1-Dodecanethiol → HCID 178442864, compound

Participants

Reaction Steps

26.6 Grams of 11-bromoundecanoic acid, 21.2 g of dodecyl mercaptan, 42.4 ml of sodium methoxide (28% methanolic solution) and 300 ml of methanol were charged in a flask equipped with a stirrer, a condenser and a calcium chloride drying tube, and refluxed with heating for 6 hours on an oil bath. The reaction mixture was cooled to room temperature, and the precipitated crystal was filtered off under reduced pressure and washed with methanol. The resulting crystal was suspended in 1000 ml of pure water and adjusted to pH 2 with addition of concentrated hydrochloric acid, followed by stirring with heating on a water bath of 60° C. for 20 minutes. After neutralization, the crystal was filtered off under reduced pressure and washed with pure water. The crystal was recrystallized from ethanol to obtain 35.2 g of 11-dodecylthioundecanoic acid. Then, 27.0 g of the resulting carboxylic acid, 10.0 g of thionyl chloride, a drop of DMF and 100 ml of chloroform were charged in a flask, and refluxed with heating for 2 hours on an oil bath. After completion of the reaction, chloroform and excess thionyl chloride were distilled off under reduced pressure to obtain an acid chloride. The whole of the resulting acid chloride was diluted with 100 ml of acetone and this was added dropwise to a previously prepared aqueous solution of 5.9 g of sodium azide in 60 ml of pure water under cooling with ice water. After completion of the addition, the solution was stirred at the same temperature for 1 hour and the reaction mixture was extracted twice with 300 ml of benzene. The benzene layers were combined and washed thrice with pure water and once with a saturated aqueous sodium chloride solution. The benzene layer was dried over anhydrous sodium sulfate and the filtrate was refluxed with heating for 1 hour. To this reaction mixture were added 11.3 g of benzyl alcohol and three drops of triethylamine, followed by refluxing with heating for 2 hours. After completion of the reaction, benzene was distilled off under reduced pressure and the residual crystal was recrystallized from ethanol to obtain 26.5 g of benzyl N-(10-dodecylthio)decylcarbamate. 24.5 Grams of the resulting N-Cbz compound, 20 ml of 48% hydrobromic acid and 180 ml of glacial acetic acid were charged in a flask and refluxed with heating for 2 hours. After completion of the reaction, glacial acetic acid was distilled off under reduced pressure and the residual crystal was recrystallized from ethanol to obtain 17.0 g of HBr salt of 10-dodecylthiodecylamine. 4.4 Grams of the resulting HBr salt of amine, 1.1 g of succinic anhydride, 1.0 g of triethylamine and 50 ml of 1,4-dioxane were charged in a flask and stirred at 50° C. on a water bath for 1.5 hours. To the resulting reaction mixture were added 1.5 g of acetic anhydride and 0.4 g of sodium acetate, followed by refluxing with heating for 3 hours. After completion of the reaction, 1,4-dioxane was distilled off under reduced pressure, and the residue was introduced into ice-dilute hydrochloric acid and the crystal was filtered off under reduced pressure. The resulting crystal was washed with water and recrystallized from a mixed solvent of methanol and 2-propanol to obtain 3.0 g of the desired product. m.p. 85.9° C.

Provenance & Evidence