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    • 82. 发明公开
    • IMPROVED HYDROGENOLYSIS OF 2,4,6,8,10,12-HEXABENZYL-2,4,6,8,10,12-HEXAAZATETRACYCLO 5.5.0.0?5,9 .0?3,11 ]DODECANE
    • 2,4,6,8,10,12-六氢萘-2,4,6,8,10,12-六氢邻苯二酚的改进氢解5.5.0.0.5,9.0,0.3,11]十二烷
    • EP0865417A1
    • 1998-09-23
    • EP96942112.0
    • 1996-12-04
    • THIOKOL CORPORATION
    • WARDLE, Robert, B.EDWARDS, W., Wayne
    • B01J23C06B25C07B61C07D487
    • C07D487/22
    • A process for the hydrogenolysis of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazatetracyclo [5.5.0.0?5,9.03,11¿]dodecane ('HBIW') is disclosed in which a quantity of HBIW, cosolvent and a bromine source are placed into a reaction vessel. Acetic anhydride and a substantially water-free palladium catalyst are then rapidly added. The reaction vessel is purged of an atmosphere capable of reacting with hydrogen, and hydrogen is quickly introduced to convert the HBIW to tetraacetyl-dibenzylhexaazaisowurtzitane ('TADB'). The acetic anhydride is added immediately prior to hydrogen introduction so that it does not have time to react with the HBIW to form an acetylated derivative prior to commencement of the desired hydrogenation reaction. The process requires very little palladium catalyst, preferably less than 10 % wt./wt. based on the HBIW substrate. The TADB, precipitated on the palladium hydrogenation catalyst, is subjected to a second hydrogenation step using formic acid solvent in the presence of hydrogen to form tetraacetyldiformylhexaazaisowurtzitane ('TADF').
    • 2,4,6,8,10,12-六苄基-2,4,6,8,10,12-六氮杂四环[5.5.0.0,5,9.03,11]十二烷氢解('HBIW' ),其中将一定量的HBIW,助溶剂和溴源置于反应容器中。 然后迅速加入乙酸酐和基本上无水的钯催化剂。 将反应容器清除能够与氢反应的气氛,并迅速引入氢气以将HBIW转化为四乙酰基 - 二苄基六氮杂异纤锌矿型结构烷烃('TADB')。 在引入氢气之前立即加入乙酸酐,使得在开始期望的氢化反应之前没有时间与HBIW反应形成乙酰化衍生物。 该方法需要非常少量的钯催化剂,优选少于10wt%/ wt。 基于HBIW基板。 在钯氢化催化剂上沉淀的TADB在氢存在下使用甲酸溶剂进行第二氢化步骤以形成四乙酰基二十六氮杂异纤锌矿型结构烷烃('TADF')。