Patent GB-957831-A (GB)
Title: Amino-trichloropicolinic acid compounds
IPC: C07D213/84
Filed: 1963-02-15
Abstract: Compounds of the formula <FORM:0957831/C1/1> where Y is a carboxylic acid group or a functional derivative thereof, L is an integer, and Z is the residue of a nitrogen base (see Division C2) are plant growth regulants.  They are said to speed up the germination of seeds, and to stimulate the formation of roots, buds and flowers; they may be used to produce seedless fruits without the use of pollen and to prevent or retard the formation of the abscission layer on fruit trees to prevent premature fruit drop. In other applications the compounds may be used to cause fruit drop, set flowers or defoliate plants.  The compounds of the above formula may be used as compositions (see Division A5). Specification 957,277 is referred to.ALSO:The invention comprises compounds of the formula: <FORM:0957831/C2/1> where Y is a carboxylic acid group or a functional derivative thereof (e.g. a cyano, carboxylic acid salt, carboxylic acid ester, carboxylic acid hydrazide or carboxylic acid amide group), L is an integer, and Z is the residue of a nitrogen base having at least one >NH group (the other valencies being attached to C, H or N) which has a basic dissociation constant of 10-7 or greater, Z being attached to the pyridine ring by way of the nitrogen of the above group. The free valencies of the >NH group can be satisfied by hydrogen, alkyl, alkenyl, alkynyl, hydroxyalkyl, aralkyl, cycloalkyl, amino, dialkylamino, guanyl, aminoalkyl, poly(aminoalkylene)-aminoalkyl, pyridyl, pyrimidinyl or triazyl, or they may make up a ring, such as ethyleneimine, trimethyleneimine, pyrrolidine, alkylpyrrolidine, piperidine, alkylpiperidine, piperazine, alkylpiperazine or morpholine. When L is 2 Z may be -NHNH-, -(NHCmH2m)xNH-, -NHCnH2nNH-, <FORM:0957831/C2/2> and <FORM:0957831/C2/3> where m, n and x are integers.  Many nitrogen bases ZHL are specified.  The group Y is e.g. COOH, COOM, CN CONH2, CONHR1, CONR1R2, CONHNH2, CONHNHR3 or COOR4.  M is a salt group, e.g. NH4, Na, K, Li, Mg, Ca, Cu, Fe, Zn, Co, and Ni, or a substituted or quaternary ammonium group, several of which are specified; R1 and R2 are lower aliphatic radicals (including hydroxyalkyl); R3 is aliphatic or aromatic; and R4 is the residue of a compound R4OH, many of which are specified.  Compounds in which Y is COOH may be prepared by heating the corresponding compound having Y=CCl3 with aqueous acid, or by hydrolysis of a corresponding lower alkyl ester. Esters are prepared by esterifying the acid or a derivative thereof; or lower alkyl esters may be prepared by reacting the compound with Y=CCl3 with the alkanol and water in the presence of AgNO3.  Some esters may be prepared by reacting a salt of the acid with a halide corresponding to the alcohol, or the acid chloride (from the acid and SOCl2) with the hydroxy compound in the presence of a tertiary amine. Salts are prepared by reacting the acid with a suitable base, or, for metals which form difficulty soluble hydroxides, by reacting an alkali metal salt of the acid with a soluble mineral acid salt of the metal.  Amides and hydrazides are prepared from a suitable ester and the appropriate base. Nitriles are prepared from P2O5 and the corresponding -CONH2 compound.  Many examples are given.  The compounds of the invention are pesticides and plant growth regulants (see Division A5).  Specification 957,277 is referred to.ALSO:Compounds of the formula <FORM:0957831/A5-A6/1> where Y is a carboxylic acid group or a functional derivative thereof, L is an integer, and Z is the residue of a nitrogen base (see Division C2) are plant-growth regulants and pesticides.  The growth of plants or plant parts may be modified by applying to them a compound of the above formula or a composition containing it in admixture with a plant growth control or herbicide additive and/or an inert carrier. Specified carriers are water, organic solvents, petroleum distillates, surface-active dispersing agents, aqueous oil emulsions, chalk, talc, bentonite and other clays. The Compositions may also contain other plant growth control agents (many of which are specified), hormones, contact herbicides, pesticides and/or modifying agents.  Specified additional plant growth regulants are aminotriazines; phenylureas; 3 - phenyl - 1,1 - dimethylurea trichloracetate; chlorinated phenoxy aliphatic acids and their salts and esters; carbamates; chlorinated benzoic acids and their salts and esters; chlorinated lower aliphatic acids and their salts and esters; nitrophenols; pentachlorophenol; 5-bromo - 3 - isopropyl - 6 - methyluracil; arsenic compounds; sodium chlorate; sodium borates; 3,6 - endox - o - hexahydrophthalic acid; o-(2,4 - dichlorophenyl) - o - methyl isopropyl phosphoramidothioate; 3,4 - dichloropropionahilide; 1,2 - dihydroxypyridazine - 3,6 - dione; 3 - amino - 1,2,4 - triazole; 2,3,6 - trichlorophenylacetic acid and its salts and esters; 1,11-ethylene - 2,21 - dipyridylium dibromide; 2,6 dinitro - N,N - di - n - propyl - 2,2,2 - trifluoro - p - toluidine; a  - chloro - N - diallyl acetamide and herbicidal oils.  Specification 957,277 is referred to.