Reissert reaction
| Reissert reaction | |
|---|---|
| Named after | Arnold Reissert |
| Reaction type | Addition reaction |
The Reissert reaction is a series of chemical reactions that transforms quinoline to quinaldic acid,[1][2] with concomitant reduction of an acylant to an aldehyde.[3]
Quinolines will react with acid chlorides and potassium cyanide to give 1-acyl-2-cyano-1,2-dihydroquinolines, also known as Reissert compounds. Hydrolysis gives the desired quinaldic acid via a 1,3-dipolar fused-oxazolium intermediate.[4]: 521 [5]
Other nucleophiles than cyanide can also be used to quench the acylquinolium intermediate, possibly enantioselectively.[6]
Alternatively, the Reissert compound has an acidic proton α to the cyanide moiety, and the conjugate base is susceptible to alkylation. The resulting alkylated compounds hydrolyze in aqueous base, eliminating both an equivalent of hydrogen cyanide and the carboxylic acid corresponding the acyl moiety.[4]: 527–528
The Reissert reaction is also successful with isoquinolines.[7] Pyridines do not undergo the Reissert reaction per se, but slowly form para adducts under Reissert conditions.[4]: 514–515, 539–542 Quinoline N-oxides react to form the cyanoquinoline immediately; it is unclear if the intermediate Reissert adduct exists stably.[4]: 543–544
References
[edit]- ^ Reissert, Arnold (1905). "Ueber die Einführung der Benzoyl-gruppe in tertiäre cyclische Basen". Berichte der deutschen chemischen Gesellschaft. 38 (2): 1603–1614. doi:10.1002/cber.19050380260.
- ^ Grosheintz, J. M.; Fischer, Hermann O. L. (1941). "Preparation of 1-Acyl-1,2-dihydroquinaldonitriles and their Hydrolysis to Aldehydes". Journal of the American Chemical Society. 63 (7): 2021–2022. Bibcode:1941JAChS..63.2021G. doi:10.1021/ja01852a066.
- ^ Mosettig, E. Org. React. 1954, 8, 220. doi:10.1002/0471264180.or008.05
- ^ a b c d McEwen, William E.; Cobb, R. Lynn (1955). "The Chemistry of N-Acyldihydroquinaldonitriles and N-Acyldihydroisoquinaldonitriles (Reissert Compounds)". Chemical Reviews. 55 (3): 511–549. doi:10.1021/cr50003a002. Excerpted from Cobb's University of Kansas PhD Thesis, hdl:1808/32921
- ^ McEwen, William E.; Mineo, Isidore C.; Shen, Yvonne H. (1971). "1,3-Dipolar addition reactions of Reissert compounds". Journal of the American Chemical Society. 93 (18): 4479. Bibcode:1971JAChS..93.4479M. doi:10.1021/ja00747a023.
- ^ Ahamed, Muneer; Todd, Matthew. H. (2010). "Catalytic Asymmetric Additions of Carbon-Centered Nucleophiles to Nitrogen-Containing Aromatic Heterocycles". European Journal of Organic Chemistry. 2010 (31): 5935–5942. doi:10.1002/ejoc.201000877. (Review)
- ^ Weinstock, J.; Boekelheide, V. Organic Syntheses, Coll. Vol. 4, p. 641 (1963); Vol. 38, p. 58 (1958). doi:10.15227/orgsyn.038.0058 :Updated and improved in Uff, B. C.; Kershaw, J. R.; Neumeyer, J. L. Organic Syntheses, Coll. Vol. 6, p. 115 (1988); Vol. 56, p. 19 (1977). doi:10.15227/orgsyn.056.0019