Kalashine,a novel type aporphine-benzylisoquinoline alkaloid

$\text{Berberis orthobotrys}$ produces the new dimer kalashine ($\text{1}$), together with the previously reported pakistanamine ($\text{2}$) and pakistanine ($\text{3}$). Kalashine is the first aporphine-benzylisoquinoline known to be substituted at C-11. Acid catalyzed rearrangement of pakistanamine ($\text{2}$) in 3N HCl leads to 1-0-methylpakistanine ($\text{6}$) together with small amounts of 1-0-methylkalashine ($\text{7}$) and (+)-armepavine ($\text{8}$). Rearrangement of $\text{2}$ using methanol containing a little 3N HCl gives about equal amounts of $\text{6}$ and 1,10-di-O-methylpakistanine ($\text{9}$).