Determination of Alkyl Sulfides and Disulfides

Siggia, Sidney.; Edsberg, R. L.

doi:10.1021/ac60022a021

Cited by 44 publications

(20 citation statements)

References 4 publications

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“…We have considered for their synthesis the Meerwein reaction22 and different methods based on the oxidative bromination of various precursors19–21, 23, 24 to sulfonyl bromides. Aromatic sulfinic acid salts,20, 25 thiophenols,23 disulfides,24 and arenesulfonyl hydrazides19–21 are oxidized into aromatic sulfonyl bromides by oxidative bromination with molecular bromine (Br 2 ),8, 19, 24 or with bromine generated in situ from NaBrO 3 or a combination of NaBr and NaBrO 3 19 in aqueous acidic media. Previously, we have used the synthesis of perfluoroalkylsulfonyl bromides starting from a perfluorosulfinic acid salt 8.…”

Section: Resultsmentioning

confidence: 99%

Arenesulfonyl bromides: The second universal class of functional initiators for the metal‐catalyzed living radical polymerization of methacrylates, acrylates, and styrenes

Grigoraş

Percéc

2004

J. Polym. Sci. A Polym. Chem.

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The metal‐catalyzed living radical polymerization of methyl methacrylate, n‐butyl acrylate, and styrene, initiated with p‐toluenesulfonyl bromide and phenoxybenzene‐4,4′‐disulfonyl bromide and catalyzed with CuBr/2,2′‐bipyridine (bpy) and various self‐regulated Cu‐based catalytic systems such as Cu2O/bpy, Cu2S/bpy, Cu2Se/bpy, and Cu2Te/bpy, is reported. Similarities and differences between the arenesulfonyl chloride and arenesulfonyl bromide initiators are discussed. The arenesulfonyl bromide initiators require reduced reaction times to produce polymers in high conversions under milder reaction conditions than the corresponding arenesulfonyl chloride initiators. At the same time, they exhibit 100% initiator efficiency and generate polymers with narrow molecular weight distributions and functional chain ends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 319–330, 2005

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Section: Resultsmentioning

confidence: 99%

Arenesulfonyl bromides: The second universal class of functional initiators for the metal‐catalyzed living radical polymerization of methacrylates, acrylates, and styrenes

Grigoraş

Percéc

2004

J. Polym. Sci. A Polym. Chem.

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“…Dialkyl sulphide was estimated by the bromide-bromate reagent (20), dialkyl disulphide by the Kolthoff method (2l), and sulphur by a colorimetric method using sodium cyanide (22).…”

Section: E X P E R I M E N T a Lmentioning

confidence: 99%

Thermal Decomposition of 1-Hexanethiol

Gagnon¹,

Boivin²,

Watson³

1959

Can. J. Chem.

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The uncatalyzed thermal decomposition of I-hexanethiol was studied a t temperature varying from 300 to 700" C and was observed to give 42y0 of olefinic hydrocarbons a t 600° C. Diallcyl sulphides were also obtained a t 550° C with a maximum yield of 13.3% a t 650° C. The effect of sulphide catalyst was investigated and nickel sulphide was found to be the most effective: a t low temperature (150-450' C) dihexylsulphide was produced and a t higher temperature (450-600" C) olefinic hydrocarbons were obtained. Very little catalytic effect was observed with molybdenunl and cadmium sulphides.

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“…The method described by Siggia and Edsberg (22) for estimating thio ethers by oxidation to sulphoxides was modified. Weighed samples of pure O-octadecyl S-methyl xanthate were dissolved with difficulty in glacial acetic acid, a little hydrochloric acid was added, and the mixtures were titrated with 0.1 N potassium bromate -potassium bromide to a yellow end point.…”

Section: (B) With Brominementioning

confidence: 99%

“…Some unsuccessful attempts were made to determine the S-methyl xanthate group by titrating an acidified solutio~l of the octadecyl derivative with potassiunl bromide -potassium bromate, essentially a s described by Siggia and Edsberg (22) for the oxidation of thioethers to sulphoxides. Both sulphur Can.…”

Section: Introductionmentioning

confidence: 99%

THE CHEMICAL STABILITY OF THE S-METHYL XANTHATES OF SOME SIMPLE ALCOHOLS

Vincent¹,

Purves²

1956

Can. J. Chem.

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11-Octadecyl S-methyl xanthate, m.p. 38-39", and n-hexadecyl S-methyl xanthate, m.p. 2&28.5", were prepared for the hrst time, and were used to study the behavior of the S-methyl xanthale group toward reagents commonly used in research on carbohydrates. Although stable to some conditions of acetylation, hydrolysis, and methanolysis, the S-methyl xanthate group was destroyed by all methylating agents tried, with the exception of nitrosornethylurethane. The latter reagent converted a sodium xa~lthate salt in high yield to the S-methyl ester. Octadecyl and hexadecyl S-methyl xanthates when oxidized with hydrogen peroxide yielded crystalline substances of conlposition C?oH4oO4S~ and C I~H~G O~S ? , respectively, whose structures were not determined. These substances each contained three additional oxygen atoms. Various attempts to estimate the S-methyl xanthate group by oxidation with bromine or periodic acid, or by reduction to methyl iodide, were unsuccessful. INTRODUCTIONAs a preliminary to research on xanthates of carbohydrates, it seemed desirable to investigate some simple, crystalline derivative of the xaiithate group that was more stable than a free xanthic acid or its alkali salt toward reagents frequently used in carbohydrate chemistry. Xanthate-S-methyl esters a t once came into consideration, because they could be formed in high yield bj-the action of methyl iodide on a suitable salt. The term "xanthate ester" referred to a double ester such as C2HjOCSSC?H5, whose formal name was ethyl ethoxymethanethionothiolate, but which could be more clearly described as 0-ethyl S-ethyl xanthate (6).Simple xanthate esters were usually high-boiling liquids, and of the Smethyl compounds oiily eight were reported as crystalline. All eight were derived from aromatic, hydroaromatic, and terpene alcohols, and their carbon sltcletons were uniiccessarily complicated for the purpose in view. Nevertheless, the S-methyl xanthates oi benzyl and hexahydrobenzyl alcohol, and of menthol, were prepared for reference purposes. Whitmore and Simpson's modification (25) of tlie long-neglected Zeise (27) "one-step" process employing tlie alcohol, solid sodiurn hydroxide, carboll disulphide, and later methyl iodide, was used. The melting point of the hesahydrobenzyl derivative was confirmed as 16.5", apparently the value given by Aleltsandrovich ( I ) , and not as 1 Go, as misquoted by Chemical Abstracts and British Chemical Abstracts.The same general method was used to synthesize several S-methyl xanthates of nornial aliphatic alcohols in 60-8070 yield. I t transpired that the octyl derivative mas a liquid, and that the S-methyl xanthates of n-hexadecyl (cetyl) and ?z-octadecyl (stearyl) alcohol were crystalline solids whose melting 'il[anz~script received ilfay 28, 1956.

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Determination of Alkyl Sulfides and Disulfides

Cited by 44 publications

References 4 publications

Arenesulfonyl bromides: The second universal class of functional initiators for the metal‐catalyzed living radical polymerization of methacrylates, acrylates, and styrenes

Arenesulfonyl bromides: The second universal class of functional initiators for the metal‐catalyzed living radical polymerization of methacrylates, acrylates, and styrenes

Thermal Decomposition of 1-Hexanethiol

THE CHEMICAL STABILITY OF THE S-METHYL XANTHATES OF SOME SIMPLE ALCOHOLS

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