Patent GB-727365-A (GB)
Title: Improvements in or relating to bromophenyl cyanoacrylic acids and derivatives
IPC: A01N37/34
Filed: 1953-05-06
Abstract: The invention comprises a -cyano-b -(monobromophenyl) acrylic and thioacrylic acids and derivatives thereof (including isomeric forms) having the general formula <FORM:0727365/IV (b)/1> in which Y is O or S and Z is H or an ester-forming group or a salt-forming group or element.  Z is, for example, an alkali metal (e.g. lithium, sodium and potassium); an alkaline earth metal (e.g. magnesium, calcium, strontium, and barium); a heavy metal (e.g. nickel, iron, manganese, chromium, molybdenum, antimony, bismuth, tin, lead, aluminium, zinc, mercury, copper and silver); an ammonium radical of formula <FORM:0727365/IV (b)/2> or a hydrazonium radical of formula <FORM:0727365/IV (b)/3> wherein R1, R2, R3 and R4 are hydrogen, alkyl, cycloalkyl, aralkyl and/or aryl groups (examples are specified) which may be further substituted with halogen, hydroxyl, ether, carbonyl, nitro, nitroso, nitroamino, amino, substituted amino, hydroxylamino, sulphydryl, sulphide, and imino radicals; a thiouronium radical; an organometallo group MRn, wherein M is a metal forming organometallic compounds p  (e.g. zinc, cadmium, mercury, boron, aluminium, gallium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth and tellurium), n is an integer one less than the valence of the metal and R is one or more hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, heterocyclic, alkoxy or aryloxy groups (examples are specified); an alkyl group, cycloalkyl group, aryl group or a group derived from polyethers or polyhydric alcohols (examples of each are specified) all of which may be further substituted with chlorine, bromine, fluorine, iodine, nitro, nitroso, amino, substituted amino, mercaptyl, substituted mercaptyl, sulphide, sulphonic, sulphonyl and sulphonamide radicals; or a heterocyclic group (e.g. furfuryl).  The compounds are prepared by condensing a bromobenzaldehyde of formula <FORM:0727365/IV (b)/4> with a cyanoacetic compound of formula <FORM:0727365/IV (b)/5> and if desired reacting the product with a compound containing an ester-forming group or a salt-forming group or element.  The condensation is preferably carried out in an aqueous medium at elevated temperature and with agitation.  Specified reactants are ortho-, meta- and para-bromobenzaldehydes; cyanoacetic and cyanothioacetic acid, sodium, potassium, ammonium, ethyl, a -furfuryl, cyclohexyl and butoxyethyl cyanoacetate, and ethylene glycol monocyanoacetate.  a  - Cyano - b  - bromophenyl acrylic acid esters are prepared from bromobenzaldehyde and the appropriate cyanoacetic ester preferably in presence of a catalyst such as piperidine benzoate, and by employing a water-immiscible solvent such as benzene or toluene and conducting the reaction at boiling temperature, water formed is removed by azeotropic distillation. Organometallic salts of a  - cyano - b  - bromophenylacrylic acids are prepared by metathesis between alkali salts of the acrylic acid and an organometallic halide. The preparation of the following is described: a  - cyano - b  - (para - bromophenyl) acrylic acid (also the ethyl ester and the sodium and phenyl-mercuric salts), a -cyano-b -(ortho-bromophenyl) acrylic acid (also the a -furfuryl ester and the ammonium salt), a  - cyano - b  - (meta - bromophenyl) acrylic acid (also the potassium salt) and a  - cyano - b  - (para - bromophenyl) thioacrylic acid (also the sodium salt).  Other preferred compounds of the invention are lithium, a -furfuryltin and isoprenyl a -cyano-b -(metabromophenyl) acrylate; barium, triethyllead and 2,4 - dichlorophenyl a  - cyano - b  - (orthobromophenyl) acrylate; copper, tetramethylhydrazonium, dimethylaminophenylmercuri, b -chloroethyl, vinyl, butyl, b -thiocyanoethyl, and b -dimethylaminoethyl a -cyano-b -(para-bromophenyl) acrylate; ar.-chlorobenzyl a -cyano-b -(ortho-bromophenyl) and trichloromethyl a -cyano - b  - (para - bromophenyl) acrylate; the mono - [a  - cyano - b  - (ortho - bromophenyl) acrylate] of ethylene glycol monomethylether, the di - [a  - cyano - b  - (para - bromophenyl) acrylate] of ethylene glycol, the butoxy-propoxypropyl ester of a -cyano-b -(para-bromophenyl) acrylic acid and the mono-[a -cyano-b -(para-bromophenyl) acrylate] of polyethyleneglycol monobutylether.ALSO:A plant response composition comprises one or more a -cyano-b -(monobromophenyl) acrylic and thioacrylic acids and derivatives thereof of formula <FORM:0727365/I/1> in which Y is 0 or S and Z is H or an ester forming group or a p  salt-forming group or element, in admixture with a carrier.  Z is, for example, an alkali metal (e.g. lithium, sodium and potassium); an alkaline earth metal (e.g. magnesium, calcium, strontium and barium); a heavy metal (e.g. nickel, iron, manganese, chromium, molybdenum, antimony, bismuth, tin, lead, aluminium, zinc, mercury, copper and silver); an ammonium radical of formula <FORM:0727365/I/2> or a hydrazonium radical of formula <FORM:0727365/I/3> wherein R1, R2, R3 and R4 are hydrogen, alkyl, cycloalkyl, aralkyl and/or aryl groups (examples are specified) which may be further substituted with halogen, hydroxyl, ether, carbonyl, nitro, nitroso, nitramino, amino, substituted amino, hydroxylamino, sulphydryl, sulphide, and imino radicals; a thiouronium radical; an organometallo group MRn wherein M is a metal forming organometallic compounds (e.g. zinc, cadmium, mercury, boron, aluminium, gallium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth and tellurium), n is an integer one less than the valence of the metal and R is one or more hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, heterocyclic, alkoxy or aryloxy groups (examples are specified); an alkyl group, cycloalkyl group, aryl group or a group derived from polyethers or polyhydric alcohols (examples or each are specified) all of which may be further substituted with chlorine, bromine, fluorine, iodine, nitro, nitroso, amino, substituted amino, mercaptyl, substituted mercaptyl, sulphide, sulphonic, sulphonyl and sulphonamide radicals; or a heterocyclic group (e.g. furfuryl).  The active compounds are employed in aqueous solution; in aqueous suspension accompanied by a dispersing agent (examples are specified) in organic solvents (e.g. hydrocarbons, such as benzene, xylene or toluene; ketones, such as acetone, methylethyl ketone and cyclohexanone; chlorinated hydrocarbons, such as carbon tetrachloride, trichloro- and perchloroethylene; esters, such as ethyl, butyl, and amylacetates; alcohols, such as ethanol, isopropanol, and amyl alcohols; and monoalkyl ethers of ethylene and diethylene glycols); in emulsions; and as dusts or wettable powders with, for example, clays (e.g. Fuller's earth, Pyrophillite, Bentonite, Montmorrillonite and attaclay), talc and cellulosic powders.  Optional ingredients are (a) sticking agents (e.g. vegetable oils and naturally occurring gums) (b) humectants (c) pesticides (d) fertilizers.ALSO:A plant response composition comprises one or more a -cyano-b -(monobromophenyl) acrylic and thioacrylic acids and derivatives thereof of formula <FORM:0727365/VI/1> in which Y is O or S and Z is H or an ester forming group or a salt-forming group or element, in admixture with a carrier.  Z is, for example, an alkali metal (e.g. lithium, sodium and potassium); an alkaline earth metal (e.g. magnesium, calcium, strontium and barium); a heavy metal (e.g. nickel, iron, manganese, chromium, molybdenum, antimony, bismuth, tin, lead, aluminium, zinc, mercury, copper and silver); an ammonium radical of formula <FORM:0727365/VI/2> or a hydrazonium radical of formula <FORM:0727365/VI/3> wherein R1, R2, R3 and R4 are hydrogen, alkyl, cycloalkyl, aralkyl and/or aryl groups (examples are specified) which may be further substituted with halogen, hydroxyl, ether, carbonyl, nitro, nitroso, nitramino, amino, substituted amino hydroxylamino sulphydryl sulphide and imino radicals; a thiouronium-radical; an organo-metallo group MRn wherein M is a metal forming organometallic compounds (e.g. zinc, cadmium, mercury, boron, aluminium, gallium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth and tellurium), n is an integer one less than the valence of the metal and R is one or more hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, heterocyclic, alkoxy or aryloxy groups (examples are specified); an alkyl group, cycloalkyl group, aryl group or a group derived from polyethers or polyhydric alcohols (examples of each are specified) all of which may be further substituted with chlorine, bromine, fluorine, iodine, nitro, nitroso, amino, substituted amino, mercaptyl, substituted mercaptyl, sulphide, sulphonic, sulphonyl and sulphonamide radicals; or a heterocyclic group (e.g. furfuryl).  The active compounds are employed in aqueous solution; in aqueous suspension accompanied by a dispersing agent (examples are specified); in organic solvents (e.g. hydrocarbons, such as benzene, xylene or toluene; ketones, such as acetone, methylethyl ketone and cyclohexanone; chlorinated hydrocarbons, such as carbon tetrachloride, trichloro- and perchloroethylene; esters, such as ethyl, butyl, and amylacetates; alcohols, such as ethanol, isopropanol, and amyl alcohols; and monoalkyl ethers of ethylene and diethylene glycols); in emulsions; and as dusts or wettable powders with, for example, clays (e.g. Fuller's earth, Pyrophillite, Bentonite, Montmorrillonite and Attaclay), talc and cellulosic powders.  Optional ingredients are (a) sticking agents (e.g. vegetable oils and naturally occurring gums) (b) humectants (c) pesticides (d) fertilizers.