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With sodium hydroxide; |
Reference Example 5 <strong>[77168-63-9]4-(4-pyridyl)-1,3-thiazole-2-thiol</strong> sodium salt 4-(4-Pyridyl)-1,3-thiazole-2-thiol (194 g, 1.0 mol, powder) was added to 8N aqueous sodium hydroxide solution (1.25 L, 10 mol) and the mixture was stirred for 30 min. The precipitated crystals were collected by filtration and washed with 8N aqueous sodium hydroxide solution (0.4 L). The obtained wet crystals were recrystallized from isopropyl alcohol (200 mL) to give the title compound (166 g, 0.77 mol) as yellow crystals. yield 77percent. melting point: 272OEC (decomposition). Anal Calcd for C8H5N2S2Na*0.75H2O: C 41.82, H 2.85, N 12.19. Found: C 41.78, H 2.98, N 12.11. 1H-NMR(DMSO-d6)delta:7.35 (1H,s), 7.71 (2H,d,J=6.2Hz), 8.48 (2H,d,J=6.2Hz). |
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With sodium methylate;phosphorus pentaoxide; In methanol; |
Reference Example 6 <strong>[77168-63-9]4-(4-pyridyl)-1,3-thiazole-2-thiol</strong> sodium salt 4-(4-Pyridyl)-1,3-thiazole-2-thiol (194 g, 1.0 mol) was suspended in methanol (1 L) and a powder of sodium methylate (71.5 g, 1.2 mol) was added at 25OEC. The mixture was stirred for 30 min and the reaction mixture was concentrated under reduced pressure to 50-60 mL. The mixture was preserved overnight in a refrigerator. The precipitated crystals were collected by filtration and dried in vacuo in the presence of phosphorus pentoxide at 40OEC to give the title compound (160 g, 0.74 mol). yield: 74percent. |
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With sodium methylate; In tetrahydrofuran; methanol; at 20 - 25℃; |
A reactor was charged with 143.3 g of 4-(4-Pyridyl)-1,3-thiazole-2-thiol, 570 ml of tetrahydrofuran, 145 ml of methanol. The obtained mixture was thermo-regulated to 20-25°C, and at this temperature 126.3 g of sodium methylate solution 30percent in methanol were carefully added. The obtained mixture was left under stirring until complete dissolution then cooled to -2-0°C and maintained at that temperature. In a different reactor a solution of 450 g of benzhydryl (6R,7R)-7f3-[(phenylacetyl)amino]-3- [(methylsulfonyl)oxy]-3-cephem-4-carboxylate in 1.3 1 of tetrahydrofuran was prepared, which was cooled to -5-0°C. The <strong>[77168-63-9]4-(4-pyridyl)-1,3-thiazole-2-thiol</strong> sodium salt solution was then added to the substrate solution, by maintaining the temperature at -5-0°C. At the end of the addition thetemperature was set to -2-0°C and the mixture was maintained under stirring for about 2 h. The mixture was then diluted with 2.5 1 of ethyl acetate and washed three times with brine. The aqueous phases were eliminated and the organic phase was treated with decolorizing charcoal and concentrated under reduced pressure to about half volume and diluted with 1.5 1 of toluene two times, then concentrated again under vacuum to about half volume and diluted with 700 mlof toluene. The mixture was stirred at 25-30°C for 30±5 minutes, then cooled to 0-5°C and maintained at this temperature for 60 about 1 h. The mixture was filtered, the cake washed with toluene and dried overnight under vacuum at about 40°C yielding 455 g of crystalline toluene hemi-solvate of benzhydryl (6R,7R)-7f3 -[(phenylacetyl)amino] -3- [4-pyridyl-2-thiazolylthio] -3- cephem-4-carboxylate. MW: 1545.92 (Toluene solvated form)Yield: 82percentDSC: 104-106 °C (melting endotherm)TGA: weight loss of about 4.54percent,1H NMR: (D6-DMSO) oe 2.29, 3.54, 3.68, 3.93, 5.30, 5.87, 6.98, 7.16-7.38, 7.89, 8.54, 8.60 and9.28 ppm13C NMR: (D6-DMSO) oe20.99, 29.34, 40.13, 41.56, 58.41, 59.59, 79.24, 118.47, 120.20, 121.55,125.26, 126.47-140.12, 150.36, 125.86, 160.41, 161.23, 164.77, 170.92 ppm;IR spectrum (KBr): 3280 (NH), 3034 (CH-aromatic), 2960,(CH-aliphatic), 1791 (f3-LactumC=O), 1702 (Ester C=O), 1654 (Amide C=O), 1535 (Pyridine C=N) and 1011 (C-O), cm-iMass spectrum: mlz = [M+j = 677.13 (Non-solvated form). |
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