Vitamin B₁及び諸関係化合物の研究 (第35報)

N-置換Dithiourethaneの生成について

抄録

Application of γ-aceto-γ-chloropropyl acetate (II) (R=COCH₃) or alcohol (II) (R=H) to ammonium N-[2-methyl-4-aminopyrimidyl (5)]-methyl-dithiocarbamate (I) results in the respective formation of corresponding dithiourethane (III) (R=COCH₃ or H). The free carbamic acid (IV) is obtained by the application of the calculated amount of hydrochloric or acetic acid to (I). (IV) also reacts with (II) to form the hydrochloride (VI) of dithiourethane. Application of an equimolar amount of carbon disulfide to 2-methyl-4-amino-5-aminomethylpyrimidine results in the formation of the pyrimidine salt (V) instead of (IV). The application of (II) necessitates heating since neither (I) nor (IV) is soluble in the solvents, thereby permitting the formation of 2-thio-7-methyl-1, 2, 3, 4-tetrahydropyrimido (4, 5-d) pyrimidine (VII) as a by-product. The sodium salt (VIII) of the carbamic acid, obtained by the addition of an equimolar amount of sodium hydroxide to (I), (IV), and (V), results in facile reaction with (II) because (VIII) is easily soluble in water, and (III) is obtained in a good yield, without the formation of (VII) as a by-product. α-Methyl-α-ethoxy-β-chlorotetrahydrofuran (IX) is less reactive and hardly reacts with (I), (IV), (V), and (VIII), but yields γ-aceto-γ-chloropropyl alcohol (II) (R=H) when warmed with water and undergoes reactions as outlined above.