Hydroxyethyl Methyl Sulfide

H2N—C—NHCN + 2CH3SH + Na2S04 + 2H2O CHaSH + NaOCsHs CHaSNa + CaHaOH CHaSNa + CH2OHCH2CI CH3SCH2CH2OH + NaCl 

The solution of sodium methyl sulfide in absolute alcohol is transferred to a 3-I. three-necked flask, which is placed on a steam bath and fitted with a dropping funnel, a reflux condenser, and a mechanical stirrer. The solution is heated until the alcohol begins to boil. Heating is then discontinued and 302 g. (3.7s moles) of ethylene chlorohydrin (Note 5) is added dropwise with efficient stirring over a period of about two hours (Note 6). The reaction mixture is concentrated by distilling as much of the alcohol as possible on the steam bath. The mixture is then allowed to cool and the sodium chloride removed by filtration. The flask is rinsed, and the sodium chloride washed with three loo-cc. portions of 95 per cent alcohol. The combined filtrate and washings are concentrated on the steam bath under reduced pressure until no further distillate passes over. The residue is then transferred to a modified Claisen flask (Org. Syn. Coll. Vol. i, 125) and fractionally distilled under reduced pressure. The yield is 238-265 g. (74-82 per cent of the theoretical amount based on the sodium used) of a product boiling at 68-7o°/20 mm. 

Quantities of material five times as large as the above may be used without decreasing the yield of product. In such cases it is more convenient to filter the sodium chloride before concentrating the solution. 

The lead acetate removes any unreacted m ethyl mercaptan by precipitating it as the lead salt. 

The rate of heating controls the rate of evolution of the methyl mercaptan. After the rapid evolution of the gas begins, the reaction mixture should be heated very gentl c A slight suction aids in obtaining a regular flow of the gas. 

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In a i-l. three-necked flask are mixed 150 g. (r.63 moles) of /3-hydroxyethyl methyl sulfide (p. 54) (Note i) and 200 g. of dry chloroform (Note 2). The flask is placed on a steam bath and is fitted with a dropping funnel, a mechanical stirrer, and a condenser. The condenser is fitted with a trap to remove the vapors of hydrogen chloride and sulfur dioxide (page 2). A solution of 204 g. (1.7 moles) (Note 3) of thionyl chloride in 200 g. (135 cc.) of dry chloroform is added dropwise to the /3-hydroxyethyl methyl sulfide over a period of about two hours (Note 4). The reaction mixture is stirred vigorously during this addition and for about four hours after the addition is complete. The chloroform is distilled on the steam bath and the residue is distilled under reduced pressure. The yield is 135-153 g- (75 5 per cent of the theoretical amount) of a product boiling at 55-s6°/3o mm- (Note 5). 

The one-electron reduction potentials of the radical cations of thioanisole, benzyl methyl sulphide, and 2-hydroxyethyl benzyl sulfide in water and several organic solvents were investigated by cyclic voltammetry. For comparison, the one-electron oxidations in water were also measured using pulse radiolysis. ° The two methods are complementary and the reversible potentials determined by pulse radiolysis are fairly close to the peak potentials determined by cyclic voltammetry (Table 8) indicating that the peak potentials do correspond to the formation of sulfur radical cations for all three sulfides. 

The active substance is not toxic to mammals, the acute oral ld,o for male rats is 4900 mg/kg. The active substance is rapidly absorbed and metabolised in the animal. It is excreted in the urine and feces, llie following metabolites have been detected in the urine p-(l,l-dimethyl-2-hydroxyethyl)benzylmethyl sulfide and sulfone, and p-(l-methyl-l-carboxyethyI)benzyImethyl sulfide and sulfone and their glucuronide conjugates. In addition to these, butyl-(l,I-dimethyl-2-hydroxyethyl)benzyl-N-(3-pyridyl)dithiocarbonimidate has been detected in the feces (Ohkawa et al., 1975). 

Typical procedure. N,N -Bis(2-hydroxyethyl)urea 1024 [577] Excess ethanolamine and DMDTC were mixed and heated at 60 °C for 15 h. The released malodorous methyl sulfide by-product was absorbed and oxidized by NaOCl solution. When the reaction was complete, the unreacted ethanolamine was removed under reduced pressure by simple distillation, leaving a crude mixture of oxazolidinone 1025 and bis(2-hydroxyethyl)urea 1024, which was further purified by recrystallization from methanol/ethyl acetate (1 4.5) to give N,N -bis(2-hydroxyethyl)urea as colorless crystals. 

Na-ethoxide in anhydrous ethanol allowed to react with thiophenol, the stirred soln. of the resulting thiolate treated with dimethyl carbonate, and refluxed 15 hrs. -> methyl phenyl sulfide. Y 72%. - Similarly with ethylene carbonate ) -hydroxyethyl phenyl sulfide. Y 82%. F. e. s. Y. Tamura et al., Synthesis 1975, 641. 

Figure 5.2. Volatile sulfur compounds of wines (15) dimethyl sulfide, (16) ethylmer-captan, (17) diethyl sulfide, (18) methyl thioacetate, (19) dimethyl disulfide, (20) ethyl thioacetate, (21) diethyl disulfide, (22) 2-mercaptoethanol, (23) 2-(methylthio)-l-ethanol, (24) 3-(methylthio)-l-propanol, (25) 4-(methylthio)-l-butanol, (26) 3-mercap-tohexan-l-ol, (27) 4-methyl-4-mercaptopentan-2-one, (28) 3-mercaptohexanol acetate, (29) benzothiazole, (30) 5-(2-hydroxyethyl)-4-methylthiazole, (31) fra s-2-methylthio-phan-3-ol, (32) 2-methyltetrahydrothiophen-3-one.

Bluestone. See Cupric sulfate pentahydrate Cupric sulfate anhydrous Blue vitriol. See Cupric sulfate pentahydrate Cupric sulfate anhydrous Blue X. See FD C Blue No. 2 Acid blue 74 BM. See 1-Methoxy-2-butanol BM-723. See Methacrylic anhydride BM-729. See Tetrahydrofurfuryl methacrylate BM-801. See Methacrylamide BM-818. See N-Methylol methacrylamide BM-903. See 2-Hydroxyethyl methacrylate BM-951. See Hydroxypropyl methacrylate BMC 100] BMC 102] BMC 30a, BMC 400, BMC 404] BMC 1050. See Polyester resin, thermosetting BMC. See Carbendazim BMDS. See 4-Benzoyl-4 -methyl diphenyl sulfide... 

The acidic, basic and neutral flavor components of a YA were examined in the first published study, and 48 compounds were identified (5,7). Three sulfur compounds, i.e., 2-thiophenecarboxylic acid, its 5-methyl derivative and 4-methyl-5(2 -hydroxyethyl)thiazole were mentioned. Later, Golovnya et al. (8) identified 37 sulfur compounds from a simulated meat flavor produced by heating a bakery YA with sugar. They included aliphatic sulfides and thiols, alicyclic sulfur compounds, thiophenes and sulfur-substituted furans. 

A preferred insect repellent is liquid A,A-diethyl-m-toluamide (A,Af-diethyl-3-methylbenzamide) for indoor or outdoor use. Other such chemicals include dimeth-ylphthalate, 2-ethyl-l,3-hexanediol, stabilene, indalone, di-Bu-phthalate, citronyl, alicyclic piperidines, permethrin, di-Bu-succinate, hexahydrodibenzofuran carboxaldehyde-butadiene-furfural copolymer, f-Bu-A,A-dimethyldithiocarbamate, 2-hydroxyethyl n-octyl sulfide, pyrethrins, diazinon (0,0-diethyl-0-[4-methyl-6-(propan-2-yl)pyrimidin-2-yl]-phosphorothioate), flMcar (2-methyl-2-(methylthio)-propanal-0-((methylamino)carbonyl)-oxime), pine oil, and anthrahydroquinones... 

Sulfur compounds present in wine can have a detrimental effect on aroma character, producing odors described as garlic, onion and cauliflower, so-called Boeckser aroma. This sulfurous character is correlated with with 2-methyl-3-hydroxythiophene, 2-methyl-3-furanthiol and ethanethiol, and their concentrations in wine are influenced by winery procedures and the use of certain winemaking yeasts (105). Off-flavors in European wines were associated with the nonvolatile bis(2-hydroxyethyl) disulfide, a precursor to the poultry-like character of 2-mercaptoethanol and hydrogen sulfide (106). 

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