Up to date, only six imines have been detected in the interstellar medium. The 3-carbon imine, 2-propanimine ((CH_3_)_2_C=NH), is predicted to be the structural isomer with the lowest energy in the C_3_H_7_N group, and appears to be a good candidate for astronomical searches. Unexpectedly, no microwave or millimeter wave spectrum is available for 2-propanimine. In this work, we provide the first high-resolution millimeter wave spectrum of 2-propanimine and its analysis. With the guide of this laboratory measurement, we aim to search for 2-propanimine in two molecule-rich sources Sgr B2(N) and IRAS 16293-2422 using observations from the Atacama Large Millimeter/submillimeter Array (ALMA). Starting from a synthesized sample, we measured the spectrum of 2-propanimine from 50 to 500GHz, and the ground state lines are successfully assigned and fitted using XIAM and ERHAM programs with the aid of theoretical calculations. The barriers to internal rotation of the two CH3 tops are determined to be 531.956(64)cm^-1^ and 465.013(26)cm^-1^ by XIAM. These data are able to provide reliable prediction of transition frequencies for astronomical search. Although a few line matches exist, no confirmed detection of 2-propanimine has been found in the hot molecular core Sgr B2(N1S) and the Class 0 protostar IRAS 16293B. Upper-limits of its column density have been derived, and indicate that 2-propanimine is at least 18 times less abundant than methanimine in Sgr B2(N1S), and is at most 50-83 per cent of methanimine in IRAS 16293B.