The Trishomocyclopropenyl Cation. I. Direct Observation

1974 ◽  
Vol 52 (5) ◽  
pp. 855-857 ◽  
Author(s):  
S. Masamune ◽  
M. Sakai ◽  
A. V. Kemp-Jones ◽  
T. Nakashima
Keyword(s):  
Chemical Shift ◽  
Direct Observation ◽  
Time Scale ◽  
High Field ◽  
Positive Charge ◽  
Hydride Shift ◽  
First Time

The trishomocyclopropenyl cation has been prepared for the first time and is shown to be a remarkably stable, highly charge-delocalized species. The large [Formula: see text] value associated with the carbons formally carrying the positive charge, the high-field chemical shift of these carbons, and the absence of hydride shift, all are significant and are consistent with the formulation of 1 subject to the limit of the n.m.r. time scale.

Wallach rearrangement of azoxypyridines and azoxypyridine N-oxides — Charge distributions and dramatic reactivity differences

2008 ◽  
Vol 86 (4) ◽  
pp. 298-304 ◽  
Author(s):  
Erwin Buncel ◽  
Sam-Rok Keum ◽  
Srinivasan Rajagopal ◽  
Eric Kiepek ◽  
Robin A Cox
Keyword(s):  
Sulfuric Acid ◽  
Positive Charge ◽  
Theoretical Calculations ◽  
Medium Effect ◽  
Mulliken Charge ◽  
Reaction Intermediates ◽  
Charge Distributions ◽  
First Time ◽  
Acid Region

Extension of our studies of the generic Wallach rearrangement (of azoxybenzene to 4-hydroxyazobenzene) to the heteroaromatic series (azoxypyridines and axoxypyridine N-oxides) has revealed some dramatic reactivity differences, particularly for the α and β compounds. We have studied the 3-isomers and the 4-isomers in each series, each with α and β forms, eight compounds in all, in the 100 wt% sulfuric acid region of acidity. In those cases in which a product could be observed, the α and β isomers both give the same one, the corresponding 4′-hydroxyazo compounds. All the compounds react much more slowly than does azoxybenzene itself, presumably because of the extra positive charge present in the substrates, but the β isomers have half-lives of seconds and the α isomers half-lives of hundreds of hours in the 100 wt% H2SO4 acidity region. The α compounds have measurable pKBH+ values, but the β compounds do not, exhibiting only a medium effect in the acidity region in which the α compounds protonate. This means that for the β compounds, the protonated intermediates must be much less stable and the postulated reaction intermediates must be much more stable than for the α compounds. To clarify this, we have obtained Mulliken charge distributions for the various species concerned, calculating the charge carried by each half of the molecule, larger charge separations being taken to indicate lesser stability. As far as we can establish, this is the first time that this technique has been used to indicate the stabilities of carbocationic species.Key words: azoxypyridines, azoxypyridine N-oxides, Wallach rearrangement, excess acidity, basicities, theoretical calculations, charge distributions, reactivities.

An Effective Synthesis of N,N-Diphenyl Carbazolium Salts

Synlett ◽  
2017 ◽  
Vol 29 (10) ◽  
pp. 1314-1318 ◽  
Author(s):  
Charles Diesendruck ◽  
Sinai Aharonovich ◽  
Nansi Gjineci ◽  
Dario Dekel
Keyword(s):  
Positive Charge ◽  
Quaternary Ammonium Salts ◽  
Simple Approach ◽  
Ammonium Salts ◽  
State Structure ◽  
Pi Systems ◽  
Effective Synthesis ◽  
Short Time ◽  
First Time ◽  
General Method

Tetraaryl ammonium salts are a synthetic challenge, since there is no general method for the arylation of triaryl amines. Contrary to other quaternary ammonium salts, tetraaryl ammonium salts should be very chemically stable. The ipso carbons are not very electrophilic, since the positive charge is distributed throughout the pi systems and they have no acidic β hydrogens. Here we demonstrate a simple approach to N,N-diphenyl carbazolium salts using only three synthetic steps, allowing for an easy production of these salts in large amounts and in a relatively short time. In addition, we study the Cu(I) catalyzed multi-arylation of 2,2’-diaminobiphenyl, focusing on the regioselectivity of each step. Finally, we characterize, for the first time, the solid state structure of a tetraaryl ammonium salt.

scholarly journals Direct observation of o-benzyne formation in photochemical hexadehydro-Diels–Alder (hν-HDDA) reactions

2020 ◽  
Vol 11 (34) ◽  
pp. 9198-9208 ◽  
Author(s):  
Xiaonan Ma ◽  
Jan Maier ◽  
Michael Wenzel ◽  
Alexandra Friedrich ◽  
Andreas Steffen ◽  
...  
Keyword(s):  
Absorption Spectrum ◽  
Direct Observation ◽  
Diels Alder ◽  
Visible Absorption Spectrum ◽  
Visible Absorption ◽  
First Time

We report the transient ultraviolet/visible absorption spectrum of an o-benzyne species in solution for the first time.

scholarly journals Li–Yorke Chaos in Hybrid Systems on a Time Scale

2015 ◽  
Vol 25 (14) ◽  
pp. 1540024 ◽  
Author(s):  
Marat Akhmet ◽  
Mehmet Onur Fen
Keyword(s):  
Differential Equations ◽  
Hybrid Systems ◽  
Time Scales ◽  
Time Scale ◽  
Impulsive Differential Equations ◽  
Reduction Technique ◽  
Duffing Equation ◽  
Dynamic Equations ◽  
Definition Of ◽  
First Time

By using the reduction technique to impulsive differential equations [Akhmet & Turan, 2006], we rigorously prove the presence of chaos in dynamic equations on time scales (DETS). The results of the present study are based on the Li–Yorke definition of chaos. This is the first time in the literature that chaos is obtained for DETS. An illustrative example is presented by means of a Duffing equation on a time scale.

Observations on the turbulent fluctuations of a tidal current

1949 ◽  
Vol 199 (1058) ◽  
pp. 311-327 ◽  
Keyword(s):  
Time Scale ◽  
Tidal Current ◽  
Velocity Fluctuations ◽  
Turbulent Fluctuations ◽  
Long Period ◽  
Auto Correlation ◽  
Short Period ◽  
Wide Range ◽  
First Time ◽  
A Current

Records have been obtained of fluctuations in the speed of the tidal current in the Mersey estuary, using a current meter in a stand on the bottom, and compared with other records taken with the meter suspended freely at various depths. The fluctuations covered a wide range of periods but could be separated into two main types: ‘short period’, having periods of the order of a few seconds, and ‘long period’, with periods from 30 sec. to several minutes. The amplitudes, periods and auto-correlation of the short-period fluctuations have been examined in some detail, and it is concluded that the fluctuations observed near the bottom are evidence of the turbulence associated with bottom friction. It is believed to be the first time that the presence of turbulent velocity fluctuations of this time-scale in the sea has been established experimentally. The long-period fluctuations resemble those found in previous investigations and show features consistent with their being turbulent in origin also, although turbulence of the time-scale involved in their case would probably be mainly horizontal.

Solid State NMR Analysis for Hide Powder Tanned by Aluminum, Silicon and Phosphorus Tanning Agents before and after Hydrothermal Denaturation

2021 ◽  
Vol 116 (10) ◽  
Author(s):  
Jun Liu ◽  
Da-hai He ◽  
Hua-lin Chen ◽  
Ke-yi Ding
Keyword(s):  
Solid State ◽  
Chemical Shift ◽  
High Field ◽  
Chemical Shifts ◽  
Covalent Bond ◽  
29Si Nmr ◽  
Before And After ◽  
Collagen Molecules ◽  
Field Area ◽  
Aluminum Silicon

In order to investigate the change of chemical bonds between tanning agents and collagen molecules directly, hide powder tanned by aluminum, silicon and phosphorus tanning agents were prepared. The chemical shifts of Al, Si and P in tanned hide powder were analyzed by solid-state 27Al NMR, 29Si NMR and 31P NMR. The results showed that, the chemical shift of Al in aluminum tanned hide powder which interacted with collagen molecules through coordination bond could be regarded as unchanging after hydrothermal denaturation (only slightly moved to high field area). The chemical shift of Si in silicon tanned hide powder which interacted with collagen molecules through hydrogen bond did not change after hydrothermal denaturation. The chemical shift of P in phosphorus tanned hide powder, which interacted with collagen molecules through covalent bond, was obviously shifted to the high field area after hydrothermal denaturation.

scholarly journals An Unusually Stable and Short Spectroscopic Period of the Be Star 28 CMa

1982 ◽  
Vol 98 ◽  
pp. 167-170
Author(s):  
D. Baade
Keyword(s):  
Time Scale ◽  
Emission Lines ◽  
Be Stars ◽  
Stable Period ◽  
Be Star ◽  
First Time ◽  
Calar Alto

Spectroscopic (1970: ESO, 12 Å/mm, 6 spectra kindly put at my disposal by Prof. A. Van Hoof; 1976: ESO, 12 Å/mm; 1977: Calar Alto Observatory, 42 Å/mm; 1979: ESO, 12 Å/mm) and photometric (1976: ESO and Cerro Tololo, Hβ, uvby) observations of 28 CMa (B2-3 IV-Ve; 3.52 < mV < 4.18, irregular variations on the time scale of months or years reported; vrot = 80 km/s) revealed a very complex variability. All observed individual types of variations are known from at least a few other Be stars. In 28 CMa, however, for the first time a highly significant correlation between the various variations is established by a stable common period. The period is 1.365 days which seems to be the shortest stable period presently known of any Be star. There is no indication that the star's behaviour changed between 1970 and 1979. Only the equivalent widths of the emission lines increased noticeably.

High field carbon 13 relaxation of 5CB. Chemical shift anisotropy as a probe of nematic dynamics

1993 ◽  
Vol 14 (5) ◽  
pp. 1507-1517 ◽  
Author(s):  
John S. Lewis ◽  
E. Tomchuk ◽  
E. Bock
Keyword(s):  
Chemical Shift ◽  
High Field ◽  
Chemical Shift Anisotropy
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