Investigation of benzonorbornadien and norbornadien participation reactions

In this study, synthetically important benzonorbornadiene (1) and norbornadiene (2) compounds were taken as dienophil. The corresponding benzaldoximes (51 and 57) obtained from some aldehydes (50-56) were obtained in the form of pure products (58-61) from the separate reactions of dienophils 1 and 2 in the presence of NaOCl. Norbornadiene (2) was reacted in the presence of ethyldiazoacetate (11) Pd(OAc) 2 and the compounds of adducts 14 and 15 were obtained as a mixture. Since each product could not be separated from the mixture, the mixture was reacted separately with benzaldoxime 51, 53 and 57, to give the addition products 62-67. Further, 3,6-di-(2-pyridyl)-s-tetrazine (68) was added to the mixture of 14 and 15 to give aromatic products 69 and 70. The effects of γ-Gauche on the addition of 62-67 and 69, 70 products obtained from the nitrile oxydyl reactions were discussed. Norbornadiene (2), diacidase products 74 and 75 (single product) were obtained by two equivalents of nitrile oxides consisting of monoizaxazole products 71-73 and 53 and 55, respectively, by the addition of an equivalent of nitrile oxides of 53, 55 and 57. All cyclochemical reactions have been shown to be exo selectivity. The reaction products of monoisoxazole adducts 71 and 72 with 3,6-di-(2-pyridyl)-s-tetrazine (68) were obtained as 76 and 77. Furthermore, by the bromination of monoisoxazole adducts 71-73 at room temperature, the adducts 78, 79 were obtained as a single isomeric product, while 80 and 81 were obtained as a mixture of isomers. As a result of the photobromination of the monoisoxazole product 72, two isomeric products 78 and 82 were obtained. N-Phenyl hydrazone chloride compounds 89-91 were synthesized from the corresponding aldehyde (50, 52, 56) and N-phenylhydrazine compounds (84-86), respectively. The reaction of n-phenyl hydrazone chloride compounds with norbornadiene and benzonorbornadiene in the presence of base yielded the corresponding mono-additive products 92-96. From these products 95 and 96 with diene 68 reaction products 97 and 98 were obtained. These products have also been selected with exo-selectivity.