The Hive > Novel Discourse

Review: Epoxidations of Alkenes with H2O2

(1/3) > >>

Rhodium:
Metal-Catalyzed Epoxidations of Alkenes with Hydrogen Peroxide (Review)
Benjamin S. Lane and Kevin Burgess
Chem. Rev. 103(7) pp 2457 - 2474 (2003) (https://www.thevespiary.org/rhodium/Rhodium/pdf/metal-catalyzed.h2o2.epoxidation.review.pdf)
DOI:10.1021/cr020471z

Introduction

Hydrogen peroxide is probably the best terminal oxidant after dioxygen with respect to environmental and economic considerations. Indeed, in certain circumstances, it is better than oxygen insofar as O2/organic mixtures can sometimes spontaneously ignite. As a result, epoxidation systems that use hydrogen peroxide in conjunction with catalytic amounts of cheap, relatively nontoxic metals are potentially viable for large-scale production of inexpensive products, and for specialized applications in development, process, and research. The literature in this area is extensive and difficult to segregate into sharply delineated categories, but a fair way to attempt this is according to the catalyst precursors: "heterogeneous", "soluble metal oxides", and "homogeneous coordination complexes". Organic catalysts designed for asymmetric epoxidation may also function with hydrogen peroxide as a terminal oxidant, but they are beyond the scope of this review. The focus of this review is methods for the production of fine chemicals, but heterogeneous systems (more suitable for production of chemical commodities) are outlined for completeness.

GC_MS:
Thanks for the review, Rh. It was a nice read.

Among all things I have read in the review, there was one chapter which asked for more attention than the others, viz. "4.2 Simple metal salts". It mentions that (p 2642) [...] Bicarbonate is an essential component in this transformation. It forms peroxymoncarbonate ion, HCO4-, in this system; the presence of the intermediate was observed using NMR on mixing hydrogen peroxide and HCO3-. Such equilibria had previously been observed by Richardson et al. for formation of HCO4- from hydrogen peroxide and bicarbonate in other solvents 117, and HCO4- without metal was found to be a moderately active epoxidizing agent in aqueous acetonitrile 118.[...]

Peroxymonocarbonate? ... Sodium percarbonate!  ;D



http://www.scienceinthebox.com/en_UK/glossary/ingredientsafetyconsideration/percarbonate.shtml
http://www.solvayinterox.com/pcs.htm

I don't think I am unrealistic if I say that SPC - which even most Stimulant forum dwellers can find out to be OTC - might have something to offer us. Maybe a spoontip of the right catalyzing salt and SPC, and there might be no more need for HCOOH/H2O2, or AcOH/H2O2. Who knows...  ;) . SPC is rather useful substance... Post 377353 (GC_MS: "Sodium percarbonate and the Dakin reaction", Novel Discourse).

If somebee has access to JACS, would (s)he be so kind to check out references 116 through 119 (from the review), and post them if they are interesting?

Rhodium:
A Cheap, Catalytic, Scalable, and Environmentally Benign Method for Alkene Epoxidations
Benjamin S. Lane and Kevin Burgess
J. Am. Chem. Soc. 123(12), 2933-2934 (2001) (https://www.thevespiary.org/rhodium/Rhodium/pdf/epoxidation.h2o2-mnso4.pdf)
DOI:10.1021/ja004000a

Bicarbonate Activation of Hydrogen Peroxide: Oxidation of Sulfides by Peroxymonocarbonate
David E. Richardson, Huirong Yao, Karen M. Frank, and Deon A. Bennett
J. Am. Chem. Soc. 122(8), 1729-1739 (2000) (https://www.thevespiary.org/rhodium/Rhodium/pdf/peroxymonocarbonate.pdf)
DOI:10.1021/ja9927467

Epoxidation of Alkenes with Bicarbonate-Activated Hydrogen Peroxide
Huirong Yao and David E. Richardson
J. Am. Chem. Soc. 122(13), 3220-3221 (2000) (https://www.thevespiary.org/rhodium/Rhodium/pdf/epoxidation.bicarbonate-activated.h2o2.pdf)
DOI:10.1021/ja993935s

Manganese-Catalyzed Epoxidations of Alkenes in Bicarbonate Solutions
Lane, B. S.; Vogt, M.; DeRose, V. J.; Burgess, K.;
J. Am. Chem. Soc. 124(40), 11946-11954 (2002) (https://www.thevespiary.org/rhodium/Rhodium/pdf/epoxidation.h2o2-mn-hco3.art.pdf)
DOI:10.1021/ja025956j
Supplementary Information (http://pubs.acs.org/subscribe/journals/jacsat/suppinfo/124/i40/ja025956j/ja025956j_s1.pdf)

Rhodium:
These epoxidations, especially the last one, shows a lot of promise for our purposes - styrene being epoxidized in close to quantitative yield using aqueous bicarbonate and hydrogen peroxide with a little MnSO4 as catalyst, which in turn is easily made from KMnO4, just substitute the acetic acid with H2SO4 in my archived preparation of manganous acetate (https://www.thevespiary.org/rhodium/Rhodium/chemistry/manganous.acetate.html). For the water-insoluble alkenes they use an organic co-solvent (DMF/MeCN/tBuOH) but isopropanol will probably also do, as the solvent is not participating in the reaction.



Possibly the reaction can be performed in a dual-phase setup, with the alkene in a DCM phase and the inorganics in an aqueous phase if a PTC is added - the great thing about the DCM being that it will automatically act as a heatsink, carrying away the heat from the exothermic reaction by boiling, thus keeping the reaction relatively cool even if the hydrogen peroxide is added relatively quickly (and not over 36h as they currently do on a full molar scale).

Rhodium:
GC_MS - as you are so interested in percarbonate and epoxidations, do you have these articles?

Sodium Percarbonate (SPC) As A Hydrogen Peroxide Source For Organic Synthesis
Chem. Lett. 665-666 (1986)

Abstract: Sodium percarbonate (SPC) is an inexpensive, stable, safe and commercially available material which may be used as a hydrogen peroxide source for organic synthesis. Epoxidation, amine and sulfide oxidation reactions were simply performed with the solid reagent in moderate to excellent yield.

Sodium Perborate and Sodium Percarbonate in Organic Synthesis
Synthesis 1325-1347 (1995)

Abstract: This article reviews the oxidation of organic compounds carried out with either sodium perborate or sodium percarbonate as an oxygen source. Special attention is drawn to the differences in results provided by these two oxidants and to the influence of experimental conditions.

Sodium perborate and sodium percarbonate: further applications in organic synthesis
Alexander McKillop and William R. Sanderson 
J. Chem. Soc., Perkin Trans. 1, 2000, (4), 471 - 476 (Free access!)
DOI:10.1039/a804579h

Abstract: Review of the literature covering the years 1995 to 1998.

Navigation

[0] Message Index

[#] Next page