Quantitative Separation of Hyperconjugation Effects from Steric Substituent Constants

Hancock, C. Kinney; Meyers, Edward A.; Yager, Billy J.

doi:10.1021/ja01481a027

Cited by 179 publications

(64 citation statements)

References 1 publication

(1 reference statement)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The difference between the sensitive and resistant strains was actually reflected in the difference in intercept and transport terms in Eqs. (3) and (4). The intercept in Eq.…”

Section: Discussionmentioning

confidence: 99%

Relationships between Insecticidal Activity of 6-Alkylthio-2-pyridyl Methanesulfonates and Acetylcholinesterase Inhibition of their Sulfone Derivatives against <i>Nephotettix cincticeps</i>

et al. 1990

View full text Add to dashboard Cite

The inhibitory activity (I50) of fifteen sulfone analogs of 6-alkylthio-2-pyridyl methanesulfonates was measured against acetylcholinesterase preparations from Ageo and Izumi strains of Nephotettix cincticeps. The insecticidal activity of 6-alkylthio derivatives to both strains was highly related to the acetylcholinesterase-inhibitory activity of the corresponding sulfones when hydrophobicity factors (log h) of the molecule perhaps participating in the transport process were taken into account.Variations in insecticidal activity was due to the total of structure-activity relationships in enzyme inhibition and transport process. The combination of hydrophobicity and steric parameter terms was quite similar in the two strains.

show abstract

“…The difference between the sensitive and resistant strains was actually reflected in the difference in intercept and transport terms in Eqs. (3) and (4). The intercept in Eq.…”

Section: Discussionmentioning

confidence: 99%

Relationships between Insecticidal Activity of 6-Alkylthio-2-pyridyl Methanesulfonates and Acetylcholinesterase Inhibition of their Sulfone Derivatives against <i>Nephotettix cincticeps</i>

et al. 1990

View full text Add to dashboard Cite

show abstract

“…This may also be the case for slight increases in potency induced by the introduction of bulky alkyl groups into the 4-position. The inhibitory activity (expressed as log [IP/ (100-IP)]) of 4-substituted BPs against HAChE is related to the Hancock steric parameter Ese 11,12) of the bridgehead substituent. The relationship is shown in Fig.…”

Section: Discussionmentioning

confidence: 99%

Reaction of Toxic Bicyclic Phosphates with Acetylcholinesterases andα-Chymotrypsin

Ozoe

Mochida

Etō

1982

Agricultural and Biological Chemistry

View full text Add to dashboard Cite

“…The values used for σ* and E s are obtained empirically, and represent the results from the investigations conducted by Taft [35] and Hancock et al [36]. The inspection of the figures reveals that the pK BH + values are uniquely influenced by neither Σσ* nor ΣE s .…”

Section: Hammett-taft Correlationsmentioning

confidence: 97%

Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopy

Dimitrieska-Stojković

Popovski

2015

Maced. J. Chem. Chem. Eng.

View full text Add to dashboard Cite

The protonation of ten aliphatic amides in sulfuric acid media was studied by UV spectroscopy. (-0.57, -0.29, -0.32 and 0.36, respectively), analogous acetamides were more basic than formamides. Applying the Hammett's equation, satisfactory correlation could be gained only for some formamides, the basicities of which increased linearly with the inductive effect of the electron donating groups. From Taft's approach, it can be concluded that the polar effect slightly dominates over the steric one. Excellent correlation between pK BH + and solvation parameters m* was achieved for formamide, dimethylformamide and diethylformamide. At half-and fullprotonation, better correlation was obtained for formamides than for acetamides.Keywords: UV spectroscopy; formamides; acetamides; protonation constants; Hammett-Taft correlations ОПРЕДЕЛУВАЊЕ НА КОНСТАНТИТЕ НА ПРОТОНИРАЊЕ И СТРУКТУРНИ КОРЕЛАЦИИ НА НЕКОИ ТЕРЦИЈАРНИ ФОРМАМИДИ И АЦЕТАМИДИ ВО СУЛФУРНА КИСЕЛИНА СО УЛТРАВИОЛЕТОВА СПЕКТРОСКОПИЈАПротонирањето на десет алифатични амиди во сулфурна киселина е проучувано со примена на ултравиолетова спектроскопија. Вредностите за pK BH+ и солватационите параметри се пресметани според методот на Yates и McClelland, методот на вишок на киселост и Bunnett-Olsen-овиот метод. Вредностите за pK BH + изнесуваат -1.44, -1.15, -0.80, -0.32, -1.13 и -0.80 за формамид, диметилформамид, диетилформамид, диизопропилформамид, диизобутилформамид и дибутилформамид, соодветно. Според вредностите на pK BH+ определени за ацетамид, диметилацетамид, диетилацетамид и диизопропилацетамид (-0.57, -0.29, -0.32 и 0.36, соодветно) аналогните ацетамиди се побазни од формамидите. Со примена на Hammett-овата равенка добиени се задоволителни резултати само за некои формамиди, чија базност линеарно расте со индуктивниот ефект на електронодонорната група. Од Taft-овскиот пристап може да се заклучи дека поларниот ефект е незначително поголем од стерниот. Постигната е одлична корелација помеѓу вредностите на pK BH + и солватационите параметри m* за формамид, диметилформамид и диетилформамид. Кај полу-и целосна протонација, подобра корелација е добиена за формамиди отколку за ацетамиди.Клучни зборови: UV спектроскопија; формамиди; ацетамиди; константи на протонирање; Hammett-Taft-овски корелации G. Stojković, E. Dimitrieska-Stojković, E. Popovski Maced. J. Chem. Chem. Eng. 34 (2), 255-265 (2015) 256

show abstract

Quantitative Separation of Hyperconjugation Effects from Steric Substituent Constants

Cited by 179 publications

References 1 publication

Relationships between Insecticidal Activity of 6-Alkylthio-2-pyridyl Methanesulfonates and Acetylcholinesterase Inhibition of their Sulfone Derivatives against <i>Nephotettix cincticeps</i>

Relationships between Insecticidal Activity of 6-Alkylthio-2-pyridyl Methanesulfonates and Acetylcholinesterase Inhibition of their Sulfone Derivatives against <i>Nephotettix cincticeps</i>

Reaction of Toxic Bicyclic Phosphates with Acetylcholinesterases andα-Chymotrypsin

Determination of protonation constants and structural correlations for some tertiary formamides and acetamides in sulfuric acid with UV spectroscopy

Contact Info

Product

Resources

About