Chloride tosyl

In the flask were placed 0.20 mol of the acetylenic alcohol, 0.24 mol of tosyl chloride and 350 ml of diethyl ether. The mixture was stirred at room temperature, until the solid had passed into solution and then cooled at -5 to -10 c in a bath of dry-ice and acetone. Machine-powdered KOH (130 g) was added with vigorous stirring, initially in relatively small portions [oa. 5 g), at intervals of 2 min. The reaction was strongly exothermic at first, and efficient cooling was necessary in order to maintain the temperature of the reaction mixture between -5 and O C... 

Tosylates are generally formed from an amine and tosyl chloride in an inert solvent such as CH2CI2 with an acid scavenger such as pyridine or triethylamine. 

In general, the reaction can be performed between 0-60°C with the majority of the reactions being run at room temperature. The reactivity of the hydrazones with either the acyl or tosyl leaving group with thionyl chloride depends on the substrate. However, the acylated hydrazones generally provide gaseous by-products where as the tosyl chloride reaction products have to be separated from the reaction mixture. 

It was recently shown that the formation of a Schiff s base is the first step of the reaction between 3-aminopropan-l-ol and an aldehyde. The action of acid chlorides, such as tosyl chloride, on the SchifTs base forms the W-acyl derivative of tetrahydro-1,3-oxazine. 

The monotosylation of 2,5-dihydroxybenzenesulfonicacid iscarried out in a pyridine medium by treating it with tosyl chloride, thus preferably isolating the 2-hydroxy-5-tosyloxybenzene-sulfonic acid, pyridine salt. This product subjected to reflux with an alcoholic solution of piperazine yields 2-hydroxy-5-tosyloxybenzenesulfonic acid, piperazine salt. 

Of the four possible 5-deoxy-pent-4-enofuranoses, the D-erythro-isomer was of interest as a potential source of derivatives of L-lyxofuranose. For this purpose, a vinyl ether having the D-en/ hro-configuration has been prepared from derivatives of D-ribose. Condensation of D-ribose with acetone in the presence of methanol, cupric sulfate and sulfuric acid at 30°C., as described by Levene and Stiller(30) afforded a sirupy product consisting mainly of methyl 2,3-O-isopropylidene-D-ribofuranose (40). Treatment of a pyridine solution of the sirup with tosyl chloride... 

An analogous reaction occurs with dibenzoylacetylene, whereas the reaction fails with dimethyl acetylenedicarboxylate, benzoyl chloride and tosyl chloride. Decomplexation of compound 29 to 3-(cyclohepta-2,4,6-trienyl)-3//-azepine (73%) has been achieved with trimethylamine N-oxide. 

Unsensitized irradiation of 5-tosyl-5//-dibenz[6,/]azepine (9, R = Ts mp 166-167 C), prepared in 78 % yield by sulfonylation of the parent heterocycle with tosyl chloride in pyridine, produces a small amount (8.5%) of 2-tosyl-5//-dibenz[/>,/ ]azepine (10, R = Ts mp 230-232 C).32... 

Dibenzo[l,3]diazepines 9, together with amidines and benzimidazoles, are produced by a rearrangement reaction when certain A.A -diarylamide oximes 7 are treated with tosyl chloride. The intermediate 0-tosyl derivatives 8 cannot be isolated.176... 

The Action of Tosyl Chloride on A, /V -Diphenylbenzamide Oxime (7, R = H) Typical Procedure 176... 

Triphenyl-2//-l,2,4-triazepine reacts with tosyl chloride under standard conditions to afford the 2-tosyl derivative 20.337... 

The earliest method developed for the preparation of nonracemic aziridine-2-car-boxylates was the cyclization of naturally occurring (3-hydroxy-a-amino acid derivatives (serine or threonine) [4]. The (3-hydroxy group is normally activated as a tosyl or mesyl group, which is ideal for an intramolecular SN2 displacement. The cyclization has been developed in both one-pot and stepwise fashion [4—9]. As an example, serine ester 3 (Scheme 3.2) was treated with tosyl chloride in the presence of triethylamine to afford aziridine-2-carboxylate 4 in 71% yield [9]. Cyclization of a-hydroxy- 3-amino esters to aziridine-2-carboxylates under similar conditions has also been described [10]. 

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... 

Note Several condensing agents for the direct poly condensation reaction such as diphenyl chlorophosphate-LiBr and tosyl chloride-DMF have also been developed by Higashi et al.311,312 (see Section 2.3.3.2). 

Recently Tanabe and co-workers have found that several alcohols were smoothly and efficiently tosylated using tosyl chloride/triethylamine and a catalytic amount of trimethylamine hydrochloride as reagents.6 Compared with the traditional method using pyridine as solvent, this procedure has the merit of much higher reaction rates, and it avoids the side reaction in which the desired tosylate is converted into the corresponding chloride. 

---