反応 #1532006

反応方程式

3-tert-butylimino-1,1,1,5,5,5-hexakis(dimethylamino)-3-[tris(dimethylamino)phosphoranylidene]amino-1λ5,3λ5,5λ5-1,4-triphosphazadiene

n-hexane

hydrochloric acid

1-iodo-2-methylpropane

compound

Ethyl[1-(2-bromophenyl)-8-chloro-4-oxo-1,2,4,5-tetrahydrobenzo[d]azepin-3-yl]acetate

→

title compound

Ethyl[5-(2-bromophenyl)-7-chloro-1-isobutyl-2-oxo-1,2,4,5-tetrahydrobenzo[d]azepin-3-yl]-acetate

溶媒

water

THF

反応条件

後処理

1. 1
   workup.STIRRINGthe mixture is stirred at −78° C. for a further 3 h
2. 2
   抽出extracted three times with dichloromethane
3. 3
   洗浄The combined organic phases are washed twice with saturated sodium bicarbonate solution
4. 4
   乾燥dried over sodium sulphate
5. 5
   濃縮concentrated in a rotary evaporator
6. 6
   その他The residue is purified by preparative HPLC (eluent: acetonitrile/water with 0.1% formic acid, gradient 20:80→95:5)

実験手順

440 mg of the compound from Example 12A (1.01 mol) are dissolved in 5.2 ml of THF. At −78° C., 1.51 ml of a 1 M solution of 3-tert-butylimino-1,1,1,5,5,5-hexakis(dimethylamino)-3-[tris(dimethylamino)phosphoranylidene]amino-1λ5,3λ5,5λ5-1,4-triphosphazadiene in n-hexane (1.51 mol) are added drop wise, and the reaction mixture is stirred at −78° C. for 30 min. 278 mg of 1-iodo-2-methylpropane (1.51 mol) are added drop wise, and the mixture is stirred at −78° C. for a further 3 h. The reaction solution is mixed with 14 ml of 1 N hydrochloric acid and water and extracted three times with dichloromethane. The combined organic phases are washed twice with saturated sodium bicarbonate solution, dried over sodium sulphate and concentrated in a rotary evaporator. The residue is purified by preparative HPLC (eluent: acetonitrile/water with 0.1% formic acid, gradient 20:80→95:5). 200 mg (40% of theory) of the title compound are obtained.

出典