I have linked to the english version of the swern reaction. An efficient procedure for conversion of alcohols to the corresponding carbonyl compounds, an alternative to the classical swern oxidation, is described. The process produces foul smelling dimethyl sulfide gas. The microreactor process offers significant advantages over the batch process. Sep 15, 2010 the oxidation of primary and secondary alcohols to carbonyl compounds aldehydes and ketones from dimethyl sulfoxide dmso in combination with oxalyl chloride and triethylamine under anhydrous conditions is generally known as the moffattswern oxidation. Mechanism, references and reaction samples of the swern oxidation.
The swern oxidation, named after daniel swern, is a chemical reaction whereby a primary or secondary alcohol is oxidized to an aldehyde or ketone using oxalyl chloride, dimethyl sulfoxide dmso and an organic base, such as triethylamine. The swern oxidation of alcohols avoids the use of toxic metals such as chromium, and can be carried out under very mild conditions. Swern oxidation of different alcohols is performed in a continuous flow microreactor system. Swern oxidation the swern oxidation is an organic reaction used to convert a primary alcohol to an aldehyde and a secondary alcohol to a ketone using dmso, oxalyl chloride, and triethylamine. Directly following this ratedetermining step is the intramolecular syn. Translating a batch reaction to a continuous flow reaction. This reaction allows the preparation of aldehydes and ketones from primary and secondary alcohols, resp.
C, followed by triethylamine, is known as swern oxidation. Organic chemistry portal swern oxidation of alcohols with ionsupported. A practical and efficient alternative version of the swern oxidation has been. A swern oxidation to the aldehyde, followed by a modified hornerwadsworthemmonstype 57 reaction afforded enyne 171.
Soluble polystyrenebased sulfoxide reagents for swern author. Swern oxidation refers to the organic reaction where oxalyl chloride, organic base, and dimethyl sulfoxide are employed for the oxidation of 10 and 20 alcohols to aldehydes or ketones. The parikhdoering oxidation uses so 3 py a solid reagent that can be handled easily as the activator of dmso. The oxidation of a primary or secondary alcohol to afford, respectively, an aldehyde or a ketone, when treated with oxalyl chloride and dimethyl sulfoxide at very low temperature below 60. Article views are the countercompliant sum of full text article downloads since november 2008 both pdf and html across all institutions and individuals. The oxidation of primary and secondary alcohols with ionsupported methyl sulfoxide and oxalyl chloride in the presence of triethylamine in dichloromethane efficiently gives carbonyl compunds in good yields with high purity. Example procedures for the conversion of an alcohol to an aldehyde using swern oxidation.
Unlike the swern reaction, the reaction works at room temperature and is less prone to the methylthiomethyl ether byproduct formation. A solution of oxalyl chloride 140 mmol in 50 ml of freshly distilled ch2cl2 was cooled to. Soluble polystyrenebased sulfoxide reagents for swern. Swern oxidation oxalyl chloride, dmso, net3, 78 c, 1 h of 23 provided. Methyltrichlorosilane as an effective activation agent for swern. Notable rearrangements of the sulfone group include the rambergbacklund reaction and the trucesmiles rearrangement. Soluble polystyrenebased sulfoxide reagents for swern oxidation reactions.
Trichloroisocyanurictempo oxidation of alcohols under mild. Swern oxidation, microreactor, benzaldehyde, benzyl alcohol. This reaction is especially effective for the oxidation of allylic and secondary alcohols. The swern oxidation is one of the most useful methods for the conversion of primary and secondary alcohols to aldehydes and ketones, respectively. Procedure to a solution of oxalyl chloride 5 mmol and 3 a ms in ch 2 cl 2 1 ml at 78 c under n 2 is added dropwise a solution of dmso 10 mmol in ch 2 cl 2 1 ml. Dimethyl sulfoxide, which is at the same oxidation level as salt 24, reacts with oxalyl chloride 23 to liberate carbon monoxide, carbon dioxide and reagent 24. A mild and efficient alternative to the classical swern oxidation. A mechanistic rationale is proposed in which the kinetic acidity of a. Dcc pfitznermoffatt, tfaa modified swern, acetic anhydride albrightgoldmann, and so 3pyridine parikhdoering are alternative reagents used to activate dmso, but oxalyl chloride is a good choice in terms of causing less side reactions. The moffattswern oxidation mso is a multistep, versatile, metalfree reaction by which alcohols are transformed into aldehydes and ketones.
Phosphorus, sulfur, and silicon and the related elements. The list of named reactions quickly shows all the organic reactions listed in alphabetical order. Oct 24, 2006 abstract the swern oxidation of acyclic and cyclic. Nov 07, 2011 for a lot more videos, worksheets, problem sessions and 3d models on chemistry check out epistemeo. The swern oxidation of alcohols avoids the use of toxic metals such as chromium as in the method of jones oxidation, which is a chemical reaction described as the chromic acid oxidation of primary and secondary alcohols to carboxylic acids and. Oxidation of alcohols to the corresponding carbonyl compounds using cocl2, dmso, and quenching with et3n. Files are available under licenses specified on their description page. Request pdf swern oxidation oxidation of alcohols to the corresponding carbonyl compounds using cocl2, dmso, and quenching with et3n. Below is a standard procedure for the swern oxidation of an alcohol. Subsequent desilylation, swern oxidation, nucleophilic addition of vinylmagnesium bromide to the resulting aldehyde, and acetate formation yielded the dienyne 172 as a 1. The swern oxidation of structurally diverse alcohols 3,4,7, and11 employing the oxalyl chloridedmso protocol. However, the conventional method with use of the volatile oxalyl chloride as an activator requires the reaction to be conducted below. If you are using the second edition of klein organic chemistry, this discussion of the swern oxidation of alcohols is not included. It is the same publisher and the content is similar.
Department of chemistry, the university of hong kong, pokfulam road, hong kong, p. Selective oxidation of alcohols by dmsosio 2 cl system. Swern oxidation proceedure michigan state university. Download hires imagedownload to mspowerpointcite this. Following the dropwise addition of a solution of dimethylsulfoxide 211 ml, 2. The swern oxidation, named after daniel swern, is a chemical reaction whereby a primary or. See the article on dimethyl sulfide for a more realistic description.
In swern oxidation, the primary or secondary alcohols are oxidized to aldehydes or ketones respectively by treating them with dimethyl sulfoxide dmso activated by oxalyl chloride at low temperatures 78 o c to 60 o c and then with an organic base like triethyl amine. The mechanism begins with the activation of dsmo with oxalyl chloride which is then attacked by a chloride anion to form a chlorosulfonium cation and. Another dmso based oxidation predates the swern oxidation, and uses a mixture of dmso and 1,3dicyclohexylcarbodiimide dcc in the presence of an acid catalyst to generate an intermediate e. Aldehydes do not react further to give carboxylic acids. Swern oxidation of 3 occurs if the workup conditions are modified or if diazabicycloundecane dbu rather than triethylamine tea is used as the base in the reation. I think the statement one of the most foul odors known in organic chemistry. Moffat, swern oxidation dmso in combination with an activating agent usually an acylating agent or an acid and an amine base is a very mild and selective reagent for oxidation of alcohols to aldehydes and ketones. All structured data from the file and property namespaces is available under the creative commons cc0 license. General characteristicsthe oxidation of alcohols based on the dimethylsulfoxide dmsooxalyl chloride system is called the swern oxidation. Oct 15, 2004 oxidation of alcohols to carbonyl compounds via alkoxysulfonium ylides. If you havent done a swern oxidation before, and your substrate is hard to make or expensive, it might be worth doing a test reaction on a similar substrate or really any other nonvolatile 1. Reactions oxidant in a process termed swern oxidation.
The reaction is known for its mild character and wide tolerance of functional groups. For a lot more videos, worksheets, problem sessions and 3d models on chemistry check out epistemeo. A new mild and selective method for oxidation of primary and. Sulfoxide and oxalyl chloride daisuke tsuchiya, katsuhiko moriyama.
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