Patent GB-953897-A (GB)
Title: Substituted adenines and living plant materials preserved therewith
IPC: C07D473/40
Filed: 1961-03-29
Abstract: The invention comprises compounds of the general formula: <FORM:0953897/C2/1> and salts thereof, wherein R represents an aryl, aralkyl, aralkenyl or saturated heterocyclic radical, R1 and R11 each represent a hydrogen atom, an aliphatic radical of 1 to 8 carbon atoms the carbon chain of which may be interrupted by one or more hetero-atoms, or an aralkyl radical, at least one R1 representing an aliphatic radical as aforesaid, x and y are each 0 or 1 provided that x+y=1, the nitrogen atom of the NR1x group being linked to the carbon atom of the CR1 group by a double bond when x=0 and by a single bond when x=1, and the nitrogen atom of the NR1y group being linked by a double bond to the carbon atom of the CR1 group when y=0 and by a single bond when y=1.  The radical R may be unsubstituted or contain at least one non-hydrocarbon substituent such as a halogen atom or a hydroxy, lower alkoxy, carbonyl, lower alkoxycarbonyl, amino, nitro, cyano, mercapto, lower alkylthio or lower alkyl sulphonyl radical, the term "lower alkyl" denoting an alkyl group containing 1 to 8 carbon atoms.  The aliphatic radical which R1 and R11 may represent may be unsubstituted or may contain a substituent such as a halogen atom or a cyano, nitro, carboxy, sulphonyl, hydroxy, mercapto, alkoxy or alkylthio radical.  The compounds of the invention form salts with inorganic and organic acids and bases and with compounds which exist in the form of zwitterions. Various methods of preparation are described. Thus the 6-NRR11 group may be introduced by treating the corresponding 6-halopurine or 6-(alkylthio)-purine with the appropriate amine HNRR11.  Where R or R11 represent a mono-substituted methyl group they may be introduced by acylating the 6-amino group and reducing the resulting amido group. Derivatives containing a 6-NHR11 group may be converted to the corresponding 6-NRR11 derivatives by treatment with an alcohol ROH in the presence of a strong base.  Purine derivatives containing a 6-hydroxy, 6-chloro or 6-amino group, and optionally a substituent R1 in position 2, may be prepared by ring closure of the corresponding 4, 5-diaminopyrimidine by treatment with a carboxylic acid or its anhydride or ortho ester.  When the resulting product contains a 6-hydroxy group, this can be converted to a 6-chloro group by treatment with phosphonyl chloride, the 6-chloro group being subsequently converted to a 6-NRR11 group as described above. Alternatively, a 4-amino-5-arylazo-pyrimidine derivative containing a 6-hydroxy, 6-chloro or 6-amino group and optionally a substituent R1 in position 2 may be converted to the corresponding purine derivative by reduction in a formic acid medium, the resulting products be subsequently converted to the adenines of the invention as described above.  Compounds of the invention substituted at positions 7 or 9 may be prepared by treating on alkali metal salt of the adenine with a halide of the desired substituent. Examples are given.ALSO:The resistance of living plant materials such as fruits, vegetables and foliage to deterioration is increased by treating the plant materials before harvesting or at any time from harvesting to consumption with a compound of the general formula <FORM:0953897/A1-A3/1> or a salt thereof, wherein R represents an aryl, aralhyl, and aralhenyl or saturated heterocyclic radical, R1 and R11 each represent a hydrogen atom, an aralhyl radical or an aliphatic radical of 1 to 8 carbon atoms the carbon chain of which may be interrupted by one or more hetero-atoms, at least one R1 representing such an aliphatic radical, x and y are each 0 or 1 provided that x + y = 1, the nitrogen atom of the NR1x group being linked to the carbon atom of the CR1 group by a double bond when x = 0 and by a single bond when x = 1, and the nitrogen atom of the NR1 group being linked to the carbon atom of the CR1 group by a double bond when y = 0 and by a single bond when y = 1.  The radicals R, R1 and R11 may be unsubstituted or substituted, many suitable substituents being specified.  The compounds are preferably dissolved in a solvent prior to treatment of the plant material, and the solution may additionally contain solubilizing agents and emulsifiers.