ORGANIC DEUTERIUM COMPOUNDS: XV. SYNTHESIS OF SOME DEUTERATED ALKANES

1956 ◽  
Vol 34 (3) ◽  
pp. 354-358 ◽  
Author(s):  
Mary Elaine Leblanc ◽  
A. T. Morse ◽  
L. C. Leitch
Keyword(s):  
Carbon Tetrachloride ◽  
Methyl Iodide ◽  
Zinc Dust ◽  
Deuterium Oxide ◽  
Alkyl Halides ◽  
Ethyl Iodide ◽  
Improved Method

An improved method of preparing deuterated alkanes from the halides has been developed. Dehalogenation of ethyl iodide, 1,1-dibromoethane, and 1,1,1-trichloroethane with zinc dust in deuterium oxide – dioxane solutions, or even with deuterium oxide alone, gave excellent yields of ethane-d1, ethane-1,1-d2, and ethane-1,1,1-d3. Methane-d1, -d2, -d3, and -d4 were prepared similarly from methyl iodide, dibromomethane, chloroform, and carbon tetrachloride respectively. The isotopic purity of the products was over 90 mol.%. The reaction is also applicable to higher alkyl halides.

Infrared spectra of aqueous sodium benzoates and salicylates in the carboxyl-stretching region: chelation in aqueous sodium salicylates

1969 ◽  
Vol 47 (24) ◽  
pp. 4577-4588 ◽  
Author(s):  
G. E. Dunn ◽  
R. S. McDonald
Keyword(s):  
Salicylic Acid ◽  
Carbon Tetrachloride ◽  
Infrared Spectra ◽  
Aromatic Compounds ◽  
Deuterium Oxide ◽  
Substituent Effects ◽  
Good Evidence ◽  
Frequency Region ◽  
Aqueous Sodium ◽  
Substituent Constants

Infrared spectra in the frequency region 1300–1760 cm−1 are reported for 41 substituted sodium benzoates and 10 substituted sodium salicylates in deuterium oxide solution, and for 9 substituted salicylic acids in chloroform and carbon tetrachloride solutions. Carboxylate stretching frequencies of benzoates and salicylates correlate poorly with substituent constants, but the asymmetric frequencies of benzoates and salicylates correlate well with each other, and the asymmetric frequencies of benzoates correlate well with the asymmetric frequencies of the corresponding nitrobenzenes. It is suggested that, among substituted aromatic compounds, group vibrations which couple with the ring vibrations may correlate well with similar vibrations of other groups, but not with coupled vibrations of different symmetry, uncoupled vibrations, or substituent constants. Chelation in chloroform solutions of salicylic acid dimers can be detected by its influence on substituent effects, but infrared spectra provide no good evidence for chelation in aqueous sodium salicylates.

scholarly journals Enhancing the reactivity of 1,2-diphospholes in cycloaddition reactions

2015 ◽  
Vol 11 ◽  
pp. 169-173 ◽  
Author(s):  
Almaz Zagidullin ◽  
Vasili Miluykov ◽  
Elena Oshchepkova ◽  
Artem Tufatullin ◽  
Olga Kataeva ◽  
...  
Keyword(s):  
Room Temperature ◽  
Cycloaddition Reaction ◽  
Alder Reaction ◽  
Diels Alder ◽  
Alkyl Halides ◽  
Ethyl Iodide ◽  
Para Position ◽  
Cycloaddition Reactions ◽  
Diels Alder Reaction ◽  
Heating Up

Two different approaches have been employed to enhance the reactivity of 1-alkyl-1,2-diphospholes – the introduction of electron-withdrawing groups either at the phosphorus atoms or in the para-position of the arene ring. The alkylation of sodium 1,2-diphospha-3,4,5-triphenylcyclopentadienide with alkyl halides Hal-CH2-R (R = CN, COOEt, OMe, CH2OEt) results in corresponding 1-alkyl-3,4,5-triphenyl-1,2-diphospholes (alkyl = CH2CN (1a), CH2COOEt (1b), CH2OMe (1c), and (CH2)2OEt (1d)), which spontaneously undergo the intermolecular [4 + 2] cycloaddition reactions at room temperature to form the mixture of the cycloadducts, 2a–c, respectively. However the alkylation of sodium 1,2-diphospha-3,4,5-tri(p-fluorophenyl)cyclopentadienide with ethyl iodide leads to stable 1-ethyl-3,4,5-tris(p-fluorophenyl)-1,2-diphosphole (1e), which forms the [4 + 2] cycloadduct 2,3,4,4a,5,6-hexa(p-fluorophenyl)-1-ethyl-1,7,7a-triphospha-4,7-(ethylphosphinidene)indene (2e) only upon heating up to 60 °C. With further heating to 120 °C with N-phenylmaleimide, the cycloadducts 2a–c and 2e undergo the retro-Diels–Alder reaction and form only one product of the [4 + 2] cycloaddition reaction 3a–с, 3e with good yields up to 65%.

Spectrophotometric Determination of Thiabendazole in Feeds

1965 ◽  
Vol 48 (2) ◽  
pp. 288-295
Author(s):  
C R Szalkowski ◽  
J Kanora
Keyword(s):  
Hydrogen Sulfide ◽  
Spectrophotometric Determination ◽  
Coefficient Of Variation ◽  
Zinc Dust ◽  
Improved Method ◽  
Subsequent Oxidation ◽  
Color Development ◽  
Thiazine Dye

Abstract An improved method has been developed for thiabendazole in feeds. Thiabendazole is extracted from the feed with 0.2N HCl in 50% methanol; interfering substances are removed by making the extract alkaline and extracting into chloroform. The thiabendazole is re-extracted with dilute HCl; the solution is reduced with zinc dust in the presence of p-phenylenediamine to form a hydrogen sulfide complex. After subsequent oxidation with ferric solution to form a thiazine dye, the dye is extracted into n-butanol and measured at 605 mμ. More than 30 commercial unmedicated cattle and swine feeds show an apparent thiabendazole content of 0.00006–0.00044%. Recoveries on feeds made to contain 0.0025–10.0% thiabendazole ranged from 97.6 to 106.6%, with a coefficient of variation of 2.44%. In studies of 30 other drugs added to feeds, only nithiazide, Enheptin, and sulfathiazole interfere. Many variables involved in the color development were studied. The method gives the most accurate and reproducible results on solutions containing 0.2–2.0 μg thiabendazole/ml.

Radiolysis of ethyl iodide and carbon tetrachloride mixtures at 77°K

1968 ◽  
Vol 46 (10) ◽  
pp. 1625-1632 ◽  
Author(s):  
R. M. Leblanc ◽  
F. C. Thyrion ◽  
J. A. Herman
Keyword(s):  
Electron Spin Resonance ◽  
Charge Transfer ◽  
Carbon Tetrachloride ◽  
Electron Spin ◽  
Ethyl Iodide ◽  
Ion Molecule Reactions ◽  
Positive Ions ◽  
Spin Resonance ◽  
Γ Rays ◽  
The Difference

The radical yields of C2H5• and CCl3• observed by electron spin resonance of CCl4 + C2H5I mixtures irradiated by γ rays at 77°K are compared with yields of HCl, I2, and HI measured after thawing. The dissociative capture of thermalized electrons by CCl4 is extremely effective and accounts for most of the observed radicals. The difference between yields of HCl and CCl3• results from charge transfer from C2H5I+ to CCl3•. The formation of iodine proceeds both from neutralization processes of Cl− ions with positive ions formed from C2H5I, and from ion–molecule reactions.

scholarly journals Dynamics of the A-band ultraviolet photodissociation of methyl iodide and ethyl iodide via velocity-map imaging with ‘universal’ detection

2015 ◽  
Vol 17 (6) ◽  
pp. 4096-4106 ◽  
Author(s):  
Sara H. Gardiner ◽  
M. Laura Lipciuc ◽  
Tolga N. V. Karsili ◽  
Michael N. R. Ashfold ◽  
Claire Vallance
Keyword(s):  
Methyl Iodide ◽  
Ethyl Iodide ◽  
Velocity Map Imaging ◽  
Comprehensive Investigation ◽  
Ultraviolet Photodissociation ◽  
Universal Detection

Universal ionization combined with velocity-map imaging allows a comprehensive investigation into the photodissociation dynamics of methyl iodide and ethyl iodide at a range of UV wavelengths within their A-bands.

Radiolysis of ethyl iodide – chloromethane mixtures

1970 ◽  
Vol 48 (8) ◽  
pp. 1273-1279 ◽  
Author(s):  
R. M. Leblanc ◽  
M. A. West ◽  
R. J. Woods ◽  
J. A. Herman
Keyword(s):  
Carbon Tetrachloride ◽  
Hydrogen Chloride ◽  
Electron Capture ◽  
Radical Scavenging ◽  
Ethyl Iodide ◽  
Hydrogen Iodide ◽  
Absorbed Energy ◽  
Γ Radiation ◽  
Chlorine Anion ◽  
Ion Molecule Reactions

Mixtures of ethyl iodide with chloroform, carbon tetrachloride, and dichloromethane have been irradiated with 60Co γ-radiation. Reduced yields of iodine, hydrogen iodide, and hydrogen chloride from ethyl iodide – chloroform and ethyl iodide – dichloromethane mixtures and of chlorinated ethanes from ethyl iodide – chloroform are attributed to radical scavenging by iodine and dissociative electron capture by the chlorinated methane.Electron capture by carbon tetrachloride followed by ion–molecule reactions between ethyl iodide cations and ethyl iodide, or neutralization of these cations by chlorine anions, explains iodine yields observed at low ethyl iodide concentrations in carbon tetrachloride greater than those expected on the basis of partition of absorbed energy. In this mixture, neutralization of an ethyl iodide cation by a chlorine anion gives rise to an enhanced hydrogen chloride yield.

Sign in / Sign up

Export Citation Format

Share Document