P Toluenesulfonyl chloride

If the temperature is not kept below 25°C dunng the reaction of primary alcohols with p toluenesulfonyl chloride in pyndine it is sometimes observed that the isolated product is not the desired alkyl p toluenesulfonate but is instead the corresponding alkyl chlonde Suggest a mech anistic explanation for this observation... 

Conversion to p toluenesulfonate es ters (Section 8 14) Alcohols react with p toluenesulfonyl chloride to give p toluenesulfonate esters Sulfo nate esters are reactive substrates for nucleophilic substitution and elimma tion reactions The p toluenesulfo nate group is often abbreviated —OTs... 

The reaction of alcohols with acyl chlorides is analogous to their reaction with p toluenesulfonyl chloride described earlier (Section 8 14 and Table 15 2) In those reactions a p toluene sulfonate ester was formed by displacement of chloride from the sulfonyl group by the oxygen of the alcohol Carboxylic esters arise by displacement of chlonde from a carbonyl group by the alcohol oxygen... 

In the reaction with enamino ketones derived from dimedone (e.g., 49) p-toluenesulfonyl chloride gives the chloroiminium cation (138) isolated as the perchlorate. This indicates that initial O sulfonation is followed by addition of chloride ion and subsequent expulsion of tosylate (42) in a manner similar to the trichloroacetyl chloride reaction with 49 (Section IV.A). 

The reaction of p-toluenesulfonyl chloride (TsCl) with 1-hydroxytryptamines was expected to follow the same reaction pathways as that of MsCl described in Section IV.B. 1. In fact, it is different from the expectation (2000H2487). Thus, 39 reacts with TsCl in THF to provide 49a (42%), 51a (6%), 53a (3%), 60 (0.5%), and... 

From l-cyclohexyl-3-ethyldiaziridine, crystalline derivatives have been prepared with p-toluenesulfonyl chloride and with 3,5-dinitro-benzoyl chloride, e.g., 46/ The quantitative liberation of iodine from acid iodide solution characterizes these compounds as true diaziridines. 

Esterification of 136 with p-toluenesulfonyl chloride leads to the tosylate (139). Displacement of the ester with guanidine affords guanoxane (140). This drug, not surprisingly, shows peripheral sympathetic blocking activity and is therefore used in control of hypertension. 

A mixture of 200 grams of 2-benzoyloxyethanol in 2 liters of pyridine at -5°C is treated with 275 grams of p-toluenesulfonyl chloride and the resulting mixture is stirred at O C for 2 hours. Water is added slowly at O " to 5°C. Extracting with chloroform, washing the extract with dilute hydrochloric acid, water and potassium bicarbonate, and evaporating the solvent leaves benzyloxyethyl p-toluenesulfonate. 

Ethyl sulfonyl ethanol p-Toluenesulfonyl chloride 2-Methyl-5-nitroimidazole... 

Deoxy-D-jcylo hexose 6-(dihydrogen phosphate) (21) has also been synthesized (2) the reaction sequence makes use of 3-deoxy l 2,5 6-di-O-isopropylidene D-galactofuranose (16), a compound that can be easily prepared from D-glucose (2, 60). The mono-isopropylidene derivative (17) formed by partial hydrolysis of the di-ketal is converted into the 6-tosylate (18) by reaction with one molar equivalent of p-toluenesulfonyl chloride. From this the epoxide (19) is formed by reaction with sodium methoxide. Treatment of the anhydro sugar with an aqueous solution of disodium hydrogen phosphate (26) leads to the 6-phosphate (20)... 

When a primary alcohol is treated with p-toluenesulfonyl chloride at room temperature in the presence of an organic base such as pyridine, a tosvlate is formed. When the same reaction is carried out at higher temperature, an alkyl chloride is often formed. Explain. 

Alcohols react with p-toluenesulfonyl chloride (tosyJ chloride, p-TosCl) in pyridine solution to yield alkyl tosylates, ROTos (Section 11.1). Only the 0-H bond of the alcohol is broken in this reaction the C—O bond remains intact, so no change of configuration occurs if the oxygen is attached to a chirality center. The resultant alkyl tosylates behave much like alkyl halides, undergoing both SN1 and Sjsj2 substitution reactions. 

The yield of luminescence activity is increased by including CTAB, Tergitol 7 (a sulfate detergent), or p-toluenesulfonyl chloride to various extents. 

Triethylamine was purified by treatment with p-toluenesulfonyl chloride [Benzcncsulfonyl chloride, 4-methyl-] and distillation. 

Sulfur compounds have also been widely studied as activating agents for polyesterification reactions. p-Toluenesulfonyl chloride (tosyl chloride) reacts with DMF in pyridine to form a Vilsmeir adduct which easily reacts with carboxylic acids at 100-120° C, giving highly reactive mixed carboxylic-sulfonic anhydrides.312 The reaction is efficient both for aromatic dicarboxylic acid-bisphenol312 and hydroxybenzoic acid314 polyesterifications (Scheme 2.31). The formation of phenyl tosylates as significant side products of this reaction has been reported.315... 

TsCl was obtained from Aldrich Chemical Company, Inc. and purified by recrystallization according to the following procedure. p-Toluenesulfonyl chloride (85 g) is dissolved in 150 mL of hot CHC13 and 200 ml. of petroleum ether (room temperature) is added in one portion to the clear, colorless solution. The resulting cloudy solution is clarified by addition of ca. 5 g of charcoal, stirred for 1 min, and filtered on a Buchner funnel. The filtrate is concentrated to ca. l/5th of its original volume by rotary evaporation, and the solid which appears is collected by filtration and dried under reduced pressure (25° C, 0.03 mm) to afford 68 g of TsCl as bright white crystals. 

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