Sulfonium salts tertiary

The benzylation of a wide variety of aHphatic, aromatic, and heterocycHc amines has been reported. Benzyl chloride is converted into mono-, di-, and tribenzyl amines by reaction with ammonia. Benzylaniline [103-32-2] results from the reaction of benzyl chloride with aniline. Reaction with tertiary amines yields quaternary ammonium salts with trialkylpbospbines, quaternary phosphonium salts and with sulfides, sulfonium salts are formed. 

Thiocane (362 m.p. 33-34 °C, b.p., 71°C/10mmHg, nD 1.5152, HgCl2 complex, m.p. 128-129 °C) behaves as a typical sulfide and gives rise to a tertiary sulfonium salt with methyl iodide, and a sulfone (363) with H202 (53M1206). This sulfone is described as having a characteristic, but not unpleasant odor (presumably, unlike 362). 

Hofmann Rule Elimination from quaternary ammonium and tertiary sulfonium salts generally provides the lesser-substituted alkene as major product. 

On reacting the diazonium salt la with TTF, immediate evolution of nitrogen occurred at room temperature in undried acetone as solvent. Monitoring by TLC indicated complete consumption of the diazonium salt and the appearance of a new product, the alcohol 4a. Since 4a cannot arise by interaction of radical 2a with water, this suggests that a radical-polar crossover process had occurred with the intermediate sulfonium salt undergoing facile hydrolysis in the undried acetone solvent. Repeating the experiment with lb similarly afforded the tertiary alcohol 4b, whereas, in contrast, diazonium salt Ic afforded no primary alcohol. Further investigation indicated that the sulfonium salt 3c had formed in this reaction. NMR spectra confirmed that this... 

Tertiary amines can form stable quaternary ammonium salts (R N X ), while thioethers form sulfonium salts (RjS X ), but stable 0x0-nium salts (R30 X ) are less common. 

Tetraalkylammonium salts and primary or secondary alkyl halides usually react by E2j while tertiary alkyl halides and sulfonium salts react by... 

Hofmann rule The principal alkene formed in the decomposition of quaternary ammonium hydroxides that contain different primary alkyl groups is always ethylene, if an ethyl group is present. Originally given in this limited form by A.W. Hofmann, the rule has since been extended and modified as follows When two or more alkenes can be produced in a P-elimination reaction, the alkene having the smallest number of alkyl groups attached to the double bond carbon atoms will be the predominant product. This orientation described by the Hofmann rule is observed in elimination reactions of quaternary ammonium salts and tertiary sulfonium salts, and in certain other cases. 

Protonic acids are efficient initiators for the polymerization of both sulfides and amines. The polymerization of thiiranes initiated with perchloric acid proceeds without induction periods. Induction periods are present, however, with methyl fluorosulfonate initiator 11). Secondary sulfonium salts are more reactive than tertiary ones (the opposite is true with oxonium ions)12) and induce rapid polymerization ... 

Repeating the experiment with lb, but quenching the reaction by addition of diethyl ether as soon as the effervescence had subsided, afforded the tetrathiafulva-lenium salt 2b this compound was then subjected to solvolysis in undried deutero-acetone and afforded the corresponding alcohol 3b, consistent with its intermediacy in the reaction. The basic mechanism of the reaction can thus be represented by Scheme 2. Aryl radicals are formed following electron transfer to the diazonium cation and subsequent loss of dinitrogen. Rapid cyclization is followed by formation of the sulfonium salt 2b, and a facile solvolysis occurs to afford the alcohol 3b. Since the tertiary alcohol 3c was formed from substrate Ic, a similar pathway may have been followed, but the direct oxidation of the tertiary radical by electron transfer to a diazonium cation cannot yet be ruled out. The resistance of the primary salt to solvolysis is a classic hallmark of an Sn 1 reaction. (A refinement for the mechanism of the solvolysis step will be presented in Section 2.7.3.1 of this review, backed by very recent results). 

Methylthiomethylation. In the presence of a tertiary amine, phenols and indole derivatives undergo C-alkylation with the sulfonium salt derived from the two reagents. 

Thiolanes behave like dialkyl sulfides. With haloalkanes or alcohols in the presence of Bronsted acids, tertiary sulfonium salts are formed ... 

Nitrogen Nucleophiles. Nitrogen nucleophiles, specifically NH3, amines, azide, and nitrite, resulted in high yields of alkene addition products (eq 7). In the absence of additional nucleophiles, the resulting sulfonium salt reacted with a tertiary amine to yield the demethylated product or the ammonium salt with a retention of configuration (eq 8). ... 

Dragendorff s reagent is a solution of iodobismuthate. It gives orange to red precipitates with tertiary amines, quaternary nitrogen, or sulfonium salts and alkaloids. Among aliphatic tertiary amines, triethanolamine, for example, does not react. 

Quaternary ammonium alkyl ethers are prepared similarly an alkaline starch is reacted with a quaternary ammonium salt containing a 3-chloto-2-hydtoxyptopyl or 2,3-epoxyptopyl radical. Alternatively, such derivatives can be prepared by simple quaternization of tertiary aminoalkyl ethers by reaction with methyl iodide. Sulfonium (107) and phosphonium (108) starch salts have also been prepared and investigated. Further work has explained the synthesis of diethyl aminoethyl starch (109) as well as the production of cationic starches from the reaction of alkaline starch with... 

Brown, D.M. and Turner, D.H. (1959) Ganglionic blocking activity of tertiary sulfonium quaternary ammonium salts./. Pharm. Pharmacol., 11 (Suppl), 95T-102T. 

Dicyanoketene ethylene acetal reacts with tertiary amines to give quaternary ammonium inner salts.3 Similarly, it reacts with sulfides to give sulfonium inner salts.3 These products are generally solids that can be used to characterize tertiary amines, and sulfides. Dicyanoketene acetals can be converted to pyrimidines, pyrazoles, or isoxazoles in one step.4... 

STEVENS REARRANGEMENT. Migration of an alkyl group from a quaternary ammonium salt to an adjacent carbanionic center on treatment with strong base. The product is a rearranged tertiary amine, sulfonium, or sulfide. 

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