Dimethyl disulfide derivative

Scribe, P. Guezennec, J. Dagaut, J. Pepe, C. Saliot, A. Identification of the Position and the Stereochemistry of the Double Bond in Monounsaturated Fatty Acid Methyl Esters by Gas Chromatography/Mass Spectrometry of Dimethyl Disulfide Derivatives. Anal. Chem. 1988, 60, 928-931. 

Pepe, C. Sayer, H. Dagaut, J. Couffig-nal, R. Determination of Double Bond Positions in Triunsaturated Compounds by Means of Gas Chromatography/Mass Spectrometry of Dimethyl Disulfide Derivatives. Rapid Commun. Mass Spectrom. 1997, 77,919-921. 

Simultaneous GC-EAD analyses of the extracts of the sex pheromone gland of the female bronzed cutworm, Nephelodes minians, indicated two compounds which eficited strong EAD responses from conspecific male antennae, (2 )-ll-hexadecenal and (2 )-ll-hexadecenyl acetate. Double bond positions were confirmed by the dimethyl disulfide derivatives of the pheromone component. In a field test, a 5 1 blend of aldehyde and ester attracted male N. minians. ... 

Carlson, D. A., Roan, C.-S. and Yost, R.A. (1989). Dimethyl disulfide derivatives of long chain alkenes, alkadienes, and alkatrienes for gas chromatography/mass spectrometry. Anal. Chem., 61,1564-1571. 

Vincenti, M., G. Gugfiehnetti, G. Cassani, and C. Tonini, Determination of Double Bond Position in Diunsaturated Compounds by Mass Spectrometry of Dimethyl Disulfide Derivatives, Anal. Chem. 59 694-699 (1987). 

Vincenti, M. Guglielmetti, G. Cassani, G. Tonini, C. (1987). Determination of double bond position in diunsaturated compounds by mass spectrometry of dimethyl disulfide derivatives. Analytical Chemistry, Vol.59, No.5, (March 1987, pp. 694-699, ISSN 1520-6882... 

Carlson, D. A, C.-S. Roan, R. A. Yost, and J. Hector, Dimethyl Disulfide Derivatives of Long Chain Alkenes, Alkadienes, and Alkatrienes for Gas Chromatography/Mass Spectrometry, Analytical Chemistry 61 9i9) 56A- 51. ... 

Yuan, G., and J. Yan A Method for the Identification of the Double-Bond Position Isomeric Linear Tetradecenols and Related Compounds Based on Mass Spectra of Dimethyl Disulfide Derivatives, Rapid Communications in Mass Spectrometry 16 (2002) 11-14. 

Location oF double bonds in monounsaturated Fatty acids of Campylobacter cryaerophila with dimethyl disulfide derivatives and combined gas chromatography-mass spectrometry. 

Example The oxidative addition of dimethyl disulfide (DMDS) transforms the double bond to its 1,2-bis-thiomethyl derivative (a). Induced by charge localization at either sulfur atom, the molecular ions of DMDS adducts are prone to a-cleavage at the former double bond position (b). This gives rise to sulfonium ions that are readily identified from the mass spectrum (Chap. 6.2.5). The method can be extended to dienes, trienes, and alkynes. [70,71] (For the mass spectral fragmentation of thioethers cf. Chap. 6.12.4). 

Interestingly, if the tribromo compound is treated with five equivalents of n-BuLi, then tetralithiation occurs, as was shown by the isolation of an a-butyl-2,4,5-trimethylthio derivative after reaction with excess dimethyl-disulfide [87JCS(P1)1453]. The a-butyl group in the product is derived from reaction of the a-benzyl carbanion with the n-butyl bromide produced by the initial bromine-lithium exchange reaction (Scheme 59). However,... 

The terpenes used were mainly /3-pinene fractions provided by DRT (Soci6td des Derives Rdsiniques et Terpeniques, Vielle-S Girons) and, for certain experiments a turpentine oil containing the main three terpenes a-pinene, /3-pinene, and A -carene. The /3-pinene fractions contained 80-90% /3-pinene, 2% a-pinene, 4-5% myrcene, 2-3% dipentene and 700-1500 ppm S. GC-MS analyses showed that sulfur impurities were composed of alkyl and alkenyl sulfides (mainly dimethyl sulfide), alkyl and alkenyl disulfides (mainly dimethyl disulfide), trisulfides, thiophene and alkylthiophenes (methyl, dimethyl, acetyl and tertiobutyl). 

Thus, among the sulfur amino acids, hydrogen sulfide is a likely derivative of cysteine, and dimethyl disulfide is a likely derivative of cystine. The formation of dimethyl sulfide and dimethyl disulfide from methionine is readily deduced from expected recombinations of thiomethyl and methyl free radicals. Dimethyl disulfide is the major product. 

Thietanes are also useful as analytical tool for mass spectrometric determination of pheromone 130. This type of pheromone may undergo derivatization with dimethyl disulfide to give the thietane derivative 131, which undergoes... 

Group 3 volatiles, formed by further interactions, can reach even lower threshold values than those mentioned so far, particularly when sulfur is involved, usually derived by the break down of cysteine (bis(2-methyl-3-furyl) disulfide, 0.00002 2-methyl-3-furanthiol, 0.0004 2-furylmethanethiol, 0.005 dimethyl trisulfide, 0.01 dimethyl disulfide, 0.16 dimethyl sulfide, 0.3 hydrogen sulfide, 10). Into some volatile sulfur compounds other atoms as well as the sulfur of cysteine are incorporated (2-acetylthiazoline, 1 5-acetyl-2,3-dihydro-l,4-thiazine, 1.25 2-acetylthiazole, 10). Other volatiles are more likely to be derived from methionine (methanethiol, 0.2). 

Heteroelectrophiles like dimethyl disulfide (entries 9, 18, 29) lead to trifunctional compounds. A second methoxycarbonyl group can be introduced with methyl chloro-formiate (entries 38, 42). However, the trimethylsiloxy compounds are extremely sensitive and undergo very fast ring opening to malonic ester derivatives 61). 

A convenient preparation of tetrathiafulvalenes is achieved by the reduction of 2-methylthio-l,3-dithiolylium salts (207) with zinc dust in the presence of bromine (76ZC317). This reaction proceeds with formation of the radical (341) which dimerizes to (342) the latter produces dimethyl disulfide and the tetrathiafulvalene derivatives (343). 

Alkyl sulfides and thiols. Some alkyl thiols and sulfides, notably those from commonly ingested Allium sativum (garlic) and Allium cepa (onion) (Alliaceae), are variously bioactive as odorants and antimicrobials. Propanethial S-oxide (CH3-CH2-CH=S=0) is a lachrymatory irritant principle of onion. Allicin (S-oxodiallydisulfide CH2=CH—CH2-SO-S-CH2— CH=CH2), diallyldisulfide (CH2=CH-CH2-S-S-CH2-CH=CH2) and diallylsulfide (CH2=CH—CH2—S—CH2-CH=CH2) are major odorants of garlic that are reactive and irritant because of the allyl groups. Dimethyl disulfide (CH3—S—S-CH3), dipropyl disulfide (CH3-CH2-CH2-S-S-CH2-CH2-CH3), methyl allyl disulfide (CH3-S-S-CH2-CH=CH2) and propane-1-thiol (CH3-CH2—CH2—SH) are further Allium odorants. Methane thiol (methyl mercaptan CH3—SH) is a widespread plant volatile and notably derives from anaerobic bacterial degradation of cysteine as in human flatus and bad mouth odour. The aliphatic disulfides allicin and ajoene inhibit proinflammatory expression of iNOS. 

Pyrrole 843 (R = Me) was formed in moderate yield (30%) by treatment of 3,4-dibromo pyrrole 842 with Bu"Li and then with dimethyl disulfide. Pyrrole 843 (R = Bu") was prepared according to Klingsberg s method, by treatment of dibromide 842 with copper(l) -butanethiolate in a mixture of quinoline and pyridine to give the desired product in 33% yield. In both cases, the monosubstituted derivatives 844 were obtained as intermediates in 45% and 10.5% yields, respectively. 

The direct sulfenylation of yv.A -dimethylhydrazones via the reaction of the a-lidiio derivative (14) with dimethyl disulfide (Scheme 13) has been reported, and the initially formed product (15) shown to isomerize to the more stable ( )-isomer (16). l ile further transformations have been carried out on compound (16), attempts do not appear to have been made to introduce unsaturation by the elimination of the thiol group. 

These reactions are convenient methods for incorporating a sulfur-containing group onto an aromatic ring. With Ar S, diazosulfides Ar—N=N—S—Ar are intermediates/° which can in some cases be isolated. ° Thiophenols can be made as shown above, but more often the diazonium ion is treated with EtO-CSS or 82, which give the expected products, and these are easily convertible to thiophenols. Aryldiazonium salts are prepared by the reaction of an aniline derivative with an alkyl nitrite (RONO), and when formed in the presence of dimethyl disulfide (MeS-SMe), the product is the thioether, Ar-S-Me. ° Aryl triflates have been converted to the aryl thiol using NaST(P5) and a palladium catalyst, followed by treatment with tetrabutylammonium fluoride ° (see also, 14-22). 

Gem-dibromocyclopropanes can be converted into synthetically useful cyclopropanone equivalents by a process consisting of lithium-halogen exchange followed by reaction of lithiocyclopropane (113) with dimethyl disulfide (Scheme 43) . The resulting bromo-methylthio derivative (114) undergoes a variety of substitution reactions. Methanolysis gives S,0-dimethylketal (115) which can be converted into l,l bis(methyl-thio)cyclopropane (116) with methyl mercaptan in trifluoroacetic acid. Reaction of 114 with other nucleophiles provides the derivatives shown in Scheme 44 . The sulfur-... 

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