An easy synthesis of four steps to afforded 12 new derivatives of 3,3‐dimethyl‐2,3,4,5,10,11‐hexahydro‐8‐[(o‐; and p‐methyl)phenoxy]‐11‐[(o‐; and p‐substituted)phenyl]‐1H‐dibezo‐[b,e][1,4]diazep‐in‐1‐ones IV, IV,1, IV,2, IV,3, IV,4, IV,5, IV,6, IV,7, IV,8, IV,9, IV,10, IV,11, IV,12 with potential biological and pharmacological activity as sedative, hypnotic‐muscular relaxing, anticonvulsant, and schizophrenia treatment of the central nervous system (CNS). The final products have been obtained with good yields, by condensation and cyclization between 3‐{4‐[(o‐; and p‐methyl)phenoxy]‐1,2‐phenylendiamine}‐5,5‐dimethyl‐2‐cyclohexanone III, with the corresponding (o‐; and p‐R)benzaldehyde. The structure of all derivatives was corroborated by spectroscopy of ir, 1H, and 13C NMR, with bi‐dimensional experiments and EI‐MS in low and high resolution with collision‐induced dissociation experiments (CID). J. Heterocyclic Chem., (2009).