Divinyl sulfide

Methyl vinyl sulfide Divinyl sulfide (Vinyl sulfide) Allyl methyl sulfide Diethyl sulfide (Ethyl sulfide)... 

Aryl and alkenyl phenyl sulfides are prepared by the reaction of aryl and alkenyl halides and inflates with tributylstannyl phenyl sulfide. 2-Chloropyrimidine (737) is used for the coupling[606,607]. The diaryl or divinyl sulfide 739 is prepared by the reaction of distannyl sulfide (738)[548], N,N-Diethylaminotributyltin (740) reacts with aryl halides to give arylamines[608]. 

Vinyl chloride reacts with sulfides, thiols, alcohols, and oximes in basic media. Reaction with hydrated sodium sulfide [1313-82-2] in a mixture of dimethyl sulfoxide [67-68-5] (DMSO) and potassium hydroxide [1310-58-3], KOH, yields divinyl sulfide [627-51-0] and sulfur-containing heterocycles (27). Various vinyl sulfides can be obtained by reacting vinyl chloride with thiols in the presence of base (28). Vinyl ethers are produced in similar fashion, from the reaction of vinyl chloride with alcohols in the presence of a strong base (29,30). A variety of pyrroles and indoles have also been prepared by reacting vinyl chloride with different ketoximes or oximes in a mixture of DMSO and KOH (31). 

B. A Trofimov and S. V. Amosova, Divinyl Sulfides, and Its Derivatives, Nauka, Novosibirsk, 1983. 

Nucleophilic addition to a, -unsaturated sulfones has long been known. For example, treatment of divinyl sulfone with sodium hydroxide has been known to afford bis( -hydroxyethyl) sulfone "", while the reaction of a- and -naphthyl allyl sulfones and allyl benzyl sulfone " with alkali hydroxide or alkoxide gave -hydroxy or alkoxy derivatives. In the latter reaction, the allyl group underwent prototropy to the 1-propenyl group, which in a subsequent step underwent nucleophilic attack . Amines, alcohols and sulfides are known to add readily to a, -unsaturated sulfones, and these addition reactions have been studied widely. In this section, the addition of carbon nucleophiles to a, ji-unsaturated sulfones and the reactions of the resulting a-sulfonyl carbanions will be examined. 

Divinyl sulfide, 25 630 Divinylsulfone method, for covalent ligand immobilization, 6 3961 Division of Chemical Nomenclature and Structure Representation (IUPAC),... 

The reaction of R —C=C—with the electrogenerated Sx ions provides a convenient method for the synthesis of substituted thiophenes (Eq. 30) [263]. Besides thiophenes, some dithiols, divinyl-sulfides and 2,4,6-tricarboxyethyl-l,3,5-trithiophenol were formed, the product distribution being governed by the nature of the substituents in the starting acetylenic substrate. 

Silathietanes were first introduced as a new heterocyclic system in 1976 by a Soviet research groups who prepared them by addition of substituted silanes to divinyl sulfide (Scheme 19). The two possible intermediates 288... 

Dioxins, 1,4-oxathiins, and 1,4-dithiins have often been prepared by elimination reactions from saturated analogs as described in CHEC-II(1996) <1996CHEC-II(6)447>. Since then, a synthesis of tetramethyl l,4-dithiin-2,3,5,6-tetracarboxylate 241 has been reported in low yield (12%) by thermal decomposition of the 1,4,2,5-dithiadiazine system 240 in refluxing o-dichlorobenzene in the presence of DMAD <1997J(P1)1157>. Recently, 2,6-divinyl-l,4-dithiin 68 has been isolated from the reaction of l,4-bis(4-bromobut-2-ynyloxy)benzene with an excess of alumina-supported sodium sulfide. The formation of 68 has been presumed to take place via cyclic sulfide 242 <2003S849>. 

As early as 1969, Block and Corey (73) observed the photochemical transformation of divinyl sulfide 37 to a mixture of isomeric cyclization products (39 and 40) (Scheme 5.13). A pathway involving the cyclic thiocarbonyl ylide 38 was proposed. A theoretical study concerning the nature of intermediates in the photochemical cyclization of divinyl sulfides was recently carried out (74). Several examples are known in which the vinyl group is part of an aromatic system. 

Divinyl DMDT DMF DMS DMSO DNT DOA 1-Dodecanethiol Dodecanol Dodecanol Dodecanol Peroxide Dodecene 1-Dodecene Dodecene (Non-Linear) Dodecene (Non-Linear) Dodecyl Alcohol Dodecylbenzene Butadiene, Inhibited Methoxychlor Dimethylfbrmamide Dimethyl Sulfide Dimethyl Sulfoxide 2,4-Dinitrotoluene Dioctyl Adipate Lauryl Mercaptan Linear Alcohols (12-15 Carbons) Dodecanol Lauroyl Peroxide Dodecene 1-Dodecene Propylene Tetramer Dodecene Dodecanol Dodecylbenzene... 

Calcium carbide desulfurization slag has a distinctive odor. Since pure acetylene is odorless, the odor must be produced by other trace constituents in the off-gases. A calcium carbide desulfurization slag sample from one ductile foundry was treated with water at a 1 1 solid-to-liquid ratio, and the gas was collected in a Tedlar bag for analysis by GC-MS. Several trace gases were identified, including arsine, divinyl sulfide (CHj-CH S, ethanethiol (ethyl mercaptan), methane, phosphine, and carbon monoxide. 

All three gases are of particular concern for human health reasons. The TLV (8-hour average) for carbon monoxide is 5.5 mg/M, and the National Ambient Air Quality Standard (NAAQS) is 10 mg/M. No standard for divinyl sulfide has been established in the United States. However, in the Soviet Union, where toxicological research on laboratory animals indicates that divinyl sulfide is a central nervous system depressant (Trofimov and Amosova, 1984), a maximum allowable concentration (MAC) of 0.2 mg/M has been recommended (Glukharev, et al., 1980). ... 

Trofimov, B.A., andS.V. Amosova. 1984. Divinyl sulfide synthesis, properties, and applications. Sulfur Reports 3(9) 323-400. 

Certain divinyl disulfides (a) are readily available by oxidation of dithioic esters in basic solution (Scheme 9). Heating (a R = Me or Ph) in toluene converted it to a mixture of the 3,4-disubstituted 2,5-di(methylthio)thiophene (b) and the corresponding 5-methylthio-2-thiophenethiol (c). Addition of potassium f-butoxide to the toluene resulted in a nearly quantitative yield of the thiol (c), but further addition of methyl iodide in a second step converts (c) to (b) so that the yield of either product can be maximized (74RTC258). The mechanism is the same as that shown in Scheme 7 (Scheme 9). Photolysis of enethiol esters gives divinyl sulfides such as those shown in Scheme 7, and these form thiophenes under the conditions of photolysis (77JOC1142). 

Much milder conditions are used in the double Michael addition approach, in which a divinyl ketone is condensed with hydrogen sulfide in mildly basic medium (equation 77) (77JOC2777). Enol acetates (R1 = MeCC>2) may be used, and the product obtained then contains a 2-mercapto function (R1 = SH see also equation 82) (59% yield). Although this is a very versatile synthesis, its biggest drawback is the lability of simple divinyl ketones, and phenyl substitution at position 2 is frequently used to overcome this. 

AH- Thiopyrans are directly accessible only in relatively poor yield, and then only by condensation of a suitable 1,5-dicarbonyl compound with sulfide (690PP21). As has been described earlier, this particular reaction is bedevilled with the problem of disproportionation to tetrahydrothiopyrans and thiopyrylium compounds. Thiopyran-4-ones may be prepared in a related manner by addition of sulfur dichloride to divinyl ketones, followed by base treatment (76MI22500). 

Very little work on the addition of HCI to nonconjugated dienes has been reported. The reaction of divinyl sulfide with HCI can be controlled to give either the mono- or di-chloride (equation 44), 69 70... 

Evidence has been presented591 that favours the involvement of thiirane intermediates in the formation of ( , )-divinyl sulfides (455) from the reaction of thiocarbonyl ylides (454) with activated alkynes, while the reaction of l-alkynyl-2,3-epithio alcohols (456) with a catalytic amount of Hg(II) has been shown to afford592 substituted thiophenes (457) (see Scheme 117). 

The classical reaction with chlorosulfonyl isocyanate has been extended to it-vinyl sulfide 449 to give a 2.5 1 diastereomeric mixture of 4-(phenylthio)azetidin-2-ones 343 and 450 (Equation 180) <2000MI935>. The facial selectivity in the cycloaddition has been explained by the conformational preference of the allylic groups in the transition structure. A similar reaction with styrene resulted into synthesis of the racemic 4-aryl-azetidin-2-one (Equation 181) <2000TA2351>. The divinyl ether 451 reacted with acid-free chlorosulfonylisocyanate to form 4-vinyloxyazetidin-2-one 452 (Equation 182) <1996SL895, 1997TA2553, 1998TL8349>. Most of the results in the reactions of isocyanate with vinyl ethers could be rationalized by a -conformational preference of the ether in... 

A quantum-chemical interpretation of the MS fragmentation of organic molecules has been reported <1987CHE512>. Based on the bond orders, the weakest bond is the C(3)-C(4) bond and hence should fragment first and to a much greater extent than the S-C or the C(2)-C(3) bond. This then forms the divinyl sulfide radical cation which cyclizes to intermediate 94 and then eliminates acetylene to form thiirene 93 (Figure 16). On the other hand, it is also possible that the bicyclic intermediate 95 is formed first, which could fragment to form radical cation 96 and/or intermediate 94 both of which lose acetylene to form thiirene 93. 

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