Mixed sulfoxides

The total yield of sulfinic acid from the mixed sulfoxides is higher than that from diphenyl sulfoxides (31%) but lower than that from the corresponding dialkyl sulfoxides, and accounts for about 45% of the OH radicals (Table 1). 

Olah et al.466 observed immediate formation of protonated benzenesulfinic acid upon addition of SO2 to benzenium ion formed in H SO3F-Sb I 5-SO2C11 solution at —78°C. Based upon this observation, Laali and Nagvekar467 developed a method for the synthesis of aromatic sulfoxides [Eq. (5.169)]. Product formation was interpreted in terms of dehydration of protonated benzenesulfinic acid followed by nucleophilic attack by the aromatic to the formed arenesulfinyl cation. Mixed sulfoxides (4-fluorophenyl-4-methylphenyl and 4-fluorophenyl-3-trifluoromethyl sulfoxides) were also prepared by sequential addition of the two aromatics. The direct synthesis of symmetric diaryl sulfoxides in high yields (room temperature, 2—48 h, 50-95%) has been reported through the electrophilic activation of thionyl chloride with triflic acid.468... 

By treatment with HSOsF-SbFs (1 1) and sulfur dioxide, alkylbenzenes, haloben-zenes, and alkylhalobenzenes are converted to their corresponding diaryl sulfoxides along with small amounts of diaryl sulfides as minor products (Eq. 35) [81]. In the absence of SO2 aryl sulfone formation is the dominant process, although sulfoxide is also formed. Unsymmetrical (mixed) sulfoxides can be prepared by adding one molar equivalent of an arene to the solution of the second arene and magic acid-SOa in Freon at low temperatures. 

Solution Properties. Lignin in wood behaves as an insoluble, three-dimensional network. Isolated lignins (milled wood, kraft, or organosolv lignins) exhibit maximum solubiUty in solvents having a Hildebrand s solubiUty parameter, 5, of 20.5 — 22.5(J/cm ) (10 — ll(cal/cm ) > and A// in excess of 0.14 micrometer where A]1 is the infrared shift in the O—D bond when the solvents are mixed with CH OD. Solvents meeting these requirements include dioxane, acetone, methyl ceUosolve, pyridine, and dimethyl sulfoxide. 

The first aromatic sulfone polymer produced commercially was introduced as Bakelite polysulfone but now is sold by Union Carbide under the trade name Udel. It is made by reaction of the disodium salt of bisphenol A (BPA) with 4,4 -dichIorodiphenyl sulfone in a mixed solvent of chlorobenzene and dimethyl sulfoxide (eq. 12). 

Scheme 6 depicts a typical penicillin sulfoxide rearrangement (69JA1401). The mechanism probably involves an initial thermal formation of a sulfenic acid which is trapped by the acetic anhydride as the mixed sulfenic-acetic anhydride. Nucleophilic attack by the double bond on the sulfur leads to an episulfonium ion which, depending on the site of acetate attack, can afford either the penam (19) or the cepham (20). Product ratios are dependent on reaction conditions. For example, in another related study acetic anhydride gave predominantly the penam product, while chloroacetic anhydride gave the cepham product (7lJCS(O3540). The rearrangement can also be effected by acid in this case the principal products are the cepham (21) and the cephem (22 Scheme 7). Since these early studies a wide variety of reagents have been found to catalyze the conversion of a penicillin sulfoxide to the cepham/cephem ring system (e.g. 77JOC2887).

Tin, nitratodiphenyltris(dimethy) sulfoxide)-structure, 1,77 Tin, nitratotris(triphenyltin)-structure, 1, 47 Tin,tetrakis(acetato)-stereochemistry, 1,94 Tin, tetrakis(diethyldithiocarbamato)-angular parameters, 1, 57 Tin, tetrakis(ethyldithiocarbamato)-angular parameters, 1, 57 Tin, tetranitrato-stereochemistry, 1, 94 Tin, tri-n-butylmethoxy-, 3, 208 Tin alkoxides physical properties, 2, 346 Tin bromide, 3, 194 Tin bromide hydrate, 3,195 Tin carboxylates, 3, 222 mixed valence, 3, 222 Tin chloride, 3, 194 hydroformylation platinum complexes, 6, 263 Tin chloride dihydrate, 3,195 Tin complexes, 3, 183-223 acetyl ace tone... 

While water has been used as a solvent more than any other media, nonaqueous solvents [e.g., acetonitrile, propylene carbonate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or methanol] have also frequently been used. Mixed solvents may also be considered for certain applications. Double-distilled water is adequate for most work in aqueous media. Triple-distilled water is often required when trace (stripping) analysis is concerned. Organic solvents often require drying or purification procedures. These and other solvent-related considerations have been reviewed by Mann (3). 

Other examples of the photochemical a-cleavage of cyclic sulfoxides have been noted. Lawesson and coworkers22 have proposed that the mixed sulfenic-carboxylic anhydride (16) is formed on photolysis of 17, by a-cleavage followed by the loss of benzaldehyde. The... 

The reaction of OH radicals with dimethyl sulfoxide in aqueous solution was studied already in 1964 by Norman and coworkers37 38. They used the system T1m-H202 to produce OH radicals and using ESR/rapid mixing techniques they were able to demonstrate elimination of a methyl radical during the OH induced oxidation. Further studies showed the formation of sulfmic radicals in this reaction either directly or by spin trapping experiments39-44. 

In the case of diaryl sulfoxides the formation of both the aryl radical and the hydroxycyclohexadienyl radical was observed optically. Veltwisch and coworkers45 studied also the reaction of OH radicals from radiolysis of aqueous solutions of mixed (alkyl phenyl) sulfoxides (PhSOR). They found the formation of both alkylsulfinic and phenylsulfinic acids. 

Some other processes are known for sulfoxidation but have no technical importance. The acetic anhydride process has attracted some interest because it does not need exposure to light and enables conversion rates up to 15% of paraffin feedstock. Once started by peroxide or UV light initiation, it propagates without further radical-forming initiation steps. The addition of some 2.5% acetic anhydride to the reacting alkane is crucial to form a mixed anhydride of par-... 

Hydroxy-L-prolin is converted into a 2-methoxypyrrolidine. This can be used as a valuable chiral building block to prepare optically active 2-substituted pyrrolidines (2-allyl, 2-cyano, 2-phosphono) with different nucleophiles and employing TiQ as Lewis acid (Eq. 21) [286]. Using these latent A -acylimmonium cations (Eq. 22) [287] (Table 9, No. 31), 2-(pyrimidin-l-yl)-2-amino acids [288], and 5-fluorouracil derivatives [289] have been prepared. For the synthesis of p-lactams a 4-acetoxyazetidinone, prepared by non-Kolbe electrolysis of the corresponding 4-carboxy derivative (Eq. 23) [290], proved to be a valuable intermediate. 0-Benzoylated a-hydroxyacetic acids are decarboxylated in methanol to mixed acylals [291]. By reaction of the intermediate cation, with the carboxylic acid used as precursor, esters are obtained in acetonitrile (Eq. 24) [292] and surprisingly also in methanol as solvent (Table 9, No. 32). Hydroxy compounds are formed by decarboxylation in water or in dimethyl sulfoxide (Table 9, Nos. 34, 35). 

DMSO or other sulfoxides react with trimethylchlorosilanes (TCS) 14 or trimefhylsilyl bromide 16, via 789, to give the Sila-Pummerer product 1275. Rearrangement of 789 and further reaction with TCS 14 affords, with elimination of HMDSO 7 and via 1276 and 1277, methanesulfenyl chloride 1278, which is also accessible by chlorination of dimethyldisulfide, by treatment of DMSO with Me2SiCl2 48, with formation of silicon oil 56, or by reaction of DMSO with oxalyl chloride, whereupon CO and CO2 is evolved (cf also Section 8.2.2). On heating equimolar amounts of primary or secondary alcohols with DMSO and TCS 14 in benzene, formaldehyde acetals are formed in 76-96% yield [67]. Thus reaction of -butanol with DMSO and TCS 14 gives, via intermediate 1275 and the mixed acetal 1279, formaldehyde di-n-butyl acetal 1280 in 81% yield and methyl mercaptan (Scheme 8.26). Most importantly, use of DMSO-Dg furnishes acetals in which the 0,0 -methylene group is deuter-ated. Benzyl alcohol, however, affords, under these reaction conditions, 93% diben-zyl ether 1817 and no acetal [67]. 

Researchers studying polypeptide and polypeptide hybrid systems have also processed vesicles using two solvents. This method usually involves a common organic solvent that solubilizes both blocks and an aqueous solvent that solublizes only the hydrophilic block. The two solvents can be mixed with the polypeptide or polypeptide hybrid system at the same time or added sequentially. The choice of organic solvent depends heavily upon the properties of the polypeptide material, and commonly used solvents include dimethylformamide (DMF) [46, 59], methanol (MeOH) [49], dimethyl sulfoxide (DMSO) [50, 72], and tetrahydrofuran (THF) [44, 55]. Vesicles are usually formed when the organic solvent is slowly replaced with an aqueous solution via dialysis or removed through evaporation however, some vesicles have been reported to be present in the organic/aqueous mixture [49]. 

Table 1 shows values of fcj and for various sulfoxides. In the case of the mixed... 

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