2-아미노페놀 그룹을 갖는 모노머 합성

Abstract

하위 단위로 1,1'-spirobisindane 빌딩 블록을 가지고 있는 인트리직 미세 다공성 고분자(PIMs)는 기체 분리막의 매우 뛰어난 구성요소이다. 여기에서 중요한 단량체는 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol이다. 본 논문에서는 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol를 합성하는 두 가지 새로운 합성 방법을 제시하였다.

첫 번째 실험에서는 Bisphenol A를 시작물질로 해서 합성한 3,3,3',3'-tetramethyl-1,1'-spirobisindane-6,6'-diol를 O-methylation을 하여 6,6'-dimethoxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane를 합성하였다. 여기에 니트로화 반응을 통해 6,6'-dimethoxy-3,3,3',3'-tetramethyl-5,5'-dinitro-1,1'-spirobisindane를 합성한 후 BBr3를 이용하여 메틸기를 수소로 디메틸레이션하였다. 마지막으로 환원 반응을 통하여 니트로 그룹을 아민기로 변화시켜 최종적으로는 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol를 합성 하였다. 두 번째 실험에서는 BBr3를 사용하지 않고 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol를 합성하는 방법에 대해 기술하였다. Bisphenol A를 시작물질로 해서 합성한 3,3,3',3'-tetramethyl-1,1'-spirobisindane-6,6'-diol를 O-benzylation을 하여 6,6'-dibenzyloxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane을 합성하였다. 여기에 니트로화 반응을 통해 6,6'-dibenzyloxy-3,3,3',3'-tetramethyl-5,5'-dinitro-1,1'-spirobisindane를 합성한 후 환원 반응 조건에서 디벤질레이션과 니트로 그룹을 아민기로 환원하는 반응을 동시에 수행하여 효과적으로 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol를 합성 하였다.|Polymers of intrinsic microporosity (PIMs) containing 1,1'-spirobisindane building blocks as subunits are very attractive for the construction of gas separation membranes. One of the key monomers is 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol. In this thesis, we develop a couple of new methods of synthesizing for 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol. At first, the starting material 3,3,3',3'-tetramethyl-1,1'-spirobisindane-6,6'-diol was prepared by the skeletal rearrangement of bisphenol A. O-methylation of spirobisindanediol with dimethyl sulfate afforded 6,6'-dimethoxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane. Nitration of O-methylated spirobisindane gave single nitro-substituted compound, 6,6'-dimethoxy-3,3,3',3'-tetramethyl-5,5'-dinitro-1,1'-spirobisindane followed by methylation with boron tribromide and by reduction with Pd/C and hydrazine hydrate in refluxing ethanol resulted in 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol efficiently. Secondly, O-benzylation of 3,3,3',3'-tetramethyl-1,1'-spirobisindane-6,6'-diol with benzyl chloride in the presence of K2CO3 followed by nitration with nitric acid in the presence of sulfuric acid gave 6,6'-dibenzyloxy-3,3,3',3'-tetramethyl-5,5'-dinitro-1,1'-spirobisindane. On concomitant reduction and debenzylation of the latter with hydrazine hydrate and 10% Pd/C in refluxing ethanol, the corresponding spirobisindanediaminodiol was produced in moderate yield by the simple precipitation and filtration.; Polymers of intrinsic microporosity (PIMs) containing 1,1'-spirobisindane building blocks as subunits are very attractive for the construction of gas separation membranes. One of the key monomers is 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol. In this thesis, we develop a couple of new methods of synthesizing for 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol. At first, the starting material 3,3,3',3'-tetramethyl-1,1'-spirobisindane-6,6'-diol was prepared by the skeletal rearrangement of bisphenol A. O-methylation of spirobisindanediol with dimethyl sulfate afforded 6,6'-dimethoxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane. Nitration of O-methylated spirobisindane gave single nitro-substituted compound, 6,6'-dimethoxy-3,3,3',3'-tetramethyl-5,5'-dinitro-1,1'-spirobisindane followed by methylation with boron tribromide and by reduction with Pd/C and hydrazine hydrate in refluxing ethanol resulted in 3,3,3',3'-tetramethyl-1,1'-spirobisindane-5,5'-diamino-6,6'-diol efficiently. Secondly, O-benzylation of 3,3,3',3'-tetramethyl-1,1'-spirobisindane-6,6'-diol with benzyl chloride in the presence of K2CO3 followed by nitration with nitric acid in the presence of sulfuric acid gave 6,6'-dibenzyloxy-3,3,3',3'-tetramethyl-5,5'-dinitro-1,1'-spirobisindane. On concomitant reduction and debenzylation of the latter with hydrazine hydrate and 10% Pd/C in refluxing ethanol, the corresponding spirobisindanediaminodiol was produced in moderate yield by the simple precipitation and filtration.