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Nitration of substituted benzene

However, there are two key differences between their reactions with electrophiles. First, benzene is very stable and thus less reactive. Second, unlike the alkenes, it undergoes an electrophilic substitution and not an electrophilic addition reaction :. The first difference of benzene being less reactive brings the need for using a Lewis acid FeBr 3 which turns the Br 2 into a stronger electrophile and makes the reaction possible.

We will see how that works next. The second difference is that the Br in the electrophilic aromatic substitution reaction replaces the hydrogen while both hydrogens are still there when they are on the alkene.

nitration of substituted benzene

And in fact, this is still related to the stability of the aromatic ring. Even though the reaction goes through an intermediate where the aromaticity is broken, it still ends up restored because that brings a lot of stability and energetically is very favorable. Regardless of what electrophile is used, the electrophilic aromatic substitution mechanism can be divided into two main steps. Because of the new sigma bond formed, this intermediate is called a sigma complex.

This, energetically unfavorable process of interrupting aromaticity, is the slow- rate determining step of the reaction. On the other hand, the arenium ion is not the worst carbocation you will ever see. It is secondarythere two conjugated double bondswhich in turn are conjugated with the empty p orbital of the positively charged carbon.

It has three resonance formswhere the positive charge appears on three carbons and the resonance hybrid can be shown with these carbons having a partial positive charge:. The deprotonation is the driving force of the reaction making it energetically possible to proceed.

nitration of substituted benzene

The activation energy of this step is a lot smaller and the reaction occurs very fast:. Benzene only reacts with bromine and chlorine in the presence of Lewis acids as they coordinate to the halogens and generate strong electrophilic species.

The Lewis acids are usually aluminum chloride AlCl 3 or iron chloride FeCl 3 used for the chlorination, and iron bromide FeBr 3 for the bromination of the aromatic ring:. Once the electrophile is formed, it follows the same general mechanism as we have discussed earlier. First, the addition of the electrophile, forming the sigma complex which is then deprotonated by — AlCl 4. The rest of the mechanism is identical to what we saw for the chlorination of benzene.

Iodine is unreactive under identical conditions and the iodination of benzene is achieved in the presence of an oxidizing agent such as nitric acid or a mixture of hydrogen peroxide and sulfuric acid. Fluorination of benzeneon the other hand, is a violent reaction and cannot be achieved directly. Plus, handling F 2 is not really what you want to do unless you absolutely have to, and are trained to do so.

Instead, it is done by converting benzene into an arenediazonium salt which is then replaced by fluorine by reacting it with fluoroboric acid HBF 4. This is the Schiemann reaction. The rest is according to the general mechanism of electrophilic aromatic substitution:. The nitration of benzene is an important reaction since nitrobenzene is an essential precursor for the synthesis of aniline which is used in many other reactions, including the one we have just seen for the synthesis of fluorobenzene.

Benzene can be converted into benzenesulfonic by reacting it with fuming sulfuric acid which is prepared by adding sulfur trioxide SO 3. Depending on your needs, you may shift the equilibrium to either side. If you need a sulfonation of the aromatic ring, then use a concentrated solution of H 2 SO 4. This selective placing of the SO 3 group on the aromatic ring is used as a protecting groupto temporarily block its position from other electrophiles, or as a directing group which we will discuss in the following posts.

By joining Chemistry Steps, you will gain instant access to the answers and solutions for All the practice problems including over 20 hours of problem-solving videos and.

If you are already registered, upgrade your subscription to CS Prime under your account settings. The Mechanism of Electrophilic Aromatic Substitution Regardless of what electrophile is used, the electrophilic aromatic substitution mechanism can be divided into two main steps.

Nitration and Sulfonation of Benzene

Halogenation of Benzene Benzene only reacts with bromine and chlorine in the presence of Lewis acids as they coordinate to the halogens and generate strong electrophilic species. Iodination of Benzene Iodine is unreactive under identical conditions and the iodination of benzene is achieved in the presence of an oxidizing agent such as nitric acid or a mixture of hydrogen peroxide and sulfuric acid.

Fluorination of Benzene Fluorination of benzeneon the other hand, is a violent reaction and cannot be achieved directly. Sulfonation of Benzene Benzene can be converted into benzenesulfonic by reacting it with fuming sulfuric acid which is prepared by adding sulfur trioxide SO 3.By using our site, you acknowledge that you have read and understand our Cookie PolicyPrivacy Policyand our Terms of Service.

nitration of substituted benzene

Chemistry Stack Exchange is a question and answer site for scientists, academics, teachers, and students in the field of chemistry. It only takes a minute to sign up. However, from what I also understand, oxygen is also a highly electronegative atom and therefore inductively draws electron density away from the benzene ring. Am I right in concluding that resonance effects are stronger than inductive effects, if not in general, then at least for electrophilic substitution of substituted aryls?

Often, but not always, mesomeric displacement leads to a shift in prevailing over the inductive effect. Pi-electrons are at the peripheral orbitals.

Electrophilic Substitution Of Benzene

Association with the nucleus is less strong than at the sigma-electrons. The ionization potential of pi-electrons is smaller and chemical bond is more polarizable. Therefore, the dipole moment associated with the mesomeric effect can prevail over the dipole moment associated with the inductive effect.

Also, you can read about hyperconjugation.

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Hyperconjugation can have influence to the mesomeric and inductive effects too. Source: Reutov O. Consider the case of electrophilic aromatic substitution of fluorobenzene.

Fluorobenzene undergoes electrophilic nitration roughly 10 times slower than benzene, yet it strongly directs ortho and para. The fluorine is donating electrons through resonance into the benzene ring - but only to the ortho and para positions; resonance structures cannot be drawn that donate electron density to the meta position this applies to both the ground state and transition state resonance structures.

Fluorine is much more electronegative than hydrogen, so inductively fluorine will remove electron density from the ring -I effect. Since the reaction rate for electrophilic nitration is decelerated in fluorobenzene compared to benzene, this indicates that there is less stabilization less electron density to stabilize the positive charge of the transition state in the fluorobenzene reaction than in the benzene raection.

There is a continuous rebalancing of inductive and resonance effects as we move through the series benzene, toluene, dimethyl aniline, anisole and fluorobenzene. With dimethyl aniline and anisole, the resonance effects far outweigh the inductive effects, but by the time we reach fluorine the inductive effect outweighs the resonance effect.

I thought the previous answers were incomplete, mainly because previous answers have talked about halo arenes, particularly about fluorobenzene. Your question reminds me of a doubt I had once. Consider the two structures shown below:. Can I say these two are geometrical isomers? It sounds a pretty dumb question, but here is the thing.

nitration of substituted benzene

Therefore one could say that the rotation of the carbon is restricted and hence are geometrical isomers. By inductive effect.

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Or at least that is what my teacher said.In contrast to nitration of alcohols, the nitration of benzene produces relatively stable nitro compounds that are much more difficult to detonate. The remarkable stability of the unsaturated hydrocarbon benzene has been discussed in an earlier section. Adding an alkyl group to the benzene ring. Deactivation of the product toward further substitution. A substituent -X is said to be deactivating if the rate of A wide variety of sulfonation of benzene options are available to you, There are 4, suppliers who sells sulfonation of benzene on Alibaba.

Ad by DuckDuckGo. Sulfonation, chlorination, nitration. So we would have our benzene ring. In an aromatic sulfonation reaction, a sulfonyl group -SO3H replaces a hydrogen on an aromatic ring such as benzene. Like benzene, thiophene forms an azeotrope with ethanol. Linear alkyl benzene sulphonic acid, also known as LABSA is a synthetic chemical surfactant, which is a widely used industrial detergent.

Sulfonation with sulfur trioxide and sulfuric acid converts benzene into benzene sulfonic acid. The reaction was stopped and products were analysed by extraction with water and benzene. Since R groups activate the ring, the alkylated product C6H5R is now more reactive than benzene itself towards further substitution, and it reacts again with RCl to give products of polyalkylation.

Why is this so?

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The reaction of benzene with concentrated sulfuric acid at room temperature produces benzenesulfonic acid. Sulfonation is a reversible reaction that produces benzenesulfonic acid by adding sulfur trioxide and fuming sulfuric acid. After a nitro group is connected to the benzene ring, the nitro group can inhibit the further nitration of benzene, and a nitro group is a passivation group. There are two equivalent ways of sulphonating benzene: Heat benzene under reflux with concentrated sulphuric acid for several hours.

Let us help you simplify your studying. The sulphonation of benzene can be done when benzene is treated with concentrated H 2 SO 4 acid and heat the mixture. The primary alkylation of benzene by Friedel-Crafts reaction works only for methyl and ethyl halides since longer chains undergo rearrangement.Animation controls: Display controls:. Click the structures and reaction arrows in sequence to view the 3D models and animations respectively.

Nitration of benzene firstly involves the formation of a very powerful electrophile, the nitronium ion, which is linear. This occurs following the interaction of two strong acids, sulfuric and nitric acid. Sulfuric acid is the stronger and it protonates the nitric acid on the OH group so that a molecule of water can leave. This is followed by rapid loss of a proton to regenerate the aromaticity.

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It is mandatory to procure user consent prior to running these cookies on your website. Close Animation controls: Display controls:. Click the structures and reaction arrows in sequence to view the 3D models and animations respectively Nitration of benzene firstly involves the formation of a very powerful electrophile, the nitronium ion, which is linear. How useful was this page? Click on a star to rate it! As you found this page useful Follow us on social media!

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Necessary Always Enabled. Non-necessary Non-necessary.Aromatic Substitution Reactions. The remarkable stability of the unsaturated hydrocarbon benzene has been discussed in an earlier section. The chemical reactivity of benzene contrasts with that of the alkenes in that substitution reactions occur in preference to addition reactions, as illustrated in the following diagram some comparable reactions of cyclohexene are shown in the green box.

Nitration of Benzene

A demonstration of bromine substitution and addition reactions is helpful at this point, and a virtual demonstration may be initiated by clicking here. Many other substitution reactions of benzene have been observed, the five most useful are listed below chlorination and bromination are the most common halogenation reactions. Since the reagents and conditions employed in these reactions are electrophilic, these reactions are commonly referred to as Electrophilic Aromatic Substitution.

The catalysts and co-reagents serve to generate the strong electrophilic species needed to effect the initial step of the substitution. The specific electrophile believed to function in each type of reaction is listed in the right hand column. A two-step mechanism has been proposed for these electrophilic substitution reactions.

In the first, slow or rate-determining, step the electrophile forms a sigma-bond to the benzene ring, generating a positively charged benzenonium intermediate. In the second, fast step, a proton is removed from this intermediate, yielding a substituted benzene ring.

The following four-part illustration shows this mechanism for the bromination reaction. Also, an animated diagram may be viewed. These may be viewed repeatedly by continued clicking of the "Next Slide" button. This mechanism for electrophilic aromatic substitution should be considered in context with other mechanisms involving carbocation intermediates. To summarize, when carbocation intermediates are formed one can expect them to react further by one or more of the following modes:.

The cation may bond to a nucleophile to give a substitution or addition product. The cation may transfer a proton to a base, giving a double bond product. The cation may rearrange to a more stable carbocation, and then react by mode 1 or 2. S N 1 and E1 reactions are respective examples of the first two modes of reaction. The second step of alkene addition reactions proceeds by the first mode, and any of these three reactions may exhibit molecular rearrangement if an initial unstable carbocation is formed.

The carbocation intermediate in electrophilic aromatic substitution the benzenonium ion is stabilized by charge delocalization resonance so it is not subject to rearrangement. In principle it could react by either mode 1 or 2, but the energetic advantage of reforming an aromatic ring leads to exclusive reaction by mode 2 ie.

When substituted benzene compounds undergo electrophilic substitution reactions of the kind discussed above, two related features must be considered:.

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The first is the relative reactivity of the compound compared with benzene itself. Experiments have shown that substituents on a benzene ring can influence reactivity in a profound manner. For example, a hydroxy or methoxy substituent increases the rate of electrophilic substitution about ten thousand fold, as illustrated by the case of anisole in the virtual demonstration above.

In contrast, a nitro substituent decreases the ring's reactivity by roughly a million.Are you a chemistry student? Visit A-Level Chemistry to download comprehensive revision materials - for UK or international students! Nitration of benzene is an example of elctrophilic aromatic substitution reaction. As for example Benzene reacts with concentrated nitric acid in presence of concentrated sulphuric acid as a catalyst, and form nitrobenzene.

When benzene is treated with concentrated nitric acid and concentrated sulphuric acid at below 55 o C temperature, nitrobenzene is formed. If we increase the temperature there is a greater chance of entering more than one nitro group in the benzene ring. This ion is formed by the reaction between the concentrated nitric acid and concentrated sulphuric acid. This positive charge is then delocalised all through the benzene ring just like it shows in above scheme.

The hydrogen attached to the same carbon where the nitro group is attached is also shown in figure which will be removed in next step. The hydrogensulphate ion HSO 4 — which was formed during the formation of electrophile- nitronium ion, removes the hydrogen attached with the nitro group containing carbon. Thus the positive charge of the ring neutralized and delocalisation reestablished. Nitrobenzene is very reactive and it can produce dinitrobenzene in presence of same reagent.

The formation of ortho, meta and para-dinitrobenzene is as follows:. Nitrobenzene is very toxic and it can readily absorb through the skin. So precaution must need to be taken during and after the reaction. Nitrobenzene may cause:. In United states it is classified as a extremely hazardous substance and likely human carcinogenic.

Rate this note. Introduction to nitration of benzene Nitration of benzene is an example of elctrophilic aromatic substitution reaction. Nitration of benzene When benzene is treated with concentrated nitric acid and concentrated sulphuric acid at below 55 o C temperature, nitrobenzene is formed.

The formation of ortho, meta and para-dinitrobenzene is as follows: Safety issues Nitrobenzene is very toxic and it can readily absorb through the skin.Nitration and sulfonation of benzene are two examples of electrophilic aromatic substitution.

The source of the nitronium ion is through the protonation of nitric acid by sulfuric acid, which causes the loss of a water molecule and formation of a nitronium ion. The first step in the nitration of benzene is to activate HNO 3 with sulfuric acid to produce a stronger electrophile, the nitronium ion.

Because the nitronium ion is a good electrophile, it is attacked by benzene to produce Nitrobenzene. Resonance forms of the intermediate can be seen in the generalized electrophilic aromatic substitution. Sulfonation is a reversible reaction that produces benzenesulfonic acid by adding sulfur trioxide and fuming sulfuric acid.

The reaction is reversed by adding hot aqueous acid to benzenesulfonic acid to produce benzene. To produce benzenesulfonic acid from benzene, fuming sulfuric acid and sulfur trioxide are added. Fuming sulfuric acid, also refered to as oleumis a concentrated solution of dissolved sulfur trioxide in sulfuric acid. The sulfur in sulfur trioxide is electrophilic because the oxygens pull electrons away from it because oxygen is very electronegative.

The benzene attacks the sulfur and subsequent proton transfers occur to produce benzenesulfonic acid. Sulfonation of benzene is a reversible reaction.

Sulfur trioxide readily reacts with water to produce sulfuric acid and heat. Therefore, by adding heat to benzenesulfonic acid in diluted aqueous sulfuric acid the reaction is reversed. Nitration is used to add nitrogen to a benzene ring, which can be used further in substitution reactions. The nitro group acts as a ring deactivator.

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Having nitrogen present in a ring is very useful because it can be used as a directing group as well as a masked amino group. The products of aromatic nitrations are very important intermediates in industrial chemistry. Because sulfonation is a reversible reaction, it can also be used in further substitution reactions in the form of a directing blocking group because it can be easily removed.

The sulfonic group blocks the carbon from being attacked by other substituents and after the reaction is completed it can be removed by reverse sulfonation. Benzenesulfonic acids are also used in the synthesis of detergents, dyes, and sulfa drugs. Bezenesulfonyl Chloride is a precursor to sulfonamides, which are used in chemotherapy.

Draw an energy diagram for the nitration of benzene. Draw the intermediates, starting materials, and products. Label the transition states. For questions 1 and 2 see Electrophilic Aromatic Substitution for hints. Sulfuric acid is needed in order for a good electrophile to form. Sulfuric acid protonates nitric acid to form the nitronium ion water molecule is lost. The nitronium ion is a very good electrophile and is open to attack by benzene.

Without sulfuric acid the reaction would not occur. Nitration of Benzene The source of the nitronium ion is through the protonation of nitric acid by sulfuric acid, which causes the loss of a water molecule and formation of a nitronium ion. Sulfuric Acid Activation of Nitric Acid The first step in the nitration of benzene is to activate HNO 3 with sulfuric acid to produce a stronger electrophile, the nitronium ion.

Nitration of Benzene

Mechanism Resonance forms of the intermediate can be seen in the generalized electrophilic aromatic substitution. Sulfonation of Benzene Sulfonation is a reversible reaction that produces benzenesulfonic acid by adding sulfur trioxide and fuming sulfuric acid.


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