反应详情

Under nitrogen, 0.0968 g (0.4 mmols) of 3,4-dibromothiophene and 0.0131 g (0.016 mmols) of commercially available Pd(dppf)2Cl2 were added to DMF (4 ml) and were dissolved under stirring at room temperature for 5 minutes. To the thus obtained solution, 0.1326 g (0.96 mmols) of commercially available diethyl phosphate and 0.1241 g (0.96 mmols) of diisopropylethylamine were added at room temperature. Thereafter, the reaction mixture was heated to 110° C. and stirred for 4 hours. After the reaction, the reaction mixture was cooled down to room temperature, to which a disodium hydrogen phosphate/sodium dihydrogen phosphate buffer solution, adjusted to pH=7.0, was added, followed by extraction with ethyl acetate. The resulting organic phase was washed with a saturated saline and dried over anhydrous sodium sulfate. The solvent was removed by distilling off under reduced pressure, and the resulting crude product was purified with a PTLC plate (developed with ethyl acetate:hexane=1:1) to obtain a specified substance 1 in the form of a brown solid and the specified substance 2 in the form of a yellow oil. The thus obtained substances were used for the reaction of Example 2(2) as they are. The yields of the compounds 1 and 2 are shown in Table 1.

1. dissolutionwere dissolved
2. temperatureThereafter, the reaction mixture was heated to 110° C.
3. stirringstirred for 4 hours
4. customAfter the reaction
5. additionwas added
6. extractionfollowed by extraction with ethyl acetate
7. washThe resulting organic phase was washed with a saturated saline
8. dry with materialdried over anhydrous sodium sulfate
9. customThe solvent was removed
10. distillationby distilling off under reduced pressure
11. customthe resulting crude product was purified with a PTLC plate (developed with ethyl acetate:hexane=1:1)
12. customto obtain a specified substance 1 in the form of a brown solid
13. customThe thus obtained substances were used for the reaction of Example 2(2) as they