A 'green' route to adipic acid: Direct oxidation of cyclohexenes with 30 percent hydrogen peroxide

Science

Volumn 281, Issue 5383, 1998, Pages 1646-1647

  Sato, Kazuhiko ^a   Aoki, Masao ^a   Noyori, Ryoji ^a  

^a NAGOYA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ADIPIC ACID; CYCLOHEXANOL; CYCLOHEXANONE; HYDROGEN PEROXIDE; OZONE;

ARTICLE; CHEMICAL REACTION; GREENHOUSE EFFECT; OXIDATION; OZONE LAYER; PRIORITY JOURNAL; REACTION ANALYSIS;

EID: 0032508584     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.281.5383.1646     Document Type: Article

References (27)

1. D. D. Davis and D. R. Kemp, in Kirk-Othmer Encyclopedia of Chemical Technology, J. I. Kroschwitz and M. Howe-Grant, Eds. (Wiley, New York, 1991), vol. 1, pp. 466-493.
2. M. H. Thiemens and W. C. Trogler, Science 251, 932 (1991).
3. A. Scott, Chem. Week 160 (no. 6) 37 (1998); R. A. Reimer, C. S. Slaten, M. Seapan, M. W. Lower, P. E. Tomlinson, Environ. Prog. 13, 134 (1994).
4. A. Scott, Chem. Week 160 (no. 6) 37 (1998); R. A. Reimer, C. S. Slaten, M. Seapan, M. W. Lower, P. E. Tomlinson, Environ. Prog. 13, 134 (1994).
5. R. E. Dickinson and R. J. Cicerone, Nature 319, 109 (1986).
6. For synthesis from D-glucose, see K. M. Draths and J. W. Frost, J. Am. Chem. Soc. 116, 399 (1994).
7. For international regulations, see Regulations Concerning the International Carriage of Dangerous Goods by Rail (RID), European Agreement Concerning the International Carriage of Dangerous Goods by Road (ADR), International Maritime Dangerous Goods Code (IMDG Code), International Civil Aviation Organization Technical Instructions for the Safe Transport of Dangerous Goods by Air (ICAO TI), and International Air Transport Association Dangerous Goods Regulation (IATA DGR).
8. K. Sato, M. Aoki, M. Ogawa, T. Hashimoto, R. Noyori, J. Org. Chem. 61, 8310 (1996); K. Sato et al., Bull. Chem. Soc. Jpn. 70, 905 (1997).
9. K. Sato, M. Aoki, M. Ogawa, T. Hashimoto, R. Noyori, J. Org. Chem. 61, 8310 (1996); K. Sato et al., Bull. Chem. Soc. Jpn. 70, 905 (1997).
10. K. Sato, M. Aoki, J. Takagi, R. Noyori, J. Am. Chem. Soc. 119, 12386 (1997).
11. 2, see J. Rudolph, K. L. Reddy, J. P. Chiang, K. B. Sharpless, ibid., p. 6189; C. Copéret, H. Adolfsson, K. B. Sharpless, Chem. Commun. 1997, 1565 (1997).
12. 2, see J. Rudolph, K. L. Reddy, J. P. Chiang, K. B. Sharpless, ibid., p. 6189; C. Copéret, H. Adolfsson, K. B. Sharpless, Chem. Commun. 1997, 1565 (1997).
13. Cyclohexene is produced by the hydrogenation of benzene for the industrial preparation of 1; see O. Mitsui and Y. Fukuoka, Japanese Patents 59-184138 and 59-186929 (1984); H. Nagahara and Y. Fukuoka, ibid. 61-50930 (1986); H. Nagahara and M. Konishi, ibid. 62-45541 (1987).
14. Cyclohexene is produced by the hydrogenation of benzene for the industrial preparation of 1; see O. Mitsui and Y. Fukuoka, Japanese Patents 59-184138 and 59-186929 (1984); H. Nagahara and Y. Fukuoka, ibid. 61-50930 (1986); H. Nagahara and M. Konishi, ibid. 62-45541 (1987).
15. Cyclohexene is produced by the hydrogenation of benzene for the industrial preparation of 1; see O. Mitsui and Y. Fukuoka, Japanese Patents 59-184138 and 59-186929 (1984); H. Nagahara and Y. Fukuoka, ibid. 61-50930 (1986); H. Nagahara and M. Konishi, ibid. 62-45541 (1987).
16. 2. After the mixture was vigorously stirred at room temperature for 10 min, 100 g (1.217 mol) of 1 was added. This mixture was heated successively at 75°C for 30 min, at 80°C for 30 min, at 85°C for 30 min, and at 90°C for 46.5 hours, with stirring at 1000 rpm; the homogeneous solution was allowed to stand at 0°C for 12 hours. The resulting white precipitate was separated, washed, and dried in a vacuum to produce 138 g (78% yield) of analytically pure 2 as a white solid.
17. Y. Ishii et al., J. Org. Chem. 53, 3587 (1988); T. Oguchi, T. Ura, Y. Ishii, M. Ogawa, Chem. Lett. 1989, 857 (1989).
18. Y. Ishii et al., J. Org. Chem. 53, 3587 (1988); T. Oguchi, T. Ura, Y. Ishii, M. Ogawa, Chem. Lett. 1989, 857 (1989).
19. C. Venturello and M. Ricci, European Patent 0 122 804 (1984).
20. 4 catalyst, only a trace amount of 2 was obtained (12).
21. L. Knof, Liebigs Ann. Chem. 656, 183 (1962); G. M. Rubottom, J. M. Gruber, R. K. Boeckman Jr., M. Ramaiah, J. B. Medwid, Tetrahedron Lett. 1978, 4603 (1978).
22. L. Knof, Liebigs Ann. Chem. 656, 183 (1962); G. M. Rubottom, J. M. Gruber, R. K. Boeckman Jr., M. Ramaiah, J. B. Medwid, Tetrahedron Lett. 1978, 4603 (1978).
23. Under the standard conditions of alcohol oxidation, Baeyer-Villiger ring enlargement of simple cyclohexanones is negligible (8). A separate experiment showed that 1,2-cyclohexanedione is not a reaction intermediate.
24. For nitric acid oxidation, see J. E. Franz, J. F. Herber, W. S. Knowles, J. Org. Chem. 30, 1488 (1965).
25. Eur. Chem. News 66, 41 (1996); L. W. Gosser, U.S. Patent 4,681,751 (1987).
26. Eur. Chem. News 66, 41 (1996); L. W. Gosser, U.S. Patent 4,681,751 (1987).
27. We are grateful to N. Imaki and T. Setoyama (Mitsubishi Chemical Company, Tokyo), M. Kagotani (Daicel Chemical Industries, Osaka), T. Kurai (Mitsubishi Gas Chemical Company, Tokyo), M. Minai (Sumitomo Chemical Industry, Tokyo), and K. Nakagawa (Asahi Chemical Industry Company, Tokyo) for their valuable comments from industrial points of view. This work was supported by the Ministry of Education, Science, Sports, and Culture, Japan (grant 07CE2004).