Abstract： In order to effectively control the quality of naltrexone hydrochloride,seven related substances were synthesized in this study:17-(1-butenyl)-4,5-epoxy-3,14-dihydroxymorphine-6-one(related substance C),bis-naltrexone(related substance D),3-cyclopropylmethoxy-17-(cyclopropylmethyl)-4,5-epoxy-14-hydroxymorphine-6-one(related substance E),17-n-butyl-4,5-epoxy-3,14-dihydroxymorphine-6-one(related substance H),17-(cyclopropylmethyl)-3-methoxyl-4,5-epoxy-14-hydroxymorphine-6-one(related substance J),17-(cyclopropylmethyl)-4,5-epoxy-3,14-dihydroxymorphin-7-ene-6-one(related substance K),naltrexone nitrogen oxide(related substance L).The related substances K and L were not included in European pharmacopoeia 10.0.The synthetic routes of substances C,D and H had not been reported.The structures of these compounds were confirmed by MS,1H NMR and 13C NMR.