A series of 2,3‐dihydro‐1,3,2‐benzodiazaborin‐4(IH)‐ones have been prepared and their ir spectra compared with those of their carbon isosteres. Solvolysis of these boron compounds in ethanol has been followed by uv and reveals a relationship between structure and rates of ethanol‐ysis. Unexpectedly, these boron heterocycles, in contrast to their carbon isosteres, dissolve in aqueous alkali to form stable anions and the significance of this is discussed. The 1 :1 adducts of 1 and phosphorus oxychloride has been utilized to prepare two derivatives of the very stable 1,2‐dihydro‐2‐phenyl‐1,3,2‐benzodiazaborin heterocycle.