42983-07-3

Upstream product

• 124-38-9 carbon dioxide 
• 918-20-7 tert-butyl chloride-d9 
• 75160-24-6 1,1,1,4,4,4-hexadeuterio-2,3-bis(trideuteriomethyl)-2,3-butanediol 
• 75160-22-4 3,3-dimethyl-2-butanone-d₁₂ 
• 75-98-9 Trimethylacetic acid 

Downstream Products

• 1423119-98-5 N-(3-(5-(2-aminopyrimidin-4-yl)-2-tert-butylthiazol-4-yl)-2-fluorophenyl)-2,6-difluorobenzenesulfonamide-d₉ 
• 1423120-07-3 N-(3-(2-tert-butyl-5-(2-chloropyrimidin-4-yl)thiazol-4-yl)-2-fluorophenyl)-2,6-difluorobenzenesulfonamide-d₉ 
• 102307-70-0 C₁₂H₇⁽²⁾H₁₁O₃S 
• 5152-54-5 neopentane-d12 

Relevant academic research and scientific papers

Effect of ligand deuteration on the decay of Eu3+(5D0) in tris(2,2,6,6-tetramethyl-3,5-heptanedionato)europium(III)

Contributions to the first-order rate constant for the decay of the Eu3+(5D0) state of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)europium(III), Eu(thd)3, from radiative and multiphonon mechanisms are evaluated independently by measuring the luminescence decay rates in undeuterated Eu(thd)3, fully deuterated Eu(thd-d19)3, and α-deuterated Eu(thd-d1)3, which is also designated Eu(α-D,thd)3. In the latter case, deuterium substitution is at the α-carbon, between the carbonyl groups of the β-diketonate ligand. These measurements yield a multiphonon contribution of 332 s-1, of which 157 s-1 is attributed to relaxation via the Cα-H stretching vibration and 175 s-1 to relaxation via the C-H stretching modes of the tert-butyl groups. By use of the measured total Eu3+(5D0) relaxation rate constant and the multiphonon rate constants given above, the Eu3+(5D0) radiative relaxation rate constant is inferred to be 1930 s-1. It is suggested that this unusually high radiative rate constant may be due to an increased allowedness in the 5D0 → 7FJ transitions due to contributions to the predominantly 4f crystal-field wave functions from a low-lying ligand-to-metal charge-transfer state.

Late-Stage β-C(sp3)-H Deuteration of Carboxylic Acids

Carboxylic acids are highly abundant in bioactive molecules. In this study, we describe the late-stage β-C(sp3)-H deuteration of free carboxylic acids. On the basis of the finding that C-H activation with our catalysts is reversible, the de-deuteration process was first optimized. The resulting method uses ethylenediamine-based ligands and can be used to achieve the desired deuteration when using a deuterated solvent. The reported method allows for the functionalization of a wide range of free carboxylic acids with diverse substitution patterns, as well as the late-stage deuteration of bioactive molecules and related frameworks and enables the functionalization of nonactivated methylene β-C(sp3)-H bonds for the first time.

Deuterated Benzene Sulfonamide Thiazole Compounds

Deuterated forms of N-{3-[5-(2-Amino-4-pyrimidinyl)-2-(1,1-dimethylethyl)-1,3-thiazol-4-yl]-2-fluorophenyl}-2,6-difluorobenzenesulfonamide and pharmaceutical compositions containing the same.

Secondary deuterium isotope effects on the acidity of carboxylic acids and phenols

Secondary deuterium isotope effects (IEs) on acidities have been accurately measured by an NMR titration method applicable to a mixture of isotopologues. Deuteration definitely decreases the acidity of carboxylic acids and phenols, by up to 0.031 in the ΔpK per D. For aliphatic acids, the IEs decrease as the site of deuteration becomes more distant from the OH, as expected, but a surprising result is that IEs in both phenol and benzoic acid do not decrease as the site of deuteration moves from ortho to meta to para. The experimental data are supported by ab initio computations, which, however, substantially overestimate the IEs. The discrepancy does not seem to be due to solvation. The IEs originate in isotope-sensitive vibrations whose frequencies and zero-point energies are lowered upon deprotonation. In the simplest case, formate, the key vibration can be recognized as the C-H stretch, which is weakened by delocalization of the oxygen lone pairs. For the aromatic acids, delocalization cannot account for the near constancy of IEs from ortho, meta, and para deuteriums, but the observed IEs are consistent with calculated vibrational frequencies and electron densities. Moreover, the ability of the frequency analysis to account for the IEs is evidence against an inductive origin.

Kinetic Isotope Effects for Hydrogen Abstraction from a Series of Cycloalkanes and Branched Alkanes by Hydrogen Atoms in the Gaseous Phase

Hydrogen atoms produced in the radiolysis of water vapor were used to determine the kinetic isotope effects for the reactions H(.) + RH(RD) -> H2(RD) + R(.) H(KD)>, where RH is a perprotiated alkane and RD is the corresponding perdeuterated alkane.The alkanes studied include a homologous series of cycloalkanes, cyclopentane through cyclododecane, and isobutane, 2,3-dimethylbutane, 2,3,4-trimethylpentane, and neopentane.The results were expressed in terms of the Arrhenius-type equation kH/kD = AH/AD expD-EH)(kJ mol-1)/RT>, over the temperature range of 363-463 K.The values for the ratio AH/AD range from 0.32 to 0.75, and the activation energy differences ED-EH vary from 6.8 to 11.0 kJ/mol, depending on the molecular structures of the reactants.The variation in the values of ED-EH was correlated with the bond dissociation energies of the C-H bond being broken.Theoretical calculations based on transition-state theory combined with the London-Eyring-Polanyi-Sato potetial energy surfaces could reproduce the major features of the experimental results when tunnel effects were taken into consideration.

RAMAN SPECTRA OF 4-CYANO-4 prime -PENTYLBIPHENYL AND 4-CYANO-4 prime -PENTYL-d11-BIPHENYL.

The Raman spectra of the solid, nematic, and isotropic liquid phases of 4-cyano-4 prime -pentylbiphenyl (5CB) and 4-cyano-4 prime -pentyl-d//1//1-biphenyl (5CB-d//1//1) are reported together with the method of synthesis of 5CB-d//1//1. A comparison of the spectra of the isotropic liquid phases of 5CB and 5CB-d//1//1 has led to a partial assignment of these spectra. For each compound, the spectra of the fluid phases resembled each other, but differed from the corresponding spectrum of the solid phase. In particular, the cyano stretching vibration occurred as a doublet in the spectra of the solid phases of 5CB and 5CB-d//1//1, but as a single band in spectra of the fluid phases. The nematic to isotropic liquid transition temperature of 5CB-d//1//1 was 1 degree lower than that of 5CB.