With sulfones

Sulfonation has been used to change some characteristics of blends. Poly(2,6-diphenyl-l,4-phenylene oxide) and polystyrene are immiscible. However, when the polymers were functionalized by sulfonation, even though they remained immiscible when blended, the functionalization increased interfacial interactions and resulted in improved properties (65). In the case of DMPPO and poly(ethyl acrylate) the originally immiscible blends showed increased miscibility with sulfonation (66). 

B. Reaction of 1 -Hydroxytiyptamines with Sulfonic Chlorides and Sulfonic Acid. Ill... 

The antiarrhythmic activity of local anesthetics has been noted several times previously. Another such agent is prepared by first alkylating isopropylamine with sulfone 199. Reaction of the ])ioduct (200) with diethylethylenediamine and carbonyldiimidazole results in transfer of the CDI carbonyl group and formation of the urea suricainide (201) [52]. The transform in all likelihood involves stepwise replacement of the imidazole groups by the basic groups in the other reactants. 

In experiments with [sulfone]o = 3.15 x 10 5 M and excess N2H4, the reaction follows pseudo-first-order kinetics. Values of k vary with [N2H4]. Formulate the rate law and evaluate the constants therein ... 

Sometimes the mass spectra of related sulfoxides and sulfones have been discussed very compactly in the original literature. In these cases a detailed discussion on both will appear under the heading sulfoxides, but will be mentioned also in context with sulfones. 

Generally, in the nucleophilic addition to carbonyl groups, either magnesium compounds or alkali metal compounds (such as the Li, Na and K derivatives) are used. In some cases even potassium carbonate or piperidine were used as the base for condensation with sulfones. Good results were obtained when concentrated aqueous NaOH was used under phase-transfer conditions288,297,333. 

Figure 5.15 Naphthalenic copolyimides with sulfonated block.

Alcohol ether sulfates are used in mixture with sulfonates, either alkyl-benzenesulfonates or a-olefinsulfonates, and other surfactants, such as fatty alkanolamides, in manual liquid dishwashing detergents and light-duty detergents. These combinations show the excellent emulsifying and foaming properties required in dishwashing. 

The analytical methods for a-sulfo fatty acid esters reported in the literature deal with the determination of the surfactants in different matrices like detergents or product mixtures from the fabrication. The methyl esters of a-sulfo fatty acids can be separated from a mixture of different surfactants together with sulfonated surfactants by adsorption on an anionic exchanger resin such as Dowex 1X2 or 1X8. Desorption from the exchanger resin is successful with sodium hydroxide (2%) in a 1 1 mixture of isopropanol and water [105]. 

Only the a-olefins are sulfonated commercially to make a-olefinsulfonate (AOS). The chemistry of a-olefin sulfonation is usually described in terms of three stages. The initial sulfonation reaction involves the formation of 3-sul-tones. This initial step is so fast as to be almost instant. Reaction of the initially formed B-sultones with more S03 is competitive with sulfonation of the olefin. This side reaction produces a byproduct believed to be a cyclic pyro-sulfonate ester, i.e., a pyrosultone ... 

Me-ester sulfonation has to be carried out at relatively high temperatures as the initial reactions and the decomposition of intermediate products is relatively slow compared with sulfonation reaction rates for alkylbenzenes, primary alcohols, ethoxylated alcohols, and a-olefins. The required aging time for conversion of the intermediates to FAME sulfonation acid is long (about 45 min at 85°C). It is not possible to sulfonate Me-esters without an excess of S03. 

Sulfones and sulfoxides with a P hydrogen, on the other hand, undergo elimination on treatment with an alkoxide or, for sulfones,even with Sulfones... 

Cleavage of phenolic ethers with sulfonic acids... 

Sulfonic peracids (66) have also been applied recently to the preparation of acid sensitive oxiranes and for the epoxidation of allylic and homoallylic alcohols, as well as relatively unreactive a, p - unsaturated ketones. These reagents, prepared in situ from the corresponding sulfonyl imidazolides 65, promote the same sense of diastereoselectivity as the conventional peracids, but often to a higher degree. In particular, the epoxidation of certain A -3-ketosteroids (e.g., 67) with sulfonic peracids 66 resulted in the formation of oxirane products (e.g., 68) in remarkably high diastereomeric excess. This increased selectivity is most likely the result of the considerable steric requirements about the sulfur atom, which enhances non-bonded interactions believed to be operative in the diastereoselection mechanism <96TET2957>. 

In view of this behavior, the next step involved a search for an anionic sohd that was more similar to triflate. Several organic polymers with sulfonic groups were tried as supports [52]. Dowex and Deloxan were used as supports for the enf-6a-Cu(II) complex. The solid catalysts were used in the same cyclopropanation reaction (Scheme 7) and some relevant results are gathered in... 

Mass spectrometry was applied in conjunction with thermolysis studies leading mainly to sulfines and rearranged products with four-membered sulfoxides and to a loss of sulfur dioxide with sulfones The fragmentation pattern of thietes under electron impact can be explained by the sequential loss of the elements of sulfur monoxide and oxygen from an intervening cyclic sulfmate intermediate . ... 

Laboratory experiments have been conducted with a chromium lignite-chromium lignosulfonate mud system both without and with solid lubricants. These studies include filtration loss, cake quality, and their impact on the formation. A comparative evaluation has led to the conclusion that Gilsonite is a better additive compared with sulfonated asphalt as it results in less filtration... 

Anionic galactomannans, which are derived from guar gum, in which the hydroxyl groups are partially esterified with sulfonate groups that result from 2-acrylamido-2-methylpropane sulfonic acid and l-allyloxy-2-hydroxypropyl sulfonic acid [1872], have been claimed to be suitable as thickeners. The composition is capable of producing enhanced viscosities, when used either alone or in combination with a cationic polymer and distributed in a solvent. 

Scheme 8.24 Hydrogenations of enamides with sulfonated diphosphines.

As will be shown below in subsequent chapters, CDI reacts in a corresponding way with sulfonic acids, which lead via the corresponding imidazolides to sulfonamides or sulfonic esters, and with phosphoric acid, which reacts with CDI to give the corresponding imidazolides of phosphoric acids that can in turn be used for phosphorylations. 

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