A-Toluenesulfonyl chloride

A. 3-Methyl-3-(toluenesulfonyloxymethyl)oxetane [Oxetane tosylate, ( )]. A dry, 1-L, round-bottomed flask is charged with a-toluenesulfonyl chloride (57.20 g, 0.30 mol) (Note 1) to which pyridine (250 mL) (Note 2) is added while stirring is carried out under nitrogen with a magnetic stir bar (Note 3). The reaction flask is placed inside a container to which an ice/water mixture may be added in the event that the reaction becomes too exothermic. 3-Methyl-3-oxetanemethanol (20.4 g, 0.2 mol) (Note 4) is added slowly and stirred for 1.5 hr. The mixture is slowly added to a vigorously (Note 3) stirred mixture of deionized water (700 mL) and crushed ice (700 g) in a 2-L Erlenmeyer flask and allowed to stir for ein additional 0.5 hr. The white precipitate is collected on Whatman filter paper 1 and washed with cold water (HjO, Note 5). The product is dried under high vacuum and/or phosphorus pentoxide (P2O5) to obtain the white powder of oxetane tosylate 1 (39.8-44.60 g, 78-87%) (Note 6). 

A solution of the Step 8 product (3.418 mmol) in 5.5 ml THF and 2.0 ml DMF was treated with 1.20 ml At-methyl morpholine, then stirred 10 minutes at 0°C and then treated over 5 minutes with a-toluenesulfonyl chloride (3.767mmol) dissolved in 5.5 ml THF. The mixture was stirred 2 hours at 0°C and was then diluted with 150 ml EtOAc. The organic solution was washed twice with 25 ml 1M HC1, twice with 25 ml saturated NaHCOs solution, once with 50 ml brine, dried, and concentrated. The yellow residue was triturated with diethyl ether, dried, and the product isolated in 74% yield as a white solid. 

When treated with a-toluenesulfonyl chloride in pyridine, (+ )-lunacridine is converted in low yield into (4- )-lunacrine, the enantio-morph of the natural alkaloid. The cycle of reactions whereby (- )-lunacrine is converted through (+ )-lunacridine to (+ )-lunacrine thus includes a stereochemical inversion and requires that the alkaloids contain a single center of asymmetry which, in view of the reactions involved, must be adjacent to tbe ring oxygen. This leads to the representation (130) of the processes shown on p. 240. 

The benzoyl chloride—functionalized resin 7 was prepared in three steps (eq 7) from a toluenesulfonyl chloride resin (prepared, in turn, by chlorination of Dowex SOW ion-exchange resin). Resin 7 was coupled with a variety of alcohols and amines to afford the corresponding resin-bound benzoate esters and benza-mides, which were tracelessly cleaved under Pd -catalyzed reductive conditions in 13-85% yields (eq 8). ... 

A remarkable rearrangement of a cephamycin derivative to a 6a-sub-stituted penam-type product was reported by Kobayashi and Hiraoka (1977). Protected cephamycin C (531) reacted with a-toluenesulfonyl chloride and A -trimethylsilylphthalimide in acetonitrile at 40°C for 20 hr. 

In the reaction of p-nitro-a-toluenesulfonyl chloride with excess diazomethane the [3+2] cycloadduct 30 is obtained". ... 

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... 

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 a typical case, ethylamine is allowed to react with ethylene oxide to produce N-ethyldiethanolamine (5). The latter is then treated with additional ethylene oxide to afford N,N-di(polyoxyethylene)ethylamine (6) where the sum a -t b is 3. This material is then stirred at room temperature for 3 h with toluenesulfonyl chloride and powdered sodium hydroxide in dioxane solution. After filtration and Kugelrohr distillation, N-eth-ylmonoaza-15-crown-5 is isolated in 75% yield as illustrated below in Eq. (4.7). 

Selective hydroxylation with osmium tetroxide (one equivalent in ether-pyridine at 0 ) converts (27) to a solid mixture of stereoisomeric diols (28a) which can be converted to the corresponding secondary monotoluene-sulfonate (28b) by treatment with /7-toluenesulfonyl chloride in methylene dichloride-pyridine and then by pinacol rearrangement in tetrahydrofuran-lithium perchlorate -calcium carbonate into the unconjugated cyclohepte-none (29) in 41-48 % over-all yield from (27). Mild acid-catalyzed hydrolysis of the ketal-ketone (29) removes the ketal more drastic conditions by heating at 100° in 2 hydrochloric acid for 24 hr gives the conjugated diketone (30). 

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). 

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. 

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)... 

Alternatively, an alcohol can be made more reactive toward nucleophilic substitution by treating it with p ra-toluenesulfonyl chloride to form a tosylate. As noted on several previous occasions, tosylates are even more reactive than halides in nucleophilic substitutions. Note that tosylate formation does not change the configuration of the oxygen-bearing carbon because the C-0 bond is not broken. 

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. 

Carbodiimides have been prepared by desulfurization of thioureas by metal oxides, by sodium hypochlorite,4 or by ethyl chloroformate in the presence of a tertiary amine by halogena-tion of ureas or thioureas followed by dehydrohalogenation of the N,N -disubstituted carbamic chloride 8 and by dehydration of disubstituted ureas using -toluenesulfonyl chloride and pyridine.7 The method described above is a modification of that of Campbell and Verbanc. ... 

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