865-50-9Relevant articles and documents
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.
Selective Catalytic Frustrated Lewis Pair Hydrogenation of CO2 in the Presence of Silylhalides
Grimme, Stefan,Jupp, Andrew R.,Qu, Zheng-Wang,Stephan, Douglas W.,Wang, Tongtong,Xu, Maotong
supporting information, p. 25771 - 25775 (2021/11/09)
The frustrated Lewis pair (FLP) derived from 2,6-lutidine and B(C6F5)3 is shown to mediate the catalytic hydrogenation of CO2 using H2 as the reductant and a silylhalide as an oxophile. The nature of the products can be controlled with the judicious selection of the silylhalide and the solvent. In this fashion, this metal-free catalysis affords avenues to the selective formation of the disilylacetal (R3SiOCH2OSiR3), methoxysilane (R3SiOCH3), methyliodide (CH3I) and methane (CH4) under mild conditions. DFT studies illuminate the complexities of the mechanism and account for the observed selectivity.
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
Nickel and Nucleophilic Cobalt-Catalyzed Trideuteriomethylation of Aryl Halides Using Trideuteriomethyl p-Toluenesulfonate
Komeyama, Kimihiro,Yamahata, Yuta,Osaka, Itaru
supporting information, p. 4375 - 4378 (2018/07/29)
Herein, a novel approach for the trideuteriomethylation of aryl halides using nickel and nucleophilic cobalt catalysts and the readily available trideuteriomethyl p-toluenesulfonate (CD3OTs) is described. This method provides access to a wide r
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.
Synthesis of stable isotope labeled D9-Mabuterol, D9-Bambuterol, and D9-Cimbuterol
Tu, Yahui,Zhong, Jiaqi,Wang, Haoran,Pan, Jie,Xu, Zhongjie,Yang, Weicheng,Luo, Yong
, p. 546 - 551 (2016/11/23)
Three stable and simple synthetic routes of labeled D9-Mabuterol, D9-Bambuterol, and D9-Cimbuterol were described with 98.5%, 99.7%, and 98.4% isotopic abundance and good purity. These structures and isotope-abundance were confirmed according to 1H NMR and liquid chromatography-tandem mass spectrometry.
Isotope-labeled methyl ketofuran, intermediate and method for preparing same
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Paragraph 0105; 0106; 0107, (2016/10/09)
The invention discloses isotopically labeled methyl furanone, an intermediate and a preparation method of isotopically labeled methyl furanone. The invention provides isotopically labeled methyl furanone 6. The invention further provides a preparation method of isotopically labeled methyl furanone 6, and the preparation method comprises the following steps: performing removal of a hydroxy protecting group and isomerization reaction on a compound 20 in the presence of an acid. The method provided by the invention comprises short reaction steps, labeling loci are stable, are labeled on a common D ring of a strigolactone type compound family and are successfully butted with ABC rings of strigolactone type compounds to obtain a variety of isotopically labeled strigolactone type compounds with different isotopic abundances which are more than 99% respectively, and the isotopically labeled methyl furanone is applicable to wide substances, is used as an internal source standard matter for GC-MS and LC-MS/MS analysis and has high detection sensitivity and good accuracy, thereby having broad market application prospects.
Synthesis of stable isotopically labelled 3-methylfuran-2(5H)-one and the corresponding strigolactones
Cheng, Yun,Ding, Wen-Hui,Long, Qin,Zhao, Min,Yang, Jun,Li, Xiao-Qiang
, p. 355 - 360 (2015/08/11)
Conventional synthetic procedures of strigolactones (SLs) involve the independent synthesis of ring ABC and ring D, followed by a coupling of the two fragments. Here we prepared three kinds of stable, isotopically labelled D-ring analogues productively using a facile protocol. Then, a coupling of the D-rings to ring ABC produced three isotope-labelled SL derivatives. Moreover, (+)-D3-2′-epi-1A and (-)-ent-D3-2′-epi-1A with high enantiomeric purity were obtained via chiral resolution. We developed a convenient method to synthesize three kinds of stable, isotopically labelled D-ring analogues for subsequent production of isotope-labelled strigolactones. With this simple and universal method, three labelled 5-deoxystrigols (D3-1, 13C-1 and D313C-1) were synthesized.
CYTOMEGALOVIRUS INHIBITOR COMPOUNDS
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Page/Page column 32, (2013/10/22)
Compounds of Formula (I) wherein n, A, R1, R2, R3 and R5 are defined herein, are useful for the treatment of cytomegalovirus disease and/or infection.
Hydrodehalogenation of 1,1-dibromocyclopropanes by Grignard reagents promoted by titanium compounds
Dulayymi, Juma'a R. Al,Baird, Mark S.,Bolesov, Ivan G.,Nizovtsev, Alexey V.,Tverezovsky, Viacheslav V.
, p. 1603 - 1618 (2007/10/03)
1,1-Dibromocyclopropanes are converted into the corresponding monobromocyclopropanes (as mixtures of stereoisomers where appropriate) by reaction with 1.0-1.3 mol equiv. of ethylmagnesium bromide and 2-10 mol% titanium isopropoxide for 90%). With ethylmagnesium bromide, the reaction occurs very slowly in the absence of catalyst; with methylmagnesium bromide, the reaction does occur in the absence of catalyst, but is only slightly promoted in the presence of titanium isopropoxide. Reactions with a number of other Grignard reagents are also discussed. In the case of phenethylmagnesium bromide, the major product containing the phenethyl-group is ethylbenzene, together with small amounts of styrene and ethyl 4-phenyl-2-butyl ether, a product of trapping of the solvent, ether. In other cases, relatively large amounts of a diether, formally derived by hydrogen ion adjacent to the ether oxygen followed by dimerisation, are isolated. No products were identified incorporating the cyclopropane and either the Grignard alkyl group or the solvent. Labelling studies indicate that the hydrogen introduced into the cyclopropane is not derived from either the α- or β-positions of the Grignard reagent. When the reduction is carried out with phenethylmagnesium bromide in d8-tetrahydrofuran both monobromides contain deuterium.
