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    • 48. 发明授权
    • Synthesis of stable water-soluble chemiluminescent 1,2-dioxetanes and
intermediates therefor
    • 稳定的水溶性化学发光1,2-二氧杂环丁烷及其中间体的合成
    • US5225584A
    • 1993-07-06
    • US680783
    • 1991-04-03
    • Edwards BrooksJuo Rhou-Rong
    • Edwards BrooksJuo Rhou-Rong
    • C07C43/174C07C45/29C07C45/71C07C47/575C07D321/00C07F9/40C07F9/655C07F9/6561
    • C07F9/6561C07C43/1747C07C45/292C07C45/71C07C47/575C07D321/00C07F9/4056C07F9/65512C07F9/65517C07F9/65522C07C2103/74
    • A novel synthesis of compounds having the formula: ##STR1## wherein T is a stabilizing spiro-linked polycycloalkylidene group, R.sup.3 is a C.sub.1 -C.sub.20 alkyl, aralkyl or heteroatom containing group, Y is an aromatic fluorescent chromophore, and Z is a cleavable group which, when cleaved, induces decomposition of the dioxetane ring and emission of optically detectable light, is disclosed. A tertiary phosphorous acid alkyl ester of the formula:(R.sup.1 O).sub.3 Pwherein R.sup.1 is a lower alkyl group, is reacted with an aryl dialkyl acetal produced by reacting a corresponding aryl aldehyde with an alcohol of the formula:R.sup.3 OHwherein R.sup.3 is as defined above, to produce a 1-alkoxy-1-arylmethane phosphonate ester of the formula: ##STR2## reacting the phosphonate with base to produce a phosphonate-stabilized carbanion, reacting the carbanion with a ketone of the formula:T.dbd.Owherein T is as defined above, to produce an enol ether of the formula: ##STR3## then oxygenating the double bond in the enol ether to give the corresponding 1,2-dioxetane compound.
    • 具有下式的化合物的新合成:其中T是稳定螺环连接的多环亚烷基,R 3是C 1 -C 20烷基,含芳烷基或杂原子的基团,Y是芳族荧光发色团,Z是可裂解基团 当其被切割时,引入二氧杂环丁烷环的分解和光学可检测光的发射。 与其中R1是低级烷基的式(R1O)3P的叔亚磷酸烷基酯与芳基二烷基缩醛反应,该芳基二烷基缩醛通过使相应的芳基醛与下式的醇反应:其中R 3如上定义 ,以产生下式的1-烷氧基-1-芳基甲烷膦酸酯:将膦酸酯与碱反应以产生膦酸酯稳定的碳负离子,使碳负离子与下式的酮反应:T = O,其中T为 以产生下式的烯醇醚:然后对烯醇醚中的双键进行氧化,得到相应的1,2-二氧杂环丁烷化合物。