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| Decreases acidity in solution (makes it harder to solvate) |
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| Increase Acidity by stabilizing the anion |
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| esters, nitriles, sulfones |
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| Acids prefer the Z-form by about 5 kcal/mol |
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| More substituted carbons more stable cation because of electron donating methyls and hyperconjugation/resonance |
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| Stability affected by Electronegativity, delocatiolization of charge |
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Activation Energy -> half life
3 5 10 15 20 30 |
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3->17E-12s
5->4.8E-10s
10->2E-6s
15->0.0084s
20->35s
30->6916 days |
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| More substituted carbons also more stable radicals |
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Equilibrium Constants and Free Energy Difference
0
-1.36
-2.72
-4.08 |
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0 -> K = 1 50% each
-1.36 -> K = 10 90% 10%
-2.72 -> K = 100 99% 1%
-4.08 -> K = 1000 99.9% 0.1% |
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Thorpe-Ingold Effect
Gem-dimethyl Effect |
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| Increasing size of substituents of tetrahedral center increases reaction rate between other two and decreases the angle |
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| Explains why OCH3 prefers axial when in a heterocycle, and why hydrogen peroxide is at 120 |
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| Withdrawing Electrons through sigma bonds to the more electronegative group |
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| polarization through charges that interact through space |
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| 1/2(Ionization Potential + Electron Affinity) |
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log ([SL]/[S]) vs. log [L]
expect 1 but if slope greater than one hints at cooperativity |
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Double Reciprocal
1/[Fraction of S] vs. 1/[L] |
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| calculates affinity constant of ligand with protein |
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R lnKa =
(with heat capacity) |
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| Measured by the shielding a solvent gives when put between a capacitor by opposing the E-field |
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Related to the Bell Equation and Dielectric Constant
e-1/2e+1 |
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Hildebrand
"Cohesive Energy Density"
d^2 = dH(vap) - RT/molar volume |
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Kosover Z-Scale (Z)
Reichardt Scale (Et) |
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From Absorption Spectra of salts
The more polar the solvent the higher the frequency of light needed to go from ion pair to two radicals |
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Winstein and Grunwald
Used rates of solvolysis of t-Bu chloride
log ky/k0 = mY
m - substrate specificity
Y = solvent scale and also related to Et
k0 based off 80% aquaous ethanol (20% water) |
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1) Temperature of max density higher than melting point
2)thermal expansion 1/V(dV/dT) is negative from -20 to 4
3) Bulk Modulus Kappa= -VdP/dV
has minimum at 46 C
4)Cp pretty much constant from 0-100 but changes a lot at low temperatures |
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| Crown Ethers and Macrocycles pioneered by: |
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| Kemp's Triacid to bind DNA bases |
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| Cyclophane like things to make bind adenine |
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Molecular Tweezers
3 aromatic portions with acid moeity to bind |
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| Secondary vs. Primary H-bonding |
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Primary worth 7.5
Secondary worth 2.5 |
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Diederich
evolved from Pedersens crown ethers
Had solubilizing Ammonium Groups |
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| larger anions not as well solvated, originally thought to be lone-pair lone-pair repulsions |
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log Kx/Ko = sigmax * rho
a positive sigma -> electron withdrawing
negative -> electron donating
ρ>1, the reaction is more sensitive to substituents than benzoic acid and negative charge is built during the reaction.
0<ρ<1 , the reaction is less sensitive to substituents than benzoic acid and negative charge is built.
ρ=0, no sensitivity to substituents, and no charge is built.
ρ<0, the reaction builds positive charge. |
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log (k/ko) = sn
n = nucleophilicity
s = substrate specificity |
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| Grunwald-Winstein Equation |
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log(k/ko) = mY
Y is solvent scale
m is sensitivity of substrate
based of solvolysis of t-butyl chloride in 80% aqueous ethanol |
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| alpha-carbonyl effect on Sn2 |
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| has to be in the same plane with p orbital of carbonyl and siqma star LUMO |
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