A novel process for preparing a steroid of the following formula (to be referred to as compound .circle.13 ) is provided. ##STR1## This compound is known to have marked anti-inflammatory and anti-rheumatoid arthritic activity with very much reduced side effects on humans, such as weight loss, sodium retention, potassium loss and adrenal and pituitary inhibition which are observed in many steroids. The process is characterized in that starting from hydrocortisone, it can produce the desired compound .circle.13 at low cost and that it goes through the following two novel compounds (I) and (II) as intermediates. ##STR2## In the above formulae, >W--X represents >C.dbd.O or >CH--OH, >Y--Z-- represents >C.dbd.CH-- or ##STR3## Q represents a hydrogen or bromine atom, and OR.sup.1 and OR.sup.2 are identical or different and each represents an acyloxy group or a sulfuric or phosphoric acid ester residue.