تفاعل #70563

معادلة التفاعل

triphenylphosphine

sodium bicarbonate

tributyl(1-ethoxyvinyl)tin

hydrochloric acid

5-bromo-2-phenylpyrimidine

→

title intermediate

المردود 33.8%

1-(2-phenylpyrimidin-5-yl)ethanone

المردود 33.8%

المذيبات

1,4-dioxane

1,4-dioxane

ظروف التفاعل

المعالجة

1. 1
   أخرىThe dark reaction mixture
2. 2
   درجة الحرارةwas cooled to room temperature
3. 3
   workup.ADDITIONto this reaction mixture was added a solution
4. 4
   درجة الحرارةheated at 75° C. overnight
5. 5
   درجة الحرارةwas subsequently cooled to room temperature
6. 6
   استخلاصThe organic material was extracted two times
7. 7
   workup.ADDITIONwith a mixture of ethyl acetate and hexanes
8. 8
   غسيلthe combined organic phase was washed sequentially with water and brine
9. 9
   تجفيفwas dried over anhydrous magnesium sulfate
10. 10
    ترشيحfiltered through a well packed pad of magnesium sulfate
11. 11
    تركيزconcentrated under reduced pressure
12. 12
    workup.DISSOLUTIONThe residue was dissolved in dichloromethane (30 mL)
13. 13
    workup.ADDITIONdiluted with hexanes (30 mL)
14. 14
    ترشيحThe resulting precipitate was filtered

الإجراء التجريبي

A stirring mixture consisting of palladium(II) acetate (215 mg, 0.32 mmol) and triphenylphosphine (335 mg, 1.28 mmol) in 1,4-dioxane (25 mL) was heated at 80° C. for 30 minutes. The dark reaction mixture was cooled to room temperature, and to this reaction mixture was added a solution consisting of 5-bromo-2-phenylpyrimidine (Example 1A, 3.0 g, 13 mmol) and tributyl(1-ethoxyvinyl)tin (4.74 mL, 14.0 mmol) in 1,4-dioxane (63 mL). The reaction mixture was stirred and heated at 75° C. overnight and was subsequently cooled to room temperature. The reaction progress was monitored by thin layer chromatography (95:5 v/v hexanes-ethyl acetate) until completion. The reaction mixture was treated with 1 N hydrochloric acid (19 mL) for one hour at room temperature and poured into a saturated aqueous sodium bicarbonate solution. The organic material was extracted two times with a mixture of ethyl acetate and hexanes, and the combined organic phase was washed sequentially with water and brine, and was dried over anhydrous magnesium sulfate, filtered through a well packed pad of magnesium sulfate, and concentrated under reduced pressure. The residue was dissolved in dichloromethane (30 mL) and diluted with hexanes (30 mL). The resulting precipitate was filtered to give the title intermediate (872 mg). The filtrate was applied to a 80-g silica column eluted with 1:1:9 v/v/v ethyl acetate-dichloromethane-hexanes to afford 1.01 g of additional title intermediate (1.88 g total, 74%); Rf 0.23 with 9:1 v/v hexanes-ethyl acetate solvent system; 1H-NMR (400 MHz; DMSO-d6) δ 9.4 (s, 2H), 8.45-8.50 (m, 2H), 7.5-7.7 (m, 3H), 2.68 (s, 3H); MS (ESI+) m/z 199 (M+1).

المصدر