scholarly journals On differences in substituent effects in substituted ethene and acetylene derivatives and their boranyl analogs

2020 ◽  
Vol 32 (1) ◽  
pp. 285-296
Author(s):  
Mirosław Jabłoński ◽  
Tadeusz M. Krygowski
Keyword(s):  
Bond Length ◽  
Triple Bond ◽  
Wide Spectrum ◽  
Substituent Effects ◽  
Triple Bonds ◽  
External Perturbations ◽  
Substituent Constants ◽  
The Impact ◽  
Derivatives Of ◽  
Acetylene Derivatives

AbstractThis article is the first attempt to present different influence of substituent effects on double and triple bonds and, conversely, to present the impact of these bonds on the electronic structure of substituents. For this purpose, quantum-mechanical calculations were made for X-substituted derivatives of ethene and acetylene with 27 diverse substituents representing a wide spectrum of electronic properties, from strongly electron-accepting to strongly electron-donating ones. In addition to these systems, their boranyl derivatives are also investigated. It turns out that the Hammett substituent constants do not correctly describe changes in the CC bond length in any of the considered family of systems. However, the relationships with the CB bond length are significantly better. It is shown that the triple bond in acetylene derivatives is much more resistant to external perturbations than the double bond in the analogs containing an ethene unit. As a consequence, in acetylene derivatives, the substituent effects on CC bond length are about half of the substituent effects in ethene derivatives. We suggest that the observed lack of a clear linear correlation between the length of the CC triple bond in acetylene derivatives and the value of electron density on this bond is due to the disturbing additional interaction between the structure of the X substituent in the xy plane and the π bond being in the same plane in the acetylene unit—on the contrary, this interaction is not possible in ethene analogs.

Chemometrical analysis of substituent effects on 13C and 15N NMR chemical shifts in 1-aroyl-3-substituted thioureas

1989 ◽  
Vol 54 (9) ◽  
pp. 2399-2407 ◽  
Author(s):  
Oldřich Pytela ◽  
Josef Jirman ◽  
Antonín Lyčka
Keyword(s):  
Latent Variables ◽  
Chemical Shifts ◽  
Substituent Effects ◽  
The Other ◽  
15N Nmr ◽  
Nmr Chemical Shifts ◽  
Additional Constant ◽  
Substituent Constants ◽  
Derivatives Of ◽  
C Nmr

The methods of conjugated deviations and regression analysis have been used to study the substituent effects on 13C and 15N NMR chemical shifts of 12 derivatives of 1-aroyl-3-phenylthiourea and 1-aroyl-3-methylthiourea. The 13C NMR chemical shifts can be described by two latent variables, one univocally correlated with the Hammett substituent constants (r = 0.993) and the other reflecting the increased shielding of the nuclei due to overlap of the adjacent bond electrons as a consequence of electron-donor or electron-acceptor character of the substituents.This effect is less pronounced with the 15N nuclei. Application of dual substituent constants σR, σF with the additional constant σα describing the polarization has failed in giving sufficiently close correlations and explanation of the substituent effect found.

Synthesis and properties of phenyl substituted derivatives of 2-phenyl-1,1,3,3-tetramethylguanidine

1987 ◽  
Vol 65 (3) ◽  
pp. 626-629 ◽  
Author(s):  
Przemyslaw Pruszynski
Keyword(s):  
Mass Spectrometry ◽  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Phenyl Ring ◽  
Substituent Effects ◽  
Ultraviolet Spectrophotometry ◽  
Elemental Analyses ◽  
Reaction Constant ◽  
Substituent Constants ◽  
Derivatives Of

A series of 17 phenyl substituted derivatives of 2-phenyl-1,1,3,3-tetramethylguanidine was synthesized. The structure and purity of these compounds were checked by means of elemental analyses, mass spectrometry, ultraviolet spectrophotometry, and 1H nuclear magnetic resonance. The pKa values were determined and are discussed in terms of substituent effects using Hammett substituent constants. The Hammett reaction constant ρ = 1.84 ± 0.05 was found to be much lower for para and meta substituted compounds than for anilines, even though the phenyl ring is attached directly to the basic centre in both cases.

scholarly journals FUNDAMENTAL AND APPLIED ASPECTS OF THE CHEMISTRY OF ACETYLENYLQUINONES

2020 ◽  
pp. 30-43
Author(s):  
S.F. Vasilevsky ◽  
A.A. Stepanov
Keyword(s):  
Triple Bond ◽  
Biological Properties ◽  
Sonogashira Reaction ◽  
Metal Catalyst ◽  
Terminal Alkynes ◽  
Carbonyl Groups ◽  
Synthetic Routes ◽  
Derivatives Of ◽  
Acetylene Derivatives ◽  
Mechanisms Of Reactions

In addition to the reported synthetic routes for the acetylene derivatives of quinones, a detailed analysis of the fundamental chemical, physicochemical, and biological properties of this class of compounds is presented herein. The advantages of Pd- and Cu-catalyzed cross-coupling of terminal alkynes with iodarenes via the Sonogashira reaction to produce new acetylenylquinones with predetermined properties are examined. Here, combining quinoid and acetylene residues into one molecule gives the resulting compounds chemical specificity, as demonstrated by several reported examples of non-trivial transformations. In particular, the presence of the quinoid cycle significantly increases the electrophilicity of the triple bond and determines the range of transformation possibilities. Moreover, acetylenylquinones have heightened sensitivity to both external (such as the reaction temperature and the nature of the solvent) and internal (e.g., the structure of substituents in the nucleus and the acetylene fragment) factors. For example, regioselective cleavage of a strong triple bond under the action of amines is possible in the absence of a metal catalyst. Peri-substituted acetylenyl-9,10-anthraquinones are most suited for the synthetic route because of the proximity of the acetylene and carbonyl groups. Mechanisms of reactions of selective alkynylquinones are described.

Substituent effects in 1,3-indanediones

1982 ◽  
Vol 47 (5) ◽  
pp. 1486-1493 ◽  
Author(s):  
Alexander Perjéssy
Keyword(s):  
Substituent Effects ◽  
Empirical Equations ◽  
Substituent Constants ◽  
Complex Structural

The carbonyl stretching frequencies correlate well with substituent constants in a series of 166 1,3-indanediones using improved and extended Seth-Paul-Van Duyse equation. Transmissive factors and group electronegativities have been used to find empirical equations for calculation of substituent constants of more complex structural fragments.

Infrared spectra and substituent effects in 2-(3-, and 4-substituted phenylmethylene)-1,3-cycloheptanediones

1983 ◽  
Vol 48 (2) ◽  
pp. 586-595 ◽  
Author(s):  
Alexander Perjéssy ◽  
Pavol Hrnčiar ◽  
Ján Šraga
Keyword(s):  
Substituent Effects ◽  
Phenyl Group ◽  
Wave Number ◽  
Vibrational Coupling ◽  
Wave Numbers ◽  
Stretching Vibration ◽  
Stretching Vibrations ◽  
The Relationship ◽  
Derivatives Of ◽  
Effect Of Structure

The wave numbers of the fundamental C=O and C=C stretching vibrations, as well as that of the first overtone of C=O stretching vibration of 2-(3-, and 4-substituted phenylmethylene)-1,3-cycloheptanediones and 1,3-cycloheptanedione were measured in tetrachloromethane and chloroform. The spectral data were correlated with σ+ constants of substituents attached to phenyl group and with wave number shifts of the C=O stretching vibration of substituted acetophenones. The slope of the linear dependence ν vs ν+ of the C=C stretching vibration of the ethylenic group was found to be more than two times higher than that of the analogous correlation of the C=O stretching vibration. Positive values of anharmonicity for asymmetric C=O stretching vibration can be considered as an evidence of the vibrational coupling in a cyclic 1,3-dicarbonyl system similarly, as with derivatives of 1,3-indanedione. The relationship between the wave numbers of the symmetric and asymmetric C=O stretching vibrations indicates that the effect of structure upon both vibrations is symmetric. The vibrational coupling in 1,3-cycloheptanediones and the application of Seth-Paul-Van-Duyse equation is discussed in relation to analogous results obtained for other cyclic 1,3-dicarbonyl compounds.

Kinetic Study of Hydrolysis of Benzoates. Part XXVI. Variation of the Substituent Effect with Solvent in Alkaline Hydrolysis of Substituted Alkyl Benzoates

2006 ◽  
Vol 71 (11-12) ◽  
pp. 1557-1570 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Ilmar A. Koppel
Keyword(s):  
Kinetic Study ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Substituent Effect ◽  
Substituent Effects ◽  
Alkyl Substituent ◽  
Solvent Parameters ◽  
Substituent Constants ◽  
Hydrolysis Of ◽  
Main Factor

The second-order rate constants k2 (dm3 mol-1 s-1) for the alkaline hydrolysis of substituted alkyl benzoates C6H5CO2R have been measured spectrophotometrically in aqueous 0.5 M Bu4NBr at 50 and 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH, CH2C6H5, CH2CH2Cl, CH2CH2OCH3, CH2CH3) and in aqueous 5.3 M NaClO4 at 25 °C (R = CH3, CH2Cl, CH2CN, CH2C≡CH). The dependence of the alkyl substituent effects on different solvent parameters was studied using the following equations:      ∆ log k = c0 + c1σI + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆EσI + c7∆YσI + c8∆PσI     ∆ log k = c0 + c1σ* + c2EsB + c3∆E + c4∆Y + c5∆P + c6∆Eσ* + c7∆Yσ* + c8∆Pσ* .  ∆ log k = log kR - log kCH3. σI and σ* are the Taft inductive and polar substituent constants. E, Y and P are the solvent electrophilicity, polarity and polarizability parameters, respectively. In the data treatment ∆E = ES - EH2O , ∆Y = YS - YH2O , ∆P = PS - PH2O were used. The solvent electrophilicity, E, was found to be the main factor responsible for changes in alkyl substituent effects with medium. When σI constants were used, variation of the polar term of alkyl substituents with the solvent electrophilicity E was found to be similar to that observed earlier for meta and para substituents, but twice less when σ* constants were used. The steric term for alkyl substituents was approximately independent of the solvent parameters.

scholarly journals A Survey of Electromagnetic Influence on UAVs from an EHV Power Converter Stations and Possible Countermeasures

Electronics ◽  
2021 ◽  
Vol 10 (6) ◽  
pp. 701
Author(s):  
Yanchu Li ◽  
Qingqing Ding ◽  
Keyue Li ◽  
Stanimir Valtchev ◽  
Shufang Li ◽  
...  
Keyword(s):  
Electromagnetic Interference ◽  
Wide Spectrum ◽  
Electromagnetic Emission ◽  
Power Converter ◽  
Electromagnetic Environment ◽  
Communication Circuits ◽  
Electromagnetic Emissions ◽  
Surrounding Space ◽  
Extra High Voltage ◽  
The Impact

It is inevitable that high-intensity, wide-spectrum electromagnetic emissions are generated by the power electronic equipment of the Extra High Voltage (EHV) power converter station. The surveillance flight of Unmanned Aerial Vehicles (UAVs) is thus, situated in a complex electromagnetic environment. The ubiquitous electromagnetic interference demands higher electromagnetic protection requirements from the UAV construction and operation. This article is related to the UAVs patrol inspections of the power line in the vicinity of the EHV converter station. The article analyzes the electromagnetic interference characteristics of the converter station equipment in the surrounding space and the impact of the electromagnetic emission on the communication circuits of the UAV. The anti-electromagnetic interference countermeasures strive to eliminate or reduce the threats of electromagnetic emissions on the UAV’s hardware and its communication network.

scholarly journals The Impact of Fluid Loss and Carbohydrate Consumption during Exercise, on Young Cyclists’ Fatigue Perception in Relation to Training Load Level

2021 ◽  
Vol 18 (6) ◽  
pp. 3282
Author(s):  
Leonardo Cesanelli ◽  
Berta Ylaitė ◽  
Giuseppe Messina ◽  
Daniele Zangla ◽  
Stefania Cataldi ◽  
...  
Keyword(s):  
Perceived Exertion ◽  
Wide Spectrum ◽  
Load Level ◽  
Training Load ◽  
Fluid Loss ◽  
Young Athletes ◽  
Carbohydrate Consumption ◽  
Significant Difference ◽  
Training Impulse ◽  
The Impact

High-level young athletes need to face a wide spectrum of stressors on their journey to élite categories. The aims of the present study are (i) to evaluate session rate of perceived exertion (sRPE) at different training impulse (TRIMP) categories and the correlations between these two variables and, (ii) evaluate the correlations between sRPE, fluid loss, and carbohydrate consumption during exercise. Data on Edward’s TRIMP, sRPE, body mass loss pre- and post- exercise (∆), and carbohydrate consumption (CHO/h) during exercise have been acquired from eight male junior cyclists during a competitive season. One-way ANOVA and correlation analysis with linear regression have been performed on acquired data. sRPE resulted in a significant difference in the three TRIMP categories (p < 0.001). sRPE resulted in being very largely positively associated with TRIMP values (p < 0.001; R = 0.71). ∆ as well as CHO/h was largely negatively related with sRPE in all TRIMP categories (p < 0.001). The results confirmed the role of fluid balance and carbohydrate consumption on the perception of fatigue and fatigue accumulation dynamics independently from the training load. Young athletes’ training load monitoring and nutritional-hydration support represent important aspects in athlete’s exercise-induced fatigue management.

scholarly journals Acute Management Should Be Optimized in Patients with Less Specific Stroke Symptoms: Findings from a Retrospective Observational Study

2021 ◽  
Vol 10 (5) ◽  
pp. 1143
Author(s):  
Simona Halúsková ◽  
Roman Herzig ◽  
Dagmar Krajíčková ◽  
Abduljabar Hamza ◽  
Antonín Krajina ◽  
...  
Keyword(s):  
Wide Spectrum ◽  
Intravenous Thrombolysis ◽  
National Institutes Of Health ◽  
Vascular Territory ◽  
Anterior Circulation ◽  
Point Increase ◽  
Single Center Study ◽  
Mouth Corner ◽  
Specific Symptoms ◽  
The Impact

Anterior circulation stroke (ACS) is associated with typical symptoms, while posterior circulation stroke (PCS) may cause a wide spectrum of less specific symptoms. We aim to assess the correlation between the initial presentation of acute ischemic stroke (AIS) symptoms and the treatment timeline. Using a retrospective, observational, single-center study, the set consists of 809 AIS patients treated with intravenous thrombolysis (IVT) and/or endovascular treatment (EVT). We investigate the impact of baseline clinical AIS symptoms and the affected vascular territory on recanalization times in patients treated with IVT only and EVT (±IVT). Regarding the IVT-only group, increasing the National Institutes of Health Stroke Scale (NIHSS) score on admission and speech difficulties are associated with shorter (by 1.59 ± 0.76 min per every one-point increase; p = 0.036, and by 24.56 ± 8.42 min; p = 0.004, respectively) and nausea/vomiting with longer (by 43.72 ± 13.13 min; p = 0.001) onset-to-needle times, and vertigo with longer (by 8.58 ± 3.84 min; p = 0.026) door-to-needle times (DNT). Regarding the EVT (±IVT) group, coma is associated with longer (by 22.68 ± 6.05 min; p = 0.0002) DNT, anterior circulation stroke with shorter (by 47.32 ± 16.89 min; p = 0.005) onset-to-groin time, and drooping of the mouth corner with shorter (by 20.79 ± 6.02 min; p = 0.0006) door-to-groin time. Our results demonstrate that treatment is initiated later in strokes with less specific symptoms than in strokes with typical symptoms.

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