• 한국산업융합학회 논문집
• /
• 제6권2호
• /
• pp.123-129
• /
• 2003

Oxindoles(6a-g) are obtained by rhodium(II)-catalyzed Wolff rearrangement of diazoquinolinediones in moderate yields. Treatment of 6a-g oxindole derivatives reacted with CAN in acetonitrile at room temperature to gave 7a-g isatins in good yields. The structures of these compound were identified by MP, IR and NMR-spectra.

• Bulletin of the Korean Chemical Society
• /
• 제18권4호
• /
• pp.395-401
• /
• 1997

The substituent effects in the gas-phase rearrangement of carbenes to ketenes involved in the Wolff reaction have been investigated theoretically using the AM1 method. In the initial state, carbene, there is a relatively strong vicinal n-σ* interaction between the lone pair (n) and carbonyl group (σ*). In the bridged transition state (TS), electronic charge is transferred from the migrating ring (Z-ring) toward the nonmigrating ring (Y-ring). The carbenes are stabilized by an electron donor Y (δσY < 0) whereas the TS is stabilized by an electron acceptor Y (δσY > 0). Multiple regression analysis of log (kYZ/kHH)(=-δΔG≠/2.3RT) leads to a relatively large negative cross-interaction constant, ρYZ=-0.53, log (kYZ/kHH)=2.96 σY--1.40 σZ-0.53 σY-σZ reflecting an extensive structural change in the transition state due to the stabilization of the initial state by the vicinal n-σ* overlap. When the solvent (water) effects are accounted for by the SM2.1 model of the Cramer and Truhlar method, the magnitude of all the selectivity parameters, ρY-, ρZ and ρYZ (=-0.66) are increased.

• 대한화학회지
• /
• 제33권6호
• /
• pp.644-650
• /
• 1989

Phthalide sulfone 2와 naphthalenone 6을 만들어서 Hauser-Rhee가 개발한 Michael addition의 새로운 고리 접합법으로 4개의 선형 고리화합물의 구조를 갖는 tetracyclic 화합물 11을 만들었다. 화합물 11의 ring A가 갖고 있는 중요한 이중결합을 이용해서 탄소수가 한 개 증가된 carbomethoxy 화합물 16으로 변형시키는 것은 Arndt-Eistert, Wolff rearrangement를 이용하였다. 그리고 나서 이들을 고리화 반응시킨 뒤 hydroxylation시켜서 최종 생성물인 (${\pm}$)-7-Deoxyaklavinone(18)를 합성하였다.

• 한국인쇄학회지
• /
• 제12권1호
• /
• pp.17-34
• /
• 1994

Recently, the photopolymer made of novolak resin as the base and the naphthoquinonediazide(NQD) as the photoreactive compound is used for the presensitized plate(PS plate). The reaction mechanism of the NQD-novolak resin on light exposure is considered. Upon exposure it undergoes a Wolff rearrangement, via ketene intermediate which react with water ti form an 3-indene carboxylic acid. It was also found that NQD type resin in this experiment shows a high relative sensitivity compared with imported sample from Japan.