Patent GB-801942-A (GB)
Title: Production of phosphate and thiophosphate esters containing a heterocyclic nitrogen ring
IPC: C07F9/6509
Filed: 1956-03-14
Abstract: The invention comprises O,O-dialkyl O-(3-pyridazinyl) phosphates and thiophosphates having the general formula <FORM:0801942/IV (b)/1> in which R and R1 are C1-C4 alkyl radical X is oxygen or sulphur, Y and Y1 are hydrogen, halogen, phenyl, or C1-C4 alkyl radicals, or Y and Y1 taken together represent the remainder of a benzene ring and Z is halogen or hydroxyl.  They may be prepared by reacting, preferably in an inert solvent, a dialkyl phosphoric or thiophosphoric chloride of the formula <FORM:0801942/IV (b)/2> with an oxypyridazine derivative having the formula <FORM:0801942/IV (b)/3> in which Y, Y1 and Z have the meaning given above and A is an alkali metal, alkaline earth metal or hydrogen.  When A is hydrogen the reaction is carried out in the presence of a hydrogen chloride acceptor such as an alkali metal carbonate or alkaline earth metal carbonate.  The reaction may be carried out at between 10 DEG  and 100 DEG  C.  Specified inert solvents are water, dimethyl formamide, dimethyl sulphoxide, dioxane, acetonitrile, benzene, toluene, and xylene, C1-C5 aliphatic monohydric alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl butyrate and isopropyl butyrate. Examples are given for the production of O,O-dimethyl-O,O-diethyl-, O,O-di-n-propyl-, and O,O-diisopropyl-, O - (6 - hydroxy - 3 - pyridazinyl) thiophosphates; O,O - diethyl O - (8 - hydroxy - 3 - phthalazinyl) thiophosphate; O,O-di-n-butyl O - (6 - hydroxy - 3 - pyridazinyl) phosphate; O,O - diethyl O - (4,5 - dibromo - 6 - hydroxy - 3 - pyridazinyl) thiophosphate; O,O - diethyl O - (6 - chloro - 3 - pyridazinyl) thiophosphate; a mixture of the two isomers, O,O-diethyl O-(4-chloro- (and 5-chloro-)-6-hydroxy-3-pyridazinyl) thiophosphates; a mixture of the two isomers O,O-diethyl O-(6-hydroxy-4-phenyl (and -5-phenyl-)-3-pyridazinyl) thiophosphates, and a mixture of the two isomers O,O-diethyl O-(6-hydroxy - 4 - methyl (and 5 - methy.-) - 3 - pyridazinyl) thiophosphates.  Several other phosphate and thiophosphate products of the above formula which are obtainable by the above process are also specified including O,O-di-n-propyl- and O,O-di-isobutyl O-(6-chloro-3-pyridazinyl) phosphates, O,O-dimethyl O - (8 - chloro - 3 - phthalazinyl) phosphate and O,O - diisobutyl O - (8 - hydroxy - 3 - phthalazinyl) thiophosphate.  The products are stated to be valuable pesticides (see Group VI).  The hydroxy pyridazines used as starting materials may be obtained by the reaction of maleic anhydride, substituted maleic anhydride or phthalic anhydride with hydrazine or a hydrazine salt such as hydrazine dihydrochloride, e.g. 2,6-dihydroxypyridazine, may be obtained from maleic anhydride and hydrazine dihydrochloride.  The alkali metal salts of the hydroxypyridazines may be obtained by reacting the hydroxypyridazine with an alkali metal hydroxide in water followed by precipitation with ethanol.ALSO:A pesticidal composition comprises as the active ingredient a phosphate or thiophosphate ester of the general formula: <FORM:0801942/VI/1> in which R and R1 are C1-C4 alkyl radicals, X is oxygen or sulphur, Y and Y1 are hydrogen, halogen, phenyl or C1-C4 alkyl radicals or Y and Y1 taken together represent the remainder of a benzene ring, and Z is halogen or hydroxyl (see Group IV (b)).  The composition may be in the form of a spray in an organic solvent, an emulsion in water or other non-solvent, or the active ingredient may be on a solid carrier such as a clay, talc or diatomaceous earth.  Examples are given to show the pesticidal effect of compositions containing the following esters: O,O - dimethyl O - (6 - hydroxy - 3 - pyridazinyl) thiophosphate, O,O - diethyl O - (6 - hydroxy-3 - pyridazinyl) thiophosphate, O,O - di - n-propyl O - (6 - hydroxy - 3 - pyridazinyl) thiophosphate, O,O - diisopropyl O - (6 - hydroxy-3 - pyridazinyl) thiophosphate, O,O - diethyl O - (6 - chloro - 3 - pyridazinyl) thiophosphate, and O,O - diethyl O - (6 - hydroxy - 4 - (or 5 -) methyl - 3 - pyridazinyl) thiophosphate.