Patent GB-737753-A (GB)
Title: Improvements in or relating to chlorophenyl cyanoacrylic acids and derivatives
IPC: C07C255/34
Filed: 1953-04-30
Abstract: The invention comprises cyanoacrylic acid derivatives of the formula <FORM:0737753/IV (b)/1> where x is 2-5, Y is 0 and Z is H or an ester group or a salt-forming group or element, or Y is NH, N-alkyl or N-aralkyl and Z is H or an organic group, or Y is N and Z completes a saturated heterocyclic ring.  These are made by condensing a di- or poly-chlorobenzaldehyde with cyanacetic acid or appropriate derivative thereof, preferably in aqueous medium at an elevated temperature with agitation.  If desired the ester or salt group may be introduced afterwards.  The compounds exist as stable and labile steroisomers which may be interconverted.  In examples the following are prepared by the above condensation method: sodium a -cyano - b  - (2 : 4 - dichlorophenyl) - acrylate, sodium a  - cyano - b  - (3 : 4 - dichlorophenyl)-acrylate, sodium a  - cyano - b  - (2 : 4 : 5 - trichlorophenyl) - acrylate, sodium a  - cyano - b -(2 : 3 : 4 : 5 - tetrachlorophenyl) - acrylate and ethyl a  - cyano - b  - pentachlorophenyl - acrylate.  In further examples the diethanolamine salts of the 2 : 4- and 3 : 4-dichlorophenyl acids are prepared, and also the triethanolamine and phenylmercuric salts of the 2 : 4-dichlorophenyl acid.  All the various isomeric di-, tri- and tetrachlorophenyl groups are specified, in compounds of the following types: free acids; inorganic salts of lithium, sodium, potassium, magnesium, calcium, strontium, barium, nickel, chromium, copper, zinc, silver, mercury, molybdenum, antimony, bismuth, tin, aluminium, manganese, iron and lead; organic salts of trimethylamine, triethylamine, tripropylamine, methyldipropyl amine, tribenzylamine, aniline, mono-, di- and triethanolamine, tetramethylhydrazine, and in general of bases NR1R2R3 or R1R2N.NR3R4 where R1-R4 are hydrogen, alkyl, cycloalkyl, aralkyl or aryl which may contain negative substituents such as halogen, free or etherified hydroxyl, carbonyl, nitro, nitroso, nitramino, amino, imino, hydroxylamino, thio and sulphide groups, many such groups being mentioned; also thiouronium salts; organometallic and organometalloid salts in which hydrocarbon, furfuryl, alkoxy or aryloxy groups are combined with elements such as mercury, tin, lead, antimony, bismuth, arsenic, germanium, aluminium, boron, gallium, silicon, zinc, tellurium, thallium and cadmium; many such groups are specified, including dimethylaminophenylmercuric, ethylmercaptomercuric, borohydro and boroetherate; esters in which the esterifying group is alkyl, alkenyl, alkylene, alkoxyalkyl or aryl, optionally substituted by chlorine, bromine, fluorine, iodine, nitro, nitroso, amino, thio, thioether, sulphonic, sulphonyl, sulphonamide, hydroxy or thiocyano groups; also heterocyclic esters such as furfuryl, thiophenyl and quinolyl; amides substituted on the nitrogen atom by alkyl, hydroxyalkyl, aralkyl, aryl, arylsulphonyl, pyridyl, thiophenyl or quinolyl, the aromatic nuclei being optionally substituted by chlorine, nitro, amino, alkoxy or dimethylaminomethyl; also heterocyclic amides of the type of N-(a -cyano-b -polychlorophenyl-acrylyl)-morpholine.ALSO:A plant response composition comprises one or more a -cyano-b -(polychlorophenyl)-acrylic acids and derivatives thereof of the formula <FORM:0737753/I/1> where x is 2-5, Y is O and Z is H or an ester group or a salt-forming group or element, or Y is NH, N-alkyl or N-aralkyl and Z is H or an organic group, or Y is N and Z completes a saturated heterocyclic ring, in admixture with a carrier. Many suitable compounds are mentioned of the type of:-free acids; salts of metals such as lithium, sodium, potassium, magnesium, calcium, strontium, barium, nickel, chromium, copper, zinc, silver, mercury, molybdenum, antimony, bismuth, tin, aluminium, manganese, iron and lead; salts of bases NR1R2R3 fins R1R2N.NR3R4, in which R1-R4 are hydrogen or organic groups; thiouronium salts; organometallic and similar salts in which an organic group and/or hydrogen is attached to an element such as mercury, tin, lead, antimony, bismuth, arsenic, germanium, aluminium, boron, gallium, silicon, zinc, tellurium, or cadmium; esters; amides. The active compounds can be employed in aqueous solution or suspension with a dispersing agent, in an organic solvent such as a hydrocarbon, chlorinated hydrocarbon, ketone, ester, alcohol or glycol monoether, or with a dry carrier such as fuller's earth, talc, clay or a cellulosic powder.  Other ingredients that may be present are sticking agents (e.g. vegetable oils or gums), humectants, pesticides of all kinds and fertilizers.ALSO:A plant response compostion comprises one or more a -cyano-b -(polychlorophenyl)-acrylic acids and derivatives thereof of the formula <FORM:0737753/VI/1> where #c is 2-5, Y is O and Z is H or an ester group or a salt-forming group or element, or Y is NH, N-alkyl or N-aralkyl and Z is H or an organic group, or Y is N and Z completes a saturated heterocyclic ring, in admixture with a carrier.  Many suitable compounds are mentioned of the type of: free acids; salts of metals such as lithium, sodium, potassium, magnesium, calcium, strontium, barium, nickel, chromium, copper, zinc, silver, mercury, molybdenum, antimony, bismuth, tin, aluminium, manganese, iron and lead; salts of bases NR1R2R3 and R1R2N.NR3R4 in which R1-R4 are hydrogen or organic groups; thiouronium salts; organometallic and similar salts in which an organic group and/or hydrogen is attached to an element such as mercury, tin, lead, antimony, bismuth, arsenic, germanium, aluminium, boron, gallium, silicon, zinc, tellurium, thallium or cadmium; esters; amides.  The active compounds can be employed in aqueous solution or suspension with a dispersing agent, in an organic solvent such as a hydrocarbon, chlorinated hydrocarbon, ketone, ester, alcohol or glycol monoether, or with a dry carrier such as fuller's earth, talc, clay or a cellulosic powder.  Other ingredients that may be present are sticking agents (e.g. vegetable oils or gums), humectants, pesticides of all kinds and fertilizers.