Patent GB-888239-A (GB)
Title: New 1-mono- and di-substituted amino-1-desoxy-ketoses and process for preparing same
IPC: C07H15/18
Filed: 1960-01-11
Abstract: The invention comprises (1) 1-N-R1R2-amino-1-desoxy-ketones in which R1 is a substituent which is capable of being split off by hydrogenolysis and R2 is a substituent which is not capable of being split off by hydrogenolysis, and salts and O-acyl derivatives thereof; (2) 1-N-R-amino-1-desoxy-ketones in which R is an aliphatic, an arylethyl or a heterocyclic residue, and salts and N- and/or O-acyl derivatives thereof; and (3) the preparation of 1-N-R1R2-amino-1-desoxy-ketones in which R1 is hydrogen or a substituent which is capable of being split off by hydrogenolysis and R2 is a substituent which is not capable of being split off by hydrogenolysis and salts and acyl derivatives thereof, wherein an aldose is subjected to the Amadori rearrangement with a compound of the formula R1R2NH (R1 not being hydrogen) and, if desired, the N-tertiary amino-1-desoxy-ketone so obtained is subjected to hydrogenolysis to convert the group R1 into hydrogen.  R1 may be an arylmethyl or carbobenzoxy group in which the aryl radicals may be substituted by alkyl, alkoxy, nitro or amino groups or by chlorine or bromine.  R2 may be a saturated or unsaturated aliphatic radical optionally substituted by halogen atoms or by carboxyl, carboxylic acid amide, nitrile, hydroxy, alkoxy or nitro groups; an aryl radical optionally substituted by halogen atoms or by alkyl, alkoxy or nitro groups; an aralkyl radical not capable of being split off by hydrogenolysis, e.g. phenylethyl; or a heterocyclic radical, e.g. pyridyl or piperidyl.  Subsequent acylation of hydroxyl and amino groups may be carried out with C1-7 fatty acids or with aromatic carboxylic or sulphonic acids.  Acylated groups may also be de-acylated.  Acid addition salts may be formed with hydrochloric, sulphuric, nitric, phosphoric, perchloric, acetic, propionic, oxalic, malic, citric, tartaric, methane sulphonic, hydroxyethane sulphonic, amino-carboxylic, salicylic, benzoic and benzene sulphonic acids. The examples describe the preparation of 1-(N-methyl-, N-ethyl- and (N - b  - cyanoethyl - benzylamino) - 1 - desoxy D - fructose, 1 - methylamino - 1 - desoxy - D - fructose, 1 - ethylamino - 1 - desoxy - D - fructose and 1-butylamino-1-desoxy-D-fructose.ALSO:A pharmaceutical preparation having coronary dilating activity comprises a 1-N-R1R2-amino-1-desoxy-ketose, wherein R1 is hydrogen or a substituent which is capable of being split off by hydrogenolysis (e.g. arylmethyl or carbobenzoxy groups in which the aryl radicals may be substituted by alkyl, alkoxy, nitro amino, bromine or chlorine), and R2 is a substituent which is not capable of being split-off by hydrogenolysis (e.g. aliphatic, aromatic or heterocyclic radicals with optional halogen, amide, carboxyl, cyano, hydroxy, alkoxy or nitro substituents), or acid addition salts or O- and/or N-carboxylic or sulphonic acid acyl derivatives thereof, together with a pharmaceutical organic or inorganic, solid or liquid, carrier suitable for enteral, parenteral or topical administration.  The preparation may be made up in the form of tablets, dragees or solutions and may also contain preserving and stabilizing agents, salts for regulating the osmotic pressure or buffers.