Green heterocycle synthesis, isochromenones and artemidin

Green Chemistry

Volumn 5, Issue 2, 2003, Pages 174-176

  Bryson, T A ^a   Stewart, J J ^a   Gibson, J M ^b   Thomas, P S ^b   Berch, J K ^a  

^a UNIVERSITY OF SOUTH CAROLINA   (United States)

^b WINGATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2 IODOBENZOIC ACID; 3 BUT 3 ENYLISOCHROMEN 1 ONE; 3,4 DIHYDRO 2H BENZO[C]CHROMEN 1,6 DIONE; 4 (1 OXO 1H ISOCHROMEN 3 YL)BUTYRIC ACID; CHROMENE DERIVATIVE; HETEROCYCLIC COMPOUND; NEAR CRITICAL WATER; STAINLESS STEEL; UNCLASSIFIED DRUG; WATER;

CHEMICAL BOND; CHEMICAL MODIFICATION; CHEMICAL REACTION; CONFERENCE PAPER; DRUG SYNTHESIS; HEAT TREATMENT; PRESSURE; REACTOR;

EID: 0344392731     PISSN: 14639262     EISSN: None     Source Type: Journal    
DOI: 10.1039/b211966h     Document Type: Conference Paper

References (33)

1. Isochromen-1-one and isocoumarin refer to the same fused ring system.
2. For examples of organic reactions in water, see: A. R. Katritzky and S. M. Allin, Acc. Chem. Res., 1996, 29, 399-406; J. An, L. Bagnell, T. Cablewski, C. R. Strauss and R. W. Trainor, J. Org. Chem., 1997, 62, 2505-11; P. E. Savage, Chem. Rev., 1999, 99, 603-21; M. Siskin and A. R. Katritzky, Chem. Rev., 2001, 101, 825-835; N. Akiya and P. E. Savage, Chem. Rev., 2002, 102, 2725-2750.
3. For examples of organic reactions in water, see: A. R. Katritzky and S. M. Allin, Acc. Chem. Res., 1996, 29, 399-406; J. An, L. Bagnell, T. Cablewski, C. R. Strauss and R. W. Trainor, J. Org. Chem., 1997, 62, 2505-11; P. E. Savage, Chem. Rev., 1999, 99, 603-21; M. Siskin and A. R. Katritzky, Chem. Rev., 2001, 101, 825-835; N. Akiya and P. E. Savage, Chem. Rev., 2002, 102, 2725-2750.
4. For examples of organic reactions in water, see: A. R. Katritzky and S. M. Allin, Acc. Chem. Res., 1996, 29, 399-406; J. An, L. Bagnell, T. Cablewski, C. R. Strauss and R. W. Trainor, J. Org. Chem., 1997, 62, 2505-11; P. E. Savage, Chem. Rev., 1999, 99, 603-21; M. Siskin and A. R. Katritzky, Chem. Rev., 2001, 101, 825-835; N. Akiya and P. E. Savage, Chem. Rev., 2002, 102, 2725-2750.
5. For examples of organic reactions in water, see: A. R. Katritzky and S. M. Allin, Acc. Chem. Res., 1996, 29, 399-406; J. An, L. Bagnell, T. Cablewski, C. R. Strauss and R. W. Trainor, J. Org. Chem., 1997, 62, 2505-11; P. E. Savage, Chem. Rev., 1999, 99, 603-21; M. Siskin and A. R. Katritzky, Chem. Rev., 2001, 101, 825-835; N. Akiya and P. E. Savage, Chem. Rev., 2002, 102, 2725-2750.
6. For examples of organic reactions in water, see: A. R. Katritzky and S. M. Allin, Acc. Chem. Res., 1996, 29, 399-406; J. An, L. Bagnell, T. Cablewski, C. R. Strauss and R. W. Trainor, J. Org. Chem., 1997, 62, 2505-11; P. E. Savage, Chem. Rev., 1999, 99, 603-21; M. Siskin and A. R. Katritzky, Chem. Rev., 2001, 101, 825-835; N. Akiya and P. E. Savage, Chem. Rev., 2002, 102, 2725-2750.
7. The general range of temperatures and pressures used in pressure reactors: 100-275 °C and 40-800 psi.
8. F. Bellina, D. Ciucci, P. Vergamini and R. Rossi, Tetrahedron, 2000, 56, 2533-2545
9. (a) R. D. Barry, Chem. Rev., 1964, 64, 229-259;
10. (b) F. Bohlmann and C. Zdero, Chem. Ber., 1970, 103, 2856-2859;
11. (c) F. Bohlmann and C. Zdero, Phytochemistry, 1976, 15, 1318-1319;
12. (d) G. Qabaja, E. M. Perchellet, J.-P. Perchellet and G. B. Jones, Tetrahedron Lett., 2000, 41, 3007-3010;
13. (e) W. B. Turner, Fungal Metabolites, Academic Press, London, 1971, ch. 5;
14. (f) R. A. Hill, Progress in the Chemistry of Organic Natural Products, Wein-Springer-Verlag, New York, 1986, vol. 49;
15. (g) S. Ohta, Y. Kamata, T. Inagaki, Y. Masuda, S. Yamamoto, M. Yamashita and I. Kawasaki, Chem. Pharm. Bull., 1993, 41, 1188-1190.
16. Base generally refers to KOH. For convenience alkoxides were also used to form salts of carboxylic acids and β-dicarbonyl compounds.
17. Examples: A. McKillop and D. P. Rao, Synthesis, 1977, 759-760; A. McKillop and D. P. Rao, Synthesis, 1977, 760-761; A. Bruggink and A. McKillop, Tetrahedron, 1975, 31, 2607-2619; G. Chang, seminar USC, 2001, MTP inhibitor made by the analogous o-haloacid substitution and converted to a tetrahydroisoquinoline.
18. Examples: A. McKillop and D. P. Rao, Synthesis, 1977, 759-760; A. McKillop and D. P. Rao, Synthesis, 1977, 760-761; A. Bruggink and A. McKillop, Tetrahedron, 1975, 31, 2607-2619; G. Chang, seminar USC, 2001, MTP inhibitor made by the analogous o-haloacid substitution and converted to a tetrahydroisoquinoline.
19. Examples: A. McKillop and D. P. Rao, Synthesis, 1977, 759-760; A. McKillop and D. P. Rao, Synthesis, 1977, 760-761; A. Bruggink and A. McKillop, Tetrahedron, 1975, 31, 2607-2619; G. Chang, seminar USC, 2001, MTP inhibitor made by the analogous o-haloacid substitution and converted to a tetrahydroisoquinoline.
20. Examples: A. McKillop and D. P. Rao, Synthesis, 1977, 759-760; A. McKillop and D. P. Rao, Synthesis, 1977, 760-761; A. Bruggink and A. McKillop, Tetrahedron, 1975, 31, 2607-2619; G. Chang, seminar USC, 2001, MTP inhibitor made by the analogous o-haloacid substitution and converted to a tetrahydroisoquinoline.
21. p-NCW refers to near critical water generated in a Parr pressure reactor; m-NCW refers to near critical water generated with microwaves.
22. (a) MARS5 synthetic microwave (b) Goldstar 300 watt microwave oven.
23. Without acidification isochromenone formation is incomplete.
24. Retro-Claisen reaction (e.g. formation of 2) must occur before isochromenone formation; treating isochromenone 1 with NCW (Parr, 200-250 °C) affords no 2 with good recovery of 1.
25. Isochromenone 3b is a minor product from organic solvent reflux or near critical water procedures.
26. Synthesis of artemidin: G. Batu and R. Stevenson, J. Org. Chem., 1980, 45, 1532-1534.
27. As of the present we have no green way of reducing acid 6 to an alcohol.
28. 1H NMR (ppm): signals of isochromen-1-one plus 6.68 (dt, 1H), 6.01 (dt, 1H), 2.25 (m, 2H), 1.09 (t, 3H); MS (m/z): 200 (M, B).
29. For convenience the preformed potassium salts of acid 8 and the β-dicarbonyl or β-ketoester were prepared and mixed together.
30. For this study dione 9b was prepared by dianion alkylation of acetylacetone and allyl bromide (2x); 4-pentenoyl chloride is commercially available for a malonic ester synthesis of 9b. 4-Pentenoic acid is recovered from the reaction of 8 and 9b.
31. Ethylene glycol is added to enhance energy absorption. A heat sink of water was used around a glass pressure reactor. The glass pressure reactor was briefly air-cooled by shaking between bursts. See: B. Hayes, Microwave Synthesis, Chemistry at the Speed of Light, CEM Publishing, Matthews, NC, USA, 2002, ch. 2, p. 70.
32. The minor components consist mainly of the cis isomer of 7. Long-term commercial microwave irradiation of 10 at very low power settings led to only minor amounts of olefin isomerization to 7 and 3-(but-2-enyl)isochromen-1-one.
33. As the temperature and pressure increase, the dielectric constant and hydrogen bonding decrease, and the water ionization and organic solubility increases.