We herein report an efficient synthesis of 1,2,3.5,6.7-hexaalkoxy-9,10-anthraquinones (also called rufigallol hexaethers) starting from gallic acid. These ethers are known to form columnar phases which are suitable for the study of charge transport, photoconductivity etc. Our X-ray diffraction studies show that the high-temperature mesophase is hexagonal columnar with correlation among the molecular cores alone the column (Col(h), also called Dh) and that, identified for the first time in these systems, there are one or two additional mesophases at low temperature depending on the system, some of them three-dimensionally ordered. Our results show that the mesophase thigh-temperature) range does not dramatically decrease as the length of the alkyl chains at the 1.5 positions become longer than the rest. Since these molecules have absorption in the visible region they may also be the potential candidates for studying photovoltaic effects that are of interest in developing energy conversion applications.