| 摘要 |
A novel synthesis of compounds having formula (I), wherein T is a stabilizing spiro-linked polycycloalkylidene group, R<3> is a C1-C20 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<1>O)3P, wherein R<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<3>OH, wherein R<3> is as defined above, to produce a 1-alkoxy-1-aryl-methane phosphonate ester of formula (II), reacting the phosphonate with base to produce a phosphonate-stabilized carbanion, reacting the carbanion with a ketone of formula (III), wherein T is as defined above, to produce an enol ether of formula (IV), then oxygenating the double bond in the enol ether to give the corresponding 1,2-dioxetane compound. Hydroxyaryl enol ether alkali metal salts having formula (V), in which T is a fused, substituted or unsubstituted polycycloalkylidene group, OR<3> is an ether group, Y is a light-emitting fluorophore-forming group which will be part of a luminescent substance formed by decommposition of a 1,2-dioxetane subsequently formed from the hydroxyaryl enol ether alkali metal salt, capable of absorbing energy to form an excited state from which it emits optically detectable energy to return to its ground state, and AM<+> is an alkali metal cation, processes for the preparation of these intermediate salts and their use as starting materials for acylation, phosphorylation and glycosylation reactions to give intermediates reactable to give stable, water-soluble chemiluminescent 1,2-dioxetanes, particularly ones that are enzymatically cleavable, are also disclosed. |
