Skip to main content
SpringerLink
Log in

Biradical processes in reactions between benzyne and tropone

  • Regular Article
  • Published:
Theoretical Chemistry Accounts Aims and scope Submit manuscript

Abstract

The title reactions were investigated experimentally and theoretically. The benzyne--tropone pair has been known to give a Diels–Alder [4+2] cycloadduct. However, in the present experiment using two sources of benzyne, many unexpected products were obtained. In particular, a zwitterion with a C–Cl bond is strikingly a major product, the structure of which was determined by the X-ray analysis. The bond is formed by quenching the Cl atom from the solvent CH2Cl2, which demonstrates that the reactions proceed via radical processes. DFT calculations revealed the elementary processes of the reactions. The presence of the novel zwitterion in the solid state has been interpreted in terms of the permanent dipole–dipole attractions/interactions/stabilization.

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

Similar content being viewed by others

References

  1. Roberts JD, Simmons HE, Carismith LA, Vaughan CW (1953) J Am Chem Soc 75:3290–3291

    Article  CAS  Google Scholar 

  2. Washburn WN (1975) J Am Chem Soc 98:1615–1616

    Article  Google Scholar 

  3. Washburn WN, Zahler R (1976) J Am Chem Soc 98:7827–7828

    Article  CAS  Google Scholar 

  4. Washburn WN, Zahler R (1976) J Am Chem Soc 98:7828–7830

    Article  CAS  Google Scholar 

  5. Jones RR, Bergman RG (1972) J Am Chem Soc 94:660–661

    Article  CAS  Google Scholar 

  6. Breslow R, Napierski J, Clarke TC (1975) J Am Chem Soc 97:6275–6276

    Article  CAS  Google Scholar 

  7. Fieser LF, Haddadin M J (1966) Org Synth 46: 107. http://www.orgsyn.org/orgsyn/pdfs/CV5P1037.pdf

  8. Wittig G, Pohmer L (1955) Angew Chem 67:348

    Article  CAS  Google Scholar 

  9. Friedman L, Logullo FM (1969) J Org Chem 34:3089

    Article  CAS  Google Scholar 

  10. Sustmann R, Schubert R (1972) Angew Chem Int Ed 11:840

    Article  CAS  Google Scholar 

  11. Ciabattoni J, Crowley JE, Kende AS (1967) J Am Chem Soc 89:2778

    Article  CAS  Google Scholar 

  12. Miwa T, Kato M, Tamao T (1969) Tetrahedron Lett 22:1761

    Article  Google Scholar 

  13. Logullo FM, Seitz AH, Friedman L (1968) Org Synth 48:12. http://www.orgsyn.org/orgsyn/pdfs/CV5P0054.pdf

  14. Woodward RB, Hoffmann R (1970) The conservation of orbital symmetry. Verlag Chemie, New York

    Google Scholar 

  15. Wasserman HH, Solodar AJ, Keller LS (1968) Tetrahedron Lett 21:5597

    Article  Google Scholar 

  16. Hayes DM, Hoffmann R (1972) J Phys Chem 76:656

    Article  CAS  Google Scholar 

  17. Ozkan I, Kinal A (2004) J Org Chem 69:5390

    Article  CAS  Google Scholar 

  18. Yamabe S, Minato T, Ishiwata A, Irinamihira O, Machiguchi T (2007) J Org Chem 72:2832–2841

    Article  CAS  Google Scholar 

  19. Goldstein E, Beno B, Houk KN (1996) J Am Chem Soc 118:6036–6043

    Article  CAS  Google Scholar 

  20. Wittig G, Hoffmann RW (1967) Org Synth 47: 4. http://www.orgsyn.org/orgsyn/pdfs/CV5P0060.pdf

  21. Machiguchi T, Okamoto J, Morita Y, Hasegawa T, Yamabe S, Minato T (2006) J Am Chem Soc 128:44–45

    Article  CAS  Google Scholar 

  22. Becke AD (1988) Phys Rev A 38:3098

    Article  CAS  Google Scholar 

  23. Perdew JP, Wang Y (1992) Phys Rev B 45:13244

    Article  Google Scholar 

  24. Tichy SE, Nelson ED, Amegayibor FS, Kenttamaa HI (2004) J Am Chem Soc 126:12957–12967

    Article  CAS  Google Scholar 

  25. Littleford RE, Paterson MAJ, Low PJ, Tackley DR, Jayes L, Dent G, Cherryman JC, Brown B, Smith WE (2004) Phys Chem Chem Phys 6:3257–3263

    Article  CAS  Google Scholar 

  26. Tripathi GNR, Chipman DM (2002) J Phys Chem A 106:8908–8916

    Article  CAS  Google Scholar 

  27. Cremer CJ, Nash JJ, Squires RR (1997) Chem Phys Letters 277:311

    Article  Google Scholar 

  28. Becke AD (1993) J Chem Phys 98:5648

    Article  CAS  Google Scholar 

  29. Burke K, Perdew JP, Wang Y (1998) In: Dobson JF, Vignale G, Das MP (eds) Electronic density functional theory: recent progress and new directions. Plenum, Berlin

    Google Scholar 

  30. Perdew JP (1991) In: Ziesche P, Eschrig H (eds) Electronic Structure of Solids’91. Akademie Verlag, Berlin, p 11

    Google Scholar 

  31. Perdew JP, Chevary JA, Vosko SH, Jackson KA, Pederson MR, Singh DJ, Fiolhais C (1192) Phys Rev B 46:6671–6687

    Article  Google Scholar 

  32. Perdew JP, Chevary JA, Vosko SH, Jackson KA, Pederson MR, Singh DJ, Fiolhais C (1993) Phys Rev B 48:4978

    Article  CAS  Google Scholar 

  33. Perdew JP, Burke K, Wang Y (1996) Phys Rev B 54:16533–16539

    Article  CAS  Google Scholar 

  34. Zhao Y, Schultz NE, Truhlar DG (2005) J Chem Phys 123:161103

    Article  Google Scholar 

  35. Zhao Y, Schultz NE, Truhlar DG (2006) J Chem Theor Comput 2:364–382

    Article  Google Scholar 

  36. Zhao Y, Truhlar DG (2008) Theor Chem Acc 120:215–241

    Article  CAS  Google Scholar 

  37. Cancès MT, Mennucci B, Tomasi J (1997) J Chem Phys 107:3032

    Article  Google Scholar 

  38. Cossi M, Barone V, Mennucci B, Tomasi J (1998) Chem Phys Lett 286:253

    Article  CAS  Google Scholar 

  39. Mennucci B, Tomasi J (1997) J Chem Phys 107:5151

    Article  Google Scholar 

  40. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2003) Gaussian 03(Revision E.01). Gaussian Inc., Pittsburgh

    Google Scholar 

  41. Lennard-Jones JE (1931) Proc Camb Phil Soc 27:469

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We thank five reviewers for their careful examinations and fruitful comments.

Author information

Authors and Affiliations

  1. Department of Chemistry, Nara University of Education, Takabatake-cho, Nara, 630-8528, Japan

    Shinichi Yamabe

  2. Institute for Natural Science, Nara University, 1500 Misasagi-cho, Nara, 631-8502, Japan

    Tsutomu Minato

  3. Department of Chemistry, Faculty of Science, Saitama University, 255 Shimo-Ohkubo, Sakura-ku, Saitama, 338-8570, Japan

    Teruyuki Watanabe & Takahisa Machiguchi

Authors
  1. Shinichi Yamabe
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tsutomu Minato
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Teruyuki Watanabe
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Takahisa Machiguchi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shinichi Yamabe.

Additional information

Dedicated to Professor Akira Imamura on the occasion of his 77th birthday and published as part of the Imamura Festschrift Issue

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 2617 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Yamabe, S., Minato, T., Watanabe, T. et al. Biradical processes in reactions between benzyne and tropone. Theor Chem Acc 130, 981–990 (2011). https://doi.org/10.1007/s00214-011-1039-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00214-011-1039-0

Keywords

Search

Navigation