Reversible 1,3‐dipolar cycloaddition of dimethyl 2‐thiono‐1,3‐dithiole‐4,5‐dicarboxylate with dimethyl acetylenedicarboxylate

It was shown that dimethyl 2‐thiono‐1,3‐dithiole‐4,5‐dicarboxylate ( 2 ) and dimethyl acetylenedicarboxylate (DMAD) undergo a 1,3‐dipolar cycloaddition to produce a short‐lived ylide intermediate ( 3 ). The 1,3‐dipolar cycloaddition took place even at room temperature, although sluggishly, but took place much more rapidly under application of a high pressure of 500 MPa. The 1,3‐dipolar cycloaddition is reversible and the ylide 3 immediately splits into 2 and DMAD. When the reaction of 2 with DMAD was carried out at room temperature without solvent, a spiro‐1,3‐dithiole ( 11 ) was formed in 11% yield, whereas the reaction at 150°C provided a thiophene derivative ( 13 ) in 41% yield. It was found that 11 undergoes a thermal rearrangement to 13 . Results of attempted chemical trapping of the ylide 3 are also reported. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:434–440, 2000     

Naphthol‐modified β‐cyclodextrins as fluorescent sensors for detecting contaminants in drinking water

The naphthol‐modified β‐cyclodextrins 1 and 2 have been synthesized as novel chemosensors for detecting contaminants in drinking water. They exhibit a broad fluorescence band with a peak around 505 nm for 1 and 485 nm for 2 , arising from anion species of the excited naphthol unit. Upon the addition of contaminant guests, the fluorescence intensity of 2 decreased, while that of 1 increased. These fluorescence changes may be related to the guest‐induced location change of the naphthol moiety from the inside to the outside of the cyclodextrin cavity. They exhibited high sensitivities for carbon tetrachloride, among several alkyl halides, as well as for odorants such as geosmin and 2‐methylisoborneol. These results demonstrate that 1 and 2 will be useful for monitoring the purity of drinking water.