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Electron-withdrawing groups exert an "inductive" or "electron-pulling" effect on covalent bonds. The strength of the electron-withdrawing group is inversely proportional to the pKa of the carboxylic acid. [2] The inductive effect is cumulative: trichloroacetic acid is 1000x stronger than chloroacetic acid.
The electron-withdrawing effect of the substituent makes ionisation easier, so successive pK a values decrease in the series 4.7, 2.8, 1.4, and 0.7 when 0, 1, 2, or 3 chlorine atoms are present. [49] The Hammett equation , provides a general expression for the effect of substituents.
For meta-directing groups (electron withdrawing group or EWG), σ meta and σ para are more positive than σ’. (The superscript, c, in table denotes data from Hammett, 1940. [11] [page needed]) For ortho-para directing groups (electron donating group or EDG), σ’ more positive than σ meta and σ para.
If the electronegative atom (missing an electron, thus having a positive charge) is then joined to a chain of atoms, typically carbon, the positive charge is relayed to the other atoms in the chain. This is the electron-withdrawing inductive effect, also known as the -I effect. In short, alkyl groups tend to donate electrons, leading to the +I ...
With respect to acidity, a common trend to note is that, inductively, an electron-withdrawing substituent in the vicinity of an acidic proton will lower the pKa (i.e. increase the acidity) and, correspondingly, an electron-donating substituent will raise the pKa. [7] The reorganization of charge due to field effects will have the same result.
Triflidic acid, with three strongly electron-withdrawing triflyl groups, has an estimated pK a well below −10. On the other end of the scale, hydrocarbons bearing only alkyl groups are thought to have pK a values in the range of 55 to 65. The range of acid dissociation constants for carbon acids thus spans over 70 orders of magnitude.
The negative charge that is left after deprotonation of the carboxyl group is delocalized between the two electronegative oxygen atoms in a resonance structure. If the R group is an electron-withdrawing group (such as –CF 3), the basicity of the carboxylate will be further weakened. [1]: 264–5
The mesomeric effect is negative (–M) when the substituent is an electron-withdrawing group, and the effect is positive (+M) when the substituent is an electron donating group. Below are two examples of the +M and –M effect. Additionally, the functional groups that contribute to each type of resonance are given below.