US 5,225,584 A · Synthesis of stable water-soluble chemiluminescent 1,2-dioxetanes and intermediates therefor

Abstract

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 P wherein 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 OH wherein 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.O wherein 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.

Claims22

Dependent claims

A compound having the formula:

##STR86## wherein R.sup.1 is a trialkylsilyl group or a lower alkyl group having up to 12 carbon atoms;
R.sup.2 is meta or non-conjugated with the ring carbon atom of the Y group where the phosphonate ester containing side chain is attached, and is a hydroxyl group, an ether (OR.sup.4) or a thioether (SR.sup.4) group wherein R.sup.4 is a substituted or unsubstituted alkenyl, lower alkyl or aralkyl group having up to 20 carbon atoms, an acyloxy group, a bromine atom, an amino group, a mono or di(lower) alkylamino group or its acid salt wherein each lower alkyl group has up to 7 carbon atoms and wherein each lower alkyl group may be bonded to the Y group forming one or more fused rings, a NHSO.sub.2 R.sup.5 group wherein R.sup.5 is a methyl, tolyl, or trifluoro group, a substituted aryl, heteroaryl, or .beta.-styrenyl having up to 20 carbon atoms;
R.sup.3 is a substituted or unsubstituted lower alkyl, aralyl or heteroaralkyl group having up to 20 carbon atoms, an aryl or heteroaryl group having up to 14 carbon atoms which can be further substituted;
X.sup.1 is hydrogen or a substituted or unsubstituted aryl, aralkyl, heteroaryl, or a heteroalkyl group having up to 20 carbon atoms, an allyl group, a hydroxy (lower) alkyl group having up to 6 carbon atoms, a (lower) alkyl-OSiX.sub.3 group wherein the alkyl and X radicals are as defined above, an ether (OR.sup.4) or a thioether (SR.sup.4) wherein R.sup.4 is as defined above, an SO.sub.2 R.sup.6 group wherein R.sup.6 is methyl, phenyl or NHC.sub.6 H.sub.5, a substituted or unsubstituted alkyl group having up to 7 carbon atoms, a nitro group, a CN group, an aldehyde or its oxime or dimethyl hydrazone, a haologen group, a carboxylic acid salt, ester, or hydrazide, a trialkyl silicon-based group, or a phosphoryloxy group;
and Y is phenyl, biphenyl, 9,10-dihydrophenanthryl, naphthyl, anthryl, phenanthryl, pyrenyl, dibenzosuberyl, phthalyl or derivatives thereof.

2 more elements

Dependencies are inferred from the claim text.

Synthesis of stable water-soluble chemiluminescent 1,2-dioxetanes and intermediates therefor

Life of this patent

Synthesis of stable water-soluble chemiluminescent 1,2-dioxetanes and intermediates therefor

Life of this patent

Abstract

Claims22