We report the results of a search for serendipitous [C II] 157.74 µm emitters at z ≃ 4.4-4.7 using the Atacama Large Millimeter/submillimeter Array (ALMA). The search exploits the AS2UDS continuum survey, which covers ∼ 50 arcmin 2 of the sky towards 695 luminous (S 870 1 mJy) submillimeter galaxies (SMGs), selected from the SCUBA-2 Cosmology Legacy Survey (S2CLS) 0.96 deg 2 Ultra Deep Survey (UDS) field. We detect ten candidate line emitters, with an expected false detection rate of ten percent. All of these line emitters correspond to 870 µm continuum-detected sources in AS2UDS. The emission lines in two emitters appear to be high-J CO, but the remainder have multiwavelength properties consistent with [C II] from z ≃ 4.5 galaxies. Using our sample, we place a lower limit of > 5 × 10 −6 Mpc −3 on the space density of luminous (L IR ≃ 10 13 L ⊙ ) SMGs at z = 4.40-4.66, suggesting ≥ 7 percent of SMGs with S 870µm 1 mJy lie at 4 < z < 5. From stacking the highresolution (∼ 0.15 ′′ full-width half maximum) ALMA 870 µm imaging, we show that the [C II] line emission is more extended than the continuum dust emission, with an average effective radius for the [C II] of r e = 1.7 +0.1 −0.2 kpc compared to r e = 1.0 ± 0.1 kpc for the continuum (rest-frame 160 µm). By fitting the far-infrared photometry for these galaxies from 100-870 µm, we show that SMGs at z ∼ 4.5 have a median dust temperature of T d = 55 ± 4 K. This is systematically warmer than 870 µm-selected SMGs at z ≃ 2, which typically have temperatures around 35 K. These z ≃ 4.5 SMGs display a steeper trend in the luminosity-temperature plane than z ≤ 2 SMGs. We discuss the implications of this result in terms of the selection biases of high redshift starbursts in far-infrared/submillimeter surveys.