Process for preparation of trimethylsulfoxonium salts. It has a molecular formula c3h9ios and mass of 220. Reaction of trimethylsulfonium iodide with a stron. Trimethylsulfoxonium iodide cas 1774476 scbt santa. Articles of trimethylsulfoxonium iodide are included as well. When dmso reacted with iodomethane, trimethylsulfoxonium iodide 630 was formed. Jul 08, 2019 the johnsoncoreychaykovsky epoxidation is one of the oldest methods for the synthesis of terminal epoxides from carbonyl compounds. Trimethylsulfoxonium iodide cas number is 1774476, molecular formula is c3h9ios, molecular weight is 220. Dimethyloxosulfonium methylide known as the coreychaykovsky reagent is a valuable alternative to dimethylsulfonium methylide and can be generated from trimethylsulfoxonium iodide. Trimethylsulfoxonium iodide supplier distributor cas 1774476. Trimethylsulfoxonium iodide ng major reference works wiley. The organic layer was extracted and washed with brine, dried.
Herein we present a simplified extension of the johnsoncoreychaykovsky epoxidation, where ketoacids are employed as the substrates and commercially available trimethylsulfoxonium iodide is employed as the carbonatom homologating reagent. Preferred preparation of substituted diphenylacetic acids. Sodium hydride was very effective in this reaction provided that. The present invention is concerned with an improved process for the preparation of trimethylsulfoxonium bromide. Physical properties of ethers the oh group of alcohols act as both an. Trimethylsulfoxonium iodide and potassium tertbutoxide in dimethyl sulfoxide dmso is a very efficient process for the multi kilogram scale preparation of. It may be prepared by the reaction of dimethyl sulfoxide and iodomethane. Me 3 soi, lio t bu r o r o dmso in dried and cleaned round bottom flask, charged with trimethylsulfoxonium iodide 15 mmol, 1. In our hands, as well as reported in the literature, the aldehydes are unstable. The organic layer was extracted and washed with brine, dried over sodium sulfate and. For example, the reaction of dimethyl sulfide with iodomethane yields trimethylsulfonium iodide. This chemical is used for the synthesis of methylene transfer reagents that are required in the preparation of epoxides. Nomenclature of ethers, epoxides, and sulfides please read 16.
An epoxide olefination acs publications american chemical. Structure, properties, spectra, suppliers and links for. Li, a medicinal chemist, summarizes name reactions relevant to heterocyclic chemistry. Trimethylsulfoxonium iodide, trimethylsulfoxonium iodide in. The mixture was stirred and heated under reflux for 3 days and allowed to reach 25 oc.
Titration is the concept of stoichiometry applied to find the unknown concentration of a solution. Us6657057b2 us10,797 us79702a us6657057b2 us 6657057 b2 us6657057 b2 us 6657057b2 us 79702 a us79702 a us 79702a us 6657057 b2 us6657057 b2 us 6657057b2 authority us united states prior art keywords agent process water methylcobalamin trimethylsulfoxonium prior art date 19991209 legal status the legal status is an assumption and is. An extra oxygen atom can bond to the sulfur atom to yield the trimethylsulfoxonium ion. Treatment with strong base yields the dimethylsulfonium methylide which reacts insitu with the carbonyl group of ketones to form epoxides or allylic alcohols. The latter compound is used as a methylenetransfer reagent, and is used to prepare epoxides. Buy high quality trimethylsulfoxonium iodide 1774476 from toronto research chemicals inc. The world of chemical analysis can be divided into two basic types. This was oxidized to 4methoxybenzaanthraquinone ii which was treated with methylmagnesium iodide and the grignard complex slowly added to hi in methanol affording 4methoxy7iodomethyl12. Trimethylsulfoxonium salts have a number of uses within the chemical industry, and are particularly useful when utilized as the trimethylsulfoxonium salt of nphosphonomethylglycine which is an effective herbicide. Nov 25, 1986 the present invention relates to a process for the preparation of trimethylsulfoxonium salts.
China high purity trimethylsulfoxonium iodide 1774476. Technical grade powder trimethylsulfoxonium iodide, for. Reaction of trimethylsulfonium iodide with a strong base such as nah in dimethyl sulfoxide dmso produces dimethylsulfonium methylide, a very useful sulfur ylide reagent. Trimethylsulfoxonium iodide, trimethylsulphoxonium iodide,trimethylsulfonium iodide 2181422, trimethylsulfoxoniumiodid suppliers in india. Trimethylsulfoxonium iodide, china trimethylsulfoxonium iodide, trimethylsulfoxonium iodide lowest price manufacturer supplier in china, offering high purity trimethylsulfoxonium iodide 1774476, cas 82034466 high purity loteprednol etabonate powdew, good quality best price loteprednol etabonate cas 82034466 and so on. Name reactions in heterocyclic chemistry jie jack li. Trimethylsulfoxonium iodide trimethyl sulphoxonium iodide. The reaction is an unusual example of cobaltcatalysed. Where one finds at the composition of a compound i. The reaction mixture was diluted with etoac and water and the layers were separated. Ketones and aromatic aldehydes were epoxidized in satisfactory to excellent yields with trimethylsulfonium iodide as an ylide precursor and. Trimethylsulfoxonium iodide 1774476 buy and find out price and availability, msds, properties of tcis high quality specialty chemicals.
As with the dimethyl sulfide derivative, treatment with a strong base such as n butyllithium generated the corresponding ylid, dimethylsulfoxonium methylid 631. Trimethylsulfoxonium iodide specification with the cas registry number 1774476, trimethyl sulphoxonium iodide is also named as sulfonium, trimethyl, iodide, oxide. The first coreychaykovsky epoxidation and cyclopropanation using trimethyl sulfonium iodide trimethyl sulfoxonium iodide and koh as base in the recyclable ionic liquid, bmimpf 6 are described. The improvement in the process comprises the addition of a scavenger to the reaction mixture of dimethyl sulfoxide and methyl bromide. The use of trimethylsulfoxonium iodide under different basic conditions as described did not afford the expected epoxyde i, only degradation products have been observed. Ylides are neutral molecules that have two oppositely charged atoms, each with an octet of electrons, directly bonded to each other. The process allows to prepare in good yields 17spiro epoxides, which can be easily transformed into 17spironolactosteroids. A number of catalysts that were examined either partially or completely suppressed the reaction of 1 to 3, returning unchanged starting material, epoxide 1 table 1, entries 15. On the other hand, trimethylsulfonium iodide under ptc conditions gave the expected oxiranes with yields varying from 60 % to 80% see table. Pdf trimethylsulfonium and trimethylsulfoxonium as. The procedure utilizes trimethylsulfoxonium iodide nah to convert the benzophenone 1 to the corresponding epoxide 2, which then undergoes rearrangement to the aldehyde 3 using bf 3et 2o. Ep1903051a2 epoxidation of 17oxo15,16methylene steroids.
Examples involving epoxides generated in situ by use of trimethylsulfoxonium. Instead, the enone was smoothly reduced to the allylic alcohol, and a furukawamodified simmonssmith reaction 35 afforded the cyclopropyl alcohol 22 in high yield. It can be treated with a strong base to form an ylide, which reacts with the ketone and carbonyl of the aldehyde to form an epoxide. We started our study by investigating the best reaction conditions for the epoxide ringopening reaction between racemic epoxide 9 and the lithium anion of 1,2dimethoxybenzene. The stereoselectivity is established during the formation of the epoxide, but clearly cannot be explained in terms of 1,2. Working with hazardous chemicals organic syntheses. Scheme 1 traces of cobalt salts divert the known ring expansion of epoxide 1 to oxetane 3, instead delivering homoallylic alcohol 4. A process for the epoxidation of 17oxo15,16methylene steroids, in particular of drospirenone precursors, comprising the use of sulfoxonium ylides, in particular of dimethylsulfoxonium methyl ylide. Trimethylsulfoxonium chloride has greater solubility in thf than trimethylsulfoxonium iodide. It is used to generate dimethyloxosulfonium methylide by reaction with sodium hydride. The latter compound is used as a methylenetransfer reagent, and is usedto prepare epoxides. Treatment with strong base yields the ylide which adds to the carbonyl group of ketones and aldehydes to give epoxides.
A series of sulfoxonium salts have been used for the synthesis. In general, the co bonds of ethers have low reactivity. Structure and bonding in ethers and epoxides the ether oxygen is sp3hybridized and tetrahedral. Us6657057b2 process for production of methylcobalamin. Examples involving epoxides generated in situ by use of trimethylsulfoxonium ylide starting from free anomeric carbohydrates, followed by the expected cyclization, are presented in scheme a. Remarkable influence of cobalt catalysis on epoxide ring. Preparation of epoxides trimethylsulfoxonium iodide cas. Material on each name reaction includes a description, historical perspective, and mechanism of reaction, as well as information on variations and improvements, synthetic utility, experiments, and references. Trimethylsulfoxonium iodide, 98% section 1 chemical product and company identification msds name. B 2, 2disubstituted epoxides were prepared according to literatures,910 the method has modified as followed. An expanded survey of transitionmetal catalysts has confirmed that cobalt salts uniquely instead deliver homoallylic alcohol products from epoxides, with retention of the original epoxide stereochemistry.
Trimethylsulfoxonium iodide, trimethylsulfoxonium iodide. The ylides are generated in situ by the deprotonation of sulfonium halides with strong bases dimethyloxosulfonium methylide known as the coreychaykovsky reagent is a valuable alternative to dimethylsulfonium methylide and can be generated from trimethylsulfoxonium iodide. Us4141920a us05831,726 us83172677a us4141920a us 4141920 a us4141920 a us 4141920a us 83172677 a us83172677 a us 83172677a us 4141920 a us4141920 a us 4141920a authority us united states prior art keywords reaction bromide scavenger preparation process prior art date 19770909 legal status the legal status is an assumption and is not a legal conclusion. It is used to generate dimethyloxosulfonium methylide by reaction with sodium hydride the latter compound is used as a methylenetransfer reagent, and is used to prepare epoxides.
A new approach for the synthesis of the core skeleton of icetexane diterpenoids is presented and deals with an epoxide ringopening reaction by metallated aromatic compounds. Epoxide formation from aldehydes and ketonesa modified. Name reactions in heterocyclic chemistry jie jack li download. Reactions of epoxides with boronic acids basefree ni. A comparative study article pdf available in archive for organic chemistry 20002 january 2000 with 30 reads. To assure its proper activity, tri methyl sulphoxonium iodide must be stored at the temperature below 30 degree celsius. The coreychaykovsky reaction or sometimes known as johnsoncoreychaykovsky reaction is employed in modern organic synthesis to prepare three membered rings like epoxides oxiranes, thiiranes, aziridines and cyclopropanes by reacting sulfur ylides with electrophiles such as carbonyls, thiocarbonyls, imines and olefins. Trimethylsulfoxonium iodide ng major reference works. Nmr second moments m2 and spinlattice relaxation times in the laboratory and rotating frame t1 and t1 rho for trimethyloxosulphonium fluoride, chloride, bromide and iodide are reported over a. Trimethyl sulphoxonium iodide get latest price due to our honest business standards and transparent deals, we are steadily making our way to the platform of success by offering a superior quality range of trimethylsulfoxonium iodide that is a sulfoxonium salt.
Figure 1 jacobsen co iii salen hydrolytic kinetic resolution hkr catalyst. Trimethylsulfoxonium iodide, trimethylsulphoxonium iodide. Trimethylsulfonium and trimethylsulfoxonium as versatile. Trimethylsulfonium and trimethylsulfoxonium as versatile epoxidation reagents. Buy trimethylsulfoxonium iodide cas 1774476, a product for proteomics research, from santa cruz. Tri methyl sulfoxonium iodide manufacturer, tri methyl.
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