598-50-5Relevant articles and documents
Oxidation of 1,3,7-trimethylxanthine by hypochlorite ion
Kheidorov,Ershov,Chalyi,Titorovich
, p. 1358 - 1362 (2011)
The kinetics of the oxidative conversion of 1,3,7-trimethylxanthine upon treatment with hypochlorite ions (OCl-) in aqueous medium at 283-298 K and pH 8.2 was studied. The reaction order with respect to each component was determined and proved to be 1. It was established that the temperature dependence of the reaction rate follows the Arrhenius equation. The activation parameters of the reaction were measured: E a = 33.58 kJ/mol, ΔH ≠ = 31.12 kJ/mol, ΔS ≠ = -170.02 J/(K mol), ΔG ≠ = 81.45 kJ/mol. The stoichiometry of the reaction was studied, and the chemistry of the oxidative conversion of caffeine treated with OCl- is discussed.
Oxyhalogen-sulfur chemistry: Bromate oxidation of 1-methyl-2-thiourea in acidic medium
Jonnalagadda, Sreekantha B.,Chinake, Cordelia R.,Simoyi, Reuben H.
, p. 13521 - 13530 (1996)
The reaction between bromate and 1-methyl-2-thiourea, CH3NH(NH2)C=S (MTU), has been studied in acidic medium. The stoichiometry of the reaction in excess MTU has been established as 4BrO3- + 3CH3NH-(NH2)C=S + 3H2O → 4Br- + 3SO42- + 3CH3NH(NH2)C=O + 6H+ (A); and in excess bromate the stoichiometry is: 8BrO3- + 5CH3NH(NH2)C=S + H2O → 4Br2 + 5SO42- + 5CH3NH(NH2)C=O + 2H+ (B). Stoichiometry B includes the oxidation of MTU (stoichiometry A) and the oxidation of Br- by the excess BrO3-: BrO3- + 5Br- + 6H+ → 3Br2 + 3H2O. In excess BrO3- the reaction is characterized by an induction period followed by formation of Br2. The reaction between Br2 and MTU is very fast with a bimolecular lower limit rate constant of 2.0 × 106 M-1 s-1 such that the formation of Br2 is an indicator for the complete consumption of MTU. The reaction could be followed by monitoring the depletion of MTU through its absorbance at λ = 239 nm or the formation of Br2 at λ = 390 nm. The rate of reaction was deduced as -d[BrO3-]/dt = k0[BrO3-][MTU][H+]2 with k0 = 14.7 ± 1.2 M-3 s-1. A proposed 17-step reaction mechanism gives good agreement between experimental data and computer simulations.
Activation of 1-methyl-5-nitro-2-pyrimidinone by dearomatization using a secondary amine
Asahara, Haruyasu,Yasuoka, Azusa,Nishiwaki, Nagatoshi
, p. 253 - 259 (2019/04/27)
Electron-deficient 1-methyl-5-nitro-2-pyrimidinone is easily attacked by methanol or pyrrolidine to afford the corresponding adducts, respectively, by which aromaticity of nitropyrimidinone is lost. Indeed, the amine-adduct exhibited higher reactivity than that of original structure to facilitate the reaction with 1,3-dicarbonyl compound leading to diazabicyclic compound at room temperature. The amine-adduct also underwent the ring opening reaction to furnish nitroenamines with (Z)-configuration.
Noncanonical RNA Nucleosides as Molecular Fossils of an Early Earth—Generation by Prebiotic Methylations and Carbamoylations
Schneider, Christina,Becker, Sidney,Okamura, Hidenori,Crisp, Antony,Amatov, Tynchtyk,Stadlmeier, Michael,Carell, Thomas
supporting information, p. 5943 - 5946 (2018/04/30)
The RNA-world hypothesis assumes that life on Earth started with small RNA molecules that catalyzed their own formation. Vital to this hypothesis is the need for prebiotic routes towards RNA. Contemporary RNA, however, is not only constructed from the four canonical nucleobases (A, C, G, and U), it also contains many chemically modified (noncanonical) bases. A still open question is whether these noncanonical bases were formed in parallel to the canonical bases (chemical origin) or later, when life demanded higher functional diversity (biological origin). Here we show that isocyanates in combination with sodium nitrite establish methylating and carbamoylating reactivity compatible with early Earth conditions. These reactions lead to the formation of methylated and amino acid modified nucleosides that are still extant. Our data provide a plausible scenario for the chemical origin of certain noncanonical bases, which suggests that they are fossils of an early Earth.