Patent GB-757206-A (GB)
Title: Improvements in or relating to chlorophenyl cyanoacrylic acids and derivatives
IPC: C07C255/34
Filed: 1953-05-06
Abstract: Compounds of the formula <FORM:0757206/IV(a)/1> in which Z is H or an ester-forming group or a salt-forming group or an element, are prepared for use in the treatment of plants and seeds (see Groups I and VI).  In examples: (1) sodium a  - cyano - b  - (p - chloropheyl)-acrylate is prepared by reacting sodium cyanoacetate with p-chlorobenzaldehyde in alkaline medium; (2) the sodium salt is converted to the free acid by treatment with hydrochloric acid; (3) sodium cyanoacetate and m-chlorobenzaldehyde are reacted to give sodium a -cyano - b  - (m - chlorophenyl) - acrylate which is converted to the free acid by treatment with hydrochloric acid. Esters can be produced using the appropriate ester of cyanoacetic acid, e.g. ethyl cyanoacetate and p-chlorobenzaldehyde react to give ethyl a -cyano-b -(p-chlorophenyl)-acrylate.  Other salts are obtained as in Example (1), by treatment of the free acid with the appropriate base or by metathesis between the sodium salt and an appropriate salt.  Salts mentioned include those of alkali metals, alkaline earth metals, and heavy metals.  Ammonium, hydrozanium and other nitrogencontaining salts containing the radical -NR1R2R3H and corresponding hydrazino radicals in which the R groups specified are hydrogen or numerous alkyl, cycloalkyl, aralkyl or aryl groups which may contain halogen, hydroxy, aceto or nitro substituents are also mentioned. Organo-metallic salts in which the group X represents MRn where M is a metal (of valency n + 1) such as mercury, tin, lead, antimony, bismuth, arsenic, germanium, aluminium, boron, gallium silicon, zinc and tellurium and R represents various alkyl, cycloalkyl, aryl, aralkyl and alkoxyaryl groups as well as the furfuryl group are also specified.  Specified radicals in esters of the substituted cyanoacrylates include alkyl, cycloalkyl, heterocyclic (such as furfuryl, thiophenyl, quinolyl, and morpholinyl) and aryl radicals, and radicals substituted by chloro, bromo, hydroxy, thiocyano, mercapto, amino, sulpho, and nitro groups. Esters with polyethers and polyhydric alcohols such as pentaerythritol, ethylene glycol, methoxyethanol, ethoxyethanol, butoxyethanol butoxyethoxy-propanol, and polyethylene and polypropylene glycols.  The compounds can exist in geometrically isomeric forms, the labile isomer of which can be converted to the stable form by treatment with ultra-violet light.ALSO:A composition for regulating the growth of plants and treating seeds comprises a carrier and one or more a -cyano-b -mono-chlorophenyl acrylic acid or derivative thereof (including isomeric forms) having the formula <FORM:0757206/I/1> in which Z is H or an ester-forming group or a salt-forming group or element.  Examples of suitable salts are the lithium, sodium, potassium, magnesium, calcium, strontium, barium, nickel, chromium, copper, zinc, silver, mercury, molybdenum, antimony, bismuth, tin, aluminium, magnesium, iron, lead, ammonium, and hydrazonium salts.  Substituted ammonium and hydrazonium salts can be used containing the group -NHR1R2R3 (and analogons hydrazonium groups) in which the R radicals are hydrogen, alkyl, cycloalkyl, aralkyl or aryl radicals which may contain halogen, hydroxyl, hydrocarbonoxy, carbonyl, nitro, nitroso, nitramino, amino, substituted amino, hydroxylamino, sulphydryl, sulphide or imino groups.  Organo-metallic salts containing the group -MRn wherein M is a metal (of valency n+1) such as mercury, tin, lead, antimony, bismuth, arsenic, germanium, aluminium, boron, gallium, silicon, zinc or tellurium and R represents an alkyl, cycloalkyl, aryl, aralkyl, alkoxy aryl or furfuryl radical, can also be used.  Examples of suitable esters are those containing alkyl, cycloalkyl, heterocyclic radicals (such as furfuryl, thiophenyl, quinolyl and morpholinyl) aryl radicals, radicals substituted by chloro, bromo, hydroxy, thiocyano, mercapto, amino, sulpho and nitro groups, and radicals of polyethers and polyhydric alcohols such as pentaerythritol, ethylene glycol, methoxyethanol, ethoxyethanol, butoxyethanol, butoxyethoxy propanol, polyethylene glycol and polypropylene glycol.  The carrier may be water and/or an organic solvent, an oil-in-water emulsion, powdered talc, clay or cellulosic material. Compositions prepared according to the invention may stimulate or inhibit the germination of seeds and the growth of plants.  They may, for example, delay the sprouting of tubers and the leaf and flower buds of woody plants, the blossoming of flowers and the setting of fruit.  The compositions may also contain dispersants, adhesives, e.g. gums, humectants, fungicides, insecticides, larvicides, bactericides, herbicides, growth suppressants, vermicides, miticides and fertilizers.ALSO:A plant response composition comprises a carrier and one or more 2-cyano-b -mono-chlorophenyl acrylic acids or derivatives thereof, including isomeric forms, having the formula:  <FORM:0757206/VI/1> in which Z is H or an ester forming group or a salt forming group or element.  As salts of inorganic bases these are specified the lithium, sodium, potassium, magnesium, calcium, strontium, barium, nickel, chromium, copper, zinc, silver, mercury, molybdenum, antimony, bismuth, tin, aluminium, magnesium, iron, lead, ammonium, and hydrazonium salts.  As substituted ammonium and hydraxzonium salts can be used those containing the radical -NHR1R2R3 (and analogous hydrazonium radicals) in which the R radicals are hydrogen, or numerous alkyl, cycloalkyl, aralkyl or aryl groups which may contain halogen, hydroxyl, hydrocarbonoxy, carbonyl, nitro, nitroso, nitramino, amino, substituted amino, hydroxylamino, sulfhydryl, sulphide and imino groups.  Organometallic salts in which the group-MRn where M is a metal (of valency n + 1) such as mercury, tin, lead, antimony, bismuth, arsenic, germanium, aluminium, boron, gallium, silicon, zinc and tellurium and R represents various alkyl, cycloalkyl, aryl, aralkyl, and alkoxy aryl groups as well as the furfuryl group are also specified.  As esters, those with alkyl, cycloalkyl, heterocyclic (such as furfuryl, thiophenyl, quinolyl and morpholinyl) and oxyl radicals, radicals substituted by chloro-bromo, hydroxy, thiocyano, mercapto, amino, sulpho and nitro groups, and those from polyethers and polyhydric alcohols such as pentaerythritol, ethylene glycol, methoxyethanol, ethoxyethanol, butoxyethanol, butoxyethoxy propanol and polyethylene and polypropylene glycols are specified.  The compounds can be formed into aqueous compositions containing surface-active agents, as compositions with solid carriers such as talc, clay and cellulosic diluents (such compositions being useful in the treatment of seeds), as solutions in organic solvents, as mixtures with wettable powders, as oil-in-water emulsions and with adherent or sticking agents.  The compositions have plant growth regulating properties, which may result in growth inhibition or stimulation, such as suppressing growth or delaying ripening of plants and fruits and ornamental flowers, and in preventing sprouting in tuberous plants.  As additional ingredients the compositions may contain adherents, humectants, fungicidal materials, insecticides, larvicides, bactericides, herbicides, growth suppressants, vermicides, miticides and fertilizers.