Toluenesulfonates

In the flask were placed 1.50 mol of the isopropenyl ether (conmercially available) and 0.10 mol of the (dry) acetylenic alcohol (also commercially available), and in the dropping funnel 0.4 mol of the latter compound. The mixture was cooled to 0°C and 100 mg of anhydrous p-toluenesulfonic acid were added with stirring. 

Nucleophile p Toluenesulfonate ester Product of nucleophilic substitution pi... 

The sulfonate esters used most frequently are the p toluenesulfonates They are com monly known as tosylates abbreviated as ROTs... 

All these reactions of octadecyl p toluenesulfonate have been reported in the chemical literature and all proceed in synthetically useful yield You should begin by identifying the nucleophile in each of the parts to this problem The nucleophile replaces the p toluenesulfonate leaving group in an Sn2 reaction In part (a) the nucleophile is acetate ion and the product of nucleophilic substitution IS octadecyl acetate... 

The hydrolysis of sulfonate esters of 2 octanol is stereospecific and proceeds with complete inversion of configuration Write a structural formula that shows the stereochemistry of the 2 octanol formed by hydrolysis of an opti cally pure sample of (S) (+) 1 methylheptyl p toluenesulfonate identify the prod uct as / or S and deduce its specific rotation... 

When It IS necessary to prepare secondary alkyl halides with assurance that no trace of rearrangement accompanies their formation the corresponding alcohol is first converted to its p toluenesulfonate ester and this ester is then allowed to react with sodium chloride bromide or iodide as described m Section 8 14... 

Section 8 14 Nucleophilic substitution can occur with leaving groups other than halide Alkyl p toluenesulfonates (tosylates) which are prepared from alcohols by reaction with p toulenesulfonyl chloride are often used... 

In Its ability to act as a leaving group p toluenesulfonate is even more reactive than iodide... 

Solvolysis of 1 2 dimethylpropyl p toluenesulfonate in acetic acid (75°C) yields five differ ent products three are alkenes and two are substitution products Suggest reasonable structures for these five products... 

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... 

As m other nucleophilic substitution reactions alkyl p toluenesulfonates may be used m place of alkyl halides... 

The most frequently used organocuprates are those m which the alkyl group is pri mary Steric hindrance makes secondary and tertiary dialkylcuprates less reactive and they tend to decompose before they react with the alkyl halide The reaction of cuprate reagents with alkyl halides follows the usual 8 2 order CH3 > primary > secondary > tertiary and I > Br > Cl > F p Toluenesulfonates are somewhat more reactive than halides Because the alkyl halide and dialkylcuprate reagent should both be primary m order to produce satisfactory yields of coupled products the reaction is limited to the formation of RCH2—CH2R and RCH2—CH3 bonds m alkanes... 

Compound C is more stable than compound A OTs stands for toluenesulfonate... 

The following conversion has been reported in the chemical literature It was earned out in two steps the first of which involved formation of a p toluenesulfonate ester Indicate the reagents for this step and show how you could convert the p toluenesulfonate to the desired product... 

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... 

Choose the correct enantiomer of 2 butanol that would permit you to prepare (/ ) 2 butanethiol by way of a p toluenesulfonate ester... 

Both reactants m the Williamson ether synthesis usually originate m alcohol pre cursors Sodium and potassium alkoxides are prepared by reaction of an alcohol with the appropriate metal and alkyl halides are most commonly made from alcohols by reaction with a hydrogen halide (Section 4 7) thionyl chloride (Section 4 13) or phosphorus tri bromide (Section 4 13) Alternatively alkyl p toluenesulfonates may be used m place of alkyl halides alkyl p toluenesulfonates are also prepared from alcohols as their imme diate precursors (Section 8 14)... 

Reaction of benzaldehyde with 1 2 octanediol in benzene containing a small amount of p toluenesulfonic acid yields almost equal quantities of two products in a combined yield of 94% Both products have the molecular formula C15H22O2 Suggest reasonable structures for these products... 

Aqueous caprolactam is polymerized alone and in the presence of sebacic acid (S) or hexamethylenediamine (H).t After a 24-hr reaction time, the polymer is isolated and the end groups are analyzed by titrating the carboxyl groups with KOH in benzyl alcohol and the amino groups with p-toluenesulfonic acid in trifluoroethanol. The number of milliequivalents of carboxyl group per mole caprolactam converted to polymer, [A ], and the number of milliequivalents of amino groups per mole caprolactam converted to polymer, [B ], are given below for three different runs ... 

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