NH2-PEG-N3聚乙二醇的氨基化制備路線和方法

氨基化后的聚乙二醇, 由于反應(yīng)活性的氨基了羥基, 因此, 在大分子反應(yīng)中尤為,如與另一含羧基的大分子進(jìn)行反應(yīng)形成嵌段共聚物。

Buckm ann 和Johan sson 曾經(jīng)用溴化聚乙二醇(PEG—B r) 作為通過(guò)兩種途徑來(lái)聚乙二醇胺(PEG—NH2) [ 15～ 16 ] (式4～ 5) :

PEG—B r 可用PEG 和亞硫酰二溴(SOB r2) 在甲苯和三乙胺中反應(yīng)得到[ 17～ 18 ] (式6) :

盡管方法(4) 轉(zhuǎn)化率很, 但要用到氣態(tài)氨, 需在壓釜中反應(yīng)。相比較而言, 方法(5) ,但因己二胺具有雙功能基, 在反應(yīng)過(guò)程中, 容易引起PEG 鏈之間的交接[ 19 ]。

Mutter, Geckeler 和Ciuffarin[ 10, 20, 21 ]用的蓋布瑞爾法得到了PEG-NH2 (式7) :

Harris 等[ 22 ]用聚乙二醇醛(PEG-OCH2CHO ) 和醋酸銨反應(yīng)也制得了PEG-NH2 (式8) :

利用這種方法醛基可以被氨基, 而且不會(huì)引起鏈的斷裂。

Zalipsky曾經(jīng)報(bào)道過(guò)一種的PEG-NH2 的方法, 產(chǎn)率為80% , 產(chǎn)物可以氨基化[ 17 ] (式9) :

產(chǎn)品：

DBCO-PEG-Tosylate

DBCO-PEG-Acetylthio

DBCO-PEG-Aminooxy

DBCO-PEG-NPC

DBCO-PEG-SAS

DBCO-PEG-SC

DBCO-PEG-SCM

DBCO-PEG-SG

DBCO-PEG-SS

DBCO-PEG-SVA

DBCO-PEG-Epoxides

DBCO-PEG-Valeric Acids

DBCO-PEG-Acrylamide

DBCO-PEG-Bromide

DBCO-PEG-Vinylsulfone

DBCO-PEG-Methacrylate

DBCO-PEG-Iodoacetate

DBCO-PEG-Chloride

DBCO-PEG-Folate

DBCO-PEG-CHEMS

TCO-PEG-Tosylate

TCO-PEG-Acetylthio

TCO-PEG-Aminooxy

TCO-PEG-NPC

TCO-PEG-SAS

TCO-PEG-SC

TCO-PEG-SCM

TCO-PEG-SG

TCO-PEG-SS

TCO-PEG-SVA

TCO-PEG-Epoxides

TCO-PEG-Valeric Acids

TCO-PEG-Acrylamide

TCO-PEG-Bromide

TCO-PEG-Vinylsulfone

TCO-PEG-Methacrylate

TCO-PEG-Iodoacetate

TCO-PEG-Chloride

TCO-PEG-Folate

TCO-PEG-CHEMS

Tetrazine-PEG-Tosylate

Tetrazine-PEG-Acetylthio

Tetrazine-PEG-Aminooxy

Tetrazine-PEG-NPC

Tetrazine-PEG-SAS

Tetrazine-PEG-SC

Tetrazine-PEG-SCM

Tetrazine-PEG-SG

Tetrazine-PEG-SS

Tetrazine-PEG-SVA

Tetrazine-PEG-Epoxides

Tetrazine-PEG-Valeric Acids

Tetrazine-PEG-Acrylamide

Tetrazine-PEG-Bromide

Tetrazine-PEG-Vinylsulfone

Tetrazine-PEG-Methacrylate

Tetrazine-PEG-Iodoacetate

Tetrazine-PEG-Chloride

Tetrazine-PEG-Folate

Tetrazine-PEG-CHEMS