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University of Groningen Reduction of Aldehydes and Ketones by Sodium Dithionite Vries, Johannes G. De

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University of Groningen Reduction of Aldehydes and Ketones by Sodium Dithionite Vries, Johannes G. De View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by University of Groningen University of Groningen Reduction of Aldehydes and Ketones by Sodium Dithionite Vries, Johannes G. de; Kellogg, Richard M. Published in: Journal of Organic Chemistry DOI: 10.1021/jo01309a011 IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 1980 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Vries, J. G. D., & Kellogg, R. M. (1980). Reduction of Aldehydes and Ketones by Sodium Dithionite. Journal of Organic Chemistry, 45(21), 4126-4129. https://doi.org/10.1021/jo01309a011 Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 12-11-2019 4126 J. Org. Chem. 1980,45,4126-4129 Reduction of Aldehydes and Ketones by Sodium Dithionite Johannes G. de Vries and Richard M. Kellogg* Department of Organic Chemistry, University of Groningen, Nijenborgh 16, 9747 AG Groningen, The Netherlands Received March 12, 1980 Conditions have been developed for the effective reduction of aldehydes and ketones by sodium dithionite, Nafi204. Complete reduction of simple aldehydes and ketones can be achieved with excess NafizO4 in H20/dioxane mixtures at reflux temperature. Some aliphatic ketones, for example, pentanone and 4-heptanone, are reduced only sluggishly under these conditions. Good conversions can be achieved, however, by adding dimethylformamide to the reaction mixture, again held at reflux. The reductions of 17 compounds are described and the scope of the reaction is discussed. a-Hydroxy sulfinates are suggested as probable intermediates in these reductions. In 1870 Schutzentierger described the reducing powers aldehydes can be converted to a-hydroxy sulfinates.22 of a solution of sodium bisulfite in which zinc turnings had Symmetrical sulfones can sometimes be obtained by been dissolved.' The reducing substance, which starting from halogenide~~~,~~or activated alkenes.25 Schutzenberger named sodium hydrosulfite, was isolated In view of these many applications the scarcity of reports and was assigned th,e erroneous formula NaHSO2-H20. on the reduction of carbonyl groups by sodium dithionite This substance, later obtained pure by others,%was shown becomes all the more striking. Schutzenberger claimed the in fact to be Na2S204,2a-Ccommonly known as sodium reduction of acetone and benzaldehyde with sodium di- dithionite. thionite but gave no experimental details.' The reduction Over the years sodium dithionite has found many ap- of benzil to benzoin has been twice reported1lJsb and the plications. It has achieved commercial importance as a reduction of cyclohexanone to cyclohexanol in up to 10% reductant in vat dyeing and as a bleaching agent.3 In yield has been observed as an undesired side reaction in biochemistry sodium dithionite is used to prepare the re- an NADH recycling experiment.26 duced forms of several enzymes, coenzymes, and elec- Owing to considerations arising from other workz7we tron-transfer protein^.^ It can serve as an electron source have reexamined the reduction of carbonyl compounds for the nitrogenase system5 and models thereofU6Organic with sodium dithionite and have developed conditions for chemical applicatioris of sodium dithionite include re- the effective reduction of various aldehydes and ketones.% ductions of diazo,8 diaz~nium,~ nitros^,^ N-nitroso,lo Results and Discussions and nitro c~mpoundis,~J~imines,12J3 pyridinium salts,14 oximes (to the amines15-17as well as hydrolysis to the A. Synthetic Results. The results of reduction of a parent carbonyl c~mpound'~),and nitroxides.18 Quinones variety of carbonyl compounds (eq 1) are summarized in are reduced to the hydroquin~nes,~J~~~~and vicinal di- 0 c c I halides can be dehalogenated to the corresponding al- I/ H20 (wII~or w'tnc~l co~ol~eil~ R'CR~ - 7',&2 + kenes.21 Under proper circumstances certain aromatic t N~~s~o~ -;rgarNc prodats (1) R' = alkyl, aryl; RZ = alkyl, aryl or H (1) Schutzenberger, M. P. Ann. Chim. Phys. 1870, 20, 351. Table I. For satisfactory yields to be obtained, the (2) (a) Bernthsen, A.; Bazlen, M. Chem. Ber. 1900, 33, 126. (b) Bernthsen, A. Justus Liebigs Ann. Chem. 1881,208,142. (c) Bernthsen, aqueous reaction medium must be mildly basic to prevent A. Chem. Ber. 1905, 38, 1048. too rapid decomposition of Na2S204,which is sensitive to (3) See, for instance: I3aumgarte, U. Tertilueredlung 1967, 2, 896. acid (see below). Sodium bicarbonate works best. The (4) For examples, see: Lambeth, D. 0.;Palmer, G. J. Biol. Chem. 1973, reaction temperature must not be lower than 85 "C; for 248, 6095. the solvents used reflux temperature is most convenient. (5) Hardy, R. W. F.; Knight, E. Biochim. Biophys. Acta 1966,122,520. (6) Schrauzer, G. N. Arigew. Chem. 1975,87, 579. At lower temperature little or no reaction occurs. A co- (7) Grandmougin, E. J. Prakt. Chem. 1907, 76, 124. solvent such as dioxane can be used to increase the solu- (8) Denisov, N. T.; Solov'eva, S. A,; Shilov, A. E. Kinet. Katal. 1971, bility of the organic compound. It is advisable to work 12, 579. under nitrogen to prevent air oxidation of Na2S20z9and (9) (a) Grandmougin, E. Chem. Ber. 1907,40, 422; (b) 1907,40, 858. to add the NazS204in portions to minimize its spontaneous (c) Methoden Org. Chem. (Houben-Weyl),4th Ed. 1957, Band XI/l, 140. (10) Overberger, C. G.; McGill, E. V.; Anselme, J. P. J. Am. Chem. SOC. decomposition in aqueous solution to chiefly thiosulfate 1969, 91, 687. and s~lfite.~~~~~ (11) (a) Grandmougin, E:. Chem. Ber 1906,39,3561; (b) 1906,39,3929. (12) Hawthorne, J. 0.;IMihelic, E. L.; Morgan, M. S.; Wilt, M. H. J. (22) (a) Bazlen, M. Chem. Ber. 1905, 38, 1057; (b) 1909, 42, 4634. Org. Chem., 1963, 28, 2831. (23) Wellish, E.; Gipstein, E.; Sweeting, 0. J. J. Polymer Sci. Part B-2 (13) Pojer, P. M. Austr. J. Chem. 1979, 32, 201. 1964, 35. (14) Eisner, U.; Kuthan, J. Chem. Reu. 1972, 72, 1. (24) Matsuo, K.; Kobayashi, M.; Minato, H. Bull. Chem. Soc. Jpn. (15) Ferris, J. P. US. Patent 3670007; Chem. Abstr. 1972, 77,100866. 1970, 43, 260. (16) Treibs, A,; Schmidt, R.; Zinsmeister, R. Chem. Ber. 1957, 79. (25) (a) Kerber, R., German Patent 1122941; Chem. Abstr. 1962,57, 90, 8443~.(b) Kerber, R. German Patent 1097 434; Chem. Abstr. 1961,56, (17) Smith, L. I.; Schubert, W. M. J. Am. Chem. SOC.1948, 70,2656. 1351a. (c) Kerber, R.; Starnick, J. Chem. Ber. 1971, 104, 2035. (18) (a) Haddadin, M. J.; Alkaysi, H. N.; Saheb, S. E. Tetrahedron (26) Jones, J. B.; Sneddon, D. W.; Higgins, W.; Lewis, A. J. J. Chem. 1970,26, 1115. (b) Zahn, G. E.; Rawdaw, T. N. Chelhot, N. C.; Issidorides, SOC.,Chem. Commun. 1972,856. C. H. Ibid. 1974, 30, 659. (27) (a) de Vries, J. G.; Kellogg, R. M. J. Am. Chem. SOC.1979, 101, (19) Basalkevich, E. D.; Cherepenko, T. I.; Vysatskii, N. N.; Shapo- 2759. (b) Kellogg, R. M.; van Bergen, T. J.; van Doren, H.; Hedstrand, valenko, V. F.; Svishchuk, A. A. Fiziol. Akt. Veshchestua 1971,174; Chem. D.; Kooi, J.; Kruizinga, W. H.; Troostwijk, C. B. J. Org. Chem. 1980,45, Abstr. 1972, 77, 61449. ~..2854.~. (20) Furusawa, M.; Iwastdti, S.;Matsumura, Y. Nippon Kagaku Kaishi (28) Preliminary communication: de Vries, J. G.; van Bergen, T. J.; 1974, 2228; Chem. Abstr. 1975, 82, 38271. Kellogg, R. M. Synthesis 1977, 246. (21) Kempe, T.; Norin, T.; Caputo, R. Acta Chem. Scand., Ser. B 1976, (29) See, for instance: Creutz, C.; Sutin, N. Inorg. Chem. 1974, 13, 30. 366. 2041. 0022-3263/80/1945-4126$01.00/0 0 1980 American Chemical Society ReductZionof Aldehydes and Ketones J. Org. Chem., Vol. 45, No. 21, 1980 4127 Table I. Reductions of Aldehydes and Ketones to Alcohols with Na,S,O, entry no. substrate product solvent yield, %a 1 n-hexanal n-hex ano 1 H,O 63 2 benzaldehyde benzyl alcohol H,O-dioxane 84 3 2-fury1 aldehyde 2-fury1 alcohol H 20 90 4 cyclohexanone cyclohexanol HZ0 80 5 4-tot-butylcyclohexanone 4-tert-butylcyclohexanol(cisitruns = 13/87) H,O-dioxane 94b 6 adamantanone 2-adamantanol H -0-d iox ane 97c 7 camphor no reaction owing to sublimation HfO-dioxane 8a 4-heptanone 4-heptanol H,O-dioxane 25d b H,O-DMF 69 9a 2-pentanone 2-pentanol H,O-dioxane 33d b H,O-DMF 85e 10 2-octanorie 2-octanol H,O-DMF 15f 1la cyclopenl anone cyclopen tanol H ,O -d ioxane 52d b H,O-DMF 52g 12a 2-norborrianone 2-norbornanol (exoiendo = 17/83) H ,O -d iox ane 44d b horbornanol (exolendo = 31/79) H,O-DMF lOOh 13a cycloheptanone cyclohep tanol H,O-dioxane 35d b H,O-DMF 97d 14 levulinic acid (4-oxopentanoic acid) (4-hydroxypentanoic 1,4-lactone) H*O 54' 15a ace top henone 1-phenylethanol H,O-dioxane 30d b H,O-DMF 94 16a benzophenone diphenylme thanol H,O-dioxane 50d b H,O-DMF 94" 17 4-bromo benzophenone (4-bromopheny1)phenylmethanol H,O-DMF 92 18 ethyl phenylglyoxalate ethyl mandelate H,Ok 24 Isolated yields of pure product unless otherwise indicated; purity was at least 99% as determined by GLC.
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