反应详情

A 250 mL 3-neck flask equipped with a heating mantle, mechanical stirrer and N2 blanket was charged with KOH pellets (7.26 g, 0.11 mol based on 85% actives), DMSO (100 mL) and m-cresol (12.0 g, 0.11 mol). With stirring, the mixture was warmed to 100 C for 2 hours during which time the KOH pellets dissolved and the solution became a dark brown. To the solution was added solid 4,4′-bischloromethyl-1,1′biphenyl (12.6 g, 0.05 mol) over a period of 5 minutes. During the addition, the heating mantle was removed to facilitate air cooling and the rate of addition limited such that the reaction exotherm did not cause the internal temperature to exceed 115 C. The reaction mixture quickly became a thick slurry. After holding the reaction mass at 100 C for 4 additional hours, the mixture was stirred at room temperature overnight during which time the slurry became more fluid. The reaction mass was poured into a beaker containing 300 mL rapidly stirred water resulting in the immediate precipitation of the product, and a dissolution of the KCl byproduct. The solid product was collected via vacuum filtration and washed well with water. The light tan paste was dried in a forced air oven at 70 C for several hours providing 19.2 g (97.5%) crude product. GPC analysis of the product using a UV detector demonstrated very high purity (>99%). If desired, the product may be re-crystallized from toluene (250 mL) giving 18.0 g (91.4% yield) fine crystals. 1H and 13C-NMR, IR, GC/MS all confirm the identity and purity of the product. MP=151 C.

1. dissolutiondissolved
2. additionDuring the addition
3. customthe heating mantle was removed
4. temperaturecooling
5. additionthe rate of addition
6. stirringthe mixture was stirred at room temperature overnight during which time the slurry
7. additionThe reaction mass was poured into a beaker
8. additioncontaining 300 mL rapidly stirred water resulting
9. customin the immediate precipitation of the product
10. dissolutiona dissolution of the KCl byproduct
11. filtrationThe solid product was collected via vacuum filtration
12. washwashed well with water
13. customThe light tan paste was dried in a forced air oven at 70 C for several hours
14. customproviding 19.2 g (97.5%) crude product
15. customthe product may be re-crystallized from toluene (250 mL)