A THERMAL POTENTIAL [6+4] 2H-TRANSFER REACTION IN A CYCLIC DIMER OF DIMETHYL 2a,8a-DIHYDROCYCLOPENT[c,d]AZULENE-1,2-DICARBOXYLATE

作者：Uebelhart Peter^*; Lehto Erja; Hansen Hans Jtirgen

来源：Heterocycles, 2014, 88(1): 521-534.

DOI：10.3987/COM-13-S(S)76

• Et2AlCl Catalysis
• 2a,8a-Dihyrocyclopent[c,d]azulene-1,2-dicarboxylate
• [6+4] 2H-Transfer Reaction
• Primary Kinetic H/D-Isotope Effect

Azulenes and dimethyl acetylenedicarboxylate (ADM) react under catalysis of diethylaluminum chloride (Et2AlCl) in toluene to corresponding 2a,8a-dihydrocyclopenta[cd]azulene-1,2-dicarboxylates, which on further influence of Et2AlCl dimerize by bond formation between the central C(8b) and C(8'b) atoms and inter alia C(3) and C(8') atoms. The thus formed heptacyclic compounds undergo on heating in tetralin an intramolecular disproportionation by transfer of two H-atoms from one to the other part of the heptacyclic structures. The kinetics of this process is studied with partially deuterated heptacycles.

• 出版日期2014-1-1