Berberis baluchistanica Ahrendt (Berberidaceae) has yielded two novel dimeric alkaloids, pakistanine (1) and pakistanamine (9). Pakistanine is a new type of dimeric aporphine benzylisoquinoline while pakistanamine is the first known proaporphine benzylisoquinoline. Dienone-phenol rearrangement of pakistanamine followed by O-methylationyielded l,10-di-0-methylpakistanine (2), which was also obtained by diazomethane O-methylation of pakistanine. The biogenetic sequence in the pakistanine-pakistanamine series must be benzylisoquinoline å bisbenzylisoquinoline å proaporphine benzylisoquinoline dimer å aporphine benzylisoquinoline dimer. © 1973, American Chemical Society. All rights reserved.