Thionyl Chloride → 2-(2-Methyl-4-nitrophenylimino)-3-isobutyl-4-methylene-1,3-thiazolidin-5-one

반응식

Cl.CO[C:4](=O)[C@@H:5]([CH2:11][OH:12])[NH:6][CH2:7][CH:8]([CH3:10])[CH3:9].O=S(Cl)Cl.[CH3:18][C:19]1[CH:24]=[C:23]([N+:25]([O-:27])=[O:26])[CH:22]=[CH:21][C:20]=1[N:28]=[C:29]=[S:30]>>[CH2:7]([N:6]1[C:5](=[CH2:4])[C:11](=[O:12])[S:30][C:29]1=[N:28][C:20]1[CH:21]=[CH:22][C:23]([N+:25]([O-:27])=[O:26])=[CH:24][C:19]=1[CH3:18])[CH:8]([CH3:10])[CH3:9]

참가 물질

반응물 3

HCID 24386Thionyl Chloride

HCID 1456212-Methyl-4-nitrophenyl isothiocyanate

HCID 88093438(R)-N-isobutylserine methyl ester HCl salt

생성물 1

HCID 183160452-(2-Methyl-4-nitrophenylimino)-3-isobutyl-4-methylene-1,3-thiazolidin-5-one수율 10%

실험 절차

(R)-N-Isobutylserine methyl ester HCl salt (Method B3a; 2.28 g, 10.8 mmol) was treated with SOCl2 followed by 2-methyl-4-nitrophenyl isothiocyanate in a manner analogous to Method C2a. The resulting material was purified by column chromatography (SiO2, gradient from hexane to 10% EtOAc/hex) to give 3-isobutyl-4-methylene-2-(2-methyl-4-nitrophenylimino)-1,3-thiazolidin-5-one (0.028 g, 10%) followed by (S)-3-isobutyl-4-carbomethoxy-2-(2-methyl-4-nitrophenylimino)-1,3-thiazolidine HCl salt (0.192 g, 56%). 3-Isobutyl-4-methylene-2-(2-methyl-4-nitrophenylimino)-1,3-thiazolidin-5-one: TLC (25% EtOAc/hex) Rf 0.40. (S)-3-isobutyl-4-carbomethoxy-2-(2-methyl-4-nitrophenylimino)-1,3-thiazolidine HCl salt: TLC (free base, 25% EtOAc/hex) Rf0.50.