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Starting from toluene, propose syntheses for ortho-, meta-, and para-chlorobenzoic acid.

Short Answer

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A chemical reaction in which a hydrogen atom on a benzene ring is replaced by a sulfonic acid functional group in an electrophilic aromatic substitution is known as sulphonation.

Step by step solution

01

Sulphonation

A chemical reaction in which a hydrogen atom on a benzene ring is replaced by a sulfonic acid functional group in an electrophilic aromatic substitution is known as sulphonation.

02

Step 2: The SO3H group  is a blocking group.

The SO3H group can be used to block a position on the ring. This is a common procedure to make ortho isomers when the para position is more reactive. To get an ortho product, the para position is blocked using SO3H, substituting the ortho position, and then removing the blocking group.

03

Synthesis of ortho-chlorobenzoic acid.

Here, the sulphonation of the benzene ring forms a para-substituted product. The para-substituted product undergoes chlorination at ortho of methyl (+I effect) and meta of sulpho group (-M effect).

The hydrolysis eliminates the sulpho group and the final oxidation step forms ortho-chlorobenzoic acid.

04

Synthesis of meta-chlorobenzoic acid.

Here, the oxidation of the methyl group forms benzoic acid.

The chlorination of benzoic acid adds the chlorine group at meta-position to the carboxylic group (-COOH). This is because -COOH group (-M effect) is extracting electron density from ortho and para position.

05

Synthesis of para-chlorobenzoic acid.

Here, firstly the chlorination goes at the para position as it is not occupied.

Later, the compound is oxidized to form para-chlorobenzoic acid.

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Most popular questions from this chapter

(a) Based on what you know about the relative stabilities of alkyl cations and benzylic cations, predict the product of addition of HBr to 1-phenylpropene.

(b) Propose a mechanism for this reaction.

(c) Based on what you know about the relative stabilities of alkyl radicals and benzylic radicals, predict the product of addition of HBr to 1-phenylpropene in the presence of a free-radical initiator.

(d) Propose a mechanism for this reaction.

Show how you would use Suzuki reactions to synthesize these products from the indicated starting materials. You may use any additional reagents you need.

In Chapter 14, we saw that Agent Orange contains (2,4,5-trichlorophenoxy) acetic acid, called 2,4,5-T. This compound is synthesized by the partial reaction of 1,2,4,5-tetrachlorobenzene with sodium hydroxide, followed by a reaction with sodium chloroacetate, ClCH2CO2Na.

(a) Draw the structures of these compounds, and write equations for these reactions.

(b) One of the impurities in the Agent Orange used in Vietnam was 2,3,7,8-tetrachlorodibenzodioxin (2,3,7,8-TCDD), often incorrectly called 鈥渄ioxin.鈥 Propose a mechanism to show how 2,3,7,8-TCDD is formed in the synthesis of 2,4,5-T.

(c) Show how the TCDD contamination might be eliminated, both after the first step and on completion of the synthesis

Predict the major products of treating the following compounds with hot, concentrated potassium permanganate, followed by acidification with dilute HCl.

(a) isopropylbenzene

(b) p-xylene

(c) tetralin

Propose products (if any) and mechanisms for the following AICI3-catalyzed reactions:

猞 chlorocyclohexane with benzene

猞 methyl chloride with anisole

猞 3-chloro-2,2-dimethylbutane with isopropylbenzene

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