Patent GB-875134-A (GB)
Title: Adducts of heterocyclic amides and thioamides with ª-,ª--unsaturated compounds
IPC: C07D241/08
Filed: 1957-12-03
Abstract: Polyvinyl chloride is plasticized by means of a heterocyclic amide or thioamide containing two nitrogen atoms in the hetero cycle, both of which bear substituents, the compounds being adducts of heterocyclic amides or thioamides with a  : b -ethylenically unsaturated compounds, all of specified types (see Group IV(b)).  The compounds also have fungicidal properties.ALSO:The invention comprises heterocyclic amides and thioamides containing two nitrogen atoms in the ring both of which are substituted, the compounds being adducts of (A) a heterocyclic compound of the formula <FORM:0875134/IV (b)/1> and (B) an unsaturated compound of the formula <FORM:0875134/IV (b)/2> wherein L is a divalent chain of 2 or 3 carbon atoms and one nitrogen atom which, considered in a counter-clockwise direction, is separated by at least 2 carbon atoms from the other nitrogen atom in the ring, the remaining valencies of the 2 or 3 carbon atoms in the L chain being satisfied by hydrogen atoms or alkyl groups which may or may not be joined together to form a carbocyclic system embracing the said 2 or 3 carbon atoms and whose total carbon content is no greater than 18, with the proviso that when the nitrogen atom in the L chain is vicinal to the carbon atom shown in the formula and the L chain contains 3 carbon atoms, the middle carbon of the chain may contain a hydroxy substituent; the available valency of the N atom in the L chain is satisfied by a hydrogen atom, or an alkyl, cycloalkyl, or alkyl cycloalkyl group each containing up to 18 carbon atoms, or an aryl, alkaryl, aralkyl or alkyl arylalkyl group each containing 6-18 carbon atoms, or a C2-C8 hydroxy- or amino-alkyl group in which the hydroxy or amino group is no closer than the b -position to the said nitrogen atom in the chain L, a C2-C18 alkenyl group, an alkoxyalkyl group containing up to 19 carbon atoms in which the alkoxy group contains up to 16 and the alkyl portion at least 2 carbon atoms. an alkenoxyalkyl group containing up to 19 carbon atoms in which the alkenoxy portion contains up to 17 and the alkyl portion at least 2 carbon atoms or a cyano or cyanoalkyl group in which the alkyl group contains up to 8 carbon atoms; Y is oxygen or sulphur; and T and T1, which may be the same or different, represent a cyano group, the group -CONZ2, where Z is hydrogen or C1-C8 alkyl, or the group -COOR in which R is a C1-C14 alkyl group, a C2-14 alkoxyalkyl group, an aralkyl or alkaryl group containing 7-14 carbon atoms or R is a cycloalkyl or alkyl cycloalkyl group containing up to 14 carbon atoms.  The adducts are prepared by an addition reaction between the two components at about 0 DEG -200 DEG C. in the presence of a strongly alkaline catalyst and, if desired, an inert volatile solvent.  One equivalent of the a :b  unsaturated reactant combines with the heterocyclic reactant if the nitrogen atom in the L chain of the latter is substituted; otherwise two equivalents of the unsaturated reactant react with the heterocyclic compound.  Also, when the unsaturated reactant is an ester and the N atom in the L chain bears a hydroxy alkyl substituent. in addition to adduct formation there may occur esterification of the hydroxy group by transesterification.  Those adducts containing an ester group wherein the group R is derived from a higher alcohol may be obtained advantageously by first forming the corresponding adducts wherein R represents a lower alkyl group and then subjecting the adduct to a transesterification to obtain the higher molecular weight ester, preferably by refluxing the reaction mixture in the presence of a strongly acid catalyst and, if desired, a volatile solvent.  The adduct products may be used as synthetic lubricants, fungicides and plasticizers.  In an example, 1 : 3-bis(dimethoxy carbonyl hexyl)-2-imidazolidinone is prepared from dimethyl a -methylene-a 1-methyl adipate and ethylene urea.  A large number of other examples of adducts and adduct forming materials including imidazolidinthiones, piperazinones, piperazinthiones, piperimidinones and piperimidinthiones are listed.ALSO:Fungicidal compositions comprise an inert carrier containing up to 1% of a heterocyclic amide or thio amide containing two nitrogen atoms in the ring, both bearing substituents, the compounds being adducts of heterocyclic amides or thioamides with a  : b -ethylenically unsaturated compounds, all of specified types (see Group IV (b)).  Typical adducts are 1 : 3-bis (2 : 5 - dimethoxycarbonyl hexyl) - 2 - imidazolidinone, 1 - (8 - amino octyl) - 3 - (2 : 5 - dibenzyloxy carbonyl hexyl) - 2 - imidazolidinthione, 1 - benzyl - 4 - (2 : 5 - dibutoxycarbonyl hexyl) - 5 - octyl - 6 - hexyl - 2 - piperidinthione, 1 - cyclohexyl - 3 - (2 - cyclohexoxycarbonyl - 5-cyanohexyl) - 5 : 5 - dimethyl - 2 - imidazolidinone and 1 - (2 - butenyl) - 3 - (2 - methoxy carbonyl - 5 - benzoxycarbonyl hexyl) - 4 : 5-diethyl - 2 - piperimidinone.  Many other adducts and starting materials therefor are given.