反応 #76618

反応方程式

sodium hydride

(8-bromo-1-methyl-1,2,3,4-tetrahydrobenzo[e][1,4]diazepin-5-ylidenemethyl)phosphonic acid diethyl ester

vinyl tributylstannane

3,4-dichlorobenzaldehyde

→

(E)-5-(3,4-dichlorostyryl)-2,3-dihydro-1-methyl-8-vinyl-1H-1,4-benzodiazepine dihydrochloride

収率 52.8%

溶媒

dioxane

反応条件

後処理

1. 1
   その他The solvent was removed
2. 2
   その他the product was purified by column chromatography
3. 3
   洗浄eluting with 1-4% methanol/dichloromethane
4. 4
   workup.ADDITIONtreated with 0.10 ml of 4M hydrogen chloride in dioxan
5. 5
   その他The solvent was evaporated
6. 6
   workup.DISSOLUTIONthe residue was dissolved from acetone/petroleum ether (40 60° C.)
7. 7
   その他The solvent was removed

実験手順

To 123 mg (0.32 mmol) of (8-bromo-1-methyl-1,2,3,4-tetrahydrobenzo[e][1,4]diazepin-5-ylidenemethyl)phosphonic acid diethyl ester (prepared as described in Example 41) in 2 ml of dioxane was added 120 mg (0.38 mmol) of vinyl tributylstannane, followed by 11.1 mg (0.016 mmol)of palladium (II) bis-triphenylphosphine-dichloride. The mixture was heated at 80° C. for 18 hours. To the mixture at ambient temperature was added 22 mg (0.55 mmol) of sodium hydride (60% dispersion in mineral oil). After 5 minutes 57 mg (0.33 mmol) of 3,4-dichlorobenzaldehyde was added and the mixture was stirred for 18 hours. The solvent was removed and the product was purified by column chromatography eluting with 1-4% methanol/dichloromethane and treated with 0.10 ml of 4M hydrogen chloride in dioxan. The solvent was evaporated and the residue was dissolved from acetone/petroleum ether (40 60° C.). The solvent was removed to give 25 mg of (E)-5-(3,4-dichlorostyryl)-2,3-dihydro-1-methyl-8-vinyl-1H-1,4-benzodiazepine dihydrochloride as a red solid; MS: 357 (M+).

出典