Reaktion #323203

Reaktionsgleichung

2-methylthio-4,4-dimethyl-2-imidazoline hydroiodide

methyl iodide

ethyl oximinocyanoacetate

1,2-diamino-2-methylpropane

methyl iodide

sodium

p-chlorobenzylamine

→

4,4-Dimethylimidazoline-2-thione

desired product

7-Amino-8-[(4-Chlorophenyl)Methyl]-2,3-Dihydro-2,2-Dimethyl-6-Nitrosoimidazo[1,2-a]-Pyrimidin-5(8H)-One

Lösungsmittel

methylene chloride

carbon disulfide

water

acetic acid

ethanol

EtOH

EtOH

methylene chloride

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONby adding a solution of 50 g
2. 2
   SonstigeThe product formed as a white precipitate immediately
3. 3
   workup.ADDITIONon mixing of the two solutions
4. 4
   SonstigeThe solvent was removed by distillation in vacuo
5. 5
   Temperaturthe mixture was refluxed for 7 hrs
6. 6
   EinengenIt was concentrated to one-half the original volume
7. 7
   Filtrationclarified by filtration while hot, and the product
8. 8
   Sonstigeto crystallize from the filtrate, yield 60.6 g
9. 9
   workup.ADDITION, (0.337 mole), was treated with 47.9 g
10. 10
    EinengenThe mixture was then concentrated in vacuo to an oil which
11. 11
    workup.ADDITIONwas mixed with i-Pr2O
12. 12
    Sonstigecrystallization
13. 13
    Sonstigeresulting in the formation of a light yellow solid, yield 90.7 g
14. 14
    TemperaturIt was refluxed for 41/2 hrs
15. 15
    Einengenand then concentrated in vacuo
16. 16
    Sonstigeto yield an oily solid
17. 17
    Sonstigewas collected
18. 18
    Sonstigeair dried

Vorschrift

4,4-Dimethylimidazoline-2-thione was prepared by adding a solution of 50 g. of 1,2-diamino-2-methylpropane in 35 ml. of methylene chloride dropwise with stirring to a solution of 43 g. of carbon disulfide in 200 ml. of methylene chloride during about 3 hrs. The product formed as a white precipitate immediately on mixing of the two solutions. The solvent was removed by distillation in vacuo and replaced with water, and the mixture was refluxed for 7 hrs. It was concentrated to one-half the original volume, clarified by filtration while hot, and the product allowed to crystallize from the filtrate, yield 60.6 g., m.p. 114°-115°. A portion of this material, 43.9 g., (0.337 mole), was treated with 47.9 g. (0.337 mole) of methyl iodide in 400 ml. of ethanol. The methyl iodide was added by dropwise addition. The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O to induce crystallization resulting in the formation of a light yellow solid, yield 90.7 g. (99%), of 2-methylthio-4,4-dimethyl-2-imidazoline hydroiodide. A portion of this material, 27.2 g. (0.1 mole), and 14.1 g. (0.1 mole) of p-chlorobenzylamine were dissolved in 100 ml. of abs. EtOH and added to a solution of 9.0 g. (0.4 mole) of sodium in 400 ml. of abs. EtOH at the reflux temperature. The solution was stirred for 10 min. and 14.2 g. (0.1 mole) of ethyl oximinocyanoacetate was added in portions during a period of about 5 min. The reaction solution became clear and bright yellow in color. It was refluxed for 41/2 hrs. and then concentrated in vacuo to yield an oily solid. The latter was dissolved in water and treated with acetic acid resulting in formation of the desired product as a red precipitate which was collected and air dried, m.p. 214°-215°, yield 16.7 g. (50%).

Quelle