AbstractGas-phase methanol was recently detected in a protoplanetary disk for the first time with ALMA. The peak abundance and distribution of methanol observed in TW Hya differed from that predicted by chemical models. Here, the chemistry of methanol gas and ice is calculated using a physical model tailored for TW Hya with the aim to contrast the results with the recent detection in this source. New pathways for the formation of larger complex molecules (e.g., ethylene glycol) are included in an updated chemical model, as well as the fragmentation of methanol ice upon photodesorption. It is found that including fragmentation upon photodesorption improves the agreement between the peak abundance reached in the chemical models with that observed in TW Hya (∼10⁻¹¹ with respect to H₂); however, the model predicts that the peak in emission resides a factor of 2 − 3 farther out in the disk than the ALMA images. Reasons for the persistent differences in the gas-phase methanol distribution between models and the observations of TW Hya are discussed. These include the location of the ice reservoir which may coincide with the compact mm-dust disk (≲ 60 au) and sources of gas-phase methanol which have not yet been considered in models. The possibility of detecting larger molecules with ALMA is also explored. Calculations of the rotational spectra of complex molecules other than methanol using a parametric model constrained by the TW Hya observations suggest that the detection of individual emission lines of complex molecules with ALMA remains challenging. However, the signal-to-noise ratio can be enhanced via stacking of multiple transitions which have similar upper energy levels.