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Radioligand analysis at 0-35 °C was used to find that 3-(alkylcarbonyloxy)-7-bromo-5-(o-chloro)phenyl-1,2-dihydro-3H-1,4-benzodiazepin-2-ones react differently with central benzodiazepine receptors. The complexation of the 3-acetyloxy derivative proceeds endothermally with ΔS0 as the driving force. The reaction of the other esters is accompanied by favorable change of both entropy and enthalpy.