Sulfolene

Example 4.4 Butadiene sulfone (or 3-sulfolene) is an intermediate used for the production of solvents. It can be produced from butadiene and sulfur dioxide according to the reaction ... 

Pd-catalyzed reactions of sulfur-containing nucleophiles, SO2, CSj and S, were summarized in a review[101]. When 3-sulfolene (109) is treated with butadiene at I00"C, cis- and /ra j-2,5-divinyisulfolanes (110) are obtained. Under these conditions. 3-sulfolene (109) decomposes to butadiene and SOj, which react to give divinylsulfolane (I10)[I02]. Divinylsulfolane (110) can be obtained directly by the reaction of SO2 with butadiene[103]. 

Sulfolane and sulfones Sulfolane process Sulfolane-W 3-Sulfolene [77-79-2]... 

Production. Sulfolane is produced domestically by the Phillips Chemical Company (Borger, Texas). Industrially, sulfolane is synthesized by hydrogenating 3-sulfolene [77-79-2] (2,5-dihydrothiophene-l,1-dioxide) (2), the reaction product of butadiene and sulfur dioxide ... 

Sulfolene (2) is the next most commercially important sulfone after sulfolane. Besides its precursor role in sulfolane manufacture, 3-sulfolene is an intermediate in the synthesis of sulfolanyl ethers, which are used as hydrauHc fluid additives (see Hydraulic fluids). 3-Sulfolene or its derivatives also have been used in cosmetics (qv) and slimicides. Selected physical properties of 3-sulfolene are Hsted in Table 3. 

Sulfolane (tetramethylenesulfone) [126-33-0] M 120.2, m 28.5 , b 153-154 /18mm, 285 /760mm, d 1.263, n 1.4820. Prepared commercially by Diels-Alder reaction of 1,3-butadiene and sulfur dioxide, followed by Raney nickel hydrogenation. The principle impurities are water, 3-sulfolene, 2-sulfolene and 2-isopropyl sulfolanyl ether. It is dried by passage through a column of molecular sieves. Distd... 

Twenty-five grams (0.212 mole) of 3-sulfolene, and 15.0 g (0.153 mole) of pulverized maleic anhydride are added to a dry 250-ml flask fitted with a condenser. Boiling chips and 10 ml of dry xylene are added. The mixture is swirled gently for a few minutes to effect partial solution, then gently heated until an even boil is established. During the first 5-10 minutes, the reaction is appreciably exothermic, and care must be exercised to avoid overheating. 

Sulfolene (2,5-dihydrothiophene-l,1-dioxide) EK, MCB Isopropenyl acetate MCB Dimedon EK, MCB... 

Ando K., Takayama H. Heteroaromatic-Fnsed 3-Sulfolenes Heterocycles 1994 37 1417-1439... 

The Diels-Alder reaction is usually reversible and has been used to protect double bonds. A convenient substitute for butadiene in the Diels-Alder reaction is the compound 3-sulfolene since the latter is a solid that is easy to handle while the former is gas. " Butadiene is generated in situ by a reverse Diels-Alder reaction (see 17-20). 

Subsequently, other publications have appeared involving the DA reactions of porphyrins with other dienes. For instance, the reaction of meso-tetrakis(pentafluorophenyl)porphyrin Id with the diene generated from pyrrole-fused 3-sulfolene gave rise to the isoindole-fused chlorin derivative 8 accompanied by a mixture of stereoisomeric bacteriochlorins 9 (Scheme 2) <98CC2355>. 

Scheme 2 DA Reaction of porphyrin Id with a pyrrole-fused 3-sulfolene.

The thiophene ring system can be utilized as a synthetic scaffold for the preparation of nonthiophene materials as the sulfur moiety can be removed by reduction (desulfurization) or extrusion (loss of SO2). The extrusion of sulfur dioxide from 3-sulfolenes (2,5-dihydrothiophene 1,1-dioxides) give dienes (butadienes or o-quinodimethanes) that can be utilized to prepare six-membered rings by cycloaddition chemistry. For example, thermolysis of 3-sulfolene 120 provided tricyclic pyrazole 122 via an intramolecular cycloaddition of the o-quinodimethane 121 that results by extrusion of sulfur dioxide <00JOC5760>. Syntheses of 3-sulfolenes 123 and 124 <00S507> have recently been reported. 

Regiospecilic intramolecular cycloadditions of nitrones to sulfur-substituted dienes, with 3-sulfolene precursors, has been realized (Scheme 2.217). The stereochemical outcome of these reactions is affected by the structure of the substituent (sulfide or sulfone) in the diene and by the chain length connecting the diene and nitrone (a) and (b) (see Scheme 2.211). The bicyclic products obtained from these reactions have been converted to interesting heterocyclic compounds (709). 

W-Methylpiperidine, 52, 127 3-Methyl-3-sulfolene, in Diels-Alder reaction, 50, 48 MODIFIED CLEMMENSEN REDUCTION CHOLESTANE, 53, 86... 

Electrochemical trifluoromethylation of 3-sulfolene in a CF3C02H/CF3C02Na/ CH3CN/H2O system gave a complex mixture consisting of meso- and dl-3,4-bis(trifluoromethyl)sulfolanes as the major components [108]. 

Dihydrothiophene 1,1-dioxide (butadiene sulfone, or 3-sulfolene) was purchased from the Aldrich Chemical Company, Inc. 

Sulfolene, as a source of 1,3-buta-diene in situ, 50, 43 Sulfones, bromination, 50, 31 Sulfur, reaction with organo-lithium compounds, 50,105 Sulfuryl chloride, with 1,1-cyclo-butanedicarboxylic acid to give... 

The pyrrole adduct 81 was obtained by reaction of 3,4-fused pyrrolo-3-sulfolenes, probably via a radical-mechanism [71]. Obviously, structure 81 can be regarded as part of a porphyrin-structure. Thus, fullereno-porphyrinates with up to four Cgg units surrounding the porphyrin-core were synthesized [72-74]. 

Pyrrole-fused 3-sulfolenes 221 undergo thermal extrusion of sulfur dioxide to produce highly reactive o-quinodi-methanes which can be trapped in Diels-Alder reactions (Scheme 23) <1997H(46)199, 1997TL3639>. The resulting cycloadducts 222-227 are important starting compounds in porphyrin synthesis. 

In recent years, there has been a greater interest in joining certain heterocyclic systems to [60]-fullerene with pyrimidine-fused 3-sulfolenes as one such case. Three derivatives have been examined in membrane model environments and the aggregation of these derivatives has been studied <2000J(P2)301>. Similar studies have been carried out on furo[2,3- ]pyrimidines <1996JST(385)55>. 

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