Patent GB-1005860-A (GB)
Title: Nitramino-carboxylic acid derivatives and their use in agriculture and horticulture
Inventor: HARDY RICHARD JONATHAN
Filed: 1962-10-12
Abstract: The invention consists of N-acyl, N-alkoxycarbonyl, N-alkyl derivatives, esters or amides of nitramines of the formula. NO2-HN-Y-COOH wherein Y is an unsubsituted or an alkyl substituted polymethylene group containing 2 to 10 carbon atoms or nitramines of the above formula where Y is C3 to C10, as above defined, and ammonium, alkali or alkaline earth metal salts thereof, and specifically gamma-nitramino - n - butyric acid; delta-nitramino-valeric acid; epsilon-nitramino-caproic acid; 7-nitramino-enanthic acid; 11-nitramino-undecanoic acid; N-ethoxy-carbonyl - beta - nitramino - propionic acid, and its ethyl ester; the ethyl ester of beta-nitramino - propionic acid; N - ethoxycarbonyl - gamma - nitramino - n - butyric acid; gamma - nitramino - n - butyramide; N - ethoxycarbonyl - delta - nitramino - valeric acid; N - ethoxycarbonyl - epsilon - nitramino - caproic acid; N-ethoxycarbonyl-7-nitramino-enanthic acid; 7-nitramino-enanthamide; N-ethoxycarbonyl - 11 - nitramino - undecanoic acid.  Intermediates employed in their production include N-ethoxycarbonyl-gamma-amino-n - butyric acid; N - ethoxycarbonyl - beta - amino-propionic acid; N-ethoxy carbonyl-beta-amino-propionic acid ethyl ester; N-ethoxycarbonyl - epsilon - amino - caproic acid; N - ethoxycarbonyl - delta - amino - valeric acid; N - ethoxycarbonyl - 7 - amino - enanthic acid; N - ethoxycarbonyl - 11 - amino - undecanoic acid.  The compounds of the formula NO2-HN-Y-COOH are made by acylating the corresponding amino acid H2N-Y-CO2H, nitrating the product and removing the acyl group by hydrolysis or ammonolysis.  In Example 1 beta-aminopropionic acid is reacted with ethyl chloroformate giving N-ethoxy carbonyl-beta-amino propionic acid, which on treatment with acetic anhydride and fuming nitric acid yields N-ethoxycarbonyl-beta-nitraminopropionic acid.  The latter, in ethereal solution, is treated with ammonia to give the ammonium salt from which the acid is liberated by mineral acid.  Example 2 describes the esterification of beta-amino-propionic acid hydrochloride, conversion of the ethyl ester by means of ethyl chloroformate to N-ethoxycarbonyl-beta-aminopropionic acid ethyl ester, reaction thereof with acetic anhydride and fuming nitric acid to N-ethoxycarbonyl-beta-nitramino-propionic acid ethyl ester followed by ammonolysis and decomposition of the ammonium salt. Identical methods of synthesis, i.e. protection of the amino group by means of the ethoxy carbonyl group prior to nitration are employed in preparing the other examples of the invention.ALSO:Plant growth regulating compositions which include as an essential constituent one or more nitramino compounds of the formula NO2-NA-Y-COX wherein Y is a hydrocarbon group in which at least 2 C atoms separate the NA and COX groups, A is H, R, R.CO or RO.OC-, where R is up to C6 alkyl, X is -OH, -NH2 or -OR, or ammonium, alkali metal or alkaline earth metal salts of the said nitramine compounds, specific examples of which include beta-nitramino-propionic acid, N - ethoxycarbonyl-beta - nitramino - propionic acid, beta - nitramino - isobutyric acid, gamma - nitramino - n - butyric acid, gamma - nitramino - n - butyramide, N - ethoxycarbohyl - gamma - nitramino-n-butyric acid, delta-nitramino-valeric acid, N - ethoxycarbonyl - delta - nitramino - valeric acid, epsilon - nitramino - caproic acid, N - ethoxycarbonyl - epsilon - nitramino - caproic acid, 7 - nitramino - enanthic acid, 7-nitramino - enanthamide, N - ethoxyxarbonyl-nitramino - enanthic acid, 11 - nitramino-undecanoic acid, N-ethoxycarbonyl-11-nitramino-undecanoic acid.  Solid compositions may include inert diluents, e.g. chalk, talc, kiesel-guhr, bentonite, china clay, slate dust, gypsum, anhydrite or limestone, or also a fertilizer, e.g. a mixed N.P.K. fertilizer. Liquid compositions may include an organic liquid and may be diluted to give a dispersion in water.  The compositions may be applied to the medium in which the plants are grown, or to the seeds, seedlings or plants themselves.  Meteor peas, Koga II wheat, grass, tomato and wheat seedlings are the plants treated in the examples.