Sulfuryl chloride with temperature

The reaction of sulfuryl chloride with carbohydrates to give chloro-deoxy derivatives has been reviewed briefly in this Series.98 The reaction of sulfuryl chloride with monosaccharides has been shown to afford products in which the secondary hydroxyl groups are replaced by chlorine with inversion of configuration.68-75 Jones and coworkers reported that the reaction of methyl a-D-glucopyranoside with sulfuryl chloride and pyridine in chloroform at room temperature proceeds by way of the 4,6-bis(chlorosulfate) by an Sn2 process, with chloride as the nucleophile, to give methyl 4,6-dichloro-4,6-dideoxy-a-D-galactopyranoside 2,3-bis(chlorosulfate).74... 

The selective replacement of hydroxyl groups in carbohydrates by chlorine has been achieved by the use of sulfuryl chloride.1,74,87,88 The reaction of sulfuryl chloride with maltose89,90 and methyl /3-maltoside24 has been studied. Treatment of maltose with sulfuryl chloride, initially for 2 h at — 70° and then processing at room temperature, gave, after methyl glycosidation and dechlorosulfation, a low yield... 

The reagent is prepared by reaction of sulfuryl chloride with imidazole. It is hydrolyzed by acid only at elevated temperatures, and does not react with carboxylic acids to form imidazolides.1... 

At present, thionyl chloride is produced commercially by the continuous reaction of sulfur dioxide (or sulfur trioxide) with sulfur monochloride (or sulfur dichloride) mixed with excess chlorine. The reaction is conducted in the gaseous phase at elevated temperature over activated carbon (178). Unreacted sulfur dioxide is mixed with the stoichiometric amount of chlorine and allowed to react at low temperature over activated carbon to form sulfuryl chloride, which is fed back to the main thionyl chloride reactor. 

The decomposition of sulfuryl chloride is accelerated by light and catalyzed by aluminum chloride and charcoal. Many of the reactions of sulfuryl chloride are explainable on the basis of its dissociation products. Sulfuryl chloride reacts with sulfur at 200°C or at ambient temperature in the presence of aluminum chloride producing sulfur monochloride. It hberates bromine or iodine from bromides or iodides. Sulfuryl chloride does not mix readily with water and hydrolyzes rather slowly. 

The organic chemistry of sulfuryl chloride involves its use in chlorination and sulfonation (172,175,196,197). As a chlorinating agent, sulfuryl chloride is often mote selective than elemental chlorine. The use of sulfuryl chloride as a chlorinating agent often allows mote convenient handling and measurement as well as better temperature control because of the lower heat of reaction as compared with chlorine. Sulfuryl chloride sometimes affords better selectivity than chlorine in chlorination of active methylene compounds (198—200) ... 

Strong dehydrating agents such as phosphorous pentoxide or sulfur trioxide convert chlorosulfuric acid to its anhydride, pyrosulfuryl chloride [7791-27-7] S20 Cl2. Analogous trisulfuryl compounds have been identified in mixtures with sulfur trioxide (3,19). When boiled in the presence of mercury salts or other catalysts, chlorosulfuric acid decomposes quantitatively to sulfuryl chloride and sulfuric acid. The reverse reaction has been claimed as a preparative method (20), but it appears to proceed only under special conditions. Noncatalytic decomposition at temperatures at and above the boiling point also generates sulfuryl chloride, chlorine, sulfur dioxide, and other compounds. 

Reduction of indolenines with sodium and ethanol gives indolines. The pentachloropyr-role, obtained by chlorination of pyrrole with sulfuryl chloride at room temperature in anhydrous ether, was shown by spectroscopic methods to have an a-pyrrolenine (2H-pyrrole) structure (222). It is necessary, however, to postulate that it is in equilibrium with small but finite amounts of the isomeric /3-pyrrolenine form (3//-pyrrole 223), since pentachloropyrrole functions as a 2-aza- rather than as a 1-aza-butadiene in forming a cycloadduct (224) with styrene (80JOC435). Pentachloropyrrole acts as a dienophile in its reaction with cyclopentadiene via its ene moiety (81JOC3036). 

A. Chloropyruvic acid. In a 1-1. four-necked flask (Note 1) fitted with a sealed mechanical stirrer, dropping funnel, thermometer, and reflux condenser protected with a calcium chloride tube is placed 249 g. (2.83 moles) of pyruvic acid (Note 2). The stirrer is started and 394 g. (2.92 moles) of sulfuryl chloride (Note 3) is added dropwise over a period of 2 hours. During the addition the temperature is maintained at 25-30° by cooling with a water bath. 

In absence of diluent or other effective control of reaction rate, the sulfoxide reacts violently or explosively with the following acetyl chloride, benzenesul-fonyl 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]. 

D-Lyxose yielded a D-lyxosyl chloride 2,3,4-tri(chlorosulfate) which, on treatment with chloride ion, led to a dichlorodideoxy compound, most probably 2,4-dichloro-2,4-dideoxy-L-arabinose.353 D-Glucose gave a compound presumed to be 4,6-dichloro-4,6-dideoxy-a,/3-D-galactosyl chloride 2,3-di(chlorosulfate),360 and D-xylose afforded a monochloromonodeoxy derivative formulated, on indirect evidence, as 4-chloro-4-deoxy-L-arabinopyranosyl chloride 2,3-di(chlorosulfate).360 3,4-Dichloro-3,4-dideoxy-/3-D-ribopyranosyl chloride 2-(chlorosulfate) was the major, and 4-chloro-4-deoxy-a-D-xylopyranosyl chloride 2,3-di(chlorosulfate) the minor, product from the reaction of L-arabinose with sulfuryl chloride at room temperature for 24 hours.357,361 It has been established that, on reaction with sulfuryl chloride at low temperature, crystalline a-D-xylopyranose and /3-D-lyxopyranose afford, respectively, the 2,4,6-tri(chlorosul-fate)s of /3-D-xylopyranosyl chloride and a-D-lyxopyranosyl chloride,362 363 confirming that substitution at C-l occurs by an Sn2 process on a l-(chlorosulfuric) ester intermediate. 

B. 2,4-Dinitrobenzenesulfenyl chloride. Dry 2,4-dinitrophenyl benzyl sulfide (232 g., 0.80 mole) and 400 ml. of dry ethylene chloride are placed in a 2-1., one-necked, round-bottomed flask equipped with a stirrer (Note 3). Sulfuryl chloride (119 g., 0.88 mole) (Note 4) is added to the resulting suspension at room temperature. A mildly exothermic reaction causes the solid to dissolve quickly, usually within 1 to 2 minutes, with a temperature rise of 10-15° (Note 5). The resulting clear yellow solution is concentrated to an oil by heating under aspirator vacuum on a steam bath (Note 6). Caution Do not heat with gas or electricity because the product, like many nitro compounds, can explode if overheated.) The residual oil is cooled to 50-60°, and 3-4 volumes of dry petroleum ether (b.p. 30-60°) are added with vigorous handswirling. The oil quickly crystallizes. The mixture is cooled to room temperature and filtered to separate 2,4-dinitrobenzene-sulfenyl chloride as a yellow crystalline solid. The sulfenyl chloride is washed well with dry petroleum ether and dried at 60-80° (Note 7) weight 150-170 g. (80-90%) m.p. 95-96° (Notes 8, 9). 

Treatment of iV-alkyl-iV -(2-benzothiazolyl)thioureas 294 with sulfuryl chloride, at room temperature, affords 2-aminoethyl[l,2,4]thiadiazolo[3,2-4]benzothiazolium chloride 295 (Equation 42) <1999JHC991>. 

For sulfamides with larger alkyl groups (C3 to Cg) the following j)rocedure is preferred. To a stirred mixture of 135 g. (1.00 mol( ) of sulfuryl chloride and 500 ml. of chloroform is added, dropwise and with cooling to —10° to —5°, a solution of 316 g. ( (.00 moles) of pyridine in 400 ml. of chloroform followed by, with cooling to —5° to 0°, a solution of 2.5 moles of alkylamine in 600 ml. of chloroform. After addition is complete the mixture is stirred for 30 minutes at room temperature and then evap-ora(,( d under reduced pressure to a thick brown liquid, to wbic li aqueous 2M hydrochloric acid is added until the pyridine dissolves. On cooling of the acidic solution the crystalline MiiHaiMidc precipitates and is filtered. Any dissolved sulfamide limy be recovered by extraction of the filtrate with ether. Tb( crude product may be purified by recrystallization from bd )), cf.hanol. 

Similarly, when the selective O-pivaloylation of trehalose was investigated by Richardson, Hough, and Cortes-Garcia, a number of useful derivatives were also obtained in quantities adequate to be of preparative value. Thus when 12 equivalents of pivaloyl chloride were employed for this esterification at — 20 °C, and the reactants were thereafter stored at room temperature for three days, a 61% yield of the 2,2 3,3, 4, 6,6 -heptapivalate was obtained, and following invertive chlorination with sulfuryl chloride, a displacement with different nucleophiles gave access to C-4-modified trehaloses, one example of which is shown in Scheme 17. 

SCHEME 27. Ballard, Fairclough, Hough, and Richardson s study of the selective low-temperature chlorination of sucrose with sulfuryl chloride (1973). 

In Durette s study, he treated methyl (S-maltoside with an excess of sulfuryl chloride at low temperature in chloroform-pyridine and thereafter warmed the mixture to room temperature. After dechlorosulfation with a catalytic amount of sodium iodide in methanol and O-acetylation, the stereochemically inverted 4,6,3 6 -... 

Sulfuryl chloride, SO2CI2, reacts with ice-cold water to form a hydrate, S02C12 I5H2O. However, at ambient temperature water decomposes sulfuryl chloride slowly forming sulfuric acid and hydrochloric acid ... 

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