Benzobicyclo heptenes

Eine ahnliche Umwandlung von sekundaren Alkoholen in primare Amine mittels der Mit-sunobu-Reaktion ist am Beispiel dcr 7-Hydroxy- untersucht worden1. Behandlung dieser Alkohole mit Triphenylphosphan, Phthalimid und Dieth-oxycarbonyl-diazen in Tetrahydrofuran ergibtdie 2-Phthalimido-Derivate, die isoliert und mittels Hydrazin unter Bildung der freien Amine gespalten werden. Bei dem beschriebenen System entstehen auf diese Weise aus den 7-m/o-Alkoholen die 7-exo-Amine und aus den 7-exo-Alkoholen Gemische der 1-endo- und 7-eJto-Amine. 

Examination of these points suggested skeletons 15 and 16 of Table V. Since the benzobicyclo[2.2.1]-heptene analogs (skeleton 15) are considerably more strained than the benzobicyclo[2.2.2]octene (skeleton... 

Evaluation of Some Bicyclic Systems as Conformationally-Defined Phenylethylamines. X-Ray Crystallography. Perhaps the ultimate test of the suitability of a chemical structure for preparing conformationally-defined analogs would be their ability to produce biological effects identical to those of the parent compound. Since this ideal is rarely achieved, and since a "wrong" conformer should be inactive, it is useful to have other criteria with which to evaluate these systems. The bicyclic molecules to be examined in the present study are compounds I-VIII (Figure 7), benzobicyclo[2.2.2]octenes, benzobicyclo [2.2.1]heptenes, and 1,2,3,4-tetrahydro-l,4-epoxynaphthalenes. A number of structural parameters... 

The benzobicyclo[2.2.1]heptene and 1,2,3,4-tetra-hydro-1,4-epoxynaphthalene systems were constructed from the coordinate data for benzobicyclo[2.2.1]heptene-syn- and -anti-bromobenzenesulfonates (147). Positions for the exo and endo amino groups were selected by using a standard C-N bond length with the bond angles and dihedral angles calculated from a crystallographic study of 2-exo-aminonorbornane-2-carboxylic acid (148). 

CNDO/2 Calculations on Bicyclic Systems. Calculation of the energy differences between the exo-and endo-isomers in either the benzobicyclo[2.2.2]octene or benzobicyclo[2.2.l]heptene system (e.g., I, II,... 

For the benzobicyclo[2.2.l]heptene system, using literature values for the heavy atom coordinates of a related system (147,148) and proceeding as above, a AE value of 0.01 kcal/mol is found between the 2-exo-methylamino (2M-X) and 2-endo-methylamino (2M-N5 systems. This is totally consistent with the nearly equal energy of extended and gauche conformers of amphetamine noted above. 

Treatment of the benzobicyclo[4,l,0]heptene-2,5-diols (86) with diphosphorus tetraiodide gave the corresponding 3,4-benzocycloheptatrienes. ° Similarly, substituted homotropylidenes (87) were obtained from diols (88). " ... 

Benzobicyclo [2.2.1] heptene yields di-n-methane product on sensitised irradiation, with a vinylcyanide, the cyano group dictates the triplet pathway, so the bridging delds the cyano substituted radical. 

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