google Scholar 

  38. Lorentz-Petersen, L.L.R., Nordstrøm, L.U., and Madsen, R., Eur. J. Org. Chem., 2012, vol. 34, pp. 6752–6759. https://doi.org/10.1002/ejoc.201201099

    Article  CAS  Google Scholar 

  39. US Patent 3112317, 1963.

  40. Kelly, J.W., Eskew, N.L., and Evans, S.A.Jr., J. Org. Chem., 1986, vol. 51, no. 1, pp. 95–97. https://doi.org/10.1021/jo00351a020

    Article  CAS  Google Scholar 

  41. CN Patent 102442957, 2016.

  42. Kitchen, L.J. and Pollard, C.B., J. Am. Chem. Soc., 1947, vol. 69, no. 4, pp. 854–855. https://doi.org/10.1021/ja01196a034

    Article  CAS  PubMed  Google Scholar 

  43. Karpeiskaya, E.I., Ferapontov, V.A., Tolstopyatova, A.A., and Balandin, A.A., Russ. Chem. Bull., 1968, vol. 17, no. 7, pp. 1419–1424. https://doi.org/10.1007/BF00907837

    Article  Google Scholar 

  44. Hammerschmidt, W., Baiker, A., Wokaun, A., and Fluhr, W., Appl. Catal., 1986, vol. 20, nos. 1–2, pp. 305–312. https://doi.org/10.1016/0166-9834(86)80022-7

  45. Chen, L.-G., Song, Y., Xu, Z.-S., Wang, D.-L., and Meng, Y., Chem. Ind. Eng. (China), 2001, vol. 18, no. 1, pp. 40–43.

    CAS  Google Scholar 

  46. Subrahmanyam, M., Kulkarni, S.J., and Srinivas, B., React. Kinet. Catal. Lett., 1993, vol. 49, no. 2, pp. 455–459. https://doi.org/10.1007/BF02067715

    Article  CAS  Google Scholar 

  47. Wu, G.-J. and Yan, Z.-G., J. East China Univ. Technol., Nat. Sci., 2001, vol. 27, no. 1, pp. 30–33.

    CAS  Google Scholar 

  48. CN Patent 100334078, 2007.

  49. Bai, G.Y., Li, Y., Yan, X.L., He, F., and Chen, L.G., React. Kinet. Catal. Lett., 2004, vol. 82, no. 1, pp. 33–39. https://doi.org/10.1023/b:reac.0000028802.66602.0f

    Article  CAS  Google Scholar 

  50. Wu, Z., Yang, F., Wang, H., Ma, J., Chen, L., and Li, Y., React. Kinet. Mech. Catal., 2012, vol. 106, no. 2, pp. 485–493. https://doi.org/10.1007/s11144-012-0447-z

    Article  CAS  Google Scholar 

  51. Wu, Z., Wang, H., Sun, M., Du, X., Chen, L., and Li, Y., Res. Chem. Intermed., 2012, vol. 38, nos. 3–5, pp. 1149–1157. https://doi.org/10.1007/s11164-011-0450-4

  52. Ford, M.E., Johnson, T.A., Premecz, J.E., and Cooper, C.A., J. Mol. Catal., 1988, vol. 44, no. 2, pp. 207–211. https://doi.org/10.1016/0304-5102(88)80032-4

    Article  CAS  Google Scholar 

  53. Braz, G.I. and Skorodumov, V.A., Dokl. Akad. Nauk SSSR, 1948, vol. 59, no. 3, pp. 489–492.

    CAS  Google Scholar 

  54. Trejbal, J. and Petrisko, M., React. Kinet. Catal. Lett., 2004, vol. 82, no. 2, pp. 339–346. https://doi.org/10.1023/b:reac.0000034846.59643.e6

    Article  CAS  Google Scholar 

  55. WO Patent 2013095810, 2013.

  56. Martin, W.B. and Martell, A.E., J. Am. Chem. Soc., 1948, vol. 70, no. 5, pp. 1817–1818. https://doi.org/10.1021/ja01185a049

    Article  CAS  PubMed  Google Scholar 

  57. USSR Inventor’s Certificate no. 467073, Byull. Izobret., 1975.

  58. USSR Inventor’s Certificate no. 539881, Byull. Izobret., 1976.

  59. Bhat, Y.S., Kulkarnl, B.D., and Doralswamy, L.K., Ind. Eng. Chem. Process Des. Dev., 1985, vol. 24, no. 3, pp. 525–530. https://doi.org/10.1021/i200030a00

    Article  CAS  Google Scholar 

  60. Jpn. Patent 6638364, 2020.

  61. Mosher, H.S., Cornell, J.Jr., Stafford, O.L., and Roe, T., J. Am. Chem. Soc., 1953, vol. 75, no. 20, pp. 4949–4951. https://doi.org/10.1021/ja01116a020

    Article  CAS  Google Scholar 

  62. US Patent 2809196, 1957.

  63. SU Patent 697501, Byull. Izobret., 1979, no. 42.

  64. Voutchkova, A.M., Gnanamgari, D., Jakobsche, C.E., Butler, C., Miller, S.J., Parr, J., and Crabtree, R.H., J. Organomet. Chem., 2008, vol. 693, no. 10, pp. 1815–1821. https://doi.org/10.1016/j.jorganchem.2008.02.004

    Article  CAS  Google Scholar 

  65. Nasiruzzaman, M.S., Abdul, M.A., Kalanthoden, A.N., Helal, A., Hakeem, A.S., and Bououdina, M., Catal. Sci. Technol., 2018, vol. 8, no. 18, pp. 4709–4717. https://doi.org/10.1039/c8cy00936h

    Article  CAS  Google Scholar 

  66. Kim, S., Loose, F., Bezdek, M.J., Wang, X., and Chirik, P.J., J. Am. Chem. Soc., 2019, vol. 141, no. 44, pp. 17900–17908. https://doi.org/10.1021/jacs.9b09540

    Article  CAS  PubMed  Google Scholar 

  67. Chatterjee, B., Kalsi, D., Kaithal, A., Bordet, A., Leitner, W., and Gunanathan, C., Catal. Sci. Technol., 2020, vol. 10, pp. 5163–5170. https://doi.org/10.1039/D0CY00928H

    Article  CAS  Google Scholar 

  68. Ciotonea, C., Hammi, N., Dhainaut, J., Marinova, M., Ungureanu, A., El Kadib, A., Michon, C., and Royer, S., ChemCatChem, 2020, vol. 12, no. 18, pp. 4652–4663. https://doi.org/10.1002/cctc.202000704

    Article  CAS  Google Scholar 

  69. Lei, M., Li, Y., An-Hui, L., and Yunjie, D., Chin. J. Catal., 2019, vol. 40, no. 4, pp. 567–579.

    Article  Google Scholar 

Download references

Funding

This work was supported by the RF Ministry of Science and Higher Education as part of a State Task for the Boreskov Institute of Catalysis, project no. AAAA-A21-121011390007-7.

Author information

Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk, Russia

    E. E. Sergeev, L. L. Gogin, T. B. Khlebnikova, E. G. Zhizhina & Z. P. Pai

Authors
  1. E. E. Sergeev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. L. L. Gogin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. T. B. Khlebnikova
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. E. G. Zhizhina
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Z. P. Pai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to E. E. Sergeev.

Additional information

Translated by A. Tulyabaev

APPENDIX A

APPENDIX A

AEEA—aminoethylethanolamine

DCE—1,2-dichloroethane

DEA—diethanolamine

DETA—diethylenetriamine

IDAN—iminodiacetonitrile

MOR—morpholine

MEA—monoethanolamine

PP—piperazine

PR—pyrazine

PEA—polyethyleneamines

TEDA—triethylenediamine

TEPA—tetraethylenepentamine

EG—ethylene glycol

EDA—ethylenediamine

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sergeev, E.E., Gogin, L.L., Khlebnikova, T.B. et al. Methods for the Catalytic Synthesis of Piperazine. Catal. Ind. 14, 218–230 (2022). https://doi.org/10.1134/S2070050422020076

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S2070050422020076

Keywords:

Search

Navigation