Electrophilic aromatic directing groups
In an electrophilic aromatic substitution reaction, existing substituent groups on the aromatic ring influence the overall reaction rate or have a directing effect on positional isomer of the products that are formed. An electron donating group or electron releasing group is an atom or functional group that donates some of its electron density into a conjugated π system via resonance or inductive effects —called +M or +I effects, respectively—thus making the π system more nucleophilic. As a result of these electronic effects, an aromatic ring to which such a group is attached is more likely to participate in electrophilic substitution reaction. EDGs are therefore often known as activating groups, though steric effects can interfere with the reaction.
An electron withdrawing group will have the opposite effect on the nucleophilicity of the ring. The EWG removes electron density from a π system, making it less reactive in this type of reaction, and therefore called deactivating groups.
EDGs and EWGs also determine the positions on the aromatic ring where substitution reactions are most likely to take place; this property is therefore important in processes of organic synthesis.
Electron donating groups are generally ortho/para directors for electrophilic aromatic substitutions, while electron withdrawing groups are generally meta directors with the exception of the halogens which are also ortho/para directors as they have lone pairs of electrons that are shared with the aromatic ring.
Categories
Electron donating groups are typically divided into three levels of activating ability Electron withdrawing groups are assigned to similar groupings. Activating substituents favour electrophilic substitution about the ortho and para positions. Weakly deactivating groups direct electrophiles to attack the benzene molecule at the ortho- and para- positions, while strongly and moderately deactivating groups direct attacks to the meta- position. This is not a case of favoring the meta- position like para- and ortho- directing functional groups, but rather disfavouring the ortho- and para-positions more than they disfavour the meta- position.Activating groups
The activating groups are mostly resonance donors. Although many of these groups are also inductively withdrawing, which is a deactivating effect, the resonance effect is almost always stronger, with the exception of Cl, Br, and I.| Magnitude of activation | Substituent Name | Structure | Type of electronic effect | Directing effect |
| Extreme | oxido group | -O− | +I, +M | ortho, para |
| Strong | amino groups | -NH2, -NHR, -NR2 | –I, +M | ortho, para |
| Strong | hydroxy and alkoxy groups | -OH, -OR | –I, +M | ortho, para |
| Moderate | acylamido groups | -NHCOR | –I, +M | ortho, para |
| Moderate | acyloxy groups | -OCOR | –I, +M | ortho, para |
| Moderate | alkylphosphino, alkylthio, and sulfhydryl groups | -PR2, -SR, -SH | +M | ortho, para |
| Weak | phenyl group | -C6H5 | –I, +M; though other interactions may be involved as well | ortho, para |
| Weak | vinyl group | -CH=CH2 | –I, +M; though other interactions may be involved as well | ortho, para |
| Weak | alkyl groups | -R | +I | ortho, para |
| Weak | carboxylate group | -CO2− | +I | ortho, para |
| Weak | fluoro group | -F | –I, +M | para |
In general, the resonance effect of elements in the third period and beyond is relatively weak. This is mainly because of the relatively poor orbital overlap of the substituent's 3p orbital with the 2p orbital of the carbon.
Due to a stronger resonance effect and inductive effect than the heavier halogens, fluorine is anomalous. The partial rate factor of electrophilic aromatic substitution on fluorobenzene is often larger than one at the para position, making it an activating group. Conversely, it is moderately deactivated at the ortho and meta positions, due to the proximity of these positions to the electronegative fluoro substituent.
Deactivating groups
While all deactivating groups are inductively withdrawing, most of them are also withdrawing through resonance as well. Halogen substituents are an exception: they are resonance donors. With the exception of the halides, they are meta directing groups.Halides are ortho, para directing groups but unlike most ortho, para directors, halides mildly deactivate the arene. This unusual behavior can be explained by two properties:
- Since the halogens are very electronegative they cause inductive withdrawal.
- Since the halogens have non-bonding electrons they can donate electron density through pi bonding.
| Magnitude of deactivation | Substituent Name | Structure | Type of electronic effect | Directing effect |
| Strong | trifluoromethylsulfonyl group | -SO2CF3 | –I, –M | meta |
| Strong | ammonium groups | –I | meta | |
| Strong | nitro group | –I, –M | meta | |
| Strong | sulfonic acids and sulfonyl groups | –I, –M | meta | |
| Strong | cyano group | –I, –M | meta | |
| Strong | trihalomethyl groups | -CX3 | –I | meta |
| Moderate | haloformyl groups | -COX | –I, –M | meta |
| Moderate | formyl and acyl groups | -CHO, -COR | –I, –M | meta |
| Moderate | carboxyl and alkoxycarbonyl groups | -CO2H, -CO2R | –I, –M | meta |
| Moderate | aminocarbonyl groups | -CONHR, -CONR2 | –I, –M | meta |
| Weak | fluoro group | -F | –I, +M | ortho, para |
| Weak | nitroso group | -N=O | –I, +M or –M | ortho, para |
| Weak | halo groups | -Cl, -Br, -I | –I, +M | ortho, para |
Different groups effects on benzene
Carbonyls, sulfonic acids and nitro
Because of the full or partial positive charge on the element directly attached to the ring for each of these groups, they all have a moderate to strong electron-withdrawing inductive effect. They also exhibit electron-withdrawing resonance effects, :Thus, these groups make the aromatic ring very electron-poor relative to benzene and, therefore, they strongly deactivate the ring
[Aniline]s, [Phenols] and [Ether]s (such as [anisole])
Due to the electronegativity difference between carbon and oxygen / nitrogen, there will be a slight electron withdrawing effect through inductive effect. However, the other effect called resonance add electron density back to the ring and dominate over that of inductive effect. Hence the result is that they are EDGs and ortho/para directors.Phenol is an ortho/para director, but in a presence of base, the reaction is more rapid. It is due to the higher reactivity of phenolate anion. The negative oxygen was 'forced' to give electron density to the carbons. Even when cold and with neutral electrophiles, the reaction still occurs rapidly.
Alkyl groups
are electron donating groups. The carbon on that is sp3 hybridized and less electronegative than those that are sp2 hybridized. They have overlap on the carbon-hydrogen bonds with the ring p orbital. Hence they are more reactive than benzene and are ortho/para directors.Carboxylate
Inductively, the negatively charged carboxylate ion moderately repels the electrons in the bond attaching it to the ring. Thus, there is a weak electron-donating +I effect. There is an almost zero -M effect since the electron-withdrawing resonance capacity of the carbonyl group is effectively removed by the delocalisation of the negative charge of the anion on the oxygen. Thus overall the carboxylate group has an activating influence.Alkylammonium and trifluoromethyl group
These groups have a strong electron-withdrawing inductive effect either by virtue of their positive charge or because of the powerfully electronegativity of the halogens. There is no resonance effect because there are no orbitals or electron pairs which can overlap with those of the ring. The inductive effect acts like that for the carboxylate anion but in the opposite direction Hence these groups are deactivating and meta directing:Halides competing effects
Induction versus Resonance
is something of an anomaly in this circumstance. Above, it is described as a weak electron withdrawing group but this is only partly true. It is correct that fluorine has a -I effect, which results in electrons being withdrawn inductively. However, another effect that plays a role is the +M effect which adds electron density back into the benzene ring. This is called the mesomeric effect and the result for fluorine is that the +M effect approximately cancels out the -I effect. The effect of this for fluorobenzene at the para position is reactivity that is comparable to that of benzene. Because inductive effects depends strongly on proximity, the meta and ortho positions of fluorobenzene are considerably less reactive than benzene. Thus, electrophilic aromatic substitution on fluorobenzene is strongly para selective.This -I and +M effect is true for all halides - there is some electron withdrawing and donating character of each. To understand why the reactivity changes occur, we need to consider the orbital overlaps occurring in each. The valence orbitals of fluorine are the 2p orbitals which is the same for carbon - hence they will be very close in energy and orbital overlap will be favourable. Chlorine has 3p valence orbitals, hence the orbital energies will be further apart and the geometry less favourable, leading to less donation the stabilize the carbocationic intermediate, hence chlorobenzene is less reactive than fluorobenzene. However, bromobenzene and iodobenzene are about the same or a little more reactive than chlorobenzene, because although the resonance donation is even worse, the inductive effect is also weakened due to their lower electronegativities. Thus the overall order of reactivity is U-shaped, with a minimum at chlorobenzene/bromobenzene : PhF > PhCl ~ PhBr < PhI. But still, all halobenzenes reacts slower than benzene itself.
Notice that iodobenzene is still less reactive than fluorobenzene because polarizability plays a role as well. This can also explain why phosphorus in phosphanes can't donate electron density to carbon through induction although it is less electronegative than carbon and why hydroiodic acid being much more acidic than hydrofluoric acid.
Directing Effect
Due to the lone pair of electrons, halogen groups are available for donating electrons. Hence they are therefore ortho / para directors.Nitroso group
Induction
Due to the electronegativity difference between carbon and nitrogen, the nitroso group has a relatively strong -I effect, but not as strong as the nitro group.Resonance
The nitroso group has both a +M and -M effect, but the -M effect is more favorable.Nitrogen has a lone pair of electrons. However, the lone pair of its monomer form is unfavourable to donate through resonance. Only the dimer form is available for +M effect. However, the dimer form is less stable in a solution. Therefore, the nitroso group is less available to donate electrons.
Oppositely, withdrawing electron density is more favourable:.As a result, the nitroso group is a deactivator. However, it has available to donate electron density to the benzene ring during the Wheland intermediate, making it still being an ortho / para director.
Steric">Steric effects">Steric effects
There are 2 ortho positions, 2 meta positions and 1 para position on benzene when a group is attached to it. When a group is an ortho / para director with ortho and para positions reacting with the same partial rate factor, we would expect twice as much ortho product as para product due to this statistical effect. However, the partial rate factors at the ortho and para positions are not generally equal. In the case of a fluorine substituent, for instance, the ortho partial rate factor is much smaller than the para, due to a stronger inductive withdrawal effect at the ortho position. Aside from these effects, there is often also a steric effect, due to increased steric hindrance at the ortho position but not the para position, leading to a larger amount of the para product.The effect is illustrated for electrophilic aromatic substitutions with alkyl substituents of differing steric demand for electrophilic aromatic nitration.
| Substrate | toluene | ethylbenzene | cumene | tert-butylbenzene |
| ortho product | 58 | 45 | 30 | 16 |
| meta product | 5 | 6 | 8 | 11 |
| para product | 37 | 59 | 62 | 73 |
| ortho/para ratio | 1.57 | 0.76 | 0.48 | 0.22 |
The methyl group in toluene is small and will lead the ortho product being the major product. On the other hand, the t-butyl group is very bulky and will lead the para product as the major one. Even with toluene, the product is not 2:1 but having a slightly less ortho product.
Directing effect on multiple substituents
When two substituents are already present on the ring, the third substituent's place will be on a located place. The rules for the substituent are as follows:- When two ortho/para directors are meta to each other, the third substituent will not be located between them.
- When both an ortho/para director and a meta director is present on the ring, the third substituent's place depends on the ortho/para director.
- When both group are the same director, the third substituent depends on the stronger one.
- When both group have similar directing effect and are para to each other, the third substituent depends on the less hindered one.
Rationalization of directing effects
The perturbation of a conjugating electron-withdrawing or electron-donating group causes the π electron distribution to resemble that of the electron-deficient benzyl cation or electron-excessive benzyl anion, respectively, although the change in electron distribution occurs to a smaller degree than in these limiting cases. Thus, we can use these simple species, whose π electron distribution can be calculated using simple Hückel theory, as models to rationalize the regiochemical outcome of electrophilic aromatic substitution. As can be seen, the π electron population at the ortho and para positions is depleted for the case of an electron-withdrawing group, causing meta attack to be occur as the least disfavourable option. In contrast, when an electron donating group is present, the ortho and para positions have an increased π electron population compared to the meta position, favoring attack at the ortho and para positions over the meta position.
This is precisely the result that the drawing of resonance structures would predict. For example, in nitrobenzene the resonance structures have positive charges around the ring system :
Attack occurs at the meta position, since the ortho and para positions have formal positive charges that are indicative of π electron deficiency at these positions, leaving the meta positions a slightly higher electron density.
On the other hand, in aniline the resonance structures have negative charges around the ring system :
Attack occurs at the ortho and para positions, which have formal negative charges that indicate π electron excess at these positions.
Another common argument, which makes identical predictions, considers the stabilization or destabilization by substituents of the Wheland intermediates resulting from electrophilic attack at the ortho/para or meta positions. The Hammond postulate then dictates that the relative transition state energies will reflect the differences in the ground state energies of the Wheland intermediates.
The selectivities observed with EDGs and EWGs were first described in 1892 and have been known as the Crum Brown–Gibson rule.