Mineralization of chlorofluorocarbons and aromatization of saturated fluorocarbons by a convenient thermal process

Science

Volumn 271, Issue 5247, 1996, Pages 340-341

  Burdeniuc, Juan ^a   Crabtree, Robert H ^a  

^a YALE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0030051358     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.271.5247.340     Document Type: Article

References (25)

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7. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
8. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
9. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
10. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
11. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
12. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
13. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
14. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
15. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
16. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
17. W. A Sheppard and C. M Sharts, Organic Fluorine Chemistry (Beniamin, New York, 1969); M Hudlicky, Chemistry of Organic Fluorine Compounds (Horwood. Chichester, UK, 1976); R Perry, in Fluorine-The First Hundred Years, R E Banks, D. W A Sharp, J. C. Tatlow, Eds (Elsevier, New York, 1986). pp. 293-295, D D MacNicol and C. D Robertson, Nature 332, 59 (1988), M. Weydert, R. A. Andersen, R. G. Bergman, J Am Chem. Soc. 115, 8837 (1993); R. G. Hamson and T. G Richmond, ibid, p. 5303, B K Bennett, R, G. Harrison. T G. Richmond, ibid. 116, 11165 (1994); M Aizenberg and D. Milstein, Science 265;359 (1994); T G. Richmond, Coord. Chem. Rev. 105,221 (1990); S. T. Belt, M Helliwell.W D Jones, M. G. Partridge, R. N Perutz, J. Am Chem. Soc. 115, 1429 (1993); O. Blum, F. Frolow, D. Milstein, J. Chem Soc. Chem. Commun. 1991, 258, M. J. Burk, D. L. Staley, W. Tumas, ibid 1990,809; P. L. Watson, T. H. Tulip, I. Williams, Organometallics 9, 1999 (1990)
18. 4 (20 mm by 20 cm; 34 g, 254 mmol) heated to 270°C (electrical heating tape; temperature monitored by thermocouple), and condensed in the second trap In the first pass, the substrate was introduced at 4 ml/min (flowmeter, measured at 25°C, 1 atm) for 1.5 hours, passed through the oxalate bed, and condensed in the trap. The substrate supply and flowmeter were then removed and replaced with the second trap
19. 4 (20 mm by 10 cm, 17 g, 127 mmol) heated to 270°C for mineralization and to 230°C for aromatization The vapor was then condensed and returned to the reflux flask. Typical reaction time was 2 days.
20. 2 as internal standard.
21. B Gething, C R. Patrick, M. Stacey, J. C. Tatlow, Nature 183. 588 (1959)
22. J. S. Moilliet, in Orgsnofluonne Chemistry, R. E Banks, B E Smart, J. C Tatiow, EdS- (Plenum, New York, 1994), p 212.
23. Ibid., p. 196.
24. 2 saturated with substrate vapor (aromatization) At T = 270°C and with a reac-tion bed of 20 mm by 20 cm, the typical reaction time was 2 hours (mineralization) or 10 hours (aromatization) For diagrams of all the apparatus, see J Burdeniuc and R. H. Crabtree, J Am. Chem Soc , in press.
25. Supported by 3M Company and the U.S. Depart-ment of Energy (grant FG02-84ER13297 A012).