Y-Sultones

Conditions for hydrolysis (82) of the intermediate sultone mixture also help modify the ratio of alkenesulfonate to -hydroxyalkanesulfonate, distribution of alkenesulfonate positional isomers, and completeness of conversion. Caustic hydrolysis using a slight stoichiometric excess of base is employed to ensure alkaline conditions throughout the hydrolysis phase of AOS production. The rate of hydrolysis depends a great deal on temperature. The 5-sultone requires the most time for conversion to 4-hydroxyalkanesulfonate. P-Sultones and y-sultones hydrolyze so rapidly to 2-hydroxyalkanesulfonate and 3-hydroxyalkanesulfonate that temperatures below 100°C can be used. 5-Sultone completely hydrolyzes between 120 and 175°C in 1—30 minutes. The quaUty of the final product mixture is ultimately determined by the choice of conditions. 

According to [4], the optimum conditions of the sulfonation stage are a reactor temperature of 15°C, an S03/I0 ratio of 1.08, and 2.8 vol % S03 in the gas stream. Such mild conditions lead to sulfonation mixtures consisting of 85% P-sultones (1) 10% alkenesulfonic acids (2) 5% y-sultones (3) and less than 5% unreacted olefins. The authors observe that the reaction has been completed to more than 95% at the outlet of the reactor. This means that the incomplete conversions found by earlier authors [15] must have been due to phenomena occurring after the sulfonation. Of equal importance is the observation that the reactivity of 10 toward gaseous S03 seems similar to that of AO. 

This is the last stage of the process. The neutralized mixture is heated to convert the y-sultones (3) into alkenesulfonates (6) and hydroxysulfonates (7). Here again it is advantageous to omit the aging stage as mixtures containing mainly (5) also contain the minimum amount of hydrolytically more persistent sultones. 

Impurities consist of unreacted material, including alkanes and internal or branched alkenes, and other material which can be detected in the neutral oil fraction of AOS. Examination of this fraction also indicates the amount of unhydrolyzed material (sulfonate esters and sultones) and byproducts (secondary alcohols, unsaturated and 2-chloro-y-sultones) in the sample. Salt calculations are made to determine inorganic sulfates and sodium chloride. Determinations for alkalinity, color, and water are required to meet product... 

Internal sultones, formed from internal alkenes, may also occur. These react less readily than corresponding terminal sultones. In addition, feedstock materials contain alkenes with multiple points of unsaturation, which may form unsaturated sultones such as the unsaturated y-sultone upon sulfonation. 

Numerous stationary phases were investigated by Callahan et al. [135] but only OV-101 separated C14 5-sultone from the C14 unsaturated-y/2-chloro-y-sultone combination and also separated these from other components present in the sample. Apiezon L separated all three sultones of interest but other components in the neutral oil interfered with the C14 unsaturated y-sultone. Additional stationary phases were found which will separate these sultones, but again, interfering components preclude their use for neutral oil analysis. 

A gas chromatographic method is described in this work for the analysis of tetradecane-l,4-sultone (C14 5-sultone) and the combination of 2-chloro-tetradecane-l,3-sultone (C14 2-chloro-y-sultone) and l-tetradecene-l,3-sultone (C14 unsaturated y-sultone) in neutral oils isolated from alkenesulfonate. Samples of the neutral oil are diluted in hexane and injected directly into the gas chromatograph. Quantitative data are obtained by comparison to known amounts of the respective sultones. Through the use of silica gel column chromatography followed by GC of collected fractions, separation and individual quantitation of the 2-chlorotetradecane-l,3-sultone and l-tetradecene-l,3-sultone can be obtained. 

Eluted peak areas are calculated and the levels of terminal 5- and y-sultones determined using an external standard. 

Two-dimensional thin-layer chromatography. This method is used to verify the presence of terminal 5-sultones, terminal unsaturated y-sultone, and terminal 2-chloro-y-sultone, if they are detected in the gas chromatographic determination. After extraction of the neutral oil from the AOS sample, the neutral oil is made up volumetrically to at least a 10% solution in hexane. Of this solution 3 pi is spotted onto a silica gel TLC plate together with standard sultones. It is twice developed with 2-propyl ether and then after turning the plate 90° twice developed with 60/40 n-butyl chloride/methylene chloride. The... 

Synthesis and Diels-Alder reactions of a,/f-unsaturated y-sultone [151]... 

The only other X=Y bond involved in additions to MCP derivatives is the S=0 double bond of sulfur trioxide. Actually, the reactions of MCP (1) and BCP (3) with S03 afford exclusively the y-sultones 608 and 609 (Scheme 85) [160], formal products of [3 + 2] additions of TMM species to S=0 double bond. However, by analogy with larger methylene- and cycloalkylidenecycloalkane derivatives which give stable P-sultones at low temperature, it is presumed that... 

Hydroxy-1-propanesulfonic acid y-sultone, pi97 2-Hydroxypropanoic acid, LI, L2... 

A novel thermal rearrangement with loss of sulfur dioxide leading to the stilbene or styrene derivatives 169 and 170 in highly stereospecific manner was carried out by heating (in dioxane, DMSO, dioxane-water or THF) the sulfene-tropone adducts (y-sultones) 167 or 168 (equations 51 and 52)68. 

Sulfuryl chloride isocyanate with 1 gave the expected )5-lactam 177 only as a minor product, the principal product being the y-lactam derivative 178. It is reasonable to assume that the 1,4-zwitterionic intermediate 176 is responsible for the formation of 177 and 178 (Scheme 39) [104,130]. Sulfonation of 1 with SO3 also proceeds with ring opening of one of the cyclopropyl groups to give quantitatively the spirocyclopropane-y-sultone 179 (Scheme 39) [76,132]. 

By ring-opening of the new diastereo- and enantiomerically pure y-sultones R,R) -125 a pathway to pharmacologically interesting sulfonic acid derivatives was opened proceeding via an Sn2 mechanism with inversion of configuration at the attacked y-carbon atom. In this manner, we prepared the y-alkoxy sulfonates (R,S)-126 [98], the y-hydroxy sulfonates R,S)-127 [99], and the y-amino sulfonates (R,S)-128 [100], all in excellent diastereo- and enantiomeric excesses of de, ee> 98% (Scheme 1.1.35). 

Synonyms-. 3-Hydroxy-l-propanesulfonic acid, y-sultone propane sultone... 

However, 1-methoxytrifluorocyclopropene behaves differently, and y-sultone 95 is formed even at low temperature [182] ... 

Further results on the highly stereoselective nucleophilic ring-opening of chiral y-sul tones 112 have appeared <07S1837> and the reactions of p-halo-a,p-unsaturated y-sultones 113 with nucleophiles have also been reported <07JOC6824>. 

SYNS 3-HYDROXY-l-PROPANESULFONIC ACID y-SULTONE 3-HYDROXY-l-PROPANESULPHONIC ACID SULTONE l,2-OXATHIOLANE-2,2-DIOXIDE 1-PROPANESULFONICACID-3-HYDROXY-Y-SULTONE... 

HYDROXYPROPANENITRILE see HGPOOO 3-HYDROXY-l-PROPANESULFONIC ACID y-SULTONE see PML400... 

PROPANE, 2,2 -OXYBIS(l-CHLORO)- see BII250 1 -PROPANESULFONIC ACID-3-HYDROXY-y-SULTONE see PML400 PROPANE SULTONE see PML400... 

Aliphatic y-sultones and 8-sultones may be synthesised by the sulfonation of alkenes by reaction with the sulfur trioxide-dioxan complex or gaseous sulfur trioxide (Scheme 66). 

The hydrolysis of the tropolone methyl ether 360 with concentrated HCl in boiling EtOH results in the hydroxyfluorenone 361 (equation 172) °. Thermal rearrangement with loss of sulfur dioxide occurs on heating the y-sultones 362 in dioxane, DMSO, dioxane-water or THE at 90 °C for 6-10 h to give 90% of the styrene derivatives 363 in a highly stereospecific manner (equation 173). ... 

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