Acute shortterm inhalation exposure to high levels of methylhydrazine may cause lacrimation, eye redness, nasal and respiratory irritation, headache, malaise, vomiting, diarrhea, ataxia, anoxia, cyanosis, tremors, and convulsions in humans. The orders of the decomposition reactions with respect to dimethyl trisulfide dmts, dimethyl tetrasulfide dm4s and dimethyl pentasulfide dm5s are 2. C2h3f3o3s, f3cso3ch3, methyl triflate section 2 hazards identification chemwatch hazard ratings min max flammability. It also serves as an alternative way to navigate the website, and as a means of coming up with retrosynthetic ideas.
Here we demonstrate the improved syntheses of these. Reduction with copper0 powder occurs quickly in most cases to form the copperi catalysts. Murphy westchem, department of pure and applied chemistry, university of strathclyde 295 cathedral street, glasgow g1 1xl united kingdom. The key point of this single methyl transfer stems from the use of hfip as the solvent that interferes with amines and avoids overmethylation. Although the triflate ion is not generally perceived as a nucleophile, many examples. The magic methyl banned vs meotf, mei, meoso2ome which are not banned example was just to show that there is another side to regulations and practices. Although the triflate ion is not generally perceived as a nucleophile, many examples of its behavior as such exist in the literature. The extensively crossreferenced book enables readers to avoid explosion and loss of containment of chemicals. Photocatalytic decomposition of methyl red dye by using.
For example, nbutyl triflate can be written as ch 3 ch 2 ch 2 ch 2 otf. A simple synthesis of 11cmethyl triflate sciencedirect. Jan 10, 2017 however, magic methyl is about as reactive i want to say toxic as methyl triflate meoso2cf3 which is still available for use. These radioligands are synthesized by methylation of the respective demethyl precursor with 11cmethyl iodide. Fso2me is awfuly volatile, so it is easy to poison yourself. Sciencemadness discussion board nitronium triflate. Methyl d3 triflate is a commonly used methylating reagent used in synthetic preparations of organic compounds. Pyridine doesnt do what you think it does in the pipeline. The six routes for synthesis of methyl formate from different feed stocks are reported by lee et. The immobilization and storage of agt were carried out in a black chamber to avoid decomposition. It is a colourless liquid which finds use in organic chemistry as a powerful methylating agent. The major products included hexanal, methyl 5oxopentanoate, pentane, methyl butanoate and 2,4. Copper triflate as a catalyst in atom transfer radical.
Brethericks handbook of reactive chemical hazards 8th. The pdcatalyzed carbonylation reaction of naphthyl and. Can the chemical methyl triflate meotf be used only once a time. Triflic anhydride is cf3so22o it is resistant to decay, and most decay paths take strong heating. A convenient synthesis of triflate anion ionic liquids and. Triflate is an organosulfonate oxoanion resulting from the removal of a proton from the sulfonic acid group of triflic acid. Methyl trifluoromethanesulfonate sc253036 hazard alert code key. I need to perform some pretty difficult alkylations and alcohol protections. I have to use methyl triflate,but the msds says its quite a dangerous chemical. Alkylation of in situ generated fluorinated alkoxides.
Nmethylation of 2benzyloxypyridine with methyl triflate occurs at or below room temperature to furnish triflate salt 1 in a manner of minutes. This meyerschuster rearrangement process is effectively catalyzed by methyl triflate 20 mol% to prepare a broad scope of conjugated eenals and eenones generally in good to excellent yields up to 90%. Erlenmeyer flask, and the flask is stoppered with a rubber septum. Mechanistic study of the gasphase decomposition of methyl. The gas phase system can be used as source for 11c methyl. Synthesis of c methyl triflate 11c methyl iodide was synthesized essentially as reported by marazano et al. The formation of triflates with trifluoromethanesulfonic anhydride is usually accomplished with a base ex. An automated synthesis system for 11cmethylation, manufactured by shi, was modified to adapt to the loop method by replacing solenoid valves and inserting a. Common methylating agents are dimethyl sulfate, methyl iodide, and methyl triflate.
Nov 26, 2008 nmethylation of 2benzyloxypyridine with methyl triflate occurs at or below room temperature to furnish triflate salt 1 in a manner of minutes. It was labeled with c11 from the desmethyl precursor methyl 2methoxycarbonyl2amino bicyclo2. Presently industrial processes for production of methyl formate is dominated by methanol carbonylation using potassium methoxide sodium methoxide catalyst2. Synthesis of methyl triflate by the reaction of triflic anhydride with. But it has a decomposition exotherm abouve certain temperature so it cannot be.
Methyl trifluoromethanesulfonate c2h3f3o3s cid 9526 structure, chemical. This photodegradation was investigated in water in neutral, alkaline, and acidic media under external uv light irradiation by zinc oxide nanosized catalysts on granule glass. After the solution has been cooled in an acetonedry ice cooling bath, 9. A methyl group is an alkyl derived from methane, containing one carbon atom bonded to three hydrogen atoms ch 3. Selective monomethylation of primary amines with simple.
Section 1 chemical product and company identification. Recently we have clinically used three new radioligands, 11csa4503, 11cmpdx, and 11ctmsx, for mapping sigmai, adenosine a1, and adenosine a2a receptors, respectively, in the human brain by positron emission tomography. These radioligands are synthesized by methylation of the respective demethyl precursor with 11c methyl iodide. Note 6, which is used without purification for the preparation of the triflate. Triflic acid catalyzes the arylation of nmethyl1,2,3,6tetrahydropyridine 227 to give 4phenylpiperidine. Generally abbreviated as the meotf, our range is the organic compound having the molecular formula of cf3so2och3. Can the chemical methyl triflate meotf be used only once a. This synopsis presents an overview of such reactions, in which triflate may be either a stoichiometric or catalytic nucleophile, leading to the suggestion that nucleophilic catalysis by triflate may be more common than generally accepted, albeit hidden by the. The volatile thermal and oxidative decomposition products of methyl arachidonate were separated by capillary gas chromatography and identified by mass spectrometry. Methyl trifluoromethanesulfonate c2h3f3o3s chemspider. Simple triflic esters, readily prepared by reaction with alcohols, are powerful alkylating agents and must be handled with extreme care because of their irritating effect on the lungs. I have read the msds, i know that they are quite hazardous. The triflate salt of compound 102a was prepared by treating the 1,3diselenole2selone 8 with methyl triflate equation 18.
When heated to decomposition methyl trifluoromethanesulfonate emits toxic fumes. Although there has yet to be a reported human fatality, while several cases. Can the chemical methyl triflate meotf be used only once. In contrast, reaction of methyl iodide with 2chloropyridine requires heating in acetone at reflux for 24 h 32 to provide mukaiyamas reagent 33 34 2chloro1methylpyridinium iodide. Pdf decomposition of dimethyl polysulfides under solar. Search results for methyl trifluoromethanesulfonate at sigmaaldrich. The triflate 125 is formed from the hydroxy precursor equation 1 and. Methyl trifluoromethanesulfonate chemical properties. Methanogenesis, the source of natural gas, arises via a demethylation reaction. Brethericks handbook of reactive chemical hazards, eighth edition presents the latest updates on the unexpected, but predictable, loss of containment and explosion hazards from chemicals and their admixtures and actual accidents. In the solvolysis of 1methylcyclohexylmethyl triflate, rearranged products with methyl migration slightly dominate over those with ring expansion.
Such hydrocarbon groups occur in many organic compounds. Predicted data is generated using the us environmental protection agencys episuite. This reaction procedure operates under mild conditions 70 c, in air, with short reaction times 1 h. A convenient synthesis of triflate anion ionic liquids and their. Search results for methyl triflate at sigmaaldrich. I am looking for some assistance on working with triflates. Cheap and nontoxic dimethyl and diethyl carbonate serve as source for the methyl and ethyl groups in the preparation of methyl and ethyl. Trifluoromethanesulfonate anion as nucleophile in organic. I dont know if it exists, so i cant definitively say whether itd be a solid or not or even stable at rt or stp, and it seems like the only easy way to produce it in quantitative yields would be to react triflic anhydride with a nitrate source. The ability to start with cuotf2 catalyst precursors allows for a simple experimental setup without catalyst oxidation. Decomposition of phenyl formate to phenol and co alkyl formates, particularly methyl formate, have been widely utilized as a c 1 building block in organic synthesis. Photocatalytic decomposition of methyl red mr as a pollutant in wastewater samples is investigated in this study. Triflate, also known by the systematic name trifluoromethanesulfonate, is a functional group with the formula cf 3 so 3 the triflate group is often represented by.
Not a dangerous good if item is equal to or less than 1gml and there is less than 100gml in the package. While the methyl group is usually part of a larger molecule, it can be found on its own in any of three forms. The n2 carrier 50mlmin containing the 11cch3i was passed through a column 25 mm x 5 mm of dry 4060 mesh soda lime to remove traces of hi and reduce the amount of water before passing over the agotf impregnated carbon. People fatally poisoned themselves even with dimethyl sulfate, the stuff apparently does not smell me triflate is more powerfull than magic methyl. Characterization of the volatile decomposition products of. Deuterium isotope effects upon solvolyses of alkyl sulfonates. Alternatively, the c27 alcohol in 4a was methylated using me30bf47 and 1,8. The compound is closely related to methyl fluorosulfonate fso 2 och 3. Ive had people tell me stories about how when they want to use aryl triflate in a cross coupling reaction, it has to be made from phenols quickly, then evaporated down, then immediately used in cross coupling with no water, all under inert air, because of all fragile and easy to decompose aryl triflates are. Ive had people tell me stories about how when they want to use aryl triflate in a cross coupling reaction, it has to be made from phenols quickly, then evaporated down, then immediately used in cross coupling with no water, all under inert air, because of all fragile and easy to. Methyl trifluoromethanesulfonate 333277 chemical book. Hc methyl triflate synthesis o o 0 0 0 o uo o do 0 g i i i 100 200 300 temperature c fig. The provided collection is the colorless liquid that is sensitive against heat. Extreme high moderate low section 1 chemical product and company identification product name methyl trifluoromethanesulfonate statement of hazardous nature considered a hazardous substance according to osha 29 cfr 1910.
The effect of four atmosphere types including air, nitrogen, oxygen, and argon was. Evidence for an intermediate in the methylation of cb11h12. Experimental studies have proposed that the mechanism to describe these observations involves two key steps. Convenient method for preparing benzyl ethers and esters.
Nevertheless, the different groups of cyclic monomers. The use of copper triflate complexes as catalysts for atom transfer radical polymerization atrp of styrene and methyl acrylate ma is presented. Reactions of triflate esters and triflamides with an organic. I will be using a series of different triflate derivatives, tmsotf and tbsotf. Direct monomethylation of primary amines with methyl triflate was achieved with high selectivity up to 96%. Tea or pyridine, in a solvent such as dcm, with cooling or at rt. Ok, this is not exactly a timesensitive issue, but since i took a crack at one of the most prominent toxicology myths in the biology labs ethidium bromide is not really all that bad, in case you missed it, i figured i should do the same for one of the persistent myths on the organic chemistry side. These are stable crystalline solids that store resonable well.
Methyl trifluoromethanesulfonate, also commonly called methyl triflate and abbreviated meotf, is the organic compound with the formula cf 3 so 2 och. The trideuteriomethylation of bh vertices in cb11h12. Synthesis of cmethyl triflate 11cmethyl iodide was synthesized essentially as reported by marazano et al. Synthesis of methyl triflate by reaction of the triflic acid with dimethyl sulfate. Deuterium isotope effects upon solvolyses of alkyl. How easy is it to make and use aryl triflate, technicalwise. Methyl trifluoromethanesulfonate, also commonly called methyl triflate and abbreviated meotf, is the organic compound with the formula cf 3 so 2 och 3. Working with hazardous chemicals organic syntheses. Methylhydrazine is used as a highenergy fuel in military applications. Methyl triflate, methyl triflate manufacturer, cas no. Cheap and nontoxic dimethyl and diethyl carbonate serve as source for the methyl and ethyl groups in the.
Journals az books and reference advertising media kit. The orders of the decomposition reactions with respect to dimethyl trisulfide dmts, dimethyl tetrasulfide dm4s and dimethyl pentasulfide dm5s. From our extensive collection of products, we are providing to the customers the reactive range of methyl triflate. The major products of the thermal decomposition of methyl formate in the gas phase are ch3oh, ch2o, and co. An automated synthesis system for 11cmethylation, manufactured by shi, was modified to adapt to the loop method by replacing solenoid valves and inserting a furnace heating an agotf column at 200c.
Methyl triflate is the closest thing going, as far as i know. The solid is suspended in 100 ml of dry hexane note 2 and trifluoromethanesulfonic acid 24. Effect of column temperature on the conversion of methyl iodide to methyl triflate by silver triflate impregnated carbon. The reaction map is intended to provide insight into possible reactions one step before and after the title reaction. Reactions of triflate esters and triflamides with an. People fatally poisoned themselves even with dimethyl sulfate, the stuff apparently does not smell metriflate is more powerfull than magic methyl. Methyl trifluoromethanesulfonate c2h3f3o3s pubchem. Improved synthesis of 11 csa4503, 11 cmpdx and 11 c. A1401, naman midtown, senapati bapat marg, elphinstone west, mumbai 400 0, india.
Various aldehydes, ketones, aldehyde esters, hydrocarbons and alcohols were identified. Finally, replacement of methyl triflate with less reactive methylating reagents, including dimethyl sulfate me 2 so 4, methyl tosylate meots, and methyl iodide mei, did not provide comparable results. Methyl trifluoromethanesulfonate, also commonly called methyl triflate and abbreviated meotf. It was prepared from 11cmethyl triflate by loop method. For example, n butyl triflate can be written as ch 3 ch 2 ch 2 ch 2 otf. Studies with stereochemically defined substrates cis2butenyl2mercuric chloride 1 and endonorbornyl2mercuric bromide 2 reveal that a high degree of configurational retention occurs during the bond cleavage, while studies with exo3acetoxynortricyclyl5mercuric bromide 3 and cisexo2acetoxybicyclo2. Most people in the field will have heard that pyridine is a male reproductive. A solvent and halogenfree synthesis of high purity triflate ionic liquids via direct alkylation of organic bases amines, phosphines or heterocyclic compounds with methyl and ethyl trifluoromethanesulfonate methyl and ethyl triflate has been developed. Polymers free fulltext ringopening polymerizationan. Methyld3 triflate is a commonly used methylating reagent used in synthetic preparations of organic compounds. Jolly, nadia flearyroberts, steven osullivan, eswararao doni, shengze zhou and john a. Metal and acidfree methyl triflate catalyzed meyer.