反応 #56338

反応方程式

1-(2',6'-dimethylphenyl)-4-methoxyamino-1,2-dihydro-1,3,5-triazin-2-one

DMF-DMA

1-(2',6'-dimethylphenyl)-3-methoxyamidinourea

NH4OH

→

1-(2',6'-dimethylphenyl)-4-methoxyamino-1,2-dihydro-1,3,5-triazin-2-one hydrate

溶媒

Et2O

DMF

CH3CN

反応条件

後処理

1. 1
   workup.ADDITIONTo a suspension of 10.9 g
2. 2
   温度The reaction mixture is cooled
3. 3
   workup.ADDITIONpoured into a round bottom flask
4. 4
   その他the CH3CN removed under reduced pressure
5. 5
   その他The residue is partitioned between CHCl3 and H2O
6. 6
   その他the layer separated
7. 7
   抽出The aqueous layer is extracted with CHCl3 (1×75 ml.)
8. 8
   洗浄The combined organic layers are washed with H2O (1×50 ml.)
9. 9
   乾燥dried (MgSO4)
10. 10
    濃縮concentrated under reduced pressure
11. 11
    その他to give an oily residue
12. 12
    洗浄washed with H2O (2×50 ml.)
13. 13
    乾燥The Et2O layer is dried (MgSO4)
14. 14
    濃縮concentrated under reduced pressure
15. 15
    その他to give a viscous oil
16. 16
    その他has been removed
17. 17
    温度cooled
18. 18
    ろ過a small amount of CHCl3, H2O and DMSO insoluble material filtered off
19. 19
    濃縮The filtrate is concentrated
20. 20
    その他to give a viscous oil
21. 21
    workup.ADDITIONUpon addition of MEOH
22. 22
    温度warming on a steam bath the oil
23. 23
    その他The solid is crystallized from MeOH
24. 24
    その他to give 4.6 g

実験手順

To a suspension of 10.9 g. (40.0 mmol) of 1-(2',6'-dimethylphenyl)-3-methoxyamidinourea in CH3CN (50 ml.) is added 9.5 g. (80.0 mmol) of DMF-DMA and the mixture heated at 105°-110° C. in a closed bomb for 1-1/2 hours. The reaction mixture is cooled and poured into a round bottom flask and the CH3CN removed under reduced pressure. The residue is partitioned between CHCl3 and H2O and the layer separated. The aqueous layer is extracted with CHCl3 (1×75 ml.). The combined organic layers are washed with H2O (1×50 ml.), dried (MgSO4) and concentrated under reduced pressure to give an oily residue. The residue is taken up in Et2O and washed with H2O (2×50 ml.). The Et2O layer is dried (MgSO4) and concentrated under reduced pressure to give a viscous oil. NMR shows that DMF has been removed. The oil is taken up in hot CH3CN cooled and a small amount of CHCl3, H2O and DMSO insoluble material filtered off. The filtrate is concentrated to give a viscous oil. TLC of the oil (Silicagel; 3% NH4OH, iPA) versus starting material shows one spot moves slower than starting material. Upon addition of MEOH and warming on a steam bath the oil solidifies. The solid is crystallized from MeOH to give 4.6 g. (43%) of 1-(2',6'-dimethylphenyl)-4-methoxyamino-1,2-dihydro-1,3,5-triazin-2-one as a white solid, melting point 78°-80° C.

出典