Chapter 9: Problem 66
Starting with either benzene or toluene, how would you synthesize the following substances? Assume that ortho and para isomers can be separated. (a) 2 -Bromo-4-nitrotoluene (b) \(2,4,6\) -Tribromoaniline (c) 3-Bromo-4-tert-butylbenzoic acid (d) 1,3-Dichloro-5-ethylbenzene
Short Answer
Expert verified
Use electrophilic substitution reactions, starting with nitration or chlorination/alkylation, then separate or transform as needed.
Step by step solution
01
Synthesize 2-Bromo-4-nitrotoluene
Start with toluene. First, perform nitration by reacting toluene with a mixture of concentrated nitric acid and sulfuric acid to introduce a nitro group mainly at the ortho and para positions due to the electron-donating methyl group. Then, brominate the nitration product using bromine (
Br_2
) in the presence of a Lewis acid like FeBr_3, which directs bromination to the position nearest the methyl and nitro groups. Separate the ortho isomer from any para isomer.
02
Synthesize 2,4,6-Tribromoaniline
Start with benzene. First, perform nitration to introduce a nitro group. Then, perform a bromination reaction three times with
Br_2
in the presence of a catalyst like FeBr_3 to introduce bromine atoms at the ortho and para positions. Reduce the nitro group to amine using tin (Sn) and hydrochloric acid (HCl) to obtain 2,4,6-tribromoaniline.
03
Synthesize 3-Bromo-4-tert-butylbenzoic acid
Begin with benzene. Use Friedel-Crafts alkylation to introduce a tert-butyl group, directing primarily to the para position. Next, perform bromination to introduce bromine at the meta position relative to the previously introduced tert-butyl group. After this, oxidize the position ortho to the tert-butyl group with potassium permanganate (
KMnO_4
) to convert it into a carboxyl group, yielding 3-bromo-4-tert-butylbenzoic acid.
04
Synthesize 1,3-Dichloro-5-ethylbenzene
Start with toluene. Use Friedel-Crafts alkylation to introduce an ethyl group to the meta position, creating ethylbenzene. Chlorinate this meta-ethylbenzene using Cl2 in the presence of a catalyst like FeCl3 to introduce chlorine atoms at the 1 and 3 positions, resulting in 1,3-dichloro-5-ethylbenzene.
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Key Concepts
These are the key concepts you need to understand to accurately answer the question.
Nitration
Nitration is a critical process in organic chemistry, especially for synthesizing nitro compounds which serve as powerful intermediates in various chemical transformations. Generally, nitration involves the introduction of a nitro group (\(-NO_2\)) into an organic molecule such as benzene or toluene.
In the case of toluene, nitration typically uses a mixture of concentrated nitric acid and sulfuric acid. This mixture generates a nitronium ion (\(NO_2^+\)), a potent electrophile that reacts with the aromatic ring. Because the methyl group of toluene acts as an electron-donating group, the nitro group primarily attaches at the ortho and para positions
In the case of toluene, nitration typically uses a mixture of concentrated nitric acid and sulfuric acid. This mixture generates a nitronium ion (\(NO_2^+\)), a potent electrophile that reacts with the aromatic ring. Because the methyl group of toluene acts as an electron-donating group, the nitro group primarily attaches at the ortho and para positions
- Toluene enhances nitration at ortho and para positions.
- A mixture of nitric and sulfuric acid is used to nitrate.
- Nitration provides a useful route to multi-substituted aromatic compounds.
Bromination
Bromination is a fundamental reaction in organic chemistry which is used to introduce bromine atoms onto aromatic rings. This process uses a bromine (\(Br_2\)) reactant, typically in the presence of a catalyst such as iron(III) bromide (\(FeBr_3\)), to facilitate the substitution reaction by forming a complex intermediate.
Toluene and benzene undergo bromination readily due to their aromatic characteristics. In the synthesis of 2-bromo-4-nitrotoluene, bromination follows nitration. The position of bromine in such syntheses is often close to the electron-donating or electron-withdrawing groups already present in the molecule, depending on their directing effects.
Toluene and benzene undergo bromination readily due to their aromatic characteristics. In the synthesis of 2-bromo-4-nitrotoluene, bromination follows nitration. The position of bromine in such syntheses is often close to the electron-donating or electron-withdrawing groups already present in the molecule, depending on their directing effects.
- In bromination, the presence of Lewis acid catalysts enhances the electrophilicity of bromine.
- The reaction proceeds with the substitution of a hydrogen atom by a bromine on the aromatic ring.
- The position of substitution is influenced by existing groups on the molecule.
Friedel-Crafts Alkylation
Friedel-Crafts Alkylation is a method used to attach alkyl groups to an aromatic ring, significantly impacting organic synthesis. It involves the use of a catalyst, typically a Lewis acid like aluminum chloride (\(AlCl_3\)), and an alkyl halide.
This procedure is notable for its ability to introduce substituents that further dictate future reactions. For example, in the synthesis of 3-bromo-4-tert-butylbenzoic acid, a tert-butyl group is added using Friedel-Crafts Alkylation. The new substituent often directs subsequent reactions based on its electron-donating or -withdrawing nature.
This procedure is notable for its ability to introduce substituents that further dictate future reactions. For example, in the synthesis of 3-bromo-4-tert-butylbenzoic acid, a tert-butyl group is added using Friedel-Crafts Alkylation. The new substituent often directs subsequent reactions based on its electron-donating or -withdrawing nature.
- Highly selective for directing substitution sites on aromatic rings.
- Uses Lewis acids to facilitate the formation of carbocation intermediates.
- Versatile method for installing complex hydrocarbon frameworks on aromatic structures.
Chemical Reduction
Chemical reduction in organic synthesis typically involves the gain of electrons or the loss of oxygen from a compound. One of the common reductions involves converting nitro groups (\(-NO_2\)) to amines (\(-NH_2\)), a transformation crucial in producing aniline derivatives.
A common methodology employs metals like tin or iron in the presence of hydrochloric acid to achieve the reduction. This transformation is seen in the synthesis of 2,4,6-tribromoaniline from its nitro precursor. This reduction is essential for converting aromatic nitro groups, facilitating the synthesis of amines which serve as building blocks for a variety of organic compounds.
A common methodology employs metals like tin or iron in the presence of hydrochloric acid to achieve the reduction. This transformation is seen in the synthesis of 2,4,6-tribromoaniline from its nitro precursor. This reduction is essential for converting aromatic nitro groups, facilitating the synthesis of amines which serve as building blocks for a variety of organic compounds.
- Reduction changes functional groups, allowing new reactivity in the compound.
- Converts nitro groups to amines using metals and acids.
- Creates important intermediates for pharmaceuticals and dyes.