The Synthesis and Chemistry of Cyclopropenes

• Main Authors: Chen, Ko Chou, 陳科州
• Other Authors: Lee, Gon-Ann
• Format: Others
• Language: zh-TW
• Published: 2008
• Online Access: http://ndltd.ncl.edu.tw/handle/11567698066824258913

博士 === 輔仁大學 === 化學系 === 96 === Treatment of 1-bromo-2,2-dichloro-3-trimethylsilylcyclopropane (75) with CsF in THF refluxing temperature gave chlorocyclopropenyl cation (99), which reacted with various nucleophiles to generate 3-monosubstituted 1-chlorocyclopropenes. The Diels-Alder reactions of 3-monosubstituted 1-chlorocyclopropenes with 1,3-diphenylisobenzofuran (DPIBF) yielded only the exo-anti adducts in excellent yield. When cation 99 was treated with water and trapped with DPIBF, an aldehyde, 178, was isolated. Used 20 equivalents of cyclopentadiene in the reaction of compound 75 with methyllithium at -78 ℃, compound 158 was generated. Compound 158 underwent hydrogenation to give compound 180. The vacuum gas-solid reaction (VGSR) procedure was employed to convert the compound 180 to compound 181 with tetrabutylammonium fluoride at 25 ℃ and 20 mtorr. Compound 162, was generated by compound 161 reacted with tetrabutylammonium fluoride and DPIBF. Compound 162 converted to compound 186 in acidic condition. Compound 169 underwent oxidation reaction to from compound 190, compound 190 was treated tetrabutylammonium fluoride and DPIBF at THF refluxing temperature to give compound 191. Compound 191 underwent coupling reaction with Pd(PPh3)4、CuI at 0 ℃ to give diyne 192. Diyne 192 reacted with 4 equivalents of t-BuOK and 2.5 equivalents of CH3I to give methylenecyclopropane product 193.