反応 #1375806

反応方程式

intermediate 1-b

1,1-dimethylethyl [(4-chlorophenyl)(1 -methyl-1H-benzotriazol-6-yl)-methylene]hydrazine carboxylate

hydrochloric acid

water

→

(±)-6-[(4-chlorophenyl)hydrazinomethyl]-1-methyl-1H-benzotriazole monohydrochloride

溶媒

tetrahydrofuran

tetrahydrofuran

反応条件

後処理

1. 1
   温度The whole was heated
2. 2
   温度to reflux
3. 3
   温度refluxed for 1.5 hours
4. 4
   温度The mixture was cooled to room temperature
5. 5
   workup.STIRRINGAfter stirring for 1 hour
6. 6
   ろ過the reaction mixture was filtered
7. 7
   workup.ADDITIONThe filtrate was mixed with 75 ml of methylbenzene
8. 8
   その他The layers were separated
9. 9
   抽出The product was extracted with dichloromethane
10. 10
    その他the extract was dried
11. 11
    ろ過filtered
12. 12
    その他evaporated
13. 13
    workup.ADDITIONby adding 3ml of a mixture of hydrochloric acid in 2-propanol (4.8N)
14. 14
    workup.STIRRINGAfter stirring for 2 hours the product
15. 15
    ろ過was filtered off
16. 16
    洗浄washed with 2-propanol
17. 17
    その他dried in vacuo at 50° C.

実験手順

To a suspension of 10 g of intermediate 1-b in 60 ml of tetrahydrofuran under a nitrogen atmosphere were added dropwise over 15 minutes 26 ml of a borane tetrahydrofuran complex in tetrahydrofuran (1M). After stirring for 15 minutes at ±22° C. there were added 13 ml of hydrochloric acid (6N). The whole was heated to reflux and refluxed for 1.5 hours. The mixture was cooled to room temperature and 50 ml of water were added. After stirring for 1 hour, the reaction mixture was filtered. The filtrate was mixed with 75 ml of methylbenzene. The layers were separated and the aqueous layer was basified (pH 7.5-8) with NH4OH. The product was extracted with dichloromethane and the extract was dried, filtered and evaporated. The residue was converted into the hydrochloride salt in 2-propanol by adding 3ml of a mixture of hydrochloric acid in 2-propanol (4.8N). After stirring for 2 hours the product was filtered off, washed with 2-propanol and dried in vacuo at 50° C., yielding 2.1 g of (±)-6-[(4-chlorophenyl)hydrazinomethyl]-1-methyl-1H-benzotriazole monohydrochloride (interm. 2-e).

出典