Syntheses Of Imides And Triptycene Derivatives And The Cross-couplings Between The Ion Pairs In Sulfonium Tetraphenylborates

This thesis is mainly composed of three parts: synthesis of imides by directoxidation of amides, synthesis of10-amino-triptycene-9-carboxylic acid and itsderivatives, and the cross-couplings between the ion pairs in sulfoniumtetraphenylborates.1. Synthesis of imides by direct oxidation of amidesA series of amides derived from benzylamine were oxidized to imides bypersulfate using Ag+and Cu2+as catalysts in the presence of excess KF in water. Theoptimal conditions are: AgNO3(20mol%), CuSO4(20mol%), KF (20eq),(NH4)S2O8(3.0eq), room temperature, and overnight or6h under N2. Under these conditions,the amides derived from aliphatic acid and4-methoxybenzylamine achieved goodyields (52-83%). Furthermore, the1-benzylurea and1-(4-methoxybenzyl)biuret wereoxidized to1-benzoylurea and1-(4-methoxybenzoyl)biuret in71%and79%yields,respectively.2. Synthesis of10-amino-triptycene-9-carboxylic acid and its derivativesStarting from anthracene, we synthesized10-amino-triptycene-9-carboxylic acidvia six steps, and its carboxyl group can react with the amino of glycine benzyl ester,alanine methyl ester and methionine methyl ester to give the amidation products in63-74%yields. Furthermore,9-triptycylisothiocyanate can be successfully prepared in91%yield from sterically hindered9-triptycylamine and CS2(8.0eq) in the presenceof DBU (3.0eq) in DMSO at room temperature for60h.3. Cross-couplings between the ion pairs in sulfonium tetraphenylboratesWhen the sulfonium tetraphenylborates were heated at120-150C, the phenylgroup of the tetraphenylborate anion can couple with the substituent of sulfoniumcation; for carbonylmethyl sulfonium, allyl sulfonium, and benzyl sulfonium, thecarbonylmethyl-phenyl, allyl-phenyl and benzyl-phenyl coupling products can beobtained, respectively. This reaction is metal-free, and the sulfoniumtetraphenylborates are easily prepared and crystalline solids, so a convenient methodfor the construction of carbon-carbon bonds has been developed.