Specific deuteration of phenols and aromatic ethers using boron trifluoride and deuterium oxide

Banijamali, Ali R.; Charalambous, Avgui; Schyf, Cornelis J. Van der; Makriyannis, Alexandros

doi:10.1002/jlcr.2580241210

Cited by 7 publications

(4 citation statements)

References 8 publications

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“…24 h). It had been reported that the aromatic protons on 3,4,5-trimethoxytoluene were easily exchanged with deuterium under acidic conditions . We also observed the complete disappearance of the aromatic protons on the 3,4,5-trimethoxyphenyl ring when the 1 H NMR spectrum of 1b was measured in CF 3 COOD.…”

Section: Resultssupporting

confidence: 69%

Air Oxidation of 2-Aryl-1-tetralones in Basic, Neutral, and Acidic Media: An Unprecedented Oxidative Aryl Migration to 2-Aryloxy-1-naphthols under Acidic Condition

et al. 1999

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Section: Resultssupporting

confidence: 69%

Air Oxidation of 2-Aryl-1-tetralones in Basic, Neutral, and Acidic Media: An Unprecedented Oxidative Aryl Migration to 2-Aryloxy-1-naphthols under Acidic Condition

et al. 1999

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“…Investigation of the OE in 1,3-bisdiphenylene-2-phenylallyl (BDPA) radicals required the development of synthetic routes that would enable selective 2 H labeling of orthogonal positions on the fluorene moieties, i.e., 1, 3, 6, 8 and 2, 4, 5, 7. Conventionally, the deuteration of aromatic compounds requires harsh reaction conditions, costly catalysts, and/or extended reaction times as aromatic hydrogens are not labile and often lead to poor deuterium incorporation. − Efficient direct H/D exchange at alternating positions on arenes is typically achieved by using activating groups, specifically ortho/para directors such as phenols and anilines. − …”

Section: Experimental Methodsmentioning

confidence: 99%

Overhauser Dynamic Nuclear Polarization with Selectively Deuterated BDPA Radicals

Delage-Laurin

Palani²,

Golota³

et al. 2021

J. Am. Chem. Soc.

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The Overhauser effect (OE), commonly observed in NMR spectra of liquids and conducting solids, was recently discovered in insulating solids doped with the radical 1,3-bisdiphenylene-2-phenylallyl (BDPA). However, the mechanism of polarization transfer in OE-DNP in insulators is yet to be established, but hyperfine coupling of the radical to protons in BDPA has been proposed. In this paper we present a study that addresses the role of hyperfine couplings via the EPR and DNP measurements on some selectively deuterated BDPA radicals synthesized for this purpose. Newly developed synthetic routes enable selective deuteration at orthogonal positions or perdeuteration of the fluorene moieties with 2 H incorporation of >93%. The fluorene moieties were subsequently used to synthesize two octadeuterated BDPA radicals, 1,3-[α,γ-d 8 ]-BDPA and 1,3-[β,δ-d 8 ]-BDPA, and a BDPA radical with perdeuterated fluorene moieties, 1,3-[α,β,γ,δ-d 16 ]-BDPA. In contrast to the strong positive OE enhancement observed in degassed samples of fully protonated h 21 -BDPA (ε ∼ +70), perdeuteration of the fluorenes results in a negative enhancement (ε ∼ −13), while selective deuteration of αand γ-positions (a iso ∼ 5.4 MHz) in BDPA results in a weak negative OE enhancement (ε ∼ −1). Furthermore, deuteration of βand δ-positions (a iso ∼ 1.2 MHz) results in a positive OE enhancement (ε ∼ +36), albeit with a reduced magnitude relative to that observed in fully protonated BDPA. Our results clearly show the role of the hyperfine coupled α and γ 1 H spins in the BDPA radical in determining the dominance of the zero and double-quantum cross-relaxation pathways and the polarization-transfer mechanism to the bulk matrix.

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“…[2,4- 2 H 2 ]Δ 8 -THC and [2,4- 2 H 2 ]Me-Δ 8 -THC (Figure 1) were synthesized in our laboratory. 21 All 31 P- and 2 H-NMR samples were prepared by the same procedure as described briefly below. [2,4- 2 H 2 ]Δ 8 -THC or [2,4- 2 H 2 ]Me-Δ 8 -THC, DMPC and DHPC were mixed in chloroform (99% pure, Aldrich, Milwaukee, WI), which was then evaporated using an N 2 stream.…”

Section: Methodsmentioning

confidence: 99%

“…1,2-Dimyristoyl- sn -glycero-3-phosphocholine (DMPC) and 1,2-dihexanoyl- sn -glycero-3-phosphocholine (DHPC) were purchased from Avanti Polar Lipids (Alabaster, AL). [2,4- 2 H 2 ]Δ 8 -THC and [2,4- 2 H 2 ]Me-Δ 8 -THC (Figure ) were synthesized in our laboratory . All 13 P and 2 H NMR samples were prepared by the same procedure as described briefly below.…”

Section: Methodsmentioning

confidence: 99%

Magnetically Aligned Bicelles To Study the Orientation of Lipophilic Ligands in Membrane Bilayers

et al. 2008

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Magnetically aligned bicelles were used as a model membrane to study the orientation and dynamic properties of two cannabinoids (Δ8-THC and Me-Δ8-THC) using 31P- and 2H-NMR. The uniform alignment of the bicelles allowed us to obtain well resolved deuterium spectra from a solution NMR spectrometer. The preferred orientations of Δ8-THC and Me-Δ8-THC were calculated based on the measurements of individual quadrupolar splittings. Our results agree with previous experiments using multilamellar membranes as well as with molecular dynamics simulation data described here. In conjunction with our earlier report using small and fast tumbling bicelles, the present work of well aligned bicelles shows that bicelle preparations can provide either pseudo-isotropic or anisotropic NMR spectra to study the conformation, orientation and dynamic properties of ligands in membrane bilayers. Such data are of critical value for understanding the interactions of lipophilic drug molecules with membrane proteins.

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Specific deuteration of phenols and aromatic ethers using boron trifluoride and deuterium oxide

Cited by 7 publications

References 8 publications

Air Oxidation of 2-Aryl-1-tetralones in Basic, Neutral, and Acidic Media: An Unprecedented Oxidative Aryl Migration to 2-Aryloxy-1-naphthols under Acidic Condition

Air Oxidation of 2-Aryl-1-tetralones in Basic, Neutral, and Acidic Media: An Unprecedented Oxidative Aryl Migration to 2-Aryloxy-1-naphthols under Acidic Condition

Overhauser Dynamic Nuclear Polarization with Selectively Deuterated BDPA Radicals

Magnetically Aligned Bicelles To Study the Orientation of Lipophilic Ligands in Membrane Bilayers

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