摘要
该文经氟化、酰胺化和还原3步反应合成了2,2-二氟丙烷-1,3-二胺(DFPDA)。以丙二酸二乙酯为基本原料,首先经选择性氟化剂1-氯甲基-4-氟-1,4-二氮双环[2.2.2]辛烷双氟硼酸盐(Selectfluor)氟化得第一中间体2,2-二氟丙二酸二乙酯(DFDEM),DFDEM再经氨水酰胺化反应得到第二中间体2,2-二氟丙二酰胺(DFMA),最后以硼烷为还原剂,将中间体DFMA还原得到最终产品2,2-二氟丙烷-1,3-二胺(DFPDA),总收率最高可达45%。考察了3步反应的工艺条件对产品收率的影响,结果表明,较理想的反应条件为:氟化反应温度0℃,n(丙二酸二乙酯):n(氢化钠):n(Selectfluor)=1:3:3,氟化反应收率达58.18%;酰胺化反应8 h,n(氨水):n(DFDEM)=5:1,酰胺化反应收率可达96%以上;在65℃还原反应3～4 h,n(DFMA):n(BH3)=1:7.5,还原反应收率达91.1%。用IR、1HNMR和GC-MS分析了每个产物的化学结构。
The common aromatic polyamide composite reverse osmosis （RO） membrane is liable to oxidation. 2,2-difluoropropan-1,3-diamine （DFPDA） as a key functional monomer can be used to prepare the chlorine-resistant composite reverse osmosis membrane by way of interracial polymerization technology. In this study, DFPDA was synthesized through three reactions including fluorination, amidation and reduction. The diethyl malonate as substrate first reacted with the fluorination reagent of selectfluor to get the first intermediate 2,2-difluoro-diethyl-malonate （DFDEM） , and then the DFDEM was amidated by ammonia water to prepare the second intermediate 2,2-difluoro-malonamide （DFMA）. Lastly ,the resulting DFMA was reduced via boron hydride（ BH3 ） to obtain the final product DFPDA. The total yield of the product DFPDA reached 45 %. The reaction conditions of the three reactions were investigated. Furthermore, the chemical structures of all the products were identified via infrared spectra （IR） , hydrogen nuclear magnetic resonance （^1HNMR） and mass spectrograph （MS）.
出处
《精细化工》
EI
CAS
CSCD
北大核心
2012年第6期621-624,共4页
Fine Chemicals
基金
国家自然科学基金项目(21006096)
国家重点基础研究发展计划(973计划)项目(2009CB623402)~~
