Conversion of hydrazones to alkyl chlorides under Swern oxidation conditions

Tetrahedron Letters

Volumn 47, Issue 44, 2006, Pages 7731-7733

  Brewer, Matthias ^a  

^a UNIVERSITY OF VERMONT   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; AROMATIC COMPOUND; CHLORIDE; HYDRAZONE DERIVATIVE; KETONE;

ARTICLE; CHEMICAL REACTION; ELIMINATION REACTION; OXIDATION; REDUCTION; SWERN OXIDATION;

EID: 33748975897     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2006.08.120     Document Type: Article

References (16)

1. Holton T.L., and Shechter H. J. Org. Chem. 60 (1995) 4725-4729
2. Regitz M., and Mass G. Diazo Compounds Properties and Synthesis (1986), Academic Press, Orlando
3. Böshar M., Fink J., Heydt H., Wagner O., and Regitz M. In: Klaman D., and Hagemann H. (Eds). Methoden Der Organischen Chemie (Höuben-Weyl) Vol. E14B (1990), Georg Thieme, New York 996-1010
4. Pross A., and Sternhell S. Aust. J. Chem. 23 (1970) 989-1003
5. Barton D., Bashiardes G., and Fourrey J. Tetrahedron Lett. 24 (1983) 1605-1608
6. Barton D., Bashiardes G., and Fourrey J. Tetrahedron 44 (1988) 147-162
7. Rozen S., and Zamir D. J. Org. Chem. 56 (1991) 4695-4700
8. Fry A.J., and Cawse J.N. J. Org. Chem. 32 (1967) 1677-1679
9. Todd D. Org. React. 4 (1948) 378-422
10. Mancuso A.J., Huang S.-L., and Swern D. J. Org. Chem. 43 (1978) 2480-2482
11. 4), and concentrated to provide 0.38 g (93% yield) of chlorodiphenylmethane in greater than 95% purity as determined by proton NMR and GC analysis.
12. All products display characterization data identical to literature values.
13. An alternative, but similar, mechanism can be written in which the internal nitrogen of the hydrazone acts as the initial site of reactivity.
14. Pross and Sternhell reported the formation of 2-chloro-1-phenylpropane in a 9% yield upon treatment of the hydrazone of benzyl methyl ketone with chlorine. [Pross, A.; Sternhell, S. Aust. J. Chem. 1971, 24, 1437-1447.] They propose a mechanism in which an electrophilic addition of chlorine to the carbon-nitrogen double bond leads to a diimide derivative that reacts further to provide the alkyl chloride. I would like to thank a reviewer for noting that in the present work an alternative mechanism (similar to that proposed by Pross and Sternhell) could be written in which the dimethylchlorosulphonium ion adds chlorine to the carbon-nitrogen double bond.
15. Maskill H., and Whiting M.C. J. Chem. Soc., Perkin Trans. 2 13 (1976) 1462-1470
16. Debono M., and Molloy R.M. J. Org. Chem. 34 (1969) 1454-1455