98821-07-9

Upstream product

• 421-83-0 trifluoromethane sulfonyl chloride 
• 824-94-2 p-methoxybenzyl chloride 
• 2926-29-6 Langlois reagent 
• 2746-25-0 p-Methoxybenzyl bromide 
• 1612253-29-8 1-methoxy-4-{[(trifluoromethyl)sulfanyl]methyl}benzene 
• 104-93-8 p-methylanizole 
• 41804-89-1 potassium triflinate 
• 105-13-5 4-Methoxybenzyl alcohol 
• 66788-48-5 p-Anisyltriflenat 

Downstream Products

• 446867-23-8 4-methoxybenzyl 2,2,2-trifluoroethyl ether 
• 123-11-5 4-methoxy-benzaldehyde 
• 1389250-50-3 C₁₄H₁₀N₃O₅^(1-) 

Relevant academic research and scientific papers

Base promotedgem-difluoroolefination of alkyl triflones

A new synthesis ofgem-difluoroalkenes from readily available alkyl triflones and difluorocarbene precursors such as TMSCF2Br has been reported. The reaction, regardless of electronic effect, givesgem-difluoroalkenes in good to excellent yields. The mechanism may involve deprotonation of triflones, nucleophilic addition, and the elimination of SO2CF3

Copper-catalyzed direct trifluoromethylthiolation of benzylic C-H bonds via nondirected oxidative C(sp3)-H activation

A copper-catalyzed trifluoromethylthiolation of benzylic sp3 C-H bonds was developed via nondirected oxidative C-H activation using readily prepared and stable AgSCF3. This reaction provides a novel and straightforward method for the preparation of various benzyl trifluoromethyl sulfides.

Kinetic studies of reactions of 4-nitrobenzofuroxan with carbanions derived from benzyltriflones in methanol

This paper reports the rate measurements for the reactions of carbanions derived from benzyltriflones, 2, with 4-nitrobenzofuroxan, 4, in methanol, to give anionic σ-adducts. 1H NMR studies in DMSO-d6 indicate that the products formed by the reaction of 2 and 4 in the presence of triethylamine are consistent with the products formed by the elimination of trifluoromethylsulfinic acid from σ-adducts, initially formed by a carbanion attack at the 5 position of 4. The low value of β, which is the slope of the linear plot of log k5 versus pKa, provides evidence for the high steric requirements of the benzyltriflone anions.

Ramberg-Backlund rearrangement vs. β-Elimination of haloform from trichloro and trifluoromethyl sulfones

A new and convenient method for the preparation of trichloro and trifluoromethanesulfinates is described. These esters readily undergo rearrangement to the corresponding sulfones at room temperature, in high yields. In contrast to trichloromethyl sulfoxides which undergo base-induced β-elimination of chloroform to sulfines, the corresponding sulfones undergo an unusually facile Ramberg-Backlund rearrangement with formation of dichloromethylene products. Replacement of CCl3 by CF3 results in complete loss of reactivity, even under drastic basic conditions.

THE SYNTHESIS, SOLVOLYSIS AND REARRANGEMENT OF BENZYL TRIFLUOROMETHANESULFINATES

The synthesis and reactivity of benzyl trifluoromethanesulfinates have been investigated.These esters are easily and almost quantitatively obtained by selective oxidation of the corresponding sulfenates.A study of their behavior has revealed some unique features.In sharp contrast to benzyl arenesulfinates, which undergo ethanolysis with complete sulfur-oxygen bond fission, the corresponding trifluoromethanesulfinates undergo ethanolysis with exclusive carbon-oxygen bond fission, and with a rate enhancement by a factor of 6 powers of ten.The unusual high reactivity of these esters, comparable to that of the corresponding tosylates, is discussed.A kinetic study of the solvent and substituents effects on the rate of solvolysis has been performed.Also in contrast with benzyl arenesulfinates, these esters undergo facile rearrangement to sulfone on heating in polar nonhydroxylic solvents such as acetonitrile, in high yields.The mechanisms of solvolysis and rearrangement are discussed.

Nucleofugality of the Sulfinate Group in Carbocation-Forming Processes

The solvolytic reactivity of a variety of sulfones and sulfinate esters has been determined which allows one to place the sulfinate leaving group in a relative nucleofugality scale.Cumyl trifluoromethyl sulfone (1) reacts in a variety of solvents to give substitution products.The mOTs value of 0.82 is indicative of the involvement of the cumyl cation (9) formed in kc process.In terms of rate, 1 is 170 times less reactive than cumyl chloride but 286 times more reactive than cumyl p-nitrobenzoate.The analogous cumyl methyl sulfone (2) and cumyl phenyl sulfone (3) solvolyze approximately 107 times more slowly than 1.The sulfinate esters cumyl methanesulfinate (6) and cumyl p-toluenesulfinate (7) are considerably more reactive than the analogous sulfones.Methanolysis of 6 was also subject to acid catalysis, where a mechanism analogous to the AAL1 mechanism of hydrolysis of esters of carboxylic acids was suggested.The less hindered α-phenethyl trifluoromethyl sulfone (4) and p-methoxybenzyl trifluoromethyl sulfone (5) solvolyzed at rates that approached those of the analogous p-nitrobenzoates.This was indicative of the importance of relief of steric congestion in solvolyses of the more hindered tertiary sulfone 1.