Oxidative cleavage of α-diols, α-diones, α-hydroxy-ketones and α-hydroxy- and α-keto acids with calcium hypochlorite [Ca(OCl)2].

doi:10.1016/S0040-4039(00)88578-0

Tetrahedron Letters

Volume 23, Issue 31, 1982, Pages 3135-3138

https://doi.org/10.1016/S0040-4039(00)88578-0 Get rights and content

Abstract

α-Diols, α-diones, α-hydroxy ketones, and α-hydroxy- and α-keto acids are easily cleaved oxidatively with calcium hypochlorite. The reaction is carried out at ambient temperature in aqueous acetonitrile/acetic acid solution. The yields are good to excellent and the products, depending on the starting material, are aldehydes, ketones or acids.

References (18)

L.J. Heidt et al.
Tappi
(1945)
W. Rigby
J. Chem. Soc.
(1950)
Kenneth B. Wiberg
R.C. Cambie et al.
J. Chem. Soc.
(1978)
R. Criegee et al.
Ann.
(1939)
K.H. Pausacker
J. Chem. Soc.
(1953)
A.Y. Drummond et al.
J. Chem. Soc.
(1953)
A.Y. Drummond et al.
J. Chem. Soc.
(1955)
Robert L. Augustine
B. Jaselskis et al.
J. Am. Chem. Soc.
(1964)

There are more references available in the full text version of this article.

Cited by (56)

Selective oxidation of vinylbenzenes & acyloins in the presence of silver catalyst using molecular oxygen as terminal oxidant
2023, Tetrahedron Letters
Selective oxidation of styrene to benzaldehyde continues to be a quest for synthetic chemists. A number of transition metal based, metal free, nanocomposite-based catalysts have been developed for this transformation. We hereby report the oxidation of styrene into corresponding benzaldehydes using molecular oxygen as oxidant in the presence of catalytic amount of Ag₂O. The reaction proceeded with a well-known oxidation of styrene-to-styrene oxide giving intermediates which lead to decarboxylative generation of aldehydes. One such intermediate was hydroxyketone. In view of the formation of hydroxyketone intermediate, we explored the oxidative dehomologation of α-hydroxy ketone via decarboxylation of 2-oxo-2-phenylacetic acid into benzoic acid using the same strategy. Both the reactions exhibited high functional group tolerance and a broad substrate scope.
Simple and low-cost transition metal-free borophosphate glass catalyst for aromatic alcohol oxidation by sodium hypochlorite
2022, Journal of Materials Research and Technology
Citation Excerpt :
Stevens and co-workers applied “Swimming Pool Chlorine” (an inexpensive commercial sodium hypochlorite solution) to oxidize secondary alcohols to ketones [21] and diols/aldehydes to their respective ketones and methyl esters [22]. At the same time, calcium hypochlorite was applied to oxidize secondary methyl ethers into ketones [23], aldehydes to their corresponding carboxylic acids [24], secondary alcohols to ketones, primary alcohols to esters, and ethers to esters [25]. All these applications report hypochlorite as a versatile, effective, safer, and potential substitute for traditional chromium VI salts [3] and pyridine-based [4] oxidants in organic synthesis.
The oxidation of primary and secondary alcohols to their respective aldehydes/ketones is one of the most important reactions in fine chemistry due to the industrial application of these products. Based on this, a large number of new catalysts and oxidants have been tested using this reaction as a catalytic model, mainly looking for a process that ensures high aldehyde selectivity. In this paper, we have used moisture stable borophosphate glass doped with 10 mol% Al₂O₃ as a heterogeneous catalyst in the oxidation of sodium hypochlorite, an effective, greener, and low-cost oxidant, using acetonitrile as solvent under mild conditions. The glass catalyst mass and the particle size were evaluated, as were the reaction temperature and oxidant amount, to determine the ideal reaction conditions where the conversions achieved 87.0 mol% for 1-phenylethanol to acetophenone and 79.4 mol% for benzyl alcohol to benzaldehyde, with benzaldehyde selectivity above 95%. Although sodium hypochlorite is a strong oxidant, benzaldehyde was the main product of the oxidation of benzyl alcohol due to the formation of a biphasic organic-aqueous system that protects the aldehyde from oxidation and allows the reaction to occur without the use of a phase transfer catalyst (PTC). HPLC analysis of both phases showed that alcohols, aldehyde, and ketone were mostly present in the organic phase (concentrations above 98.7%). During the reaction, a small amount of alcohol is transferred to the aqueous phase, where the oxidation took place. Once formed, the products are transferred back to the organic phase. ICP-OES analysis indicates that borophosphate glass acts in the reaction by partially releasing phosphate-based groups, reducing the pH of hypochlorite to 9. In this sense, borophosphate glasses prove to be a simple and inexpensive alternative for the development of new catalysts.
Deciphering the chemical instability of sphaeropsidin A under physiological conditions-degradation studies and structural elucidation of the major metabolite
2020, Organic and Biomolecular Chemistry
The fungal metabolite sphaeropsidin A (SphA) has been recognised for its promising cytotoxicity, particularly towards apoptosis- and multidrug-resistant cancers. Owing to its intriguing activity, the development of SphA as a potential anticancer agent has been pursued. However, this endeavour is compromised since SphA exhibits poor physicochemical stability under physiological conditions. Herein, SphA's instability in biological media was explored utilizing LC-MS. Notably, the degradation tendency was found to be markedly enhanced in the presence of amino acids in the cell medium utilized. Furthermore, the study investigated the presence of degradation adducts, including the identification, isolation and structural elucidation of a major degradation metabolite, (4R)-4,4′,4′-trimethyl-3′-oxo-4-vinyl-4′,5′,6′,7′-tetrahydro-3′H-spiro[cyclohexane-1,1′-isobenzofuran]-2-ene-2-carboxylic acid. Considering the reduced cytotoxic potency of aged SphA solutions, as well as that of the isolated degradation metabolite, the reported antiproliferative activity has been attributed primarily to the parent compound (SphA) and not its degradation species. The fact that SphA continues to exhibit remarkable bioactivity, despite being susceptible to degradation, motivates future research efforts to address the challenges associated with this instability impediment.
Vanadium catalyzed aerobic carbon-carbon cleavage
2015, Coordination Chemistry Reviews
Citation Excerpt :
Since the earliest discovery in 1928 [26,27], the cleavage of 1,2-diols has been traditionally performed with stoichiometric high-valent inorganic oxidants, like periodates [28,29] or lead tetracarboxylates [30,31]. Occasionally, other reagents such as chromium trioxide [32,33], manganese dioxide [34,35], iron(III) trisphenantrolines [36], calcium hypochlorite [37], pyridinium chlorochromate [38], N-iodosuccinimide, [39] have been also used. However, most of these oxidants suffer from severe drawbacks in terms of toxicity and issues related to their storage, handling, cost and solubility.
In recent years, the use of vanadium complexes as catalysts and air or oxygen as oxidants has emerged as a new method for the effective oxidative carbon–carbon bond cleavage in a series of substrates, including 1,2-diols and α-hydroxy ethers. In addition to the advantageous use as a synthetic tool, vanadium catalyzed aerobic CC bond cleavage becomes even more appealing if applied to the degradation of lignocellulosic biomass and in particular in the oxidative depolymerization/degradation of lignin or cellulose. In this review, this chemistry, the most recent advances and the role played by homogeneous vanadium complexes are presented and discussed.
Heterogeneously catalyzed oxidation of butanediols in base free aqueous media
2014, Tetrahedron
Citation Excerpt :
For instance, oxidants other than oxygen have been used including H2O2, and pyridinium bromochromate.15,16 In addition, solvents, such as acetonitrile, and alkaline or acidic media have been used.17–20 Homogeneous catalysts have been successfully used21 but the difficulty of catalyst recovery and reuse has to be overcome.
The oxidation of four butanediols under base-free conditions has been investigated using a set of Au, Pd and Pt catalysts prepared using sol-immobilization. The supported nanoparticles are found to be active with bimetallic alloys having much higher activity when compared with the monometallic counterparts. In general the AuPt catalysts are the most active and in all cases the corresponding C4 oxidation products were observed with high selectivity; sequential reaction of these products leads to the formation of acetic acid as an undesired by-product.
A metal-free protocol for direct oxidative de-alkoxycarbonylation of alkyl phenyl acetate by molecular iodine
2014, Tetrahedron Letters

View all citing articles on Scopus

¹: Dreyfus Teacher-Scholar 1979–1984.

View full text

Oxidative cleavage of α-diols, α-diones, α-hydroxy-ketones and α-hydroxy- and α-keto acids with calcium hypochlorite [Ca(OCl)2].

Abstract

Tappi

J. Chem. Soc.

J. Chem. Soc.

Ann.

J. Chem. Soc.

J. Chem. Soc.

J. Chem. Soc.

J. Am. Chem. Soc.

Oxidative cleavage of α-diols, α-diones, α-hydroxy-ketones and α-hydroxy- and α-keto acids with calcium hypochlorite [Ca(OCl)₂].