Abstract
The photochemistry of the derivatives of o-nitrobenzylcarboxyl esters or benzylsulfonyl derivatives has been well studied separately. But little attempt has been made to combine the fruits these two studies. Being photochemically active, benzylsulphonyl and intro groups should influence the reactivity of each other's, especially when the excited states are fully mixed due to the proximity of their location. The questions which should be clearly answered are; what kind of effect will be excerted to the other group, and whether these two functional groups are coupled in the course of the reaction. To answer the questions raised above, wer have synthesized two sulfonyl esters and four amides from the newly available starting material, 2-nitro-${\alpha}$-toluenesulfonyl chloride. The products identified from the exploratory solution photochemistry were cyclohexanol, phenol, cyclohexylamine, and sulfur dioxide. The results are not much different from the products originally anticipated. It has been temporarily concluded that there is little interaction between the benzyl sulfonyl group and ortho-nitro chromophore. The fact that a base (an amine) has been photochemically generated in solution photochemistry was further confirmed by and utilized in the solid phase quantitative photochemistry done on the film, so as to carry out the photochemical epoxide cure.
개별적인 반응성이 알려진 니트로기와 벤질술포닐기가 벤젠 고리 위에서 서로 인접하여 위치할 때 광반응성에 미치는 상호 작용에 대해서 연구하고자 하였다. 니트로기를 포함하는 술포닐 에스테르(cyclohexyl 및 phenyl 2-nitro-${\alpha}$-toluenesulfonate)와 슬포닐아미드(시클로헥실, 페닐, 벤질, 및 피페리딜 2-nitro-${\alpha}$-toluenesulfonamide)의 용액 중 광반응 생성물로부터 벤질술포닐기와 그 ortho 위치에 존재하는 니트로기가 광반응시 서로 상승작용을 하지 않는다는 것을 알 수 있었다. 용액상의 광반응은 이어 필름 상에서의 광반응으로 확인 및 응용되었다. 즉, 두 가지의 2-nitro-${\alpha}$-toluensulfonamide를 포함한 poly(methacrylonitrile)(PMAN) 박막을 NaCl 판 위에 입히고 여기에 254 nm 자외선을 쪼이면서 관찰된 필름의 IR 스펙트럼의 변화로부터도 용액상의 광반응을 일부 확인하였으며 정량실험도 실시하였다. 또한, 본 용액실험의 결과인 광화학적 아민 발생은 poly(glycidyl methacrylate)를 이용한 상 발생 실험에 응용되어 성공적으로 광화학적 에폭시 가교를 수행할 수 있었다.