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157:. Previously it was discovered that the hydroxylation of butter yellow or its demethylated derivatives exist within rats, and thus rats were deemed suitable for the comparison. Absorption spectra were examined to confirm the results of the experiment, which found that the product of the Milas hydroxylation was one of the obtained products.
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One variation of the Milas hydroxylation (shown in the mechanism above) requires stoichiometric amounts of osmium tetroxide, which is toxic (highly volatile) and expensive. Furthermore, in Milas's own experiments his yields ranged from 37.6% to 60.2% for the cis-vicinal diol. Note that a vicinal diol
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In 1949, the Milas hydroxylation was applied to a study of the demethylation of N-Dimethyl-p-Amino-azobenzene, otherwise known as butter yellow. Hydrogen peroxide in tertiary butyl alcohol with osmium tetroxide as a catalyst (Milas reagents) was examined to determine the parallels of the reaction
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The catalyst, osmium tetroxide, also known as Merck osmic acid, dissolves readily in tertiary butyl alcohol which implies that the solution in which the reaction occurs is stable, unless isobutylene is already present. In the presence of isobutylene most of the osmium tetroxide is reduced to an
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insoluble black colloidal oxide. This colloidal oxide is a very active catalyst in decomposition of hydrogen peroxide. Thus, in aqueous solutions osmium tetroxide decomposes hydrogen peroxide, whereas an anhydrous tertiary butyl alcohol decomposes at a much slower rate.
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The proposed mechanism for the Milas hydroxylation involves the initial combination of hydrogen peroxide and the osmium tetroxide catalyst to form an intermediate, which then adds to the alkene, followed by a cleavage that forms the product and regenerates the
246:
Milas, Nicholas A.; Trepagnier, Joseph H.; Nolan, John T.; Iliopulos, Miltiadis I. (September 1959). "A Study of the
Hydroxylation of Olefins and the Reaction of Osmium Tetroxide with 1,2-Glycols".
302:"An Osmium(III)/Osmium(V) Redox Couple Generating OsV(O)(OH) Center for cis-1,2-Dihydroxylation of Alkenes with H2O2: Os Complex with a Nitrogen-Based Tetradentate Ligand"
273:
Milas, Nicholas A. (November 1937). "The
Hydroxylation of Unsaturated Substances. III. The Use of Vanadium Pentoxide and Chromium Trioxide as Catalysts of Hydroxylation".
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is a molecule in which two hydroxy atoms are located on adjacent carbon atoms. Vicinal diols can be oxidized to aldehydes and ketones, rendering their synthesis useful.
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The Upjohn dihydroxylation and the
Sharpless asymmetric dihydroxylation both result in cis-vicinal diols as well, and do not require the toxic, expensive catalyst.
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375:"An improved catalytic OsO4 oxidation of olefins to cis-1,2-glycols using tertiary amine oxides as the oxidant"
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414:"Demethylation of N : N-Dimethyl-p-Amino-azobenzene (Butter Yellow) with Hydrogen Peroxide"
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Ouellette, Robert J.; Rawn, J. David (2018-01-01), Ouellette, Robert J.; Rawn, J. David (eds.),
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Hideki
Sugimoto, Sugimoto; Kazuhiro Kitayama, Kitayama; Seiji, Mori; Shinobu, Itoh (2012).
8:
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Milas, Nicholas A.; Sussman, Sidney (July 1936). "The
Hydroxylation of the Double Bond".
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in the 1930s. The cis-diol is formed by reaction of alkenes with
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The reaction has been superseded in synthetic chemistry by the
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VanRheenen, V.; Kelly, R. C.; Cha, D. Y. (1976-06-01).
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211:Comprehensive Organic Name Reactions and Reagents
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74:and either ultraviolet light or a catalytic
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341:"16 - Alcohols: Reactions and Synthesis"
275:Journal of the American Chemical Society
248:Journal of the American Chemical Society
181:Journal of the American Chemical Society
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347:, Academic Press, pp. 463–505,
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102:Sharpless asymmetric dihydroxylation
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345:Organic Chemistry (Second Edition)
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479:Organic oxidation reactions
412:Anderson, Wm (March 1949).
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209:"Milas Hydroxylation".
66:, and was developed by
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98:Upjohn dihydroxylation
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19:Milas hydroxylation
379:Tetrahedron Letters
312:(46): 19270–19280.
287:10.1021/ja01290a072
260:10.1021/ja01526a070
217:: 1948–1951. 2010.
193:10.1021/ja01298a065
149:with butter yellow
49:Milas hydroxylation
474:Addition reactions
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80:vanadium pentoxide
424:(4142): 444–445.
385:(23): 1973–1976.
354:978-0-12-812838-1
318:10.1021/ja309566c
281:(11): 2342–2344.
254:(17): 4730–4733.
100:and later by the
84:chromium trioxide
72:hydrogen peroxide
68:Nicholas A. Milas
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36:Addition reaction
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360:2022-12-05
161:References
438:1476-4687
399:0040-4039
108:Mechanism
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326:23113538
155:in vitro
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153:versus
151:in vivo
61:vicinal
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57:alkene
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450:S2CID
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395:ISSN
349:ISBN
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227:ISBN
64:diol
47:The
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