Reaktion #95515

Reaktionsgleichung

2-thiophenecarboxaldehyde

potassium cyanide

methanesulfonyl chloride

hexahydro-2H-1,3-diazepin-2-thione

o-chlorobenzaldehyde

→

desired product

2-(o-Chlorophenyl)-2,3,5,6,7,8-hexahydro-3-(2-thienyl)-thiazolo[3,2-a][1,3]diazepin-3-ol

Lösungsmittel

triethylamine

toluene

water

toluene

water

acetone

ethanol

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONA mixture of 9.2 ml
2. 2
   Sonstigethe oil is separated by decantation
3. 3
   workup.ADDITIONadded to toluene
4. 4
   Waschenwashed with water
5. 5
   Sonstigedried
6. 6
   Einengenconcentrated
7. 7
   Sonstigegiving 12.7 g
8. 8
   workup.ADDITIONportion of this oil is mixed with 8.4 ml
9. 9
   SonstigeThe toluene layer is separated
10. 10
    Waschenwashed with water
11. 11
    Sonstigedried
12. 12
    Einengenconcentrated
13. 13
    Sonstigegiving 10.6 g
14. 14
    workup.WAITto stand 48 hours
15. 15
    SonstigeThe solvent is removed
16. 16
    workup.ADDITIONof ammonium hydroxide are added
17. 17
    Sonstigethe aqueous layer is decanted
18. 18
    workup.ADDITIONEthanol is added
19. 19
    Temperaturthe mixture is cooled
20. 20
    Sonstigethe solid is collected
21. 21
    Sonstigegiving 3.4 g

Vorschrift

A mixture of 9.2 ml. of 2-thiophenecarboxaldehyde, 11.3 ml. of o-chlorobenzaldehyde, 8 g. of potassium cyanide and 100 ml. of 65% ethanol is refluxed for 2 hours and then refrigerated. A 30 ml. portion of water is added, refrigeration is continued, the oil is separated by decantation, added to toluene, washed with water, dried and concentrated giving 12.7 g. of an oil. A 9.0 g. portion of this oil is mixed with 8.4 ml. of triethylamine and 100 ml. of toluene and stirred as a mixture of 2.4 ml. of methanesulfonyl chloride in 100 ml. of toluene is added. The mixture is stirred overnight then 100 ml. of water is added. The toluene layer is separated, washed with water, dried and concentrated, giving 10.6 g. of oily 2-thienyl α-hydroxy(2-chlorophenyl)ketone. This oil is combined with 3.9 g. of hexahydro-2H-1,3-diazepin-2-thione in 150 ml. of acetone and allowed to stand 48 hours. The solvent is removed, 100 ml. of water and 2 ml. of ammonium hydroxide are added and the aqueous layer is decanted. Ethanol is added, the mixture is cooled and the solid is collected, giving 3.4 g. of the desired product, m.p. 120°-122° C.

Quelle