反応 #1509633

反応方程式

potassium thiocyanate

L-ornithine methyl ester hydrochloride

HCl

ethanol

→

desired compound

4-(3-amino-propyl)-1,3-dihydro-imidazole-2-thione hydrochloride

溶媒

water

water

反応条件

後処理

1. 1
   温度to maintain the above stated temperature
2. 2
   workup.ADDITIONAfter the addition
3. 3
   その他bubbling
4. 4
   その他was decanted from the solution
5. 5
   その他The remaining aqueous portion was drained into a separate flask
6. 6
   温度the flask was then heated at 95° C. while open to the atmosphere for 1.5 h
7. 7
   温度After cooling to room temperature
8. 8
   その他the reaction was evaporated to dryness
9. 9
   ろ過filtered
10. 10
    その他to remove NaCl
11. 11
    その他After all of the NaCl had been removed the crude residue
12. 12
    その他was purified by column chromatography (CH2Cl2/MeOH sat. with NH3 80:20)

実験手順

To an Erlenmeyer flask was prepared a solution of L-ornithine methyl ester hydrochloride (10.50 g, 47.9 mmol) in water (125 mL) The solution was cooled to 5° C. and pH adjusted to a value of 1.5 with concentrated HCl. While being careful to maintain the above stated temperature and pH, 5% Na(Hg) (250 g) was added slowly to the solution over a time period of 35 min After the addition was complete and bubbling had calmed the Hg was decanted from the solution. The remaining aqueous portion was drained into a separate flask where potassium thiocyanate (14.0 g, 144 mmol) and water (75 mL) was added. The pH of solution was adjusted to a value of 4.30 and the flask was then heated at 95° C. while open to the atmosphere for 1.5 h. After cooling to room temperature, ethanol (75 mL) was added and the reaction was evaporated to dryness. The residue was taken up in methanol and filtered to remove NaCl. After all of the NaCl had been removed the crude residue was purified by column chromatography (CH2Cl2/MeOH sat. with NH3 80:20) to afford the desired compound in its free base form. Addition of concentrated hydrochloric acid to a methanol solution (50 mL) of the free base followed by evaporation to dryness gave 4.51 g (48%) of the title compound 42 as a tan solid: 1H NMR (300 MHz, DMSO-d6) δ 11.92 (s, 1H), 11.69 (s, 1H), 7.77 (s, 2H), 6.58 (s, 1H), 2.73 (m, 2H), 2.42 (t, 2H, J=6.6 Hz), 1.76 (tt, 2H, J=7.5, 13.8 Hz); 13C NMR (100 MHz, DMSO-d6) δ 160.23, 128.03, 111.69, 38.08, 25.75, 21.27; HRMS (FAB) calcd for C6H12N3S (MH+) 158.0752, found 158.0743.

出典