Reactions of diazines with nucleophiles--IV. The reactivity of 5-bromo-1,3,6-trimethyluracil with thiolate ions--substitution versus X-philic versus single electron transfer reactions.
Reaction of 5-Bromo-1,3,6-trimethyluracil (1) with alkylthiolate (propane-1-, toluene-alpha-, allyl-, etc.) ions under phase transfer catalytic conditions follows nucleophilic substitution and X-philic (Br and S) elimination to give 5-alkylthio-1,3,6-trimethyluracils, 6-alkylthiomethyl-1,3-dimethyluracils and 1,3,6-trimethyluracil. Reaction of compound 1 with heteroarylthiolate ions (pyridine-2-, quinazoline-4-, uracil-2- and 4,6-dimethylpyrimidine-2-thiolate) gives only nucleophilic substitution products. However, arylthiolate (phenyl-, 4-chlorophenyl-, 2-aminophenyl-) ions follow a single electron transfer (SET) mechanism to give 5-arylthio-6-arylthiomethyl-1,3-dimethyluracils along with normal substitution products. 1,3,6-Trimethyluracil does not react with alkyl- or heteroaryl-thiolate ions but reacts with arylthiolate ions (SET) providing mainly 5-arylthio-1,3,6-trimethyluracils.
Kumar
S
S
Department of Chemistry, Guru Nanak Dev University, India.
Chimni
S S
SS
Cannoo
D
D
Arora
J S
JS
D000478:Alkylation; D001976:Bromouracil / Q000031:analogs & derivatives* / Q000737:chemistry*; D002384:Catalysis; D004579:Electron Transport; D007477:Ions; D009153:Mutagens / Q000737:chemistry*; D013329:Structure-Activity Relationship; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D007477:Ions; D009153:Mutagens; D013438:Sulfhydryl Compounds; C096829:5-bromo-1,3,6-trimethyluracil; D001976:Bromouracil