The present invention relates toaprocess for the preparation of N-[5-(4-Bromophenyl)-6-[2-[(5-bromo-2-pyrimidinyl)oxy]ethoxy]-4- pyrimidinyl]-Npropylsulfamide or Macitentan of Formula (I). (I) The present invention further relates to a process for the preparation highly pure N-[5-(4-Bromophenyl)-6-[2-[(5-bromo-2-pyrimidinyl)oxy]ethoxy]-4-pyrimidinyl]-Npropylsulfamide or Macitentan of Formula (I). Said substantially pure Macitentan is useful in the preparation of pharmaceutical composition for the treatment of cardiac disorders.