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Review: Epoxidations of Alkenes with H2O2
GC_MS:
I don't have the Chem Lett reference, but it is not that hard to acquire.
If you would have read the Addendum during correction from the Synthesis article, you would have found an equally interesting sodium percarbonate (SPC) / sodium perborate (SPB) review:
A McKillop, W R Sanderson. Sodium perborate and sodium percarbonate: cheap, safe and versatile oxidising agents for organic synthesis. Tetrahedron 51(22) (1995) 6145-6166. DOI:10.1016/0040-4020(95)00304-Q
This review is complementary to the one published in Synthesis, and for sure is a must-read as well.
My interest was usually in SPB, and not SPC, because it was easier to get this compound in smaller quantities. I was unable to locate a company which wanted to deliver me less than 1 m3 SPC, or didn't make a 100x profit on the substane.
Useful SPB references in my collection:
1. Alexander McKillop, J A Tarbin. Functional group oxidation using sodium perborate. Tetrahedron 43(8) (1987) 1753-1758. DOI:10.1016/S0040-4020(01)81484-8
Abstract - Sodium perborate in acetic acid is an effective reagent for the oxidation of anilines to nitroarenes and of sulphides to either sulphoxides or sulphones. it is also an excellent reagent for the oxidative deprotection of ketone dimethylhydrazones. Baeyer-Villiger oxidation of ketones can be carried out with sodium perborate in either trifluoroacetic acid or acetic acid/trifluoroacetic acid mixtures, and hydroquinones and certain highly substituted phenols are smoothly converted into quinones.
2. Alexander McKillop, Duncan Kemp. Further functional group oxidations using sodium perborate. Tetrahedron 45(11) (1989) 3299-3306. DOI:10.1016/S0040-4020(01)81008-5
Abstract - Sodium perborate in acetic acid is an effective reagent for the oxidation of aromatic aldehydes to carboxylic acids, iodoarenes to (diacetoxyiodo)arenes, azines to N-oxides, and various types of sulphur heterocycles to S,S-dioxides. Nitriles are unaffected by the reagent in acetic acid, but undergo smooth dehydration to amides when aqueous methanol is employed as solvent.
3. Amalendu Banerjee, Banasri Hazra, Atashi Bhattacharya, Santanu Banerjee, Gopal C Banerjee, Saumitra Sengupta. Novel application of sodium perborate to the oxidation of aromatic aldehydes, ?-hydroxycarboxylic acids, 1,2-diketones, ?-hydroxyketones, 1,2-diols and some unsaturated compounds. Synthesis (1989) 765-766.
Abstract - Sodium perborate in acetic acid at 95°C oxidizes aromatic aldehydes, ?-hydroxycarboxylic acids, 1,2-diketones, benzoin, 1,2-diols and some unsaturated compounds.
4. Gaoyang Xie, Linxiao Xu, Jun Hu, Shiming Ma, Wei Hou, Fenggang Tao. Sodium perborate oxidations of cyclic and acyclic alkenes to oxiranes or vicinal acetoxy alcohols. Tetrahedron Letters 29(24) (1988) 2967-2968. DOI:10.1016/0040-4039(88)85059-7
Abstract - Under different reaction conditions, sodium perborate/acetic anhydride oxidized alkenes into oxiranes or vicinal acetoxy alcohols in good yields.
5. Pakawan Nongkunsarn, Chistopher A Ramsden. Oxidative rearrangement of imines to formamides using sodium perborate. Tetrahedron 53(10) (1997) 3805-3830. DOI:S0040-4020(97)00101-4
6. Didier Roche, Kapa Prasad, Oljan Repic, Thomas J Blacklock. Mild and regioselective oxidative bromination of anilines using potassium bromide and sodium perborate. Tetrahedron Letters 41 (2000) 2083-2085. DOI:10.1016/S0040-4039(00)00119-2
Abstract - The selective monobromination of various deactivated anilines using potassium bromide and sodium perborate as oxidant has been achieved. The use of ammonium molybdate as catalyst accelerates the rate of reaction but is not essential to obtain good yields and high selectivities.
7. G W Kabalka, K Yang, N K Reddy, C Narayana. Bromination of alkenes using a mixture of sodium bromide and sodium perborate. Synthetic Communications 28(5) (1998) 925-929.
Abstract - Bromination of alkenes with sodium bromide in the presence sodium perborate provides a simple, high yield route to dibromoalkanes.
8. B P Bandgar, Miss Neeta J Nigal. Regioselective catalytic halogenation of aromatic substrates. Synthetic Communications 28(17) (1998) 3225-3229.
Abstract - Regioselective chlorination and bromination of some aromatic substances have been carried out using KCl and KBr in presence of sodium perborate as an oxidant and sodium metavanadate, sodium tungstate, ammonium metavanadate and ammonium molybdate as efficient catalysts. This environmentally friendly catalytic halogenation method gave good yields of products under mild conditions.
Except for the McKillop review and the imine>formamide rearrangement article, all articles can be req'd.
Some notes: The Kabalka article can be applied on propenylbenzenes to yield their dibromo derivatives (tested in the lab). I tried a iodination as well, but the end product was not purified nor analysed. However, upon addition of KI to the acetic acid/SPB mixture, there was an immediate formation of I2 (colour) and heat.
The Xie article has been evaluated a loooong time ago (before I found this board) and seems to work as well. I used Ac2O as reactant/solvent though, so I don't know how many bees are waiting for this adaptations. Reaction was over very quickly though. The method is solvent sensitive. DCM, for instance, has been tested and failed. Usually, acetic acid or acetic anhydride (or trifluoro analogues) are involved.
Rhodium:
Here is the review from Tetrahedron. I didn't download the imine to formamide article, as it only concerned aromatic imines, and used trifluoroacetic acid as solvent.
Sodium perborate and sodium percarbonate: cheap, safe and versatile oxidising agents for organic synthesis. (Review)
A McKillop, W R Sanderson
Tetrahedron 51(22), 6145-6166 (1995) (https://www.thevespiary.org/rhodium/Rhodium/pdf/perborate-percarbonate.review.pdf)
DOI:10.1016/0040-4020(95)00304-Q
Rhodium:
As mentioned in Post 446838 (GC_MS: "SPC/SPB", Novel Discourse):
Sodium perborate oxidations of cyclic and acyclic alkenes to oxiranes or vicinal acetoxy alcohols
Gaoyang Xie, Linxiao Xu, Jun Hu, Shiming Ma, Wei Hou, Fenggang Tao
Tetrahedron Letters 29(24), 2967-2968 (1988) (https://www.thevespiary.org/rhodium/Rhodium/pdf/perborate-epoxidation.pdf)
DOI:10.1016/0040-4039(88)85059-7
Abstract
Under different reaction conditions, sodium perborate/acetic anhydride oxidized alkenes into oxiranes or vicinal acetoxy alcohols in good yields.
GC_MS:
In Post 446630 (missing) (GC_MS: "SPC alkene oxidation", Novel Discourse), they didn't use solely SPC but also urea-hydrogen peroxide for alkene epoxidation purposes. Here is an article describing the synthesis of urea.H2O2.
G S Patil, G Nagendrappa. Epoxidation of cyclic vinylsilanes by urea-hydrogen peroxide complex.
Synthetic Communications 32(17) (2002) 2677-2681. (https://www.thevespiary.org/rhodium/Rhodium/djvu/patil.djvu)
DOI:10.1081/SCC-120006032
[...]
Preparation of urea-hydrogen peroxide complex (UHP)
Urea (65 g, 1.08 mol) was dissolved in 100 mL water of 30% w/v of H2O2 (0.88 mol) by warming to 40°C on a water bath. The resultant clear solution was cooled to 5-10°C for 30 min, when white crystals of UHP precipitated, which were filtered and air dried overnight. The complex was further dried oon P2O5 in a vacuum desiccator and stored in a refrigerator; yield, 34 g (41% based on H2O2 used); mp 90-92°C (Lit mp 90-93°C). The dry UHP complex was found to be >98.5% pure on the basis of molar ration of H2O2 and urea as estimated by iodimetric titration method using standard sodium thiosulfate solution.
And yes, the SPC epoxidation method is being tested ;) .
Vitus_Verdegast:
The Urea-Hydrogen Peroxide Complex: Solid-State Oxidative Protocols for Hydroxylated Aldehydes and Ketones (Dakin Reaction), Nitriles, Sulfides, and Nitrogen Heterocycles.
Varma, Rajender S.; Naicker, Kannan P.
Organic Letters (1999), 1(2), 189-191
DOI:10.1021/ol990522n
CAN 131:102060, AN 1999:334353
An efficient solid-state oxidn. of org. mols. is described using a stable, inexpensive, and easily handled reagent, the urea-H2O2 adduct. The generality of the reaction was demonstrated in oxidn. of several mols., hydroxylated aldehydes and ketones (to hydroxylated phenols), sulfides (to sulfoxides and sulfones), nitriles (to amides), and N heterocycles (to N-oxides).
Asymmetric epoxidation of enones employing polymeric a-amino acids in non-aqueous media.
Bentley, Paul A.; Bergeron, Sophie; Cappi, Michael W.; Hibbs, David E.; Hursthouse, Michael B.; Nugent, Thomas C.; Pulido, Rosalino; Roberts, Stanley M.; Wu, L. Eduardo.
Chemical Communications (Cambridge) (1997), (8), 739-740
CAN 127:34072, AN 1997:330663
Urea-hydrogen peroxide complex in an org. solvent and in the presence of DBU and poly-(L)-leucine causes rapid asym. epoxidn. of the enones R1CH:CHCOR2 (R1 = R2 = Ph; R1 = CH:CHPh, R2 = 2-naphthyl; R1 = Ph, R2 = Me2CH, Me).
A very simple oxidation of olefins and ketones with UHP [urea-hydrogen peroxide] - maleic anhydride.
Astudillo, Luis; Galindo, Antonio; Gonzalez, Antonio G.; Mansilla, Horacio.
Heterocycles (1993), 36(5), 1075-80
CAN 119:202722, AN 1993:602722
The oxidn. of olefins and ketones to oxiranes and esters, resp., is carried out with the UHP (urea-hydrogen peroxide complex)-maleic anhydride system in a mild and very simple procedure. Byproducts urea and maleic acid are readily removed by filtration.
Enantioselective epoxidation of non-functionalized alkenes using a urea-hydrogen peroxide oxidant and a dimeric homochiral Mn(III)-Schiff base complex catalyst.
Kureshy, Rukhsana I.; Khan, Noor-ul H.; Abdi, Sayed H. R.; Patel, Sunil T.; Jasra, Raksh V.
Tetrahedron: Asymmetry (2001), 12(3), 433-437
DOI:10.1016/S0957-4166(01)00057-X
CAN 135:107192, AN 2001:259373
The catalytic enantioselective epoxidn. of chromenes, indene and styrene using a urea-hydrogen peroxide adduct as an oxidizing agent and a novel dimeric homochiral Mn(III)-Schiff base catalyst has been investigated in the presence of carboxylate salts and nitrogen and oxygen coordinating co-catalysts. Conversions of >99% were obtained with all alkenes except styrene. Abs. chiral induction, as detd. by 1H NMR using the chiral shift reagent (+)-Eu(hfc)3, was obtained in the case of nitro- and cyanochromene. The catalyst could be re-used for up to five cycles with some loss of activity due to degrdn. of the catalyst under epoxidn. conditions with retention of e.e.'s.
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