Methanol sulfonyl compounds

In this method, an oligoethylene glycol is treated with 0.3 eq. of sodium bromoace-tate in methanol. The resulting monocarboxylic acid salt is then treated with toluene-sulfonyl chloride, sodium carbonate and dioxane. After heating the reaction mixture at 50° for an hour, the product was obtained either by Kugelrohr distillation or extraction. The two compounds produced in the reaction below (i.e., n = 1 and n = 2) were formed in 38% and 42% yields respectively . 

Lissamine rhodamine B sulfonyl chloride is relatively insoluble in water, but may be dissolved in DMF prior to the addition of a small aliquot to an aqueous reaction. Do not dissolve in DMSO, as sulfonyl chlorides will readily react with this solvent (Boyle, 1966). The compound has a maximal absorptivity at 556 nm with an extremely high extinction coefficient of up to 93,000M em-1 (in methanol) in highly purified form. Its emission maximum occurs at 576 nm, emitting red luminescence. 

The reaction of alkynyllithium compounds with alkoxycarbene tungsten complexes leads to anionic propargyl tungsten complexes (Figure 2.33 see also Figure 3.9). These intermediates are stable at low temperatures and react upon Lewis acid catalysis with aldehydes or A -sulfonyl imines to yield five-membered heterocycles [280]. Oxidative methoxycarbonylation [375] of the intermediate vinyl tungsten complex, followed by elimination of methanol leads to pyrroles or furanes (Figure 2.33 Entry 6, Table 2.22). 

Mixed anhydride 6b is a sulfonylating rather than a phos-phorylating agent. Thus, hydrolysis with 0 gives acid 6c and propylsulfonic acid in which the - -°0 isotope is incorporated only in the sulfonic acid (Eq. 2). Compound 6b reacts with either alcohols (methanol, ethanol, sec-butanol) or L-cysteine to yield acid 6c and with triethylamine to give the anion of 6c. probably via propylsulfene (4) (Eq. 2). 

In the tetrahydrofuran compounds there is opportunity for the existence of cis and irans isomers. They have been separated81 in the case of XL and XLII, the cis-form of which forms an anhydride. Evidence for the existence of the cts-form of 2,5-dishydroxymethyltetra-hydrofuran (XXXVIII) is found in the behavior of either its dichloro-or di-toluene-p-sulfonyl derivative with methanolic ammonia. From this reaction the dicyclic compound, 8-oxa-3-aza6fcyeZo [3,2,1] octane (XLIII) is obtained which can have been formed only from the m-form of the dicarbinol.82 An example of the addition of bromine to the furan... 

The chemical reactivity of all of the compounds of this series is governed by the powerful, electron-withdrawing influence of the sulfonyl groups this renders the acyclic, saturated members liable to eliminations, and the acyclic, unsaturated members susceptible to attack at C-2 by nucleophiles, and makes both the cyclic and the acyclic members unstable in basic solutions. This last feature provides the main source of interest in these compounds, all of which are degraded by aqueous ammonia to diethyl-sulfonylmethane and the aldose derived from the parent sugar by loss of C-1. Treatment with hydrazine in methanol, followed by cleavage of the derived hydrazone, offers a satisfactory means for degrading the acetylated sulfone (148) to n-arabinose (yield, 73%). ... 

Physical organic studies have demonstrated that lerl-butylsulfonyl chloride decomposes cleanly to the tert-butyl cation in water over a pH range 3.5 to 13.0. Clean teri-butyl cation formation is also the only significant reaction in methanol-chloroform. The subsequent product spectrum is a function of the reaction conditions. tert-Butylsulfonyl chloride, is used for the tert-butylation of aromatic compounds in a Friedel-Crafts desulfonylative alkylation in the presence of aluminum chloride-nitromethane as catalyst at 25 °C (eq 1). Alkylation products were obtained free of contamination by the sulfonylation product. 

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