Acidity sulfoxide

The sulfated compounds MM 13902 (3, n = (5) and MM 17880 (4) are also broad-spectmm agents, but not as potent as thienamycia and all lack any significant activity against Pseudomonas (73). Many carbapenems are excellent inhibitors of isolated P-lactamases, particularly the olivanic acid sulfoxide MM 4550 (3, n = 1) (3). The possible mechanism of action of the carbapenems as inhibitors of P-lactamases has been discussed in some detail (74). Other carbapenems such as PS-5 (5) (75), the carpetimycins (76), asparenomycins (77), and pluracidomycins (8) are all highly active as antibiotics or P-lactamase inhibitors. The parent nucleus itself (1, X = CH2) is intrinsically active, but chemically unstable (9). 

The preparation of isothiazolidin-3-one 5-oxide and 5,5-dioxide derivatives of azetidin-3-ones was described (99EUP100069), starting from penicillanic acid sulfoxide amides in the presence of halogenating agents in anhydrous inert solvents or even without them. Through rearrangement and oxidation with conventional methods, compounds 73 could be obtained. For some derivatives the usefulness, as intermediates for the preparation of novel p-lactam analogs or active substances in formulations for antimicrobial therapy, is claimed. 

Nishimura and coworkers57-59 studied the y-radiolysis of aqueous solutions of sulfoxide amino acids. Sulfoxide amino acids are the precursors of the flavors of onions (S-propyl-L-cysteine sulfoxide, S-methyl-L-cysteine sulfoxide and S-(l-propenyl)-L-cysteine sulfoxide) and garlic (S-allyl-L-cysteine sulfoxide). In studies on sprout inhibition of onion by /-irradiation it was found that the characteristic flavor of onions became milder. In the y-radiolysis of an aqueous solution of S-propyl-L-cysteine sulfoxide (PCSO)57,58 they identified as the main products alanine, cysteic acid, dipropyl disulfide and dipropyl sulfide. In the radiolysis of S-allyl-L-cysteine sulfoxide (ACSO) they found that the main products are S-allyl-L-cysteine, cysteic acid, cystine, allyl alcohol, propyl allyl sulfide and diallyl sulfide. The mechanisms of formation of the products were partly elucidated by the study of the radiolysis in the presence of N20 and Br- as eaq - and OH radicals scavengers, respectively. 

Coupling of Organometallic Reagents With Esters of Sulfuric and Sulfonic Acids, Sulfoxides and Sulfones... 

See Carbonyl diisothiocyanate, and Dinitrogen tetraoxide, and Hexachlorocyclot-riphosphazine, and Sodium hydride, all below See Perchloric acid Sulfoxides... 

See Chromium(III) perchlorate. 6 dimethyl sulfoxide Magnesium perchlorate Dimethyl sulfoxide Mercury(II) perchlorate. 6(or 4)dimethyl sulfoxide Silver perchlorate Dimethyl sulfoxide See Perchloric acid Sulfoxides... 

As in the case of propachlor mercapturic acid sulfoxide, the biological significance of xenobiotic mercapturic acids that contain oxidized sulfur is not known. Casida et al. (39) have reported that sulfoxidation of some thiocarbamate herbicides is a beneficial step in the detoxication process. However, cysteine conjugates can exhibit adverse biological activities. Smith (40) has reviewed work on the metabolism of the toxic principle in kale and has shown that C-S lyase action on S-methylcysteine sulfoxide produces the toxic principle. Virtanen ( ) has reviewed the processes in other plants that lead to the production of compounds with biological activity from -substituted cysteine sulfoxides. 

Single-Ring Heterocyclic Sulfur Compounds Single-Ring Heterocyclic Sulfur Compounds Tetrachlorothiophene Sodium Strontium Sulfides, Disulfides Dimethyl Disulfide Dimethyl Sulfide Sulfides, Disulfides Sulfonic Acids Sulfonic Acids, Sulfoxides Sulfoxides... 

In rats exposed to 600 mg/m [150 ppm] 1,2-dichloroethane for 6 h or administered 150 mg/kg bw by gavage, there was no significant difference in the route of excretion of non-volatile metabolites (Reitz et al., 1982). The major urinary metabolites identified following exposure of rats by either route were thiodiacetic acid (67-68%) and thiodi-acetic acid sulfoxide (26-29%). 

Urinary metabolites are S-methylthioacetic acid sulfoxide, V-acetyl-.S -methyl-L-cysteine and /-(methylthioacetyl)glycine, which are metabolites of Y-methyl-i-cysteine and 5-methylglutathione. These last two compounds were found after incubation of methyl chloride with rodent liver, kidney and brain homogenates. The methyl group of methyl chloride is metabolized via -methyl-L-cysteine to formate which is found in urine and blood of rats, whereas formaldehyde is found in rat liver microsomes and blood of mice and rabbits (lARC, 1986). 

Urinary metabolites recovered within the first 16 h and representing 80% of the excretion products resulted from an initial methylation of cysteine residues by methyl methanesulfonate. These were mcthylmercapturic acid sulfoxide, 2-hydroxy-3-methyl-sulfmylpropionic acid, methylsulfmylacetic acid, methylmercapturic acid and 7V-(methyl-thioacetyl)glycine. Glutathione conjugation has been shown to occur in rat liver (lARC, 1974). 

In absence of diluent or other effective control of reaction rate, the sulfoxide reacts violently or explosively with the following acetyl chloride, benzenesulfonyl chloride, cyanuric chloride, phosphorus trichloride, phosphoryl chloride, tetrachlorosilane, sulfur dichloride, disulfur dichloride, sulfuryl chloride or thionyl chloride [1]. These violent reactions are explained in terms of exothermic polymerisation of formaldehyde produced under a variety of conditions by interaction of the sulfoxide with reactive halides, acidic or basic reagents [2]. Oxalyl chloride reacts explosively with DMSO at ambient temperature, but controllably in dichloromethane at —60°C [3]. See Carbonyl diisothiocyanate, and Dinitrogen tetraoxide, and Hexachlorocyclo-triphosphazine, and Sodium hydride, all below See Perchloric acid Sulfoxides... 

Mixtures of the sulfoxide with metal salts of oxoacids are powerful explosives. Examples are aluminium perchlorate, sodium perchlorate and iron(III) nitrate [1], The water in hydrated oxosalts (aluminium perchlorate, iron(m) perchlorate, iron(III) nitrate) may be partially or totally replaced by dimethyl (or other) sulfoxide to give solvated salts useful as explosives [2], Metal nitrates and perchlorates solvated with DMSO are generally powerfully explosive, and under certain conditions a violent reaction is easily triggered [3]. Several other explosions involving perchlorates and the sulfoxide have been reported. See Perchloric acid Sulfoxides... 

Thus, the bromination of oxides 448 and 449 leads to bromo derivatives 451-454 (Scheme 122). When brominated in the absence of sodium acetate, 448b yields a small amount of thiazine 364b. When heated with zinc in acetic acid, sulfoxide 453 is 5-desoxygenated and partly debrominated to give thiazines 454 and 362. 

A versatile non-Friedel-Crafts approach to naphthols is provided by condensation of the toluic acid sulfoxide with substituted acrylates or methyl vinyl ketone. Sequential conjugate addition and acylation of the first formed anion leads to the tetralone. Pyrolysis leads to aromatiza-tlon by loss of sulfinic acid. 

New metab. of propylbrotnide (I) in rat is n-propylmercapturic acid sulfoxide ilk%), trace of S contg. metab. suggest that S-alkyl. cystein residues formed only with (I) (1). Haloalkanes gen. metab. to mercap-turic ac. and similar S-linked conj. Addl. metab. reaction is hydroxy-lation (2). 

U Hofmann, M Eichelbaum, S Seefried, CO Meese. Identification of thiodiglycolic acid, thiodiglycolic acid sulfoxide, and (3-carboxymethylthio)lactic acid as major human biotransformation products of S-carboxymethyl-l-cysteine. Drug Metab Disp 19 222, 1991. 

Another mechanism for the removal of surface films was discovered by Wheeler (1972), who found that fatty acid films on seawater collapsed to form particles when exposed to near-ultraviolet radiation. The results indicated that there was an introduction of hydroperoxide groups into the parent fatty acid molecule with resultant polymerization of the products. Instead of polymerization, Timmons (1962) found that the constituents of plankton oil films were converted to smaller and more soluble fragments when exposed to artificial sunlight. Photochemically initiated solubilization appears to be a process common to some constituents of crude oil and fuel oil films as well, with low molecular weight acids, sulfoxides, and peroxides comprising some of the product soluble fraction (Burwood and Speers, 1974 Hansen, 1975 Larson et al., 1977). The rate of photo-oxidation of films of various fractions of crude oil spread on water was greatly increased... 

Fig. 32.24 Tienilic acid biotransformation to tienilic acid sulfoxide.

Aldehydes and sulfides were oxidized with the Ni catalyst (3 mol%) in good yields (60% to 90%) in a single phase solvent system at 64 (PhCH3/ perfluorodecalin or CgF 7Br) under 1 atm of O2 (see Figure 4 for carboxylic acid, sulfoxide/sulfone, and... 

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