Method for Small-Scale Production of Deuterochloroform

Tansukawat, Natha D; See, Alyaa E; Jiranuntarat, Sadudee; Corbin, Joshua R.; Schomaker, Jennifer M.

doi:10.1021/acs.joc.8b01018

Cited by 4 publications

(7 citation statements)

References 7 publications

(8 reference statements)

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“…Deuterated chloroform, one of the most used NMR solvents, is mainly produced by either haloform reaction or by treatment of chloral hydrate with sodium deuteroxide. − Recently, some catalytic methodologies were presented for the generation of CDCl 3 . For example, pyridine-based catalysts were investigated by Schomaker using hexachloro-2-propanone and deuterium oxide as an isotope source . Specifically, sodium 3-pyridine sulfonate (SPS) and poly(4-vinylpyridine) (PVPy) proved to be useful catalysts on a laboratory scale.…”

Section: Miscellaneous Transformations With Deuterium Incorporationmentioning

confidence: 99%

Recent Developments for the Deuterium and Tritium Labeling of Organic Molecules

et al. 2022

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Organic compounds labeled with hydrogen isotopes play a crucial role in numerous areas, from materials science to medicinal chemistry. Indeed, while the replacement of hydrogen by deuterium gives rise to improved absorption, distribution, metabolism, and excretion (ADME) properties in drugs and enables the preparation of internal standards for analytical mass spectrometry, the use of tritium-labeled compounds is a key technique all along drug discovery and development in the pharmaceutical industry. For these reasons, the interest in new methodologies for the isotopic enrichment of organic molecules and the extent of their applications are equally rising. In this regard, this Review intends to comprehensively discuss the new developments in this area over the last years (2017−2021). Notably, besides the fundamental hydrogen isotope exchange (HIE) reactions and the use of isotopically labeled analogues of common organic reagents, a plethora of reductive and dehalogenative deuteration techniques and other transformations with isotope incorporation are emerging and are now part of the labeling toolkit.

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Section: Miscellaneous Transformations With Deuterium Incorporationmentioning

confidence: 99%

Recent Developments for the Deuterium and Tritium Labeling of Organic Molecules

et al. 2022

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“…The search of efficient catalysts to make deuterated compounds has experienced an intensive growth in consequence of the fast-increasing commercial importance of deuterated compounds for a wide range of scientific applications, including nuclear magnetic resonance (NMR) solvents. [1,2] Deuterated compounds have been used to study reaction mechanism to enhance drugs pharmacokinetic, pharmaco-dynamic, and toxicological properties. [1] Deuterated solvents such as CDCl 3 are essential on the NMR daily routine, not only for the analyte solubilization purposes, but also for minimizing the interference of strong solvents signals in 1 H NMR as well as locking and shimming procedures.…”

Section: Introductionmentioning

confidence: 99%

“…[3,4] The preparation of deuterated-labelled molecules normally uses laborious procedures, employing high temperatures and pressure. [1,2,[5][6][7][8] CDCl 3 is normally manufactured through the reaction between deuterated acetone/ethanol and an alkali metal hypochlorite or by chloral hydrate treatment with NaOD. [9][10][11][12] Based on the synthesis of CDCl 3 by the reduction and decarboxylation of hexachloro-2-propanone, using D 2 O as deuterium source and pyridine as catalyst, Tansukawat et al, proposed an interesting experimental approach using sodium 3-pyridine sulfonate (SPS) and poly(4-vinylpyridine) (PVP) as catalyst.…”

Section: Introductionmentioning

confidence: 99%

“…These two compounds are immiscible with CDCl 3 , a useful feature for facile recycling. [2] However the reaction with PVP and SPS must be performed at higher temperatures, 85 C and 105 C, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, using 1 H or 2 H NMR, it is possible to monitor the reaction using only one compound and is necessary to use a more sophisticated method for the quantification of H/D exchange. [2] Figure 2 shows the expanded 13 C NMR spectra (76 to 79 ppm) without proton decoupling, obtained from the reaction media. Figure 2a is the spectrum before the reaction showing two peaks at 76.5 and 78 ppm due to the (Figure 2d).…”

Section: Introductionmentioning

confidence: 99%

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A straightforward catalytic approach to obtain deuterated chloroform at room temperature

Higuera-Padilla

Kock

Batista

et al. 2020

Magnetic Reson in Chemistry

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We report the catalytic activity for the complexes—cis‐[RuCl2(dppb)(bipy)] (A), and [η6‐(p‐cymene)Ru (dppb)Cl]PF6 (B), wherein dppb = 1,4‐bis(diphenylphosphine)butane, and bipy = 2,2′‐bipyridine—for the synthesis of CDCl3 from CHCl3 using D2O as deuterium source. H/D exchange reactions were performed using a chloroform/D2O, 1:2 molar ratio, vigorously stirred, at room temperature. One mole of KOH was dissolved in D2O fraction and catalytic complexes from 0.002 to 0.05 mmol were dissolved in chloroform. The H/D exchange reactions were monitored using 13C nuclear magnetic resonance sequences without proton decoupling. The reaction using 0.01 mmol of compound A reached approximately 55% of H/D conversion in 1 h. In the same time, the reactions with 0.002 mmol of compound A and without catalyst show approximately 28% and 3% H/D exchange, respectively. Without the catalysts, the H/D exchange was only 12.0% in 5 h. For compound B, 55% H/D conversion was observed in 1 h, only when 0.05 mmol was used, which is much higher catalyst concentration. After the isolation of the chloroform fraction and two more addition of D2O, it was possible to obtain 95.0% H/D exchange in approximately 3 h, using 0.01 mmol of the compound A. Therefore, compound A is an efficient catalyst for a rapid and straightforward synthesis of CDCl3 from CHCl3 at room temperature and using D2O as deuterium source.

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Cost and Energy Saving Process for the Laboratory-Scale Production of Chloroform-d

Zaharani

Johan

Khaligh

2022

Org. Process Res. Dev.

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Deuterochloroform (CDCl 3 ), a commonly deuterated solvent in research and undergraduate laboratories and widely employed for nuclear magnetic resonance analyses, could be prepared using a more sustainable and efficient catalytic process. The synthesis includes a one-pot reaction of hexachloroacetone with deuterium oxide (D 2 O) in the presence of poly(N-vinylimidazole). The catalyst is more sustainable, highly recyclable, highly chemical and thermally stable, soluble in D 2 O, and high in efficiency.

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Method for Small-Scale Production of Deuterochloroform

Cited by 4 publications

References 7 publications

Recent Developments for the Deuterium and Tritium Labeling of Organic Molecules

Recent Developments for the Deuterium and Tritium Labeling of Organic Molecules

A straightforward catalytic approach to obtain deuterated chloroform at room temperature

Cost and Energy Saving Process for the Laboratory-Scale Production of Chloroform-d

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