865-50-9Relevant articles and documents
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Nolin
, p. 1 (1954)
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Method for efficiently preparing deuterated iodomethane and application of deuterated iodomethane
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Paragraph 0020; 0022; 0024; 0026; 0028; 0030; 0032, (2021/08/07)
The invention discloses a method for efficiently preparing deuterated iodomethane and an application of the deuterated iodomethane; according to the method, deuterated methanol and iodine elementary substance are used as reaction raw materials, in a hydrogen atmosphere, a transition metal catalyst and a ligand are added, and the deuterated iodomethane is generated in situ at the temperature of 0 DEG C-120 DEG C. The application is the application of deuterated iodomethane as a methylation reagent in preparation of S-(methyl-D3)homocysteine, and mainly comprises the steps: carrying out methylation reaction on a compound a, namely (t-butyloxycarboryl)-L-homocysteine methyl ester and deuterated iodomethane in an organic solvent under the action of a base catalyst to obtain a product b; and performing deprotection on the product b to obtain a target product c, namely S-(methyl-D3)homocysteine. Anhydrous hydrogen iodide is prepared through catalysis of a transition metal catalyst, the anhydrous hydrogen iodide and deuterated methanol directly react through a one-pot method to obtain deuterated iodomethane with the high yield (88%), and the deuterated iodomethane serves as a deuterated methyl reagent to prepare S-(methyl-D3)homocysteine with the high deuterium doping rate and the yield (75%). The method is simple and easy to operate, and reaction conditions are mild.
Trialkylammonium salt degradation: Implications for methylation and cross-coupling
Assante, Michele,Baillie, Sharon E.,Juba, Vanessa,Leach, Andrew G.,McKinney, David,Reid, Marc,Washington, Jack B.,Yan, Chunhui
, p. 6949 - 6963 (2021/06/02)
Trialkylammonium (most notably N,N,N-trimethylanilinium) salts are known to display dual reactivity through both the aryl group and the N-methyl groups. These salts have thus been widely applied in cross-coupling, aryl etherification, fluorine radiolabelling, phase-transfer catalysis, supramolecular recognition, polymer design, and (more recently) methylation. However, their application as electrophilic methylating reagents remains somewhat underexplored, and an understanding of their arylation versus methylation reactivities is lacking. This study presents a mechanistic degradation analysis of N,N,N-trimethylanilinium salts and highlights the implications for synthetic applications of this important class of salts. Kinetic degradation studies, in both solid and solution phases, have delivered insights into the physical and chemical parameters affecting anilinium salt stability. 1H NMR kinetic analysis of salt degradation has evidenced thermal degradation to methyl iodide and the parent aniline, consistent with a closed-shell SN2-centred degradative pathway, and methyl iodide being the key reactive species in applied methylation procedures. Furthermore, the effect of halide and non-nucleophilic counterions on salt degradation has been investigated, along with deuterium isotope and solvent effects. New mechanistic insights have enabled the investigation of the use of trimethylanilinium salts in O-methylation and in improved cross-coupling strategies. Finally, detailed computational studies have helped highlight limitations in the current state-of-the-art of solvation modelling of reaction in which the bulk medium undergoes experimentally observable changes over the reaction timecourse. This journal is
A stable isotope labeled β receptor agonist synthetic method of compound
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Paragraph 0064-0065; 0075; 0076; 0085; 0086; 0090; 0091, (2017/04/29)
The invention relates to a synthesis method of a stable isotope-labeled beta receptor agonist type compound. The synthesis method comprises the following steps: (1) by taking stable isotope-labeled methanol as a raw material, reacting with acetone or stable isotope-labeled acetone, and ammonifying to obtain stable isotope-labeled tert-butylamine; and (2) by taking a bromoketone type compound as a precursor of the beta receptor agonist type compound, reacting with stable isotope-labeled tert-butylamine to prepare the stable isotope-labeled beta receptor agonist type compound. Compared with the prior art, the method for preparing the stable isotope-labeled beta receptor agonist, provided by the invention, is simple, safe and reliable, the chemical purity of the product after separation and purification is above 99.0%, the isotopic abundance is above 98.0% atom, and the product can fully meet the requirements of residual detection in the field of food safety.
