Protonation and Acid-catalyzed Rearrangement of 1,2-Diazepines

1974 ◽  
Vol 52 (15) ◽  
pp. 2805-2817 ◽  
Author(s):  
David John Harris ◽  
M. T. Thomas ◽  
Victor Snieckus ◽  
E. Klingsberg
Keyword(s):  
Activation Energy ◽  
Trifluoroacetic Acid ◽  
Water Solution ◽  
Spectral Characteristics ◽  
Lone Pair ◽  
Pair Interaction ◽  
Protonated Form ◽  
Open Chain ◽  
Ring Inversion ◽  
The Difference

The protonation of the 1,2(4H)-diazepines 2a, 2b, and the 1,2(1H)-diazepine 3a in various acidic media has been studied by u.v. and n.m.r. spectroscopy. Compounds 2a and 3a undergo protonation to give 4a and 7a, respectively, whereas 2b provides the monoprotonated species 4b in dilute acid and the diprotonated form 4c in strongly acidic solution. Spectral characteristics of crystalline 1,2(4H)-diazepinium perchlorates 4a, 4d, 7a, and 7c correlate well with those observed for the corresponding free bases in acidic solutions; 7a-ClO4 and 7c-ClO4 were obtained either from 2a and 2c or from 3a and 3c, respectively. In trifluoroacetic acid-d-D2O, deuterium exchange at C4 and C6 of 2a, 2b, and 3a was observed indicating the presence of small equilibrium concentrations of species 1a, 1c and/or 1d, and 1b under these conditions. Temperature variable n.m.r. spectroscopy provides evidence for ring inversion phenomena for the protonated forms 4a and 7a. In the case of 4a, the activation energy, ΔGc≠ = 10.2 ± 0.2 kcal/mol (Tc = 8 ± 3°) has been estimated. The difference in the activation energy between the free base and the protonated form, ΔG≠ (2a)—ΔG≠ (4a) = 6–7 kcal/mol is attributed to strong repulsive N1—N2 lone pair interaction in 2a in the transition state for the ring inversion process.Under vigorous acidic conditions, the 1, 2(4H)-diazepines 2a–c give pyrazoles (10a–c), pyridines (12a–c), and acetophenone. Using identical conditions, the 1,2(4H)-diazepinium salt, 7a-ClO4 provides pyrazole 11a and pyridine 12a and, in addition, the 1-methylaminopyridinium salt 13a. However, rearrangement also proceeds under very mild conditions (ethanol–water) as shown for 7a-ClO4 and 7c-ClO4 which yield compounds 11a and 12a, and 11c, 12c, and 13c, respectively. The 1, 2(1H)-diazepine 3a gives 11a, 12a, and 13a in ethanol–water solution and exclusively 13a in trifluoroacetic acid. The mechanism of these reactions is discussed in terms of formation of open-chain (15) and diaziridine-type (19) intermediates. Electrocylic mechanisms are eliminated from consideration on the basis of the absence of products 23, 24, and 25 which should have been observed from the reactions of 2b, 2c, and 7c-ClO4 if these pathways were operative.

Microscopic Interpretation of Arrhenius Parameters

2018 ◽  
Author(s):  
Niels Engholm Henriksen ◽  
Flemming Yssing Hansen
Keyword(s):  
Activation Energy ◽  
Transition State ◽  
Transition State Theory ◽  
Average Energy ◽  
Zero Point ◽  
State Theory ◽  
Exponential Factor ◽  
Quantum Tunnelling ◽  
Microscopic Interpretation ◽  
The Difference

This chapter reviews the microscopic interpretation of the pre-exponential factor and the activation energy in rate constant expressions of the Arrhenius form. The pre-exponential factor of apparent unimolecular reactions is, roughly, expected to be of the order of a vibrational frequency, whereas the pre-exponential factor of bimolecular reactions, roughly, is related to the number of collisions per unit time and per unit volume. The activation energy of an elementary reaction can be interpreted as the average energy of the molecules that react minus the average energy of the reactants. Specializing to conventional transition-state theory, the activation energy is related to the classical barrier height of the potential energy surface plus the difference in zero-point energies and average internal energies between the activated complex and the reactants. When quantum tunnelling is included in transition-state theory, the activation energy is reduced, compared to the interpretation given in conventional transition-state theory.

scholarly journals Theoretical Study of the Structures of 4-(2,3,5,6-Tetrafluoropyridyl)Diphenylphosphine Oxide and Tris(Pentafluorophenyl)Phosphine Oxide: Why Does the Crystal Structure of (Tetrafluoropyridyl)Diphenylphosphine Oxide Have Two Different P=O Bond Lengths?

Molecules ◽  
2020 ◽  
Vol 25 (12) ◽  
pp. 2778
Author(s):  
Joseph R. Lane ◽  
Graham C. Saunders
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Phosphine Oxide ◽  
Density Functional ◽  
Lone Pair ◽  
Diphenylphosphine Oxide ◽  
Functional Theory ◽  
Weak Hydrogen Bonding ◽  
Independent Molecules ◽  
The Difference

The crystal structure of 4-(2,3,5,6-tetrafluoropyridyl)diphenylphosphine oxide (1) contains two independent molecules in the asymmetric unit. Although the molecules are virtually identical in all other aspects, the P=O bond distances differ by ca. 0.02 Å. In contrast, although tris(pentafluorophenyl)phosphine oxide (2) has a similar crystal structure, the P=O bond distances of the two independent molecules are identical. To investigate the reason for the difference, a density functional theory study was undertaken. Both structures comprise chains of molecules. The attraction between molecules of 1, which comprises lone pair–π, weak hydrogen bonding and C–H∙∙∙arene interactions, has energies of 70 and 71 kJ mol−1. The attraction between molecules of 2 comprises two lone pair–π interactions, and has energies of 99 and 100 kJ mol−1. There is weak hydrogen bonding between molecules of adjacent chains involving the oxygen atom of 1. For one molecule, this interaction is with a symmetry independent molecule, whereas for the other, it also occurs with a symmetry related molecule. This provides a reason for the difference in P=O distance. This interaction is not possible for 2, and so there is no difference between the P=O distances of 2.

Thermogravimetric Analysis of Glucose-Based and Fructose-Based Carbohydrates

2013 ◽  
Vol 805-806 ◽  
pp. 265-268 ◽  
Author(s):  
Fang Ming Cui ◽  
Xiao Yuan Zhang ◽  
Li Min Shang
Keyword(s):  
Activation Energy ◽  
Thermogravimetric Analysis ◽  
Kinetic Parameters ◽  
Degree Of Polymerization ◽  
Experiment Data ◽  
Pyrolysis Characteristics ◽  
The Difference ◽  
Kinetic Calculations

Thermogravimetric analysis (TGA) was employed to study the pyrolysis characteristics of four glucose-based and three fructose-based carbohydrates. Kinetic parameters were calculated based on the experiment data. The results indicated that the starting and maximal pyrolysis temperatures of the glucose-based carbohydrates were increased steadily as the rising of their degree of polymerization (DP). The fructose-based carbohydrates exhibited similar pyrolysis behaviors as the glucose-based carbohydrates, but the difference was smaller. Kinetic calculations revealed that the activation energy values of the glucose-based carbohydrates were higher than those of the fructose-based carbohydrates, indicating the glucose-based carbohydrates were more difficult to decompose than the fructose-based carbohydrates.

Kinetic Model of the 1,2-Propanediol Oxidation Reaction in the Presence of 3wt%Pd/α-Al2O3 Catalyst

2021 ◽  
Vol 903 ◽  
pp. 143-148
Author(s):  
Svetlana Cornaja ◽  
Svetlana Zhizhkuna ◽  
Jevgenija Vladiko
Keyword(s):  
Activation Energy ◽  
Lactic Acid ◽  
Kinetic Model ◽  
Catalytic Oxidation ◽  
Molecular Oxygen ◽  
Oxidation Reaction ◽  
Main Product ◽  
Oxidation Process ◽  
Water Solution ◽  
Reaction Conditions

Supported 3wt%Pd/α-Al₂O₃ catalyst was tested in selective oxidation of 1,2-propanediol by molecular oxygen. It was found that the catalyst is active in an alkaline water solution. Lactic acid was obtained as the main product of the reaction. Influence of different reaction conditions on 1,2-PDO conversion and oxidation process selectivity was studied. Partial kinetic orders of the reaction with respect to 1,2-propanediol, c0(NaOH), p(O2), n(1,2-PDO)/n(Pd)) were determined and an experimental kinetic model of the catalytic oxidation reaction was obtained. Activation energy of the process was calculated and was found to be about 53 ± 5 kJ/mol.

Flow Properties of Utah Shale Oils

1981 ◽  
Vol 21 (06) ◽  
pp. 679-686 ◽  
Author(s):  
W.H. Seitzer
Keyword(s):  
Shear Stress ◽  
Shear Rate ◽  
Pour Point ◽  
Water Solution ◽  
Shale Oil ◽  
Concentric Cylinder ◽  
Long Distance ◽  
Time Calibration ◽  
The Difference ◽  
Cylinder Viscometer

Abstract In a concentric cylinder viscometer. Utah shale oils have different characteristics, both at equilibrium flow and during start-up from rest, depending on whether the wax has crystallized as needles or spherulites. Compared with waxy crude oils, which are thixotropic, shale oil had the added rheological property of being antithixotropic. Introduction The most likely liquid synthetic fuel to be produced initially in the U.S. will be raw shale oil from western oil shale. This abundant resource is located principally in the western Rocky Mountain states of Colorado. Utah. and Wyoming (Fig. 1). Ultimate commercial production probably will be transported to marketing, distribution, and refining centers by pipeline. It has been reported that Utah shale oils produced by the Union "B" and Paraho DH retorting processes gave similar physical and chemical properties. Some properties of the two Utah shale oils are given in Table 1. The only major difference is that the Union shale oil has a pour point of - 1 degree C compared with a pour point of 25 degrees C for the Paraho oil. Wax Crystallization The difference in the pour points of the oils from the Utah shale retorted by Union Oil Co of California and Paraho is caused mainly by the difference in how the wax in the respective oils crystallizes. In the high- pour-point (25 degrees C) Paraho DK oil, the wax, under a microscope, appears as fine (1 to 10 m) needles, as expected for normal paraffins. However, the wax in the low-pour-point (−1 degrees C) Union oil forms small spherulites.Wax spherulites have not been reported before: however, this type of crystal is seen commonly in polymer. Spherulites show up as round areas containing a maltese cross when observed between crossed polars under a microscope.Photomicrographs of these crystals are shown in Figs. 2 and 3. The former, showing spherulites, is of the Union oil. In contrast, they are very different from the customary needles as typified by the Paraho oil in the latter micrograph. Presumably, these highly ordered spheres are made up of wax needles grown out radially from the center as described by Hartshorne and Stuart. The polarized light is scattered only by those needles not parallel nor perpendicular to the plane of polarization. Viscometer Measurements To understand the effect of these spherulites on the flow characteristics of raw shale oil at flow conditions expected in a long-distance pipeline, typical stress-rate measurements were made in a rotating cylinder viscometer, the Haake Rotovisco RV3 with MK500 measuring head and MVI coaxial cylinder sensor having an 82-mm cup and radii ratio of 0.95. This equipment has provisions for varying shear rate continuously at selected values down to 23.4 sec(−1)/min and can produce and record shear stress as a function of either shear rate or time. Calibration of the sensor was verified with a sucrose/water solution at several temperatures.Changes in temperature always were made from lower to higher to keep the sensor full of oil. Also, the shear-stress/ shear-rate curves were obtained by starting at high shear, down to zero, and then back up. SPEJ P. 679^

scholarly journals Quasi-biennial and quasi-triennial oscillations in the growth rates of atmospheric chlorofluorocarbons 11 and 12

MAUSAM ◽  
2022 ◽  
Vol 53 (3) ◽  
pp. 349-358
Author(s):  
R. P. KANE
Keyword(s):  
Southern Hemisphere ◽  
Growth Rates ◽  
Southern Oscillation ◽  
Spectral Characteristics ◽  
Linear Increase ◽  
Transport Processes ◽  
Emission Rates ◽  
Low Latitude ◽  
The Difference ◽  
Prominent Peak

The 12-monthly running means of CFC-11 and CFC-12 were examined for 1977-1992. As observed by earlier workers, during 1977-1988, there was a rapid, almost linear increase of these compounds, ~70% in the northern and ~77% in the southern hemisphere. From 1988 up to 1992, growth rates were slower, more so for CFC-11 in the northern hemisphere. Superposed on this pattern were QBO, QTO (Quasi-Biennial and Quasi-Triennial Oscillations). A spectral analysis of the various series indicated the following. The 50 hPa low latitude zonal wind had one prominent QBO peak at 2.58 years and much smaller peaks at 2.00 (QBO) and 5.1 years. The Southern oscillation index represented by (T-D), Tahiti minus Darwin atmospheric pressure, had a prominent peak at 4.1 years and a smaller peak at 2.31 years. CFC-11 had only one significant peak at 3.7 years in the southern hemisphere, roughly similar to the 4.1 year (T-D) peak. CFC-12 had prominent QBO (2.16-2.33 years) in both the hemispheres and a QTO (3.6 years) in the southern hemisphere. For individual locations, CFC-11 showed barely significant QBO in the range (1.95-3.07 years), while CFC 12 showed strong QBO in the range (1.86-2.38 years). The difference in the spectral characteristics of CFC-11 and CFC 12 time series is attributed to differences in their lifetimes (44 and 180 years), source emission rates and transport processes.

scholarly journals Testing for ion-mediated enhancement of the hydraulic conductance of the leaf xylem in diverse angiosperms

2017 ◽  
Vol 4 ◽  
pp. e004 ◽  
Author(s):  
Christine Scoffoni ◽  
Grace John ◽  
Herve Cochard ◽  
Lawren Sack
Keyword(s):  
Water Solution ◽  
Pure Water ◽  
Xylem Sap ◽  
Hydraulic Conductance ◽  
Membrane Pores ◽  
Whole Plant ◽  
Pit Membrane ◽  
Major Bottleneck ◽  
The Difference ◽  
Xylem Conduits

Replacing ultra-pure water solution with ion solution closer to the composition of natural xylem sap increases stem hydraulic conductance by up to 58%, likely due to changes in electroviscosity in the pit membrane pores. This effect has been proposed to contribute to the control of plant hydraulic and stomatal conductance and potentially to influence on carbon balance during dehydration. However, this effect has never been directly tested for leaf xylem, which constitutes a major bottleneck in the whole plant. We tested for an ion-mediated increase in the hydraulic conductance of the leaf xylem (Kx) for seven species diverse in phylogeny and drought tolerance. Across species, no significant changes in Kx were observed between 0 and 15 mM KCl. We further tested for an effect of ion solution during measurements of Kx vulnerability to dehydration in Quercus agrifolia and found no significant impact. These results for leaf xylem contrast with the often strong ion effect reported for stems, and we suggest several hypotheses to account for the difference, relating to the structure of xylem conduits across vein orders, and the ultrastructure of leaf xylem pores. A negligible ion response in leaves would weaken xylem sap ion-mediated control of plant hydraulic conductance, facilitating modeling of whole plant hydraulic behavior and its influence on productivity.

Activation energy of ring inversion in 9,10-disubstituted -decalins

1967 ◽  
Vol 8 (14) ◽  
pp. 1329-1331 ◽  
Author(s):  
J. Altman ◽  
H. Gilboa ◽  
D. Ginsburg ◽  
A. Lowenstein
Keyword(s):  
Activation Energy ◽  
Ring Inversion

Photoelectron Spectra and Molecular Properties, XLVIII Carbonates and Thiocarbonates

1975 ◽  
Vol 30 (11-12) ◽  
pp. 862-874 ◽  
Author(s):  
K. Wittel ◽  
E. E. Astrup ◽  
H. Bock ◽  
G. Graeffe ◽  
H. Juslén
Keyword(s):  
Ionization Potential ◽  
Substituent Effects ◽  
Lone Pair ◽  
Emission Spectra ◽  
Low Energy ◽  
Photoelectron Spectra ◽  
Energy Bands ◽  
Open Chain ◽  
First Ionization Potential ◽  
Cndo Calculations

Photoelectron (PE) spectra of ethylene and vinylene carbonates and thiocarbonates as well as of methylene trithiocarbonate and some open-chain derivatives are reported.The low energy bands, well separated in the unsaturated compounds, are assigned to lone pair and π type ionizations. The assignment is based on comparison of PE spectra, modified CNDO calculations, and sulfur Κβ emission spectra. The pronounced substituent effects due to which the first ionization potential varies from 8.4 eV to 11.1 eV are discussed.

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