Synthesis of quinolines, pyridine ligands and biological probes in green media

Green Chemistry

Volumn 5, Issue 2, 2003, Pages 177-180

  Bryson, T A ^a   Gibson, J M ^b   Stewart, J J ^a   Voegtle, H ^a   Tiwari, A ^a   Dawson, J H ^a   Marley, W ^b   Harmon, B ^c  

^a UNIVERSITY OF SOUTH CAROLINA   (United States)

^b WINGATE UNIVERSITY   (United States)

^c PARK UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLPYRIDINE; AZACHALCONE DERIVATIVE; HETEROCYCLIC NITRO COMPOUND; PYRIDINE DERIVATIVE; QUINOLINE DERIVATIVE; TERPYRIDINE; UNCLASSIFIED DRUG;

CHEMICAL MODIFICATION; CONFERENCE PAPER; CYCLODEHYDRATION; DRUG SYNTHESIS; HEATING; ION EXCHANGE; MICROWAVE RADIATION; MOLECULAR PROBE; PRESSURE; REDUCTION; SUZUKI COUPLING;

EID: 0344824409     PISSN: 14639262     EISSN: None     Source Type: Journal    
DOI: 10.1039/b211968d     Document Type: Conference Paper

References (28)

1. A number of organic transformations have been effected in water.2 This group's long range goal is to effect multistep synthesis replacing various organic solvents and exotic or environmentally unfriendly reagents with water and green catalysts and reagents.
2. For examples of organic reactions done in water, see: A. R. Katritzky and S. M. Allin, Acc. Chem. Res., 1996, 29, 399-406; P. E. Savage, Chem. Rev., 1999, 99, 603-621; J. An, L. Bagnell, T. Cablewski, C. R. Strauss and R. W. Trainor, J. Org. Chem., 1997, 62, 2505-2511.
3. For examples of organic reactions done in water, see: A. R. Katritzky and S. M. Allin, Acc. Chem. Res., 1996, 29, 399-406; P. E. Savage, Chem. Rev., 1999, 99, 603-621; J. An, L. Bagnell, T. Cablewski, C. R. Strauss and R. W. Trainor, J. Org. Chem., 1997, 62, 2505-2511.
4. For examples of organic reactions done in water, see: A. R. Katritzky and S. M. Allin, Acc. Chem. Res., 1996, 29, 399-406; P. E. Savage, Chem. Rev., 1999, 99, 603-621; J. An, L. Bagnell, T. Cablewski, C. R. Strauss and R. W. Trainor, J. Org. Chem., 1997, 62, 2505-2511.
5. C.-C. Cheng and Y.-S. Yan, Org. React., 1982, 28, 37-201.
6. B. Mundy and M. Ellerd, Name Reactions and Reagents in Organic Synthesis, Wiley, New York, 1988, p. 86-87.
7. I. J. Dmochowski, J. R. Winkler and H. B. Gray, J. Inorg. Biochem., 2000, 81, 221-228.
8. P. Korall, A. Borje, P. Norrby and B. Akermark, Acta Chem. Scand., 1997, 51, 760-766.
9. A. Suzuki, Metal-Catalyzed Cross-Coupling Reactions, ed. F. Diederich and P.J. Stang, Wiley-VCH, Weinheim, Germany, 1998, ch. 2.
10. L. I. Smith and J. W. Opie, Org. Synth., 1948, 28, 11; this procedure produces good quality product but requires a laborious steam distillation limiting the amounts of o-aminobenzaldehyde and the scope of ortho-amino carbonyl compounds that can be prepared by this reduction; ortho-amino carbonyl compounds do not store well due to intermolecular imine formation.
11. S. Murata, M. Miura and M. Nomura, Chem. Lett., 1998, 2, 361-362.
12. J. M. Jennings, T. A. Bryson and J. M. Gibson, Green Chem., 2000, 87-88; T. A. Bryson, J. M. Jennings and J. M. Gibson, Tetrahedron Lett., 2000, 41, 3523-3526.
13. J. M. Jennings, T. A. Bryson and J. M. Gibson, Green Chem., 2000, 87-88; T. A. Bryson, J. M. Jennings and J. M. Gibson, Tetrahedron Lett., 2000, 41, 3523-3526.
14. General procedure: the amounts of liquid (primarily water) and solids used were adjusted to less than 40% of the reactor volume. A stainless steel pressure reactor containing a mix of degassed water, ethyl formate (3 to 4 eq.), Pd/C (∼0.02 eq. of Pd), o-nitrobenzaldehyde (1 eq.) and reagent ketone or aldehyde (1.5+ eq) was heated at 170-200 °C for 2 h; the quinoline product was isolated using acid-base chemistry.
15. Mixed formate systems (ethyl formate/formic acid and ethyl formate/ sodium formate) also afford the same quinolines adding to the variables that must be reviewed to optimize a green preparation of these heterocyclic products.
16. Using the best yield for ferrous sulfate reduction of o-nitrobenzaldehyde, the two-step conversion to 2-ethyl-3-methylquinoline is 61%.
17. For a typical example of an isatin-Pfitzinger synthesis, see: C. Koelsch, J. Org. Chem., 1951, 16, 1362.
18. C. Eckert, Chem. Eng. News, 2000, 3, 26-27.
19. General procedure: isatin (1 eq.), ketone or aldehyde ( > 1 eq.), degassed water (total volume less than 40% of the pressure reactor) were brought to 250-275 °C for 0.5 h. The product was purified using minimal ether extraction or acid-base chemistry.
20. The nitrobenzaldehyde substrate was used to provide an alternate (diazonium ion) coupling route.
21. The nitro azachalcone 4 formed in excellent yield but both the product and aqueous layer were highly colored. This aqueous layer was not recycled.
22. Recrystalization was done for aesthetics and is not necessary.
23. Irradiation: in a glass pressure reactor with a water heat sink, 7-10 min bursts were administered on low power in a commercial microwave totaling approximately 1 h of irradiation. Each burst was followed by a cooling period of from 5 to 35 min.
24. G. C. Blettner, W. A. König, W. Stenzel and T. Schotten, J. Org. Chem., 1999, 64, 3885-3890; general reference: B. Hayes, Microwave Synthesis, Chemistry at the Speed of Light, CEM Publishing, Matthews, NC, USA, 2002, ch. 4 (MARS5 system was used for this coupling).
25. G. C. Blettner, W. A. König, W. Stenzel and T. Schotten, J. Org. Chem., 1999, 64, 3885-3890; general reference: B. Hayes, Microwave Synthesis, Chemistry at the Speed of Light, CEM Publishing, Matthews, NC, USA, 2002, ch. 4 (MARS5 system was used for this coupling).
26. E. C. Constable and A. M. Cargill Thompson, J. Chem. Soc., Dalton Trans., 1995, 1615-1627.
27. T. Matsumura-Inoue, M. Tanabe, T. Minami and T. Ohashi, Chem. Lett., 1994, 2443-2446.
28. The mass spectra of the complex has a predominant 443 double charged ion. The remarkable chromatographic separation of 1 is the procedure of Constable and Cargill Thompson, ref. 22.