反应详情

To a 500 ml three-necked roundbottom flask was added 200 ml dry THF, 0.54 gr (1 mmol) Ni(dppp)Cl2 and 87 mmol of P-Br, fleshly prepared from 17 gr of the hydrochloride. To this was added T-MgBr, prepared from 14 gr (87 mmol) of T-Br and 2.5 gr (103 mmol) of magnesium. The mixture was refluxed for 20 hours and subsequently quenched with aqueous ammoniumchloride/HCl. About 100 ml of hexane was added and the organic layer extracted three times with dilute hydrochloric acid. Hereafter, the water layers were combined and made mildly alkaline with a strong sodium hydroxide solution. The product was extracted with three portions of 100 ml of chloroform. The chloroform solution was boiled shortly with a small amount of active coal and filtrated, whereafter the chloroform was removed on a rotation evaporator. Trituration of the remaining brown solid in boiling hexane yielded a clear yellow solution and a black unsoluble residue. After decanting the yellow solution, the solvent was evaporated and the remaining yellow solid dried in vacuo. The product was once recrystallized from 100 ml of hexane (a few hours standing at room temperature and overnight standing at 4° C.). The resulting yellow crystals were filtrated off, washed with cold pentane twice and dried in vacuo, (fraction I). From the collected pentane supernatants a second fraction of product with a lesser purity was obtained, by evaporating the solvent on a rotation evaporator and drying the remaining solid in vacuo. Yield: fraction I: light yellow powder of PT, 3.88 gr (24 mmol, 28%), fraction II: yellow powder of PT 6.00 gr (37.2 mmol, 43%), still containing some P-Br. M.p. (fraction I): 90°-91° C. (litt.: 92.5°-93.5° C.). Elemental analysis: found% (theory%) C 66.87 (67.05), H 4.38 (4.38), N 8.90 (8.69), S 18.7 (19.9). 1H-NMR (300 MHz, CDCl3): ∂=8.59 (2H, dd, J=4.6 and 1.7 Hz), ∂=7.52 (1H, dd, J=3.8 and 1.1 Hz), ∂=7.49 (2H, dd, J=4.6 and 1.7 Hz), ∂=7.43 (1H, dd, J=5.0 and 1.1 Hz), ∂=7.14 (1H, dd, J=3.8 and 5.0 Hz). M/z: 161 D (M.W.=161).

1. temperatureThe mixture was refluxed for 20 hours
2. customsubsequently quenched with aqueous ammoniumchloride/HCl
3. additionAbout 100 ml of hexane was added
4. extractionthe organic layer extracted three times with dilute hydrochloric acid
5. extractionThe product was extracted with three portions of 100 ml of chloroform
6. filtrationfiltrated, whereafter the chloroform
7. customwas removed on a rotation evaporator
8. customyielded a clear yellow solution
9. customAfter decanting the yellow solution
10. customthe solvent was evaporated
11. customthe remaining yellow solid dried in vacuo
12. customThe product was once recrystallized from 100 ml of hexane (a few hours standing at room temperature and overnight standing at 4° C.)
13. filtrationThe resulting yellow crystals were filtrated off
14. washwashed with cold pentane twice
15. customdried in vacuo, (fraction I)
16. customFrom the collected pentane supernatants a second fraction of product with a lesser purity was obtained
17. customby evaporating the solvent
18. customon a rotation evaporator
19. customdrying the remaining solid in vacuo
20. additionYield: fraction I: light yellow powder of PT, 3.88 gr (24 mmol, 28%), fraction II: yellow powder of PT 6.00 gr (37.2 mmol, 43%), still containing some P-Br
21. custom90°-91° C.
22. custom92.5°-93.5° C.