Patent GB-875135-A (GB)
Title: Adducts of heterocyclic amides and thioamides with ª-,ª--unsaturated compounds
IPC: C07D265/10
Filed: 1957-12-03
Abstract: Polyvinyl chloride is plasticized by means of a heterocyclic amide or thioamide containing two nitrogen atoms in the ring, both of which are substituted by different groups, 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. 1-(2- vinoxyethyl)- 3- (2- cyanoethyl)- 2- imidaxolidinone, a specified adduct, may be homopolymerized with the aid of Friedel-Crafts catalysts and co-polymerized with acrylate esters, maleic anhydride, alkyl fumarates and vinyl compounds using free-radical initiators.  Another adduct, 1- (2-methacryloyl oxyethyl)- 3-(2-methoxycarbonylpropyl)-2-imidazolidinone may be homopolymerized using free-radical type catalysts and may be copolymerized with monomers such as acrylates and acrylonitrile.ALSO:The invention comprises heterocyclic amides and thioamides containing two nitrogen atoms in the ring both of which are substituted by different groups, the compounds being adducts of heterocyclic compounds of the general formula <FORM:0875135/IV (b)/1> and unsaturated compounds of the formula <FORM:0875135/IV (b)/2> wherein L is a divalent chain of two or three carbon atoms and one nitrogen atom which, considered in a counter-clockwise direction, is separated from the other nitrogen atom in the heterocyclic ring by at least two carbon atoms, the remaining valencies of the said two or three carbon atoms in the L chain being satisfied by hydrogen atoms or alkyl groups which, if desired, may be joined together to form a carbocyclic system embracing the two or three carbon atoms of the L chain and whose total carbon content is no greater than 18, with the proviso that when the N 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 atom may bear a hydroxy substituent; the available valency of the N atom in the L chain is satisfied by an alkyl, cycloalkyl or alkyl cycloalkyl group containing up to 18 carbon atoms, an aryl, alkaryl, aralkyl or alkaralkyl group containing 6-18 carbon atoms, a C2-C8 hydroxy- or amino-alkyl group in which the hydroxy- or amino-group is no closer than the b -position to the N atom in the L chain, a C2-C18 alkenyl group, an alkoxyalkyl group containing up to 19 carbon atoms in which the alkoxy portion 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 group or cyano alkyl group having up to 8 carbons in the alkyl group; Y is oxygen or sulphur; Q is hydrogen or a C1-C8 alkyl group; and T is a cyano group, the group -CONZ2 in which Z is hydrogen or a C1-C8 alkyl group, or the group -COOR in which R is a C1-C14 alkyl group, a C2-C14 alkoxyalkyl group, an aralkyl or alkaralkyl group containing 7-14 carbons or 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.  When the substituent on the N atom of the L chain is a cyanalkyl group, the unsaturated reactant is so selected that the substituent introduced on to the other N atom is different. When the N atom of the L chain contains a hydroxyalkyl substituent and the unsaturated reactant contains an ester group, esterification of this hydroxy group may occur, in addition to adduct formation. Those adducts containing an ester group wherein R is derived from a higher alcohol may be obtained advantageously by first forming the corresponding adduct wherein R is a lower alkyl group and then subjecting this adduct to transesterification to obtain the higher molecular weight ester.  The adducts may be used as synthetic lubricants, fungicides or plasticizers and some may be polymerized (see Group IV(a)).  Examples d scribe the preparations of (1) 1-(2-vinoxyethyl)-3-(2-cyanoethyl)-2-imidazolidinone from acrylonitrile and 1-(2-vinoxyethyl)-2-imidazolidinone; (2) 1 - (2-methacryloyloxyethyl)-3-(2-methoxy carbonyl propyl) - 2 - imidazolidinone from methyl methylacrylate and 1-(2-hydroxyethyl)-2-imidazolidinone; (3) 1-(2-methoxy carbonyl ethyl) - 3:3:4:5 - tetramethyl - 2 - piperazinone from methyl acrylate and tetramethyl-2-piperazinone; (4) 1-(3-amino propyl)-3-(2-methoxy carbonyl ethyl)-2-piperimidinone from methyl acrylate and 1-(3-amino propyl)-2-piperimidinone. Numerous other adducts and adduct-forming reagents including imidazolidinthiones, piperazinthiones and piperimidinthiones are listed.ALSO:Fungicidal compositions comprise an inert carrier containing up to 1% of a heterocyclic amide or thioamide containing two nitrogen atoms in the ring both of which are substituted by different groups, the compounds being adducts of heterocyclic amides or thio amides with a  : b -ethylenically unsaturated compounds, all of specified types (see Group IV (b)).  Typical of many named adducts are 1-(2-vinoxyethyl)-3 - (2 - cyanoethyl) - 2 - imidazolidinone 1 - (2-methacryloyloxyethyl) - 3 - (2 - methoxy carbonyl propyl) - 2 - imidazolidinone, 1 - (2 - methoxy carbonyl ethyl) - 3 : 3 : 4 : 5 - tetramethyl-2 - piperazinone and 1 - (3 - amino propyl) - 3-2 - methoxycarbonyl ethyl) - 2 - piperimidinone.