Synthesis of [<sup>2</sup>H]‐diethoxymethane as a convenient source of a [<sup>2</sup>H]‐methylene unit

Hanley, John A.; Forsyth, David

doi:10.1002/jlcr.2580280307

Cited by 4 publications

(4 citation statements)

References 9 publications

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“…Simple distillation gave a crude distillate that was redistilled using a short Vigreux column to give 4.95 g (59%) of the product with a boiling point of 88 °C. NMR spectra of the samples were in accord with the literature …”

Section: Methodsmentioning

confidence: 96%

“…[2H]-Diethoxymethane was prepared using a slight modification of a literature procedure . A two-necked round-bottom flask equipped with a condenser and an addition funnel was charged with 5.00 g (119.0 mmol) lithium aluminum deuteride (Fluka, 99.5 atom% D) suspended in 150 mL dry ether and kept under an inert atmosphere (N 2 ).…”

Section: Methodsmentioning

confidence: 99%

“…[2H]-Diethoxymethane was prepared using a slight modification of a literature procedure. 51 A two-necked round-bottom flask equipped with a condenser and an addition funnel was charged with 5.00 g (119.0 mmol) lithium aluminum deuteride (Fluka, 99.5 atom% D) suspended in 150 mL dry ether and kept under an inert atmosphere (N 2 ). The mass of 11.90 g (80.3 mmol) triethylorthoformate dissolved in 12 mL dry ether was added dropwise to the magnetically stirred suspension over ∼5 min at room temperature.…”

Section: Chemicals and Synthesismentioning

confidence: 99%

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UV and IR Absorption Cross-sections of HCHO, HCDO, and DCDO

et al. 2007

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UV (240-370 nm) and IR (3200-1500 cm(-1)) absorption cross-sections of HCHO, HCDO, and DCDO in a bath gas of N(2) at atmospheric pressure and 296 K are reported from simultaneous measurements in the two spectral regions. Cross-sections were placed on an absolute scale through quantitative conversion of formaldehyde to CO and HCOOH by titration with Br atoms, also monitored by FTIR. The integrated UV absorption cross-sections of HCHO, HCDO, and DCDO are equal to within the experimental uncertainty.

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Section: Methodsmentioning

confidence: 96%

Section: Methodsmentioning

confidence: 99%

Section: Chemicals and Synthesismentioning

confidence: 99%

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UV and IR Absorption Cross-sections of HCHO, HCDO, and DCDO

et al. 2007

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“…5,5-Dimethyl-[ 2 H 1 ]-1,3-dithiane (2). [ 2 H]-diethoxymethane was synthesized by known proceedures, 37 as was the 2,2-dimethyl-1,3dithiol. 38 In a 5 mL flask equipped with a micro stirrer and a condenser, the dithiol (160 mg, 1.17 mmol) was combined with [ 2 H]diethoxymethane (150 mg, 1.43 mmol), boron trifluoride etherate (0.18 mL, 1.4 mmol), acetic acid (0.35 mL, 6.1 mmol), and chloroform (3 mL).…”

Section: ■ Conclusionmentioning

confidence: 99%

Probing Hyperconjugation Experimentally with the Conformational Deuterium Isotope Effect

2012

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Hyperconjugation underlies many chemical phenomena of fundamental and practical importance. Owing to a great deal of interest in the anomeric effect, anomeric-like hyperconjugative effects have been thoroughly investigated in oxygen-containing systems. However, such interactions in the second-and third-row chalcogens are less well-understood and have generated some controversy. Here, we show that the conformational deuterium isotope effect, in combination with Saunders' isotopic perturbation method, permits sensitive and direct experimental probing of the conformational equilibria in dioxane, dithiane, and diselenane analogues by variabletemperature, dynamic NMR spectroscopy. We find that the magnitude of the conformational deuterium isotope effect is 252.1, 28.3, and 7.1 J/mol (±10%) for the oxygen, sulfur, and selenium analogues, respectively. These results reveal the periodic trend for hyperconjugation in the chalcogens, which reflect a decreasing n x →σ C−H(D) interaction throughout the period, as supported by IR spectroscopy and in agreement with DFT calculations and a natural bond order analysis.

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Diels‐Alder Reactions of Imino Dienophiles

et al. 2005

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In comparison to all carbon [4 + 2] cycloadditions, Diesl‐Alder reactions are still in their infancy. The last four decades, however, have seen intensive research in this area. The results if that synthetic organic chemists now have a powerful tool at their disposal for rapid construction of highly functionalized six‐membered nitrogen heterocycles, often in a regio‐, diastereo‐, and enantioselective manner. This chapter encompasses the topic of imine[4 + 2] cycloaddition reactions, of which there are a number of variants. This chapter is limited exclusively to imine and iminium ion dienophiles that undergo inter‐ and intramolecular Diels‐Alder reactions with acylic and cyclic all‐carbon 1,3‐dienes affording 1,2,5,6‐tetrahydropyridines as the initial cycloadducts. In situations where there is a mechanistic ambiguity, such as reactions that proceed via Mannich reactions, these mechanisms are included since it is difficult to know where to draw the line on coverage. A comprehensive discussion of each structural type of imino dienophiles covers the literature up to the middle of 2004. A general overview of mechanistic, regiochemical, and sterochemical considerations is also presented. Specific relevant exo/endo issues, remote diasteroselectivity and the use of chiral auxiliaries are discussed under each separate imine type. Separate sections have also been included that describe intramolecular reactions, as well as more recent advances in enantioselective cycloadditions involving chiral catalysts.

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Synthesis of [²H]‐diethoxymethane as a convenient source of a [²H]‐methylene unit

Abstract: SUMMARY

Cited by 4 publications

References 9 publications

UV and IR Absorption Cross-sections of HCHO, HCDO, and DCDO

UV and IR Absorption Cross-sections of HCHO, HCDO, and DCDO

Probing Hyperconjugation Experimentally with the Conformational Deuterium Isotope Effect

Diels‐Alder Reactions of Imino Dienophiles

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Synthesis of [2H]‐diethoxymethane as a convenient source of a [2H]‐methylene unit

Abstract: SUMMARY

Cited by 4 publications

References 9 publications

UV and IR Absorption Cross-sections of HCHO, HCDO, and DCDO

UV and IR Absorption Cross-sections of HCHO, HCDO, and DCDO

Probing Hyperconjugation Experimentally with the Conformational Deuterium Isotope Effect

Diels‐Alder Reactions of Imino Dienophiles

Contact Info

Product

Resources

About

Synthesis of [²H]‐diethoxymethane as a convenient source of a [²H]‐methylene unit