Reaktion #4924

Reaktionsgleichung

fumaric acid

dimethylamine

ethanol

2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]-oxazepine-5(4H)-thione

→

2-[2-(Dimethylamino)ethyl]-2,3-dihydro-4-methylpyrido[3,2-f][1,4]-oxazepine-5(4H)-thione fumarate

Lösungsmittel

methanol

isopropyl alcohol

methylene chloride

isopropyl alcohol

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeThe ethanol was removed in a rotary evaporator
2. 2
   Sonstigeleaving some water in the residue
3. 3
   Waschenwashed with three 100 ml portions of 20% aqueous potassium carbonate solution
4. 4
   ExtraktionThe combined aqueous layers were extracted with three 150 ml portions of methylene chloride
5. 5
   workup.ADDITIONtreated with charcoal
6. 6
   FiltrationCharcoal was filtered off
7. 7
   Sonstigethe filtrate was evaporated
8. 8
   Sonstigeto give an oil
9. 9
   Temperaturthe solution was heated to a slow boil
10. 10
    SonstigeCrystalline solid was obtained
11. 11
    SonstigeThe solid was recrystallized from hot 200 proof ethyl alcohol
12. 12
    FiltrationThe crystals were filtered off
13. 13
    Sonstigetriturated in isopropyl ether at room temperature
14. 14
    Sonstigeagain separated
15. 15
    Filtrationby filtering
16. 16
    SonstigeAfter drying in a vacuum oven overnight at 85° C.
17. 17
    Sonstigecrystals in the amount of 72.45 g (79%), m.p. 130°-133° C., were obtained

Vorschrift

To a solution of 113 ml (1.0 mole) of 40% aqueous dimethylamine and 326 ml of ethanol in a steel bomb was added 48.4 g (0.189 mole) of 2-(2-chloroethyl)-2,3-dihydro-4-methylpyrido[3,2-f][1,4]-oxazepine-5(4H)-thione. The mixture was heated at 100° C. for 14 hr. The ethanol was removed in a rotary evaporator leaving some water in the residue. The residue was dissolved in 200 ml of methylene chloride and washed with three 100 ml portions of 20% aqueous potassium carbonate solution. The combined aqueous layers were extracted with three 150 ml portions of methylene chloride. Methylene chloride solutions were combined and treated with charcoal. Charcoal was filtered off and the filtrate was evaporated to give an oil. The oil was dissolved in 215 ml isopropyl alcohol and the solution was heated to a slow boil. A solution of 21.9 g (0.19 mole) of fumaric acid in 150 ml of boiling methanol was added to the isopropyl alcohol solution. Crystalline solid was obtained weighing 63.4 g (88%). The solid was recrystallized from hot 200 proof ethyl alcohol. The crystals were filtered off and triturated in isopropyl ether at room temperature and again separated by filtering. After drying in a vacuum oven overnight at 85° C., crystals in the amount of 72.45 g (79%), m.p. 130°-133° C., were obtained.

Quelle