Patent GB-997826-A (GB)
Title: C-substituted ethylene dinitramines
Inventor: HARDY RICHARD JOHNATHAN
IPC: C07D233/32
Filed: 1962-07-05
Abstract: A fertilizer composition comprises a plant growth regulant of the formula <FORM:0997826/C1/1> wherein R1, R2, R3 and R4 denote hydrogen or hydrocarbon groups optionally substituted (e.g. by hydroxy, ether, carboxy or sulpho groups), provided that the total number of carbon atoms in the groups R1, R2, R3 and R4 is at leas 1 and any two of these groups may be joined to form a ring, or an N-acyl derivative thereof, or a salt with a base such as ammonia, an alkali metal or an alkaline earth metal, in admixture with ammonium sulphate, ammonium nitrate, urea, basic slag, monammonium phosphate, diammonium phosphate, ordinary or triple superphosphate, potassium chloride, potassium sulphate, potassium nitrate, peat, spent hops and/or spent malt.ALSO:The invention comprises C-substituted ethylene dinitramines of the formula <FORM:0997826/C2/1> wherein R1, R2, R3 and R4 denote hydrogen or hydrocarbon groups optionally substituted (e.g. by hydroxy, ether, carboxy or sulpho groups), provided that the total number of carbon atoms in the groups R1, R2, R3 and R4 is at leas 1 and any two of these groups may be joined to form a ring, and also the N-acyl derivatives thereof and salts with bases such as ammonia, alkali metals and alkaline earth metals.  The acyl groups in N,N1-diacylated compounds may be joined to form a ring or, alternatively, may together constitute a single divalent group, such as a carbonyl group.  Individual N-acyl groups are preferably alkoxycarbonyl groups.  The above compounds are prepared by acylating a diamine of the formula H2N-CR1R3-CR2R4-NH2 to provide corresponding bis-acylamines, nitrating the latter to provide corresponding bis-acylnitramines of the formula <FORM:0997826/C2/2> and, if desired, converting the bis-acyl-nitramines into salts of bis-nitramines by the action of a base, and/or further converting the latter into the free acid form by acidification.  The intermediate products may be resolved into optically active forms prior to the preparation of the final products.  Cyclic products such as 1,3 - dinitro - 2 - keto - 4,4,5,5 - tetramethyl - imidazolidine may be converted to non-cyclic forms such as 2,3-dimethyl-normal-butane-2,3-dinitramine by boiling with water. 2,3 - Dinitro - 2,3 - dimethyl - normal - butane is prepared by reacting 2-nitropropane with ethanolic sodium hydroxide in the presence of iodine and potassium iodide.  2 - Keto - 4,4 - pentamethylene - imidazolidine is prepared by refluxing 1,1-pentamethylene-ethylene - bis - ethyl -carbamate with ethanollic sodium ethoxide or by reacting 1,1-pentamethylene ethylene diamine with phosgene and sodium carbonate.  1 - Amino - 1 - cyano - cyclohexane is prepared by reacting cyclohexanone in water successively with hydrogen cyanide and ammonia or by reacting cyclohexanone with a mixture of ammonium chloride and sodium cyanide in aqueous solution.  1 - Acetamino - 1 - cyano - cyclohexane is prepared by reacting 1-amino-1-cyano - cyclohexane with acetic anhydride.  2 - Methyl - 4,4 - pentamethylene - 2 - imidazolidine is prepared by hydrogenating 1-acetamino-1-cyano-cyclohexane.  1,1 - Pentamethylene ethylene diamine is prepared by refluxing 2 - methyl - 4,4 - pentamethylene-2-imidazolidine with aqueous potassium hydroxide.  2 - Keto - 4 - normal - hexyl - imidazolidine is prepared by refluxing 1-normal-hexyl-ethylene-bis-ethylcarbamate with ethanolic sodium ethoxide. Subsequent nitration yields 1-normal-hexyl-ethylene dinitramine.ALSO:A plant growth regulant composition contains as the active ingredient a C-substituted ethylene dinitramine of the formula <FORM:0997826/A5-A6/1> wherein R1, R2, R3 and R4 denote hydrogen or hydrocarbon groups optionally substituted (e.g. by hydroxy, ether, carboxy or sulpho groups), provided that the total number of carbon atoms in the groups R1, R2, R3 and R4 is at least 1 and any two of these groups may be joined to form a ring, or an N-acyl derivative thereof or a salt with a base such as ammonia, an alkali metal or an alkaline earth metal. Other ingredients present include solid and liquid diluents, plant nutrients, chlorphenoxy acids, dithiocarbamates, organic mercury compounds, organophosphorus compounds and chlorinated hydrocarbons.