3-prop-2-enyl-2-sulfanylideneimidazolidin-4-one

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A flask equipped with a reflux condenser, magnetic stirrer, and nitrogen atmosphere was charged with diglyme (10 mL), 3-allylthiohydantoin (1.0 g, 0.0064 mol), morpholine (0.56 g, 0.0064 mol), and freshly distilled butyraldehyde (0.94 g, 0.13 mol). The mixture was heated in a 70° oil bath for 250 min and, after cooling, was diluted with 20 mL of ethyl acetate. The resulting solution was washed with 2×10 mL 1.2 M HCl, 10 mL of water, and 10 mL of saturated aqueous NaCl. The solution was then filtered through 1 PS paper and concentrated to dryness at aspirator pressure and then high vacuum. The light orange crystalline residue weighed 1.26 g (97%). An HPLC trace at 215 nm indicated that the major product comprised 92% of the mixture. Another component (5%), with a nearly identical ultraviolet spectrum, eluted slightly more slowly. This possibly represents the other geometric isomer. NMR (CDCl3) δ 10 (bs, 1H), 5.2-6.3 (m, 4H), 4.6 (d, 2H), 2.3 (quart., 2H), 1.8 (sex., 2H), 1.0 (t, 3H). A flask equipped with a reflux condenser, magnetic stirrer The mixture was heated in a 70° oil bath for 250 min after cooling The resulting solution was washed with 2×10 mL 1.2 M HCl, 10 mL of water, and 10 mL of saturated aqueous NaCl The solution was then filtered through 1 PS paper concentrated to dryness at aspirator pressure Another component (5%), with a nearly identical ultraviolet spectrum, eluted slightly more slowly

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A flask equipped with a magnetic stirrer, condenser, and nitrogen pressure was charged with 3-allylthiohydantoin (15 g, 0.096 mol), water (90 mL), and benzaldehyde (10.2 g, 0.096 mol). As the mixture was stirred, triethylamine (19.4 g, 0.192 mol) was added slowly. After 18 hr, HPLC analysis indicated the absence of starting material, and the mixture was transferred to an Erlenmeyer flask. The mixture was stirred vigorously as 3 M hydrochloric acid was added dropwise until the pH reached 3 (65 mL). The mixture was stirred for an additional 90 min, and then the solid that had formed was collected by filtration. The still wet solid was resuspended in 100 mL of water, stirred for 30 min, and collected. After air drying, the orange solid weighed 18.4 g (79%). HPLC analysis indicated a purity of 95% at 215 nm. NMR (CDCl3) δ 9.3 (bs, 1H), 7.4 (s, 5H), 6.8 (s, 1H), 5.1-6.3 (m, 3H), 4.6 (d, 2H). A flask equipped with a magnetic stirrer, condenser was added dropwise until the pH The mixture was stirred for an additional 90 min the solid that had formed was collected by filtration stirred for 30 min collected After air drying

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A flask equipped with a reflux condenser and nitrogen atmosphere was charged with acetone (20 mL), 3-allylthiohydantoin (2.0 g, 0.013 mol), and morpholine (1.1 g, 0.013 mol). The mixture was heated at reflux for 80 min and, after cooling, was diluted with 40 mL of ethyl acetate. The resulting solution was washed with 2×20 mL 1.2 M HCl, 20 mL of water, and 20 mL of saturated aqueous NaCl. The solution was then filtered through 1 PS paper and concentrated to dryness at aspirator pressure and then high vacuum. The off-white crystalline residue weighed 2.3 g (92%). No other components were detectable by HPLC at 215 nm. NMR (CDCl3) δ 9.9 (bs, 1H), 5.1-6.1 (m, 3H), 4.6 (d, 2H), 2.3 (s, 3H), 2.0 (s, 3H). A flask equipped with a reflux condenser The mixture was heated at reflux for 80 min after cooling The resulting solution was washed with 2×20 mL 1.2 M HCl, 20 mL of water, and 20 mL of saturated aqueous NaCl The solution was then filtered through 1 PS paper concentrated to dryness at aspirator pressure

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Glycine (30 g, 0.40 mol), triethylamine (44 g, 0.44 mol), pyridine (100 mL), and water (100 mL) were mixed in a flask equipped with a magnetic stirrer and a temperature controller. Allyl isothiocyanate (44 g, 0.44 mol) was added, and the temperature was raised to 55° C. (the mixture became homogeneous at ca. 30°). When the mixture reached this temperature, it was allowed to cool to room temperature. The mixture was extracted with 3×200 mL of toluene to remove the pyridine and excess isothiocyanate and was then treated with 66 mL (0.8 mol) of concentrated hydrochloric acid. The mixture was heated at 90° C. for 2.5 hr and was then stirred rapidly while it cooled to room temperature. A solid mass of crystals formed instantaneously when the solution was seeded with a fragment of a crystal of authentic product. After the suspension stood at room temperature overnight, the product was collected and pressed with rubber dam. The filter cake was washed with 3×60 mL of water (the filter cake was pressed with rubber dam after each wash). After the material had dried to constant weight in a hood draft, it weighed 49 g (71% yield). NMR (CD3OD) δ 4.9-6.1 (m, 3H), 4.6 (s, 1H), 4.3 (d, 2H), 4.0 (s, 2H). HPLC analysis showed no other components at several wavelengths. equipped with a magnetic stirrer became homogeneous at ca. 30° to cool to room temperature The mixture was extracted with 3×200 mL of toluene to remove the pyridine and excess isothiocyanate The mixture was heated at 90° C. for 2.5 hr cooled to room temperature A solid mass of crystals formed instantaneously when the solution the product was collected The filter cake was washed with 3×60 mL of water (the filter cake each wash) After the material had dried to constant weight in a hood draft, it