[O-:1][CH2:2][CH3:3].[Na+].C(N=[C:8]=[S:9])C.Cl[CH2:11][C:12]1[CH:17]=[N:16][C:15]([CH3:18])=[C:14]2[O:19]C(C)(C)[O:21][CH2:22][C:13]=12.Cl.C([OH:28])C>>[CH3:18][C:15]1[C:14]([OH:19])=[C:13]([CH2:22][OH:21])[C:12]([CH2:11][S:9][C:8]([O:1][CH2:2][CH3:3])=[O:28])=[CH:17][N:16]=1To a solution of 0.1 mole sodium ethoxide in 500 ml. of ethanol cooled to 10°-20°C. and under nitrogen is added 0.1 mole ethylisothiocyanate. The reaction mixture is stirred for 30 minutes after the addition is completed. There is then added portionwise 0.1 mole of 5-chloromethyl-2,2,8-trimethyl-4H-M-dioxino[4,5-C]-pyridine. The reaction mixture is stirred at room temperature (or refluxed 3 hours) overnight, after which time 200 ml. of 6 N hydrochloric acid is added. The reaction mixture is stirred 5 hours at room temperature, concentrated in vacuo, and the residue taken up between benzene-ether (1:1) and excess saturated sodium bicarbonate. The organic layer is separated, washed well with water, dried and concentrated to give 2-methyl-3-hydroxy-4-hydroxymethyl-5-ethoxycarbonylthiomethylpyridine and hydrochloride salt.
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