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Novel synthesis of symmetrical 3,3′-allyl dithioethers as photoplastic monomer precursors by equal molar rate addition of reactants and solvent controlled oligomerization

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Abstract

An alternative method has been developed whereby novel 3,3′-allyl dithioethers, for monomers used in photoplastic polymers, have been synthesized from a synchronized, rapid addition of a concentrated mixture of 2 mol equiv alkyl halide and 1 mol equiv 3-mercapto-2-mercaptomethyl-1-propene (A) in MeOH in one syringe and an equi-volume two mol equivalent sodium methoxide in MeOH in another syringe. Thus, two-fold excess 3-chloro-2-chloromethyl-1-propene (B) with A gave B-A-B and B-A-B-A-B as the main products but no B-A or B-A-B-A due to the mechanism involved and the low solubility of the longer oligomer in MeOH. When the reaction of 2 × A with B was carried out, the main product was A-B-A-B-A-B-A.

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References

  1. Cook WD, Chen F, Nghiem QD, Scott TF, Bowman CN, Chausson S, Le Pluart L (2010) Macromol Symp 291–292:50

    Article  Google Scholar 

  2. Scott TF, Schneider AD, Cook WD, Bowman CN (2005) Science 308:1615

    Article  CAS  Google Scholar 

  3. Cook WD, Chausson S, Chen F, Le Pluart L, Bowman CN, Scott TF (2008) Polym Int 57:469

    Article  CAS  Google Scholar 

  4. Moorhoff CM, Cook WD, Chen F, Nghiem D, Braybrook C, Thang SH, Sun J, Scott TF, Bowman CN (2011) Aust J Chem 64:1083

    Article  CAS  Google Scholar 

  5. Scott TF, Draughon RB, Bowman CN (2006) Adv Mater 18:2128

    Article  CAS  Google Scholar 

  6. Kloxin CJ, Scott TF, Bowman CN (2009) Macromolecules 42:2551

    Article  CAS  Google Scholar 

  7. Evans RE, Rizzardo E (2000) Macromolecules 33:6722

    Article  CAS  Google Scholar 

  8. Evans RE, Rizzardo E (2001) J Polym Sci. Part A: Polym Chem 39:202

    Article  CAS  Google Scholar 

  9. Moorhoff CM, Cook WD, Schiller T, Braybrook C, Thang SH (2012) Aust J Chem 65:1165

    Article  CAS  Google Scholar 

  10. Pearson RG, Songstad J (1967) J Organomet Chem 32:2899

    CAS  Google Scholar 

  11. Gallucci RR, Going RC (1983) J Org Chem 48:342

    Article  CAS  Google Scholar 

  12. Tolstikov GA, Kanzafarov FY, Kanzafarova SG, Singizova VK (1986) Zh Org Khim 22:1400

    CAS  Google Scholar 

  13. Martinetz D, Hiller A (1978) Z Chem 18:61

    Article  CAS  Google Scholar 

  14. Dietrich EM, Schulze K, Muehlstaedt M (1972) 1,5-Dithiacyclanes. Patent DD 1972-163133, May 23, 1972; (1974) Chem Abstr 80:96044

  15. Pauling L (1960) The Nature of the Chemical Bond, 3rd edn. Cornell University Press, New York

    Google Scholar 

  16. Allen LC (1989) J Am Chem Soc 111:900

    Article  Google Scholar 

  17. Winkler JD, Kwak Y-S (1998) J Org Chem 63:8634

    Article  CAS  Google Scholar 

  18. Nicewicz DA, Satterfield AD, Schmitt DC, Johnson JS (2008) J Am Chem Soc 130:17281

    Article  CAS  Google Scholar 

  19. Knapp S, Malolanarasimhan K (1999) Org Lett 1:611

    Article  CAS  Google Scholar 

  20. Butler J, Kellogg RM, Van Bolhuis F (1990) J Chem Soc Chem Commun 282

Download references

Acknowledgments

The authors wish to acknowledge the support of ARC DP0877382 in this work and would like to thank Dr. Fei Chen for assisting with the photoplasticity experiments, and Drs. Tara Schiller, Daniel Keddie, and San Thang for reading the manuscript and/or helpful discussions.

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Authors and Affiliations

  1. Department of Materials Engineering, Monash University, Clayton, VIC, 3800, Australia

    Cornelis M. Moorhoff & Wayne D. Cook

  2. Materials Science and Engineering, CSIRO, Clayton, VIC, 3169, Australia

    Carl Braybrook

Authors
  1. Cornelis M. Moorhoff
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  2. Wayne D. Cook
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  3. Carl Braybrook
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Corresponding authors

Correspondence to Cornelis M. Moorhoff or Wayne D. Cook.

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Moorhoff, C.M., Cook, W.D. & Braybrook, C. Novel synthesis of symmetrical 3,3′-allyl dithioethers as photoplastic monomer precursors by equal molar rate addition of reactants and solvent controlled oligomerization. Monatsh Chem 144, 891–902 (2013). https://doi.org/10.1007/s00706-013-0942-6

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  • DOI: https://doi.org/10.1007/s00706-013-0942-6

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