N^1-(4-氨基丁基)-N^4-(9-蒽甲基)-1,4-丁二胺的合成

Synthesis of N^1-(4-Aminobutyl)-N^4-(9-anthracenylmethyl)butane-1,4-diamine

以N-叔丁氧羰基-1,4-丁二胺和N-(4-溴丁基)邻苯二甲酰亚胺为原料,经取代及保护两步反应合成N1-(4-邻苯二甲酰亚胺)丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺(Ⅳ),然后肼解得N1-氨基丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺(Ⅴ),3步反应总收率38%;Ⅴ与9-蒽甲醛缩合后用NaBH4还原,产物提纯后脱保护得目标产物N1-(4-氨基丁基)-N4-(9-蒽甲基)-1,4-丁二胺盐酸盐(Ⅶ),3步反应总收率约7 5%。化合物Ⅳ~Ⅶ的结构经13CNMR,1HNMR和ESI-MS确证,并对反应条件进行了初步优化。

N^1-（ 4-Phthalimide ） butyl-N^1 , N4-di-tert-butoxycarbonylbutane-1, 4-diamine （ Ⅳ ） was prepared by the tandem reactions of substitution and protection using N-tert-butoxycarbonylbutane-1,4- diamine and N-（ 4-bromobutyl ） phthalimide as the starting materials. Then Ⅳ was treated with hydrazine hydrate to remove its phthalimide group to give N^1-（ 4-aminobutyl ）-N^1, N^4-di-tertbutoxycarbonylbutane-1,4-diamine （ Ⅴ ）. Total yield of these three steps is 38%. Ⅴ was condensed with 9-anthraldehyde,then the crude product was reduced with NaBH4. After purification, the reduced product was deprotected to provide N^1- （4-aminobutyl）-N^4-（9-anthracenylmethyl）butane-1,4-diamine trihydrochloride salt （ Ⅶ ） with 75% total yield in these three steps. Structures of Ⅳ - Ⅶ were confirmed by ^13CNMR,^1HNMR and ESI -MS. The reaction conditions were also prelimiarily optimized.