Magic methyl

Cycloheptaquinoxaline 222c with magic methyl, instead of the expected N-methylation, suffers C-methylation and N-sulfonation to yield betaine 279 (89BCJ1158). 

Both reagents are powerful methylating agents, reacting with O, N, and S. Read precautions carefully. The Methyl fluorosulfonate (Magic Methyl) is no longer commercially avai lable. Methyl triflate is extremely (sometimes violently) reactive towards amines. Except for extremely hindered or unactivated amines, not generally required for the task. 

Step 2a Methylation using magic methyl (caution carcinogen ). 

Prior to using Magic Methyl , a consultant physician, experienced in treating pulmonary edema, should be informed of its proposed use and be prepared to accept a victim of an accident as a priority case. 

Aldrich Chemical Company, Technical Bulletin on Magic Methyl, Aldrich Chemical Company, Milwaukee, WI, April 1971. 

Another alkylative hydrolysis uses magic methyl . Thus, action of the 1,3-dithiolane (222) with methyl fluorosulfonate followed by treatment with sodium hydroxide leads to the formation of benzophenone (72S561). 

CH3I 103. (CH3)30+BF4 Or CH30S02F = Magic Methyl SEVERE POISON... 

The only R4Bi+ ion known is prepared by the reaction of magic methyl with BiMe3 BiMe3 + Me0S02CF3------------------------------- [BiMe4][CF3S03]... 

Methyl fluorosulfonate, 3, 202. Suppliers Aldrich (Magic Methyl), WBL. 

Krief et al. have shown that selenium ylides behave as their sulfur analogues and convert a variety of carbonyl compounds to oxiranes <89H(28)1203>. The latter compounds can be directly obtained by using R2Se=CHR /i-hydroxyalkylselenides (available from carbonyl compounds by addition of RSeCH2Li) may serve as suitable precursors as well, either in a two-step protocol, via the selenonium salt by alkylation with magic methyl (MeS03F), or directly by treatment with thallous ethoxide in chloroform. Oxidation of the /t-hydroxyalkylselenides with peracid, followed by treatment of the resulting selenone with base, results in oxirane formation (Scheme 60). 

Aldehyde durch Hydrolyse von Dithioacetalen nach Alkylierung mit Fluorsulfonsaure-methylester350 3 g Fluor-sulfonsaure-methylester (Magic Methyl , Aldrich) fiigt man unter Riihren zu einer Losung von 10 mmol 2-subst. 

Salts with carbenium ions and SbFg as counteranion have already been described, such as magic methyl CHj SbFg. However, these super-electrophilic species can be involved in electrophilic additions to double bonds and carbenium cations, and are therefore not suitable for fluorination reactions. 

---