비산화-환원 금속인 Ga(III), In(III), TI(III)을 포함하는 금속 포르피린을 촉매제로 NaOCl을 산화제로 하여 올레핀의 촉매적 산화반응을 $CH_2Cl_2$에서 연구하였다. 포르피린은 $(p-CH_3O)TPP,;(p-CH_3)TPP,;TPP,;(p-F)TPP,;(p-Cl)TPP $그리고 $(F_20)TPP$를 사용하였다. 올레핀은 $(p-CH_3O)-,;(p-CH_3)-,;(p-H)-,;(p-F)-,;(p-Cl)-,;(p-Br)styrene$ 그리고 cyclopentene, cyclohexene을 사용하였다. 올레핀 산화반응에서 기질의 전환율(%)은 금속 포르피린 및 기질의 치환기 효과와 중심 금속이온 성질에 따라 고찰하였다. TPP 치환기에 따른 전환율의 변화는 $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl 순서로 증가하였다. 이러한 증가는 TPP의 $4{sigma}$값의 증가 순서와 일치하였다. 기질의 치환기에 따른 전환율의 변화는 $p-CH_3O$ > $p-CH_3$ > H > p-Cl > p-Br 순서로 치환기의 ${sigma}^+$값이 증가할수록 오히려 감소하였다. 올레핀의 산화 반응에서 In(III)-, Tl(III)-포르피린은 Ga(III)-포르피린에 비하여 높은 촉매 활성을 나타내었다.???????????????????裂??????㏖????????㈀ ?????퀀??????탁????壅????퀀?????点????????????????탁???????????????났????????淇堀???¸????退??ヂ??????杻?????壕?????????堀??ジ???????????????????짇????????壅????ス??コ???????????퀀??뀀?¾?퀀??????쒸????? ????????????一?????????????????一???椀稀攀?㈀???耀???????????爀????攀爀???㈀??瓆????炬???????一???????????????????????一???椀稀攀?㈀?????一????戀??????????????????一????椀稀攀?㈀?????????????????????????????????????????????????????????????????????????戀?????戀???????一?????????????????一???椀稀攀?㈀????一??????爀?? ????戀??爀??????戀?椀??椀?????攀?攀?戀攀爀??????㈀ ?????一??????????????????????????刀????攀?????攀?一??椀?攀???攀戀爀??爀???????㈀ ???戀?????戀?????戀?????戀????????一?????????????????一???椀稀攀?㈀??爀攀?爀攀最椀??爀??椀?????????爀??? ???㈀ ???戀?????戀?????戀?????戀?????戀?????戀??????刀?????????攀爀???戀?椀??椀??????爀???
The catalytic oxidations of several olefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin (M=Ga(III), In(III), Tl(III)) complexes as catalyst and sodium hypochlorite as terminal oxidant. Porphyrins were $(p-CH_3O)TPP,;(p-CH_3)TPP,;TPP,;(p-F)TPP,;(p-Cl)TPP;and;(F_20)TPP$ (TPP=tetraphenylporphyrin), and olefins were $(p-CH_3O)-,;(p-CH_3)-,;(p-H)-,;(p-F)-,;(p-Cl)-;and;(p-Br)styrene$styrene and cyclopentene and cyclohexene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin and substrate, and the radius effect of non-redox metal ion. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{sigma}$ values of TPP. But the substituent effect of substrate on the conversion yield decreased with increasing the ${sigma}^+$ values on substrates in the order of p-CH3O > p-CH3 > H > p-Cl > p-Br. For the oxidation of several olefins, the complexes of In(III)- and Tl(III)-porphyrins turned out to be more active catalysts than Ga(III)-porphyrin.
