The Baeyer-Villiger oxidation of a-substituted cyclic ketones

The Baeyer-Villiger oxidation of 2-chlorocholestan-3-one and 2-bromo-cholestan-3-one gives the corresponding α-halo-lactones (VIIIa) and (VIIIc). The α-bromo-lactone is readily rearranged and converted into 2-methoxycarbonyl-3-oxa-5α-cholestane (Va) by boiling methanol but the α-choloro-lactone is unaffected by this treatment. Both the a-bromo-lactone and the or-chloro-lactone react with alkali to form 2-carboxy-3-oxa-5α-cholestane (Vb). α-Iodocholestan-3-one is unexpectedly converted into cholest-1-en-3-one in about 50% yield by trifluoro-peracetic acid. �� 2-Bromofriedelan-3-one did not undergo a Baeyer-Villiger reaction under the usual conditions, probably owing to the steric hindrance of the carbonyl group. The per-acid oxidation of 2β-hydroxyfriedelan-3-0110 yielded mainly the 2,3-seco-dicarboxylic acid and a smaller amount of the expected α-hydroxy-lactone. However 2β-acetoxyfriedelan-3-one underwent a Baeyer-Villiger oxidation in the expected fashion to give a high yield of the 2-acetoxy-lactone.

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EFFECT OF PERACETIC ACID OXIDATION ON N-CONTAINING COMPONENTS OF HUMIC MATERIALS

Canadian Journal of Soil Science ◽

10.4141/cjss80-059 ◽

1980 ◽

Vol 60 (3) ◽

pp. 541-548 ◽

Cited By ~ 19

Author(s):

M. SCHNITZER ◽

D. A. HINDLE

Keyword(s):

Amino Acid ◽

Peracetic Acid ◽

Amino Sugar ◽

Chemical Oxidation ◽

Acid Oxidation ◽

Mild Oxidation ◽

Total N ◽

Different Types ◽

Humic Materials ◽

Insight Into

Three humic and one fulvic acid were degraded by mild chemical oxidation with peracetic acid, with special emphasis on the effects of this type of oxidation on N-containing components. The different types of N that were considered were NH4+-N, amino acid-N, amino sugar-N, NO2−-N + NO3−-N, and by difference from total N, "unknown" N. The behaviour toward mild chemical oxidation of all four preparations was essentially similar: there were decreases in mino acid-N, amino sugar-N and "unknown" N, increases in NH4+-N, NO2−-N + NO3−-N with one material, and in N-gases. The "unknown" N was not inert. Between 16.6 and 59.1% of the latter appeared to be converted, as a result of mild chemical oxidation, to NH3 and N-gases which were expelled from the systems. The results presented provide an insight into what happens to N-containing humic components as a result of mild oxidation.

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Cp 2 TiCl 2 -catalyzed reaction of symmetrical alkynes with α,ω-dicarboxylic acid esters and ЕtAlCl 2 : An original pathway to С 5 -С 6 cyclic ketones and tetrasubstituted furans

Tetrahedron ◽

10.1016/j.tet.2018.04.008 ◽

2018 ◽

Vol 74 (20) ◽

pp. 2482-2487 ◽

Cited By ~ 1

Author(s):

Leila O. Khafizova ◽

Nuri M. Chobanov ◽

Mariya G. Shaibakova ◽

Natalya R. Popod'ko ◽

Tatyana V. Tyumkina ◽

...

Keyword(s):

Dicarboxylic Acid ◽

Cyclic Ketones ◽

Acid Esters

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Optimization of Human Tendon Tissue Engineering: Peracetic Acid Oxidation for Enhanced Reseeding of Acellularized Intrasynovial Tendon

Plastic & Reconstructive Surgery ◽

10.1097/prs.0b013e318205f298 ◽

2011 ◽

Vol 127 (3) ◽

pp. 1107-1117 ◽

Cited By ~ 29

Author(s):

Colin Y. L. Woon ◽

Brian C. Pridgen ◽

Armin Kraus ◽

Sina Bari ◽

Hung Pham ◽

...

Keyword(s):

Tissue Engineering ◽

Peracetic Acid ◽

Acid Oxidation ◽

Tendon Tissue ◽

Tendon Tissue Engineering ◽

Human Tendon

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Hydrotalcites as catalysts for the Baeyer–Villiger oxidation of cyclic ketones with hydrogen peroxide/benzonitrile

Tetrahedron ◽

10.1016/j.tet.2006.09.044 ◽

2006 ◽

Vol 62 (50) ◽

pp. 11697-11703 ◽

Cited By ~ 35

Author(s):

José Rafael Ruiz ◽

César Jiménez-Sanchidrián ◽

Rafael Llamas

Keyword(s):

Hydrogen Peroxide ◽

Cyclic Ketones ◽

Villiger Oxidation

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Pentafluoroperbenzoic acid as the efficient reagent for Baeyer–Villiger oxidation of cyclic ketones

Mendeleev Communications ◽

10.1016/j.mencom.2018.11.027 ◽

2018 ◽

Vol 28 (6) ◽

pp. 644-645 ◽

Cited By ~ 2

Author(s):

Ravil I. Khusnutdinov ◽

Tatyana M. Egorova ◽

Rishat I. Aminov ◽

Usein M. Dzhemilev

Keyword(s):

Cyclic Ketones ◽

Efficient Reagent ◽

Villiger Oxidation

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Asymmetric Baeyer–Villiger Oxidation of Cyclic Ketones Using Chiral Organoselenium Catalysts

Bulletin of the Chemical Society of Japan ◽

10.1246/bcsj.75.2233 ◽

2002 ◽

Vol 75 (10) ◽

pp. 2233-2237 ◽

Cited By ~ 26

Author(s):

Yoshihiro Miyake ◽

Yoshiaki Nishibayashi ◽

Sakae Uemura

Keyword(s):

Cyclic Ketones ◽

Villiger Oxidation

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Peracetic Acid Oxidation of Thiol Esters

Journal of the American Chemical Society ◽

10.1021/ja01174a505 ◽

1949 ◽

Vol 71 (6) ◽

pp. 2248-2249 ◽

Cited By ~ 4

Author(s):

Chester J. Cavallito ◽

Dorothy McKenica. Fruehauf

Keyword(s):

Peracetic Acid ◽

Acid Oxidation ◽

Thiol Esters

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Mechanism of interference with the Jaffé reaction for creatinine.

Clinical Chemistry ◽

10.1093/clinchem/33.7.1129 ◽

1987 ◽

Vol 33 (7) ◽

pp. 1129-1132 ◽

Cited By ~ 38

Author(s):

M H Kroll ◽

N A Roach ◽

B Poe ◽

R J Elin

Keyword(s):

Carbonyl Group ◽

Equilibrium Constants ◽

Molar Absorptivity ◽

Reaction Products ◽

Cyclic Ketones ◽

Common Structure ◽

Aliphatic Ketones ◽

Rate Of Reaction ◽

The Common

Abstract We investigated the mechanism of the Jaffé reaction for determination of creatinine by studying the spectrophotometric, kinetic, and equilibrium properties of the reaction of picrate with creatinine and with cyclic and aliphatic ketones. Absorbance spectra for the reaction products of picrate with all the ketones were superimposable with that of creatinine (Amax, 490 nm). Cyclic ketones not containing nitrogen had a molar absorptivity less than half that of creatinine and equilibrium constants approximately 0.01 that of creatinine. Aliphatic ketones, except for benzylacetone, had molar absorptivities similar to that of creatinine, but all of these compounds had equilibrium constants approximately a tenth or less that of creatinine. The common structure for all of the compounds reacting with picrate is the carbonyl group. The variable magnitude of interference for aliphatic and cyclic ketones is ascribable to the different rate constants, molar absorptivities, and equilibrium constants as compared with creatinine. Structures adjacent to the carbonyl group significantly affect the absorptivity and equilibrium constant, but steric hindrance is the major factor affecting the rate of reaction. We postulate that the carbonyl group is required for the Jaffé reaction, and we suggest a mechanism for the reaction.

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