Formation from dimethyl sulfide

A one-pot procedure combines the generation of trimethylsulfonium hydrogensulfate (Me3S HS04 ) from dimethyl sulfide, sulfuric acid and methanol, and its use in situ for oxirane formation with carbonyl compounds [451] (Table 4.5). 

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. 

Hattula, T. and Granroth, B., 1974. Formation of dimethyl sulfide from S-methyl-methionine in onion seedlings (Allium cepa). J. Sci. Food Agric., 25 1517—1521. 

Figure 8,59 Formation of dimethyl sulfide from S-methyl methionine.

Diborane [19287-45-7] the first hydroborating agent studied, reacts sluggishly with olefins in the gas phase (14,15). In the presence of weak Lewis bases, eg, ethers and sulfides, it undergoes rapid reaction at room temperature or even below 0°C (16—18). The catalytic effect of these compounds on the hydroboration reaction is attributed to the formation of monomeric borane complexes from the borane dimer, eg, borane-tetrahydrofuran [14044-65-6] (1) or borane—dimethyl sulfide [13292-87-0] (2) (19—21). Stronger complexes formed by amines react with olefins at elevated temperatures (22—24). 

Several of the lower molecular weight aliphatic compounds, in a mixture, are part of the roasted coffee aroma. A nine-compound mixture with roasted coffee aroma contained isopentane, n-hexane, acetaldehyde, dimethyl sulfide, propanal, isobutanal, isopentanal, methanol, and 2-methylfuran.20 In addition, the freshness of aroma and taste has been correlated with 2-methylpropanal and diacetyl. When the concentration of these falls off, so does the taste.21 Other aliphatic compounds that are steadily lost from ground roasted coffee, unless it is vacuum packaged, include methyl formate, methyl acetate, methyl thioacetate, and acetone.22 The concentrations in roast coffee for four compounds whose contribution to the fresh flavor have long been known are dimethyl sulfide (4 ppm), methyl formate (12 ppm), isobutanal (20 ppm), and diacetyl (40 ppm). The taste thresholds are 0.1, 0.5, 0.5, and 1.0 ppm, respectively, in the brew made with 5 g coffee per 100 ml water.15... 

The effectiveness of dimethyl sulfide as an additive for the selective formation of anti-product 22 from propargyl epoxide 20 may be due to the formation of stabilized copper species, which are less prone to undergo electron transfer processes. In this respect, other soft ligands which bind strongly to copper, in particular phosphines and phosphites [8h-j, 25, 28], have been used even more frequently. These additives also serve to suppress the formation of a common side product, i.e. an allene containing a hydrogen atom instead of the carbon substituent which should... 

Similar data for sulfate have been reported in many studies. Figure 9.36, for example, shows overall average sulfate distributions measured in marine areas as well as at continental sites (Milford and Davidson, 1987). The marine data show two modes, a coarse mode associated with sea salt and a fine mode associated with gas-to-particle conversion. Sulfate in seawater, formed, for example, by the oxidation of sulfur-containing organics such as dimethyl sulfide, can be carried into the atmosphere during the formation of sea salt particles by processes described earlier and hence are found in larger particles. The continental data show only the fine particle mode, as expected for formation from the atmospheric oxidation of the S02 precursors. 

One of the primary reactions of ionizing radiation with saturated fatty acids is decarboxylation and alkane formation (2). Dimers tend to be produced by reaction of ionizing radiation with unsaturated fatty acids (2). When meats are irradiated C -C 7 n-alkanes, C2-C17 n-alkenes, and C4-Cg iso-alkanes are the predominant products from the lipid fraction (10), Irradiation of the lipoprotein fraction of meat results in the formation of the following volatile compounds Ci-C 7 n-alkanes, C2-C1J n-alkenes, dimethyl sulfide, benzene, and toluene (10). 

The solution is neutralized to prevent bisacetal formation upon subsequent reduction. Dimethyl sulfide was purchased from Aldrich Chemical Company, Inc. and used without purification. 

The mechanism of the Parikh-Doering oxidation involves formation of O-di-methylsulfoxonium sulfate from the reaction of DMSO with S03. Displacement on the sulfur by the alcohol gives the alkoxysulfonium salt intermediate, which undergoes base-catalyzed elimination to afford the dimethyl sulfide and the aldehyde. This reaction must be carried out so the hydrogen sulfate of the alcohol is not formed first, otherwise no oxidation would occur. 1143 44 ... 

An alternative method of hydroboration is to use diisopinocampheylborane (12) (Scheme 4). This reaction is particularly useful for sterically hindered alkenes. Diisopinocampheylborane (12) is prepared from borane-dimethyl sulfide and (+)-pinene.[23-24] Treatment of 4-meth-ylenecyclohexanone ethylene ketal with diisopinocampheylborane (12) gives the borane 13.[25] Further treatment with 2 equivalents of an aldehyde results in the elimination of pinene and the formation of a new dialkyl boronate, e.g. treatment of 13 with acetaldehyde gives the diethyl cyclohexylmethylboronate 14J261 The dialkyl boronates thus produced can be transesterified with pinanediol to give 15[26] or with other cyclic diols. 

At present the exact details of the mechanisms leading to each of the products are far from well understood (7.81. However, it seems likely that oxidation of the common naturally-occurring organo-sulfur compounds (dimethyl sulfide, methyl mercaptan and dimethyl disulfide) proceeds, at least in part, through formation of the methyl thiyl radical, CHjS (4.9-111. That is the main reason for carrying out direct studies on CH3S radical reactions where the individual reactions are isolated. 

An intramolecular nucleophilic substitution of the dimethyl sulfide group by a cathodically generated radical anion is postulated in the formation of the in-dane derivative 133 from the sulfonium salt 134 (Eq. (203)). 

Unnatural amino acids are available from more readily available amino acids. A wide variety of reactions are available in the literature. An example is provided by the synthesis of L-homoserine (10) from methionine (Scheme 2.17).51 Of course, the problems associated with the formation of one equivalent of dimethyl sulfide have to be overcome. 

One method for the synthesis of hydroxyalkyl-substituted P-lactams is by the Staudinger reaction, the most frequently used method for the synthesis of P-lactams.86 This method for the preparation of 4-acetoxy- and 4-formyl-substituted P-lactams involves the use of diazoketones prepared from amino acids. These diazoketones are precursors for ketenes, in a diastereoselective, photochemically induced reaction to produce exclusively tram-substituted P-lactams. The use of cinnamaldimines 96, considered as vinylogous benzaldimines, resulted in the formation of styryl-substituted P-lactams. Ozonolysis, followed by reductive workup with dimethyl sulfide, led to the formation of the aldehyde 97, whereas addition of trimethyl orthoformate permitted the production of the dimethyl acetal 98 (Scheme 11.26). 

Fig. 17.13. Mechanism of the Swern oxidation of alcohols. The actual reagent is an "activated DMSO" (compound B or D), which reacts with an alcohol with formation of A or C, respectively. Dissociation leads to the sulfonium salt E, which is then converted into the sulfonium ylide F after NEt3 addition and raising the temperature from -60 to -45 °C. /3-Elimination via a cyclic transition state generates the carbonyl compound and dimethyl sulfide from F.

Irrespective of whether the initially formed sulfonium ion B or the subsequently formed sulfonium ion D reacts with the alcohol, the alcohol is taken up by such a sulfonium ion with formation of sulfuranes A (first case) or C (second case). Any of these sulfuranes would yield the sulfonium salt E after dissociation. Once this sulfonium salt has formed, five equivalents ofNEtj are added to the reaction mixture, which then is allowed to warm up from -60 to -45°C. Under these conditions, the sulfonium salt E is deprotonated to give the sulfonium ylide F. This ylide undergoes a /3-elimination via a cyclic transition state to form the desired carbonyl compound and dimethyl sulfide as a side-product. 

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