4,15-Diamino[2.2]paracyclophane as a useful precursor for the synthesis of novel pseudogeminal [2.2]paracyclophane compounds

Abstract

New reactions of 4,15-diamino[2.2]paracyclophane (1) are described. When 1 is reacted with acetyl, benzoyl, or phthaloyl chloride, respectively, the amides 2, 6, 7, and 9 are formed; the latter suffers loss of H2O to give the product 8. Bromination of 2 yields the pseudo-geminally substituted derivative 3 exclusively; the formation of its expected regioisomer 4 is not observed. Heating of 2 with POCl3 in ethanol furnishes the triply-bridged cyclophane 5. Condensation of 1 with some selected carbonyl compounds (phthalaldehyde, formic acid, cyclohexane- 1,3-dione, and terephthalaldehyde) provides the products 17-20. Thiourea and isothiocyanate derivatives 21 and 22 were obtained on heating 1 in CS2. The structures of the products were assigned on the basis of their spectroscopic and analytical data. Rationalizations for the formation of 3, 5, 6, and 17 are presented.