Nuhn, P. published the artcileGlycosides of heterocycles. XXX. Glucosides of imidazole-, oxazole-, and thiazole-2-thiones, Synthetic Route of 5053-24-7, the publication is Archiv der Pharmazie und Berichte der Deutschen Pharmazeutischen Gesellschaft (1968), 301(3), 186-200, database is CAplus and MEDLINE.
(cf. CA 68:39990b; 40021t. The reaction of tetra-O-acetyl-α-D-glucopyranosyl bromide (I) with thiazole-2-thiones carried out by the Sabalitschka method (CA 23:3239), i.e. under SN2 conditions, gave exclusively 1-thio-D-glucosides. Similar results were obtained with oxazole-2-thiones and imidazole-2-thiones. Under SN1 conditions the formation of 1-thio-D-glucosides was favored only when the heterocyclic ring bore bulky substituents at position 4, otherwise the formation of glycosytamines was preferred. 2-Thmzolethione (II) (0.01 mole) and 0.56 g. KOH in 5 ml. H2O was mixed with 4.1 g. I in 15 ml. Me2CO, agitated until the mixture turned neutral and worked-up to give 65% 2-(tetra-O-acetyl-β-D- glucopyranosylthio)thiazole (IIIa) (Q = tetra-O-acetyl-β-D-glucopyranosyl throughout this abstract), m. 119-22° (MeOH), [α]22D -10.7° (c 5, CHCl3). IIIb, m. 107-8° (50% MeOH), [α]22D -11.7° (c5, CHCl3), and IIIc, m. 151-3° (MeOH), [α]22D -31.7° (c5, CHCl3), were similarly prepared Deacetylation with MeONa afforded the free glucosides: 2-(β-D-glucopyranosylthio)-4-methylthiazole (IIId) (G = β-D-glucopyranosyl throughout this abstract), m. 152-5°, [α]22D -66.8° (c 2, H2O), and IIIe, m. 87-90° (H2O), [α]22D -62.9° (c 2, H2O). Using the same procedure as for IIIa, 4-methyloxazole-2-thione (IV) afforded 4-methyl-2-(tetra-O-acetyl-β-D-glucopyranosylthio)oxazole (Va), m. 105-10°, [α]22D -17° (c 5, CHCl3). Vb, m. 160-3° (MeOH), [α]22D -22° (c 5, CHCl3), and Vc, m. 117-19° (MeOH), [α]22D -13.9° (c 5, CHCl3), were prepared similarly. Tetra-o-acetylglucosides, deacetylated as previously, yielded the free glucosides: Vd, m. 125-8°, [α]22D -49.5° (c 2, H2O); Ve, m. 137-40°,α]22D -63.2° (c 2, H2O); and Vf, m. 85-90°, [α]25D -54.5° (c 1.5, Me2CO). 1-Methylimidazole-2-thione (VI) reacted with I under the Sabalitschka method gave 55% of 1-methyl-2-(tetra-O-acetyi-1-β-D-glucopyranosylthio)imidazole (VII), m. 99-102° (70% EtOH), [α]22D 0° (CHCl3). II (0.01 mole) dissolved in 10 ml. H2O containing 0.56 g. KOH and the solution treated slowly with a solution of 2.72 g. HgCl2 and 2 g. NaCl in 40 ml. H2O yielded bis(2-thiazolythio)mercury (VIII), m. 182-90° (decomposition). VIII (0.005 mole) was dissolved in 30 ml. HCONMe2, the solution mixed with 30 ml. C6H6, the latter distilled and the remaining dry solution treated with 4.1 g. I, kept 14 hrs. at 50°, diluted with 200 ml. H2O, extracted 5 times with CHCl3, the combined extracts washed with 30% KI followed by 5% Na2CO2, dried and evaporated, gave 50% 3-(tetra-O-acetyl-1-β-D-glucopyranosyl)thiazole-2-thione (IXa), m. 179-82° (MeOH), [α]22D 68.3° (c 5, CHCl3). IXa deacetylated as previously, afforded IXb, m. 173-83°, [α]22D 35° (c 2, H2O). Similarly, bis(1-methylimidazol-2-ylthio)mercury, m. 220-5° (decomposition), produced 25% 1-methyl-3-(tetra-O-acetyl-β-D-glucopyranosyl)imidazole-2-thione (X), m. 148-9° (MeOh), α]23D 36° (c 5, CHCl3). VI (0.02 mole), refluxed with 6 ml. (Me3Si)2NH for 8 hrs. gave 1-methyl-3-trimethylsilylimidazole-2-thione, b9 142-3°. This, heated for 2 hrs. with I at 120-30° in vacuo, diluted with 100 ml. CHCl3 and the solution washed with 5% Na2CO3 yielded 30% X. Similarly, 2-trimethylsilylthiothiazole, b. 143-5°, afforded IIIa, while 2-trimethylsilylthio-4-phenyloxazole, b9 147-51°, gave 72% Vb. 1-Thio-D-glucosides heated in toluene with HgBr2 were converted in high yield into glycosylamines. Thus, IIIa (2.5 millimoles) was refluxed 5 hrs. with 0.9 g. HgBr2 in 50 ml. of dry toluene, the solution washed with 30% KI followed by 5% Na2CO3, dried and evaporated to give 95% IXa. Likewise, VII produced 73% X, Va gave 20% 3-(tetra-O-acetyl-β-D-glucopyranosyl)-4-methyloxazole-2-thione (XIa), m. 163-6° (MeOH), [α]22D 73.8° (c 5, CHCl3), while Vc yielded 55% XIb, m. 143-5° (MeOH), [α]22D -47.4° (c 5, CHCl3). Deacetylation of XIb afforded XIc, m. 200-5°, [α]20D -3.5° (c2, HCONMe2). Transglycosylation of IIIb resulted in 25% IXc, m. 192-4°, [α]22D 66° (c 5, CHCl3). In the case of 4-Ph derivatives, no conversion into glycosylamines was observed. Instead, partial anomerization occurred: Vb yielded 5% of 2-(tetra-O-acetyl-α-D-glucopyranosylthio)-4-phenylthiazole, m. 102-6° (MeOH), [α]22D 156° (c 5, CHCl3), while IIIc gave 30% 2-(tetra-O-acetyl-α-D-glucopyranosylthio)-4-phenyloxazole, m. 138-40° (MeOH), [α]22D 228° (c 5, CHCl8), which on deacetylation afforded the free glucoside, an amorphous solid, [α]22D 226° (c 2, H2O). AcCH2OH (3 g.) dissolved in 40 ml. EtOH, treated with 5.8 g. KCNS and 3 ml. concentrated HCl and refluxed 24 hrs. gave 65% 4-methyloxazole-2-thione (XII), m. 149-52° (MeOH). II (2 g.), 5 g. Ag2O, and 15 g. MeI refluxed 8 hrs. gave 80% 2-methylthiothiazole, b26 59-62°. Similarly, XII yielded 2-(methylthio)-4-methyloxazole, b8 44-5°.
Archiv der Pharmazie und Berichte der Deutschen Pharmazeutischen Gesellschaft published new progress about 5053-24-7. 5053-24-7 belongs to thiazole, auxiliary class Thiazole,sulfides, name is 2-(Methylthio)thiazole, and the molecular formula is C4H5NS2, Synthetic Route of 5053-24-7.
Referemce:
https://pubchem.ncbi.nlm.nih.gov/compound/thiazole,
Thiazole | chemical compound | Britannica