Process for the preparation of monoesters or diesters of-9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid and for the preparation of symmetrical or asymmetrical methylidenemalonates

A process for the preparation of a monoester salt of a diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid, comprising the steps of:

• (A) contacting a malonic acid ester;
• with formaldehyde or paraformaldehyde;
• and with anthracene;
• in the presence of an effective amount of a catalyst, at an elevated temperature and for a time, sufficient to prepare a diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR9## wherein R.sup.1 and R.sup.2 each, independently is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl raidcal having from 2 to 6 carbon atoms, or R.sup.1 and R.sup.2 together form an alicyclic radical having from 3 to 6 carbon atoms, the alkyl, alicyclic, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• and
• (B) contacting the diester with an alkali metal or alkaline-earth metal salt, in the presence of an alcohol;
• so as to prepare a salt of a diester of 9,10-endoethano-9-10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR10## wherein Z is an alkali metal or alkaline-earth metal atom, and R.sup.4 is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, the alkyl, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups.

A process for the preparation of an asymmetrical diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid, comprising the steps of:

• (A) contacting a malonic acid ester;
• with formaldehyde or paraformaldehyde;
• and with anthracene;
• in the presence of an effective amount of a catalyst, at an elevated temperature and for a time, sufficient to prepare a diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR11## wherein R.sup.1 and R.sup.2 each, independently is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, or R.sup.1 and R.sup.2 together form an alicyclic radical having from 3 to 6 carbon atoms, the alkyl, alicyclic, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• (B) contacting the diester with an alkali metal or alkaline-earth metal salt, in the presence of an alcohol;
• so as to prepare a salt of a diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR12## wherein Z is an alkali metal or alkaline-earth metal atom, and R.sup.4 is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, the alkyl, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• and
• (C) contacting the monoester salt with a halogenated linear or branched alkane having from 1 to 6 carbon atoms, a halogenated alkene having from 2 to 6 carbon atoms, or a halogenated alkyne having from 2 to 6 carbon atoms, the halogenated alkane, alkene, and alkyne optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• so as to prepare an asymmetrical diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR13## wherein R.sup.4 and R.sup.5 are different, and each, independently is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, the alkyl, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups.

A process for the preparation of a methylidenemalonate, comprising the steps of:

• (A) contacting a malonic acid ester;
• with formaldehyde or paraformaldehyde;
• and with anthracene;
• in the presence of an effective amount of a catalyst, at an elevated temperature and for a time, sufficient to prepare a diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR14## wherein R.sup.1 and R.sup.2 each, independently is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, or R.sup.1 and R.sup.2 together form an alicyclic radical having from 3 to 6 carbon atoms, the alkyl, alicyclic, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• and
• (B) contacting the diester with an alkali metal or alkaline-earth metal salt, in the presence of an alcohol;
• so as to prepare a salt of a diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR15## wherein Z is an alkali metal or alkaline-earth metal atom, and R.sup.4 is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, the alkyl, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• and
• (C) thermally treating the diester;
• so as to prepare a methylidenemalonate corresponding to the general formula:
• ##STR16## wherein R.sup.6 and R.sup.7 each, independently is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, or R.sup.6 and R.sup.7 together form an alicyclic radical having from 3 to 6 carbon atoms, the alkyl, alicyclic, alkenyl, and alkynyl radicals optionally substituted with one or more ehter, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups.

A process for the preparation of a methylidenemalonate, comprising the steps of:

• (A) contacting a malonic acid ester;
• with formaldehyde or paraformaldehyde;
• and with anthracene;
• in the presence of an effective amount of a catalyst, at an elevated temperature and for a time, sufficient to prepare a diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR17## wherein R.sup.1 and R.sup.2 each, independently is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, or R.sup.1 and R.sup.2 together form an alicyclic radical having from 3 to 6 carbon atoms, the alkyl, alicyclic, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• (B) contacting the diester with an alkali metal or alkaline-earth metal salt, in the presence of an alcohol;
• so as to prepare a salt of a diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR18## wherein Z is an alkali metal or alkaline-earth metal atom, and R.sup.4 is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, the alkyl, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• and
• (C) contacting the monoester salt with a halogenated linear or branched alkane having from 1 to 6 carbon atoms, a halogenated alkene having from 2 to 6 carbon atoms, or a halogenated alkyne having from 2 to 6 carbon atoms, the halogenated alkane, alkene, and alkyne optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• so as to prepare an asymmetrical diester of 9,10-endoethano-9,10-dihydroanthracene-11,11-dicarboxylic acid corresponding to the general formula:
• ##STR19## wherein R.sup.4 and R.sup.5 are different, and each, independently is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, the alkyl, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydroxy functional groups;
• and
• (D) thermally treating the diester;
• so as to prepare a methylidenemalonate corresponding to the general formula:
• ##STR20## wherein R.sup.6 and R.sup.7 each, independently is a linear or branched alkyl radical having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 6 carbon atoms, or an alkynyl radical having from 2 to 6 carbon atoms, or R.sub.6 and R.sup.7 together form an alicyclic radical having from 3 to 6 carbon atoms, the alkyl, alicyclic, alkenyl, and alkynyl radicals optionally substituted with one or more ether, epoxy, halo, cyano, ester, aldehyde, keto, aryl, or hydorxy functional groups.