Tetraacetylhexaazaisowurtzitane(TAIW), the precursor to CL20, was condensed with formaldehyde, acetaldehyde or chloroacetaldehyde, and three new isowurtzitane derivatives, 3,5,9,11tetraacetyl14oxo1,3,5,7,9,11hexaazapentaacyclo［5.5.3.0²,⁶.0⁴,¹⁰.0⁸,¹²］pentadecane, 13,15dimethyl3,5,9,11tetraacetyl14oxo1,3,5,7,9,11hexaazapentaacyclo ［5.5.3.0²,⁶.0⁴,¹⁰.0⁸,¹²］ pentadecane and 13,15dichloromethyl3,5,9,11tetraacetyl14oxo1,3,5,7,9,11hexaazapentaacyclo ［5.5.3.0²,⁶.0⁴,¹⁰.0⁸,¹²］ pentadecane, were synthesized and structurally characterized by elemental analysis, IR , 1H NMR, 13C NMR and MS. The results show that characteristics of the proton spectra of this new type caged compound are two signals at δ=6.2 and 5.4 in a 21 ratio. The three new compounds may be used as potential precursors of new energetic materials.