新型离子负载羟基(对甲苯磺酰氧基)碘苯对α,β-查尔酮及其衍生物的加成产物用于1,4,5-三芳基吡唑的合成

Synthesis of 1,4,5-Triarylpyrazoles from the Addition Products of α,β-Chalcones with New Ion-Supported [Hydroxyl(tosyloxy)iodo]benzenes

以吡啶和2,4-二硝基氯苯为起始原料,经过三步反应,合成了三种N-（4-碘苯基）吡啶盐新化合物7-9,然后在间氯过氧苯甲酸氧化下,7-9分别与对甲苯磺酸反应制备了三种新的吡啶盐负载羟基（对甲苯磺酰氧基）碘苯共轭试剂：N-[4-羟基（对甲苯磺酰氧基）碘苯基]吡啶对甲苯磺酸盐10、四氟硼酸盐11和六氟锑酸盐12.三种新试剂室温下都是固体,在空气中没有吸湿性.分别研究了试剂10、11和N-[4-羟基（对甲苯磺酰氧基）碘苯甲基]吡啶四氟硼酸盐4对α,β-查尔酮及其衍生物的加成反应,成功地合成了1,3-二芳基-2,3-二对甲苯磺酰氧基-1-丙酮14（其中二个是新化合物）,共轭试剂10、11和α,β-查尔酮及其衍生物的加成产率比非共轭试剂4高.然后14和苯肼发生环合反应制备了1-苯基-4,5-二芳基吡唑（其中二个是新化合物）.回收后的离子负载碘苯容易再生成试剂,而再生试剂和查尔酮及其衍生物的加成反应活性几乎保持不变.

Three new N-（4-iodophenyl）pyridinium salts 7-9 were synthesized from pyridine and 1-chloro-2,4-dinitrobenzene by three steps. In these steps, N-（2,4-dinitrophenyl）pyridinium chloride 5 was prepared through the nucleophilic substitution reaction at first. Then N-（4-iodophenyl）pyridinium chloride was obtained from 4-iodoaniline and 5 through the Zincke＇s reaction. At last the salts 7-9 were got in aqueous solution by anion exchange. And then three new pyridinium salts supported [4-hydroxy（tosyloxy）iodo]benzene conjugated reagents [N-（4-hydroxyl（tosyloxy）iodophenyl）pyridinium p-toluenesulfonate 10, N-（4-hydroxyl（tosyloxy）iodophenyl）pyridinium tetrafluoroborate 11 and N-（4-hydroxyl（tosyloxy）iodophenyl）pyridinium hexafluorostibnate 12] were prepared from the salts 7-9 andp-toluenesulfonic acid with m-chlorobenzo- peroxoic as oxidizer. These reagents were solid at room temperature and had not the moisture absorption property. The adducts of a,β-chalcones, 1,3-diaryl-2,3-di（tosyloxy）-1-acetone 14 （two of them were new compounds）, were prepared using the reagents 10, 11 and N-[4-hydroxyl（tosyloxy）iodobenzyl]pyridinium tetrafluoroborate 4 respectively. The yields of compounds 14 from reagents 10, 11 were also found to be higher than that from reagent 4. Finally, 1-phenyl-4,5-diarylpyrazoles （two of them were new compounds） were prepared from 14 and phenylhydrazine by cyclization reaction. After the addition reaction, the reagents were transformed into the corresponding ion-supported iodobenzenes, which could be easily recovered and regenerated with no lost of the addition reaction activity.