Sultone

Sultones and Sultams. Compounds containing the group —SOj—O— as part of the ring are called -sultone. The —SOj— group has priority over the —O— group for lowest-numbered locant. 

Perfluorinated acid fluorides containing heteratoms are also accessible by ECF. Long-chain perfluorinated acid fluorides produced by ECF containing nitrogen (10—12), oxygen (13), and sulfur (14,15) have been reported. The fluorinated mixed sulfonic acid—carboxyflc acid precursors are also known. ECF of hydrocarbon sultones has led to formation of FS02(CF2) C0F, where n = 2,3 (16). 

Carbonyl sulfonyl fluorides of the formula FC0(CF2) S02F have been prepared by electrochemical fluorination of hydrocarbon sultones (41,42). More commonly in a technology pioneered by Du Pont, perfluoroalkanecarbonyl sulfonyl fluorides are prepared by addition of SO to tetrafluoroethylene followed by isomerization with a tertiary amine such as triethylamine (43). 

Naphthalenediol. This compound darkens rapidly in air. It can be made by fusion of the sultone of 8-hydroxy-1-naphthaIenesulfonic acid with 50 wt % sodium hydroxide at 200—230°C, or by the hydrolytic desulfonation of l,8-dihydroxy-4-naphthalenesulfonic acid. The diol also reacts with ammonia to give 1,8-naphthalenediamine. 

By the alkaline hydrolysis of the sultone formed on boiling an aqueous solution of the diazonium salt of S-amino-l-naphthalenesulfonic acid or its appropriate derivatives. 

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. 

Miscellaneous Reactions. Aromatic sulfonic acid derivatives can be nitrated using nitric acid [52583-42-3] HNO, ia H2SO4 (19). Sultones may be treated with hydrazine derivatives to give the corresponding ring-opened sulfonic acid (20). 

The sulfonic acid moiety has been iacorporated iato a variety of nonfluofinated polymeric materials (111). Chain-end sulfonated polymers are produced by the reaction of sultones with polymeric organolithiums (112). Polymeric sulfonic acids such as these are iacorporated ia positive-working photoresist compositions (113). 

Similar transformations are based upon 1,2-thiazine 2,2-dioxides (5-sultones), easily obtained by treating a,/3- or /3,y-unsaturated ketones with acetic anhydride and sulfuric acid. These compounds can be converted subsequently into furans, thiophenes or pyrroles (Scheme 115). 

However, certain additives can decrease the rate of thermal decomposition [28]. These additives include cyclic sulfates, sulfones, sultones, aliphatic and aromatic anhydrides, and polymers with pendant carboxylic acid functional groups. Most of these materials are latent acids, which decompose on heating in the presence of moisture to form a strong acid, as shown for cyclic sulfate, 9, in Eq. 5. 

Perfluoroallyl fluorosulfate is prepared by the treatment oiperfluoropropene with sulfur tnoxide m the presence of boron catalysts [2, 3, 4, 5, 6, 7] (equation 2) Perfluoroisopropyl allyl ether reacts similarly to give 58% polyfluoroallyl fluorosulfate in a cis/trans ratio of 6 4 [S] Sultones are the exclusive products without catalyst. Polyfluoroolefins such as 2-hydropentafluoropropylene [9], (2,3-dichloropropyl)tri-fluoroethylene [70], perfluoropropene [2, i], perfluoroisopropyl alkenyl ethers [S], and acyclic polyfluoroallyl ethers [77] undergo sulfur trioxidation to regioselectively produce the corresponding P-sultones in high yield... 

Octafluoroisobtttylene, whose double bond has reduced electron density and limited accessibility, reacts with sulfur tnoxidg under vigorous conditions The reaction mixture contains various components including bis-oi-tnfluorometh-yldifluoroethane-P-sultone, bis(a-trifluoromethyldifluoroethane)-(i-pyrosultone, the heptafluoroisobutenyl ester of fluorosulfonic acid, and the heptafluoroiso-butenyl ester of fluoropyrosulfomc acid [73] (equation 4)... 

Sulfur tnoxide adds to 2,2 difluoroethylenesulfonyl fluoride to afford the P sultone and its rearrangement product, bis(fluorosulfonyl)acetyl fluoride Potassium fluoride acts as a base and reacts with the acetyl fluoride to eliminate the elements of hydrogen fluoride and produce bis(fluorosulfonyl)ketene [IS] (equation 6)... 

Polyfluorovinyl ethers form unstable (i-sultones with sulfur trioxide The p sultones isomerize at 25 °C to give p carbonylsulfonate esters and acids [16, 17 The reaction of sulfur trioxide with ethyl pentafluoroisopropenyl ether to furnish 2-ketopentafluoropropanesulfonic acid and ethyl 2-ketopentafluoro-propanesulfonate is an example (equation 7)... 

The alkoxide formed by attack of the carbonyl group of perfluorobutyrolactone opens the oxirane ring of hexafluoropropene oxide at the central carbon atom [37] (equation 33). A fluorinated sultone reacts with halogenoalkanes in the presence of metal fluoride [3S] (equation 34). 

Tnfluoroacetic anhydnde in a mixture with sulfuric acid is an efficient reagent for the sulfonylation of aromatic compounds [44] The reaction of benzene with this system in nitromethane at room temperature gives diphenyl sulfone in 61% yield Alkyl and alkoxy benzenes under similar conditions form the corresponding diaryl sulfones in almost quantitative yield, whereas yields of sulfones from deactivated arenes such as chlorobenzene are substantially lower [44] The same reagent (tnfluoroacetic anhydride-sulfunc acid) reacts with adamantane and its derivatives with formation of isomeric adamantanols, adamantanones, and cyclic sultones [45]... 

Thiophenes can be prepared from the sultones of a,j8-unsaturated ketones. From the 8-sultone of pulegone (89), the thiophene (91) has been obtained through reduction with LiAlHi to (90), followed by dehydration of the latter. ... 

Cava and Schlessinger have reported the synthesis of 1,2,3-triphenyl-isoindole (65) in 78% yield from 1,3-diphenylisobenzofuran (68) hy reaction with thionylaniline (69) and boron trifluoride. The mechanism proposed for this remarkable transformation involves reaiTangement of the adduct (70) derived from thionylaniline and the isobenzofuran, to the tricyclic intermediate (71). This presumably collapses to the S-sultam (72), which yields the isoindole (65) upon extrusion of sulfur dioxide. Loss of sulfur dioxide, both from S-sultones and unsaturated S-sultams, is well documented. ... 

Napht-sultam, n. naphthosultam, naphsultam. -sulton, n. naphthosultone, naphsultone. 

To a cold solution of 29 g of atropine in 250 ml of acetone a solution of 1 3 g of propane-1,3-sultone in 100 ml of acetone is generally added. The combined solution is left for 48 hours. The white precipitate of fine crystalline needles is separated, washed several times with acetone, and then recrystallized from ethanol. It melts at 220°C. 

Molecular rearrangements such as that of Stevens248,265 or the sulfoxide - sulfinic acid, Ramberg-Backlund15 or sultone -> sultine rearrangements, are quite common in these classes of compounds. 

All the y-sultines were obtained as diastereomeric mixtures (ca 1 1, by NMR), and each one of y-sultines ( + )-49 and ( + )-51 (R = t-Bu) was separated into two diastereomers A and B by column chromatography. The oxidation of y-sultines (— )-49A and (+ )-49B to the corresponding optically active sultones (+ )-52A,B, which lack a chiral sulfur, may be taken as proof that the observed optical activity in the sultines is also due to the y-carbon. This result seems to exclude the intermediacy of vinylsulfene in the reaction mechanism, since its disrotatory closure would lead to racemic y-carbon in the product. 

The identity in sign and similarity in optical rotations of sultones (+)-52A,B, obtained from (—)-49A and (+)-49B, indicate that the absolute configuration of the y-carbon in both sultones as well as in both sultines is the same. In conclusion, the authors suggested113,114 that of the four possibilities shown below, y-sultines 48A-51A and 48B-51B may be assigned the (R)c-(Sf and (R)c-(Rf absolute configurations, respectively. Although initiated by mechanistic interest, this study has also resulted in a new method for selective synthesis of... 

Another way to reduce the nucleophilicity of the sulfur atom is oxidation to the corresponding sulfones, sulfonamides or sultones. Thus, diallyl sulfone undergoes RCM to the corresponding sulfolene smoothly in the presence of... 

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